JP2018158993A - Diketopyrrolopyrrole pigment composition and coloring composition based on that diketopyrrolopyrrole pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a diketopyrrolopyrrole pigment composition allowing control of the color tone more economically and freely; and a coloring composition based on the diketopyrrolopyrrole pigment composition.SOLUTION: A diketopyrrolopyrrole pigment composition comprises a diketopyrrolopyrrole pigment represented by general formula (1) and an aromatic amide compound represented by general formula (2). In the diketopyrrolopyrrole pigment composition, the diketopyrrolopyrrole pigment may be represented by general formula (3).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a diketopyrrolopyrrole pigment composition whose 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. In general, organic pigments are often classified into azo pigments and polycyclic pigments because of their chemical structures. An azo pigment has an azo group as a chromophore, has a clear hue, has a large coloring power, and is relatively inexpensive. Therefore, it mainly colors yellow to red colors such as printing inks, paints, plastics, and stationery. Although it is widely used, the weather resistance is difficult. The weather resistance is improved by introducing a benzimidazolone skeleton into the pigment structure and forming hydrogen bonds between molecules. (Patent Document 1, Non-Patent Document 1) However, when such a skeleton is introduced into the pigment, the pigment becomes economically expensive and, at the same time, the color characteristics change before and after the introduction of the skeleton, thereby improving the weather resistance. However, the pigment cannot be used due to a change in color characteristics. Examples of pigments incorporating a benzimidazolone skeleton 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 more expensive than a general azo pigment, 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 example of the polycyclic pigment is a blue copper phthalocyanine pigment, which exhibits a clear blue color. Examples of pigments exhibiting a yellow to red color include isoindoline, anthraquinone, diketopyrrolopyrrole, perylene, and quinacridone pigments, but there are few color types and variations compared to azo pigments, and the means of selection are limited. .

  As a method for controlling the hue of the organic pigment, a method for controlling the crystal type such as copper phthalocyanine (for example, α type, β type, ε type) or a solid solution such as diketopyrrolopyrrole is used to control the hue. The method (Patent Document 2) and the like can be mentioned, but the most effective method for controlling the dye is to introduce a substituent such as a halogen or an alkyl group as an auxiliary color group into the pigment skeleton. (Non-Patent Document 2) However, while this method complicates the reaction process, the cost is high, and further, when halogen is used, there is a possibility that PCB or the like is generated as an unintended by-product. There is also. (Non-Patent Document 3) Therefore, the method of hue control using halogen should not be used in consideration of future human health and the global environment.

JP-A-56-38354 JP 63-048279 A

Kentaro Shima, “Functional Pigment Technology”, Popular Edition, CMC Publishing, September 24, 2004, p. 80 Isao Hashimoto, “Organic Pigment Handbook”, first edition, Color Office, May 2006, p. 26-35 Study meeting on the level of industrially and economically reduced PCBs that are by-produced in organic pigments, "Report on the level of industrially and economically reduced levels of PCBs that are by-produced 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 is used, and a diketo whose hue can be controlled more economically without introducing a new auxiliary color group into a substituent. It is to provide a pyrrolopyrrole pigment composition, and a coloring composition using the diketopyrrolopyrrole pigment composition.

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

That is, this invention relates to the diketopyrrolopyrrole pigment composition characterized by including the diketopyrrolopyrrole pigment represented by General formula (1), and the aromatic amide compound represented by General formula (2).
[In General Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a carbon number. An alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ is represented. R _{11 to} R ₁₅ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
[In General Formula (2), R _{16 to} R ₂₅ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a carbon number. An alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ is represented. R _{11 to} R ₁₅ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y each independently represent -CONH- or -NHCO-. ]

The present invention also relates to the diketopyrrolopyrrole pigment composition described above, wherein the diketopyrrolopyrrole pigment is represented by the general formula (3).
[In General Formula (3), R ₂₆ and R ₂₇ each independently represent a hydrogen atom, a halogen atom, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 4 carbon atoms. Represents a group or an aryl group having 6 to 10 carbon atoms. ]

  The present invention also relates to a coloring composition comprising the diketopyrrolopyrrole pigment composition described above and a resin.

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

It is the reflection spectrum of the ink using the pigment red 255 type coloring composition. (Examples 15 and 17, Comparative Example 1) It is the reflection spectrum of the ink using the pigment red 254 series coloring composition. (Example 20, comparative example 2) It is the reflection spectrum of the ink using the pigment red 264 series coloring composition. (Example 23, Comparative Example 3) It is the reflection spectrum of the ink using the pigment red 272 type 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 General Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a carbon number. An alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ is represented. R _{11 to} R ₁₅ each independently represents 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 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -A butyl group, a tert- butyl group, etc. 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 include vinyl group, 1-propenyl group, aryl group, 2-butenyl group, and 3-butenyl. Group, isopropenyl group, isobutenyl group, 1,3-butadienyl group 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 such as 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 are not limited thereto.

  Preferable examples of the diketopyrrolopyrrole pigment used in the present invention include diketopyrrolopyrrole pigments represented by the following general formula (3).

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

  The halogen atom, the C1-C4 alkyl group, and the C6-C10 aryl group of General formula (3) are synonymous with the thing of General formula (1).

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

  Specific examples of the diketopyrrolopyrrole pigment include the following diketopyrrolopyrrole pigments, but the present invention is not limited thereto.

(Production method of diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment used in the present invention can be produced, for example, by reacting the corresponding aromatic nitrile and oxalic acid diester in an organic solvent as disclosed in JP-A-58-210084. The production method of the diketopyrrolopyrrole pigment is not limited to this method.

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 any crystal form called a polymorph. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  The diketopyrrolopyrrole pigments can be used alone or in admixture of two or more.

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

[In General Formula (2), R _{16 to} R ₂₅ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a carbon number. An alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ is represented. R _{11 to} R ₁₅ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y each independently represent -CONH- or -NHCO-. ]

The halogen atom of R _{16 to} R ₂₅ , 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 in the general formula (2) are those of the general formula (1). It is synonymous.

  Specific examples of the aromatic amide compound include the compounds shown below, but the present invention is not limited thereto.

(Method for producing aromatic amide compound)
The aromatic amide compound used in the present invention can be produced by reacting the corresponding aromatic amine and oxalyl chloride in the presence of a base (for example, triethylamine) 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, the diketopyrrolopyrrole pigment and the aromatic amide compound are mixed with a solvent, or dissolved in a solvent and then mixed with another solvent and precipitated. The method of mixing both using a salt milling process is mentioned. In addition, a method of mixing and depositing the aromatic amide compound of the present invention in a reaction solution immediately after synthesis of diketopyrrolopyrrole is also exemplified, but the method for producing a diketopyrrolopyrrole pigment composition is limited to this method. is not.

  Examples of the solvent for mixing or dissolving the diketopyrrolopyrrole pigment and the aromatic amide compound include sulfuric acid, N, N-dimethylformamide, N-methylformamide, tetramethylurea, N, N-dimethylacetamide. N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, glacial acetic acid, ketones such as cyclohexanone, alcohols such as n-butanol, isopropyl alcohol, cyclohexanol or benzyl alcohol, and 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, butyl acetate and the like, but not limited thereto.

  Further, when the diketopyrrolopyrrole pigment is dissolved and mixed, it is preferable to use a base in the solvent in order to facilitate 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, potassium hydroxide. However, it is not limited to these.

  The solvent used for precipitation after dissolving the diketopyrrolopyrrole pigment and the aromatic amide compound in the solvent can be mixed with the above polar solvent, and can be the solvent in which the diketopyrrolopyrrole pigment composition of the present invention is precipitated. Anything is fine.

  More preferred solvents for dissolving the diketopyrrolopyrrole pigment are sulfuric acid, N, N-dimethylformamide, N-methylformamide, tetramethylurea, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, 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 is 10 to 100 ° C, more preferably 20 to 60 ° C, although it depends on the boiling point of the solvent. The dissolution time is preferably 30 minutes to 24 hours. In the case of mixing with another solvent and precipitating, a low temperature of −10 to 30 ° C. is preferable when it is desired to make the particles fine. Furthermore, when controlling particle | grains largely, after mixing a precipitation solvent, you may heat at 40-100 degreeC, and heating time is 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, and more preferably 0.5 to 50% by mass.

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

  Salt milling is performed by mixing 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, a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, etc. In this treatment, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating. The kneading temperature in 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. Moreover, when mixing a diketopyrrolopyrrole pigment and an aromatic amide compound, they may be used in combination of two or more.

  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 cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass) in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet 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 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% by mass, and most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

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

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

In 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 represents a saturated or unsaturated alkyl group which may be substituted, or a heterocyclic ring which may be substituted containing a nitrogen, oxygen or sulfur atom in R ₂₈ or R _29. .
However, n and q represent the integer of 1-10.

In 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 NH— However, q represents the integer of 1-10.
R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ each independently represents a hydrogen atom, a saturated or unsaturated alkyl group which may be substituted, or an aryl group.
R ₃₄ represents an optionally substituted saturated or unsaturated alkyl group or aryl group.

  The dye derivative is preferably a diketopyrrolopyrrole derivative, a quinacridone derivative, or an azo dye derivative from the viewpoint of not staining the hue of the dichlorodiketopyrrolopyrrole pigment.

  As the diketopyrrolopyrrole derivative, the following compounds can be used, but are not limited thereto.

Moreover, as a quinacridone derivative, the following compounds can be used, but are not limited thereto.

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

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

In general formulas (7) and (8),
R ₃₅ and R ₃₆ each independently represents a saturated or unsaturated alkyl group which may be substituted, or R ₃₅ and R ₃₆ each independently represents a heterocyclic ring which may contain a nitrogen, oxygen or sulfur atom. . However, n represents the integer of 1-10.

As the azo dye derivative, the following compounds can be used, but are not limited thereto.

In the salt milling treatment, a resin, a surfactant, or a higher fatty acid may be added in addition to the pigment derivative as necessary.
The resin that can be used is not particularly limited, but rosin, rosin derivative, rosin-modified maleic acid resin, rosin-modified phenolic resin, rubber derivative, protein derivative, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, polyvinyl acetate, Epoxy resin, acrylic resin, maleic 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 And benzoguanamine resins and urea resins. Moreover, there is no restriction | limiting in particular also as surfactant, Any surfactant of anionicity, neutrality, and cationic may be used.

  Higher fatty acids are fatty acids that react with glycerin and react with glycerin, and are widely soluble in animal fats and vegetable oils. They are sparingly soluble in highly lipophilic water, such as palmitic acid and linoleic acid. , Stearic acid, linolenic acid, oleic acid and the like. The higher fatty acid is preferably a fatty acid having 10 or more carbon atoms, and more preferably an unsaturated higher fatty acid that is liquid at 20 to 30 ° C. In contrast, fatty acids with a small number of carbons include acetic acid, valeric acid, and lactic acid, which are free acid and hydrophilic. Higher fatty acids with strong lipophilicity are suitable as the fatty acid that wets the pigment to increase the grinding effect and promotes refinement. In addition, water-soluble inorganic salts and water-soluble organic solvents used in wet pulverization are separated from fine pigments by washing with water, but hydrophilic fatty acids having a small number of carbons are dissolved in water, resulting in BOD, COD. It is not preferable because it becomes a factor of increase. Two or more types of higher fatty acids may be used as needed.

  The colored composition of the present invention may be aqueous or non-aqueous. As a medium for dispersing the diketopyrrolopyrrole pigment composition in the colored composition of the present invention, water, an organic solvent, a polymerizable monomer, and the like can be used. When the coloring composition of the present invention is an aqueous coloring composition, a mixture containing water as a main component and optionally adding 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 Coal 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, Glycol derivatives such as triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl 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, other formamide, N, N -Dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, thiodiethanol, thiodiglycerol, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3 -Water-soluble solvents such as dimethyl-2-imidazolidinone, acetonitrile, acetone, methyl ethyl ketone, ethylene carbonate, propylene carbonate, etc. .

  Furthermore, the aqueous coloring composition of the present invention may contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

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

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin. Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based resins.

  When the coloring composition of the present invention is a non-aqueous coloring composition, the diketopyrrolopyrrole pigment composition is dispersed in a non-aqueous binder as a medium. Resins used for non-aqueous binders include, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid Rubber, phenolic 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, silicone resin, fluorine Examples thereof include resins, drying oils, synthetic drying oils, styrene / maleic acid resins, styrene / acrylic resins, polyamide resins, polyimide resins, benzoguanamine resins, melamine resins, urea resins, chlorinated polypropylene, butyral resins, and vinylidene chloride resins. 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 acetates such as ethyl acetate and 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, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, N, N-dimethylacetate Carbamines such as amides, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine and other nitrogen compound solvents, lactone solvents such as γ-butyrolactone, 48:52 mixtures of methyl carbamate and ethyl carbamate Acid ester etc. are mentioned.

(Photopolymerizable monomer)
You may add a photopolymerizable monomer to the coloring composition of this invention as needed. The photopolymerizable monomer includes a monomer or oligomer that is cured by ultraviolet rays or heat to generate 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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether 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.
These photopolymerizable compounds can be used singly or in combination 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)
If necessary, the colored composition of the present invention is cured by ultraviolet irradiation, and a photopolymerization initiator is added to form a filter segment by photolithography. Can be prepared in the form of an ionic 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- 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-methoxyphenyl) Nyl) -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 an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  It is preferable that content of a photoinitiator is 2-200 mass parts with respect to 100 mass parts of coloring agents, and it is more preferable that it is 3-150 mass parts from a viewpoint of photocurability and developability.

(Sensitizer)
Furthermore, the coloring composition of the present invention can contain a sensitizer as necessary.
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) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  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.

  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 colored composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

(Antioxidant)
The coloring composition of this invention can contain antioxidant as needed. Antioxidants, especially when used in color filter applications, are photopolymerization initiators and thermosetting compounds that are oxidized and yellowed by thermal processes during thermal curing and ITO (indium tin oxide) annealing. Therefore, 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 high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 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-tert-butyl-5-methylphenol), 2,2'-thio- Su- (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 Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-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)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (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.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. 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.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine 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 salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

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

  Further, the content of the antioxidant is more preferable in terms of hue when it is 0.5 to 5.0% by mass based on the solid content mass of the colored composition.

(Amine compounds)
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen as needed.

  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)
The coloring composition of the present invention can contain a leveling agent as necessary 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 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. In general, the leveling agent content is preferably 0.003 to 0.5% by mass based on the total mass of the coloring 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 of this invention can be made to contain a hardening | curing agent, a 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 parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additive components)
If necessary, the 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 parts by mass with respect to 100 parts by mass of the colorant.

  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 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 colored composition of the present invention can be obtained by dispersing a diketopyrrolopyrrole pigment composition, a binder resin, and an aqueous or non-aqueous medium using a dispersing device. The method for dispersing the diketopyrrolopyrrole pigment composition is not particularly limited. For the dispersion, a generally used mixing and stirring device such as an anchor blade can be used. Among the mixing and stirring devices, Ultra Disper [Asada Steel Corporation, product name], Ebara Milder [Ebara Manufacturing Co., Ltd., product name], TK Homomixer, TK Pipeline Mixer, TK Homojetter, TK Homomic Line Flow, High-speed agitating and mixing devices such as Filmix [Special Machine Industry Co., Ltd., trade name], Clear Mix [M Technique Co., Ltd., trade name], KD Mill [Kinetic Dispersion Co., Ltd., trade name] and the like are preferable. In addition, kneading machines such as roll mills, bead mills, kneaders and extruders, high-pressure homogenizers [Izumi Food Machinery Co., Ltd., trade name], mini-valve type high-pressure homogenizers represented by 8.3H type (Rannie Co., trade name), micro Fluidizer (Microfluidics, trade name), Nanomizer (Nanomizer, trade name), Ultimateizer (Sugino Machine Co., trade name), Genus PY (Shiramizu Chemical Co., trade name), DeBEE2000 (Nippon BB Corporation) , Trade name] and the like, and a dispersion method using a chamber-type high-pressure homogenizer. 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 the diketopyrrolopyrrole pigment composition is dispersed, a dye derivative may be added as necessary. The pigment derivative is synonymous with the compound described in the salt milling treatment.

  After obtaining a coloring composition by such a method, in order to remove a deposit and a coarse particle, you may further centrifuge and include the process of isolate | separating a precipitate. As a device used for centrifugal separation, centrifugal filtration generally uses a centrifugal sedimentator for centrifugally sedimenting suspended matter by rotating a non-porous rotating bowl at high speed, and a rotating basket having pores or slits on a side wall.・ Dehydrators are known. In the present invention, among these, a centrifugal settling machine can be suitably used [for example, “Chemical Equipment Handbook” edited by the Chemical Engineering Society, revised second edition, second edition, Maruzen Co., Ltd., April 5, 1996, See page 798]. Examples of the centrifugal settling machine include centrifugal settling machines such as a centrifugal sedimentation tube type, a cylindrical type, a separation plate type, a basket type, and a scriber decanter type.

  The concentration of the diketopyrrolopyrrole pigment composition contained in the colored composition of the present invention is preferably in the range of 1 to 35% by mass, and 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, electronic paper, and image sensors such as CCDs.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” represents “part by mass”.

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 over 20 minutes. After dropping, the mixture was stirred at 70 ° C. for 3 hours. After air cooling, 80 parts of methanol and 50 parts of water were added to the reaction solution. After stirring for 1 hour, the solid was collected by suction filtration. The obtained solid was reslurry washed with 100 parts of water and further with 80 parts of methanol. It dried overnight with the vacuum dryer (40 degreeC), and obtained 8.30 parts of target objects. The yield was 88.5%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). 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 process for producing the aromatic amide compound 1 to obtain 9.10 parts of the desired product. The yield was 83.6%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). 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 process for producing the aromatic amide compound 1 to obtain 8.93 parts of the desired product. The yield was 82.1%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). 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 production method of the aromatic amide compound 1, and 10.20 parts of the target product was obtained. The yield was 87.4%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 297.45 (molecular weight: 296.37), which confirmed the intended product.

Aromatic amide compound 5

Oxanilide (Tokyo Chemicals) was used.

<Method for producing diketopyrrolopyrrole pigment>
C. I. Pigment Red 254

Under a nitrogen atmosphere, 40 parts of tert-amyl alcohol dehydrated with molecular sieves 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 tert-amyl alcohol dehydrated with molecular sieves, 17.6 parts of diisopropyl oxalate, and 20 parts of 4-chlorobenzonitrile were mixed and heated to 90 ° C. with stirring to dissolve them. It was adjusted. The heated solution of the mixture was slowly added dropwise to the prepared alcoholate solution at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, 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 the cooled mixture was vigorously stirred, the previously obtained 90 ° C dichlorodiketopyrrolol reaction solution was added while cooling with a refrigerant so as to maintain a temperature of 5 ° C or lower. After stirring this liquid at 40 degreeC for 1 hour, the dichloro diketo pyrrolol pigment was separated by filtration using Nutsche. Then, it washed by sprinkling 120 parts of methanol and 200 parts of water. 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 is manufactured by C.I. I. Instead of 4-chlorobenzonitrile in the production method of Pigment Red 254, 15 parts of benzonitrile were used. 17.1 parts of the desired pigment were obtained.

C. I. Pigment Red 264

  C. I. Pigment Red 264 is manufactured by C.I. I. Instead of 4-chlorobenzonitrile in the production method of Pigment Red 254, 26.1 parts of 4-cyanobiphenyl was used. 28.2 parts of the desired pigment were obtained.

C. I. Pigment Red 272

  C. I. Pigment Red 272 is manufactured by C.I. I. Instead of 4-chlorobenzonitrile in the production method of Pigment Red 254, 17 parts of 4-cyanotoluene were used. 19.5 parts of the desired pigment are 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. Pigment Red 255 (14.4 parts) and aromatic amide compound 1 (6.0 parts) were added and dissolved, and the mixture was stirred at 30 ° C. for 3 hours. Thereafter, 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 liquid at room temperature for 2 hours, diketopyrrole pigment composition P-1 was separated by filtration using Nutsche. Then, it washed by sprinkling 2000 parts of water. 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. Diketopyrrolopyrrole pigment composition P-, except that CI Pigment Red 255, aromatic amide compound 1, sodium-tert-butoxide was changed to the diketopyrrolopyrrole pigment and the type and blending amount of aromatic amide compound shown in Table 3 In the same manner as in No. 1, diketopyrrolopyrrole pigment compositions P-2 to P-13 were prepared.

[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 into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Salt milling was performed. The obtained kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 104 parts of diketopyrrolopyrrole pigment composition P-14 were obtained.

[Example 15]
(Coloring composition (T-1))
0.5 g of the pigment composition (P-1) obtained in Example 1 and 50 parts by mass of varnish (Tamanol 361 (Arakawa Chemical Industries, Ltd .: rosin-modified phenol resin)) Solvent (Nippon Petroleum Co., Ltd .: Solvent for offset ink) added with 30 parts by mass, heated and dissolved at 200 ° C.) 2.5 g of Hoover-Muller with a load of 150 lb (= 667 N) applied at a rotational speed of 100 rpm. The mixture was kneaded once to obtain a colored composition T-1.

[Examples 16 to 28, Comparative Examples 1 to 4]
(Coloring composition (T-2 to 18))
A colored composition (T-2 to 18) was produced in the same manner as the colored composition (T-1) except that the pigment composition (P-1) was changed as shown in Table 4. Moreover, the pigment was used for the comparative example.

[Evaluation of coloring composition]
It was prepared by dispersing 0.5 g of the colored 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 in 50 parts of the varnish for offset ink). The ink was obtained by kneading and mixing 5.0 g 4 times with a Hoover Muller with a load of 50 lb (= 222 N) at a rotational speed of 25 rpm. The hue of this ink was evaluated using a spectrophotometer (V560 manufactured by JASCO Corporation). Table 5 shows the hue results (L ^* , a ^* , b ^* ), and FIGS. L ^* , a ^* and b ^* are based on JIS Z 8781-4.

For example, when the hue is made yellowish based on the colored composition of Comparative Example 1 (b ^* is increased), Comparative Example 1 is obtained by using the colored compositions of Examples 15, 16, 17, 20, and 25. A colored composition having a yellowish hue can be obtained from the colored composition. Moreover, when making the coloring composition of the comparative example 1 into a bluish hue (b ^* is made small), the coloring composition with a more bluish hue is obtained by using the coloring composition of Examples 23 and 24. be able to. Furthermore, when the hue is reddish based on the colored composition of Comparative Example 1 (a ^* is increased), the hue is more reddish by using the colored compositions of Examples 21, 22, 26, and 27. A colored 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 colored composition whose hue can be arbitrarily controlled were obtained.

1 of FIG. 1 is the reflection spectroscopy of the ink which mixed coloring composition T-1 and white ink.
1 of FIG. 1 is the reflection spectrum of the ink which mixed coloring composition T-3 and white ink.
1 of FIG. 1 is the reflection spectrum of the ink which mixed coloring composition T-15 and white ink.

2 of FIG. 2 is the reflection spectroscopy of the ink which mixed coloring composition T-6 and white ink.
2 of FIG. 2 is the reflection spectroscopy of the ink which mixed coloring composition T-16 and white ink.

3 of FIG. 3 is the reflection spectroscopy of the ink which mixed coloring composition T-9 and white ink.
Reference numeral 7 in FIG. 3 is a reflection spectrum of an ink obtained by mixing the coloring composition T-17 and white ink.

Reference numeral 8 in FIG. 4 is a reflection spectrum of an ink obtained by mixing the coloring composition T-12 and white ink.
4 of FIG. 4 is the reflection spectrum of the ink which mixed coloring composition T-18 and white ink.

Claims (3)

A diketopyrrolopyrrole pigment composition comprising a diketopyrrolopyrrole pigment represented by the general formula (1) and an aromatic amide compound represented by the general formula (2).
[In General Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, carbon It represents an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In General Formula (2), R _{16 to} R ₂₅ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an amino group, an alkyl group having 1 to 4 carbon atoms, carbon It represents an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, —OR ₁₁ , —COOR ₁₂ , —CONHR ₁₃ , —NHCOR _14, or —SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y each 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 General Formula (3), R ₂₆ and R ₂₇ each independently represent a hydrogen atom, a halogen atom, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 4 carbon atoms. Represents a group or an aryl group having 6 to 10 carbon atoms. ]
  A coloring composition comprising the diketopyrrolopyrrole pigment composition according to claim 1 or 2 and a resin.