JP5176417B2 - Method for producing violet pigment - Google Patents

Description

  The present invention relates to a method for producing a violet pigment having excellent dispersibility. More specifically, the present invention relates to a method for producing a violet pigment having a printed material or a coated material having excellent gloss, coloring power and sharpness when used in ink or paint.

  For all pigments, not just violet pigments, reduced production costs, fluidity and storage stability when used in inks and paints, and quality related to the gloss, coloring power and sharpness of printed and painted materials There is a need for improvement.

  In general, a practically useful pigment that exhibits high gloss and high coloring power in various coating compositions consists of fine particles. Conventionally, when pigments, which are aggregates of fine primary particles, are dispersed in vehicles such as paints and gravure inks, in order to loosen the particles, they can be dispersed with a strong force for a long time or the dispersion can be promoted. A method by adding a dispersing agent is known. For example, there are a method of dispersing for a long time by a ball mill or a sand mill, a method of adding a pigment derivative (see Patent Document 1), a method of adding a dispersion resin (see Patent Document 2), and the like.

However, none of the methods was fully satisfactory. On the other hand, as a method for improving the dispersibility of the gravure ink by adjusting the powder particles of the pigment, a method using coarsely pulverized particles (see Patent Document 3), and a drying temperature is adjusted to reduce dry aggregation of the pigment wet cake. A method (see Patent Document 4), a method of forming granular particles (see Patent Documents 5 and 6), and a method of adjusting particles in the presence of a polymer (see Patent Document 7) have been proposed, but dispersibility is insufficient. Moreover, use may be restrict | limited by an application with an additive. Furthermore, a method of adding a pigment derivative to form granular particles has been proposed (see Patent Document 7), and there is an example of a water-based ink for inkjet recording of a phthalocyanine pigment, but a violet pigment gravure ink, offset ink, There are no examples of paints, plastic coloring, inkjet inks, color filters, color toners and the like. Further, in the gravure ink, in the copper phthalocyanine pigment, there was not much difference in the effect of concentration, coloring power, gloss and the like between the pulverized particles and the granular particles, and the effect of forming the granular particles was insufficient.
JP 59-96175 JP 57-74330 A JP-A-64-45475 Japanese Patent Laid-Open No. 57-53568 Japanese Patent Laid-Open No. 5-57102 JP-A-5-184901 JP 2001-81349 A JP 2006-152103 A

  In the present invention, pigment particles are finely sized to have a uniform particle size, and C.I. I. The present invention relates to a method for producing pigment violet 23. More specifically, the present invention relates to a method for producing a violet pigment having excellent gloss, coloring power and sharpness in a color developed product when particles of color developing powder are dispersed in a vehicle such as gravure ink or paint. .

  That is, the present invention relates to C.I. I. Regarding the method for producing a violet pigment characterized by spray-drying an aqueous slurry of Pigment Violet 23, preferably an organic dye derivative represented by the following general formula (1), an anthraquinone derivative represented by the following general formula (2), and The organic compound includes 0.1% to 30% of an organic compound selected from triazine derivatives represented by the following general formula (3), more preferably, the organic compound is an organic dye derivative represented by the general formula (1) , P is an organic dye residue. I. The present invention relates to a method for producing a violet pigment represented by pigment violet 23 residues.

_{P- {X 1 - (Y 1} ) l 1} m 1 (1)
(In the formula, P represents an organic dye residue. X ₁ is a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR) _1- , —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a straight chain or branched chain having 1 to 12 carbon atoms A divalent linking group represented by an alkylene group, an alkyl group that can be a divalent or trivalent linking group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a benzene residue optionally substituted with a halogen atom; A triazine residue or a linking group obtained by combining two or more of these linking groups, Y ₁ represents a nitroimido group or a phthalimidomethyl group optionally substituted with a halogen atom, —NR ₂ R ₃ , —SO ₃ .M / N or Represents COO · M / n, R ₂ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group or R _2, And R ₃ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom, M is a hydrogen ion, a 1-3 valent metal ion, or at least one is an alkyl group Represents a substituted ammonium ion, n represents the valence of M. l ₁ represents an integer of 1 or 2, and m ₁ represents an integer of ₁ to 4.
_{Q- {X 2 - (Y 2} ) l 2} m 2 (2)
(In the formula, Q represents an anthraquinone residue optionally substituted with an alkyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom. X ₂ represents a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR ₁ —, —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ is a hydrogen atom, an alkyl group) Represents a hydroxyalkyl group), a divalent linking group represented by a linear or branched alkylene group having 1 to 12 carbon atoms, an alkyl group that can be a divalent or trivalent linking group, an amino group, Y ₂ represents a nitro group, a hydroxyl group, an alkoxy group, a benzene residue or a triazine residue optionally substituted with a halogen atom, or a linking group obtained by combining two or more of these linking groups, and Y ₂ represents a nitro group or a halogen. Represents a phthalimidomethyl group optionally substituted with a hydrogen atom, —NR ₂ R ₃ , —SO ₃ · M / n, or —COO · M / n, wherein R ₂ and R ₃ are each independently a hydrogen atom, substituted An optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a substituted group containing additional nitrogen, oxygen or sulfur atoms together with R ₂ and R _3. And M represents a hydrogen ion, a monovalent to trivalent metal ion or an ammonium ion at least one of which is substituted with an alkyl group, n represents the valence of M. l ₂ is 1 Or, it represents an integer of ₂ , and m ₂ represents an integer of 1 to 4.)

（式中、Ｒはトリアジン残基を表す。Ｘ_３からＸ_５はそれぞれ独立に直接結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ₂−、−ＮＲ_１−、−ＣＯＮＲ_１−、−ＳＯ₂ＮＲ_１−、−ＮＲ_１ＣＯ−、−ＮＲ_１ＳＯ₂−（ここでＲ_１は、水素原子、アルキル基、ヒドロキシアルキル基を表す）、炭素の数が１〜１２個の直鎖または枝分かれしたアルキレン基で示される２価の結合基、２価あるいは３価の結合基に成り得るアルキル基、アミノ基、ニトロ基、水酸基、アルコキシ基、またはハロゲン原子で置換されていてもよいベンゼン残基、またはこれらの結合基を２個以上組み合わせた結合基を表す。Ｙ_３はニトロ基またはハロゲン原子で置換されていてもよいフタルイミドメチル基、−ＮＲ_２Ｒ_３、−ＳＯ_３・Ｍ／ｎ、または−ＣＯＯ・Ｍ／ｎを表し、Ｒ_２とＲ_３はそれぞれ独立に水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、またはＲ_２とＲ_３とで一体となって更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表し、Ｍは水素イオン、１〜３価の金属イオンまたは少なくとも１つがアルキル基で置換されているアンモニウムイオンを表し、ｎはＭの価数を表す。Ｙ_４とＹ_５は、それぞれ独立にＹ_１と同じであるか、または、アルキル基、アミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン原子、または置換されていてもよいフェニル基を表す。ｌ_３からｌ_５は、それぞれ独立しており１または２の整数を表す。） Formula (3)

(In the formula, R represents a triazine residue. X ₃ to X ₅ are each independently a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —. , —SO ₂ NR ₁ —, —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a straight chain having 1 to 12 carbon atoms. It may be substituted with a divalent linking group represented by a chain or branched alkylene group, an alkyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom that can be a divalent or trivalent linking group. A benzene residue or a linking group obtained by combining two or more of these linking groups, Y ₃ represents a nitroimido group optionally substituted with a nitro group or a halogen atom, —NR ₂ R ₃ , —SO ₃ .M / N or -CO O · M / n, R ₂ and R ₃ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₂ And R ₃ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom, where M is a hydrogen ion, 1 to 3 metal ions or at least one substituted with an alkyl group N represents the valence of M. Y ₄ and Y ₅ are each independently the same as Y ₁ , or an alkyl group, amino group, nitro group, hydroxyl group, alkoxy group And represents a halogen atom or an optionally substituted phenyl group. L ₃ to l ₅ are each independently an integer of 1 or 2.

  In gravure ink, C.I. I. The violet pigment of Pigment Violet 23 showed significant differences in density, coloring power, gloss, etc., compared with the pulverized particles and the granular particles, and exhibited effects that could not be assumed in the prior art. That is, C.I. I. Compared with the pulverized particles of Pigment Violet 23, the granule particles have almost the same median particle size distribution, show a sharp particle distribution with almost no coarse particles or excessively pulverized particles, and the particles are spherical and hollow. When the violet pigment obtained from the above is used dispersed in a vehicle such as gravure ink or paint, it can be dispersed to finer particles with a small amount of energy, and it has excellent gloss, coloring power and sharpness. Has the effect of giving sex. In addition, C.I. I. The effect of Pigment Violet 23 is remarkable. I. In Pigment Violet 23, since the primary particles of the pigment are fine, drying and pulverizing and agglomerating act strongly, and it is presumed that the action of drying and pulverizing and agglomerating is weakened in granular particles, while the dispersibility is poor. This difference in dry pulverization and aggregation can be inferred from the large difference in specific surface area between pulverized particles and granular particles.

  C. used in the present invention I. The pigment violet 23 uses a pigment form in which the average primary particles are adjusted to 400 nm or less, preferably 200 nm or less. In order to obtain such a pigment form, for example, a solvent may be used by a solvent salt milling method in which a crude pigment is ground in the presence of an inorganic salt or an organic solvent, a sulfuric acid solution of a crude pigment, or a sulfate added to a large amount of water to form a pigment. An acid pasting method for precipitating particles, a solvent method for dry-pulverizing a crude pigment, and then loosening fine particles with an organic solvent to grow crystals, etc. are used, and a solvent salt milling method with uniform particle shapes is preferred. This pigment form C.I. I. Pigment Violet 23 is filtered and washed to remove impurities, then dispersed in water and spray-dried as a water slurry. The water slurry concentration of the present invention is preferably as high as possible from the viewpoint of production efficiency, but if the slurry viscosity is high, quantitative supply becomes difficult, so 5 to 30% is preferable, and more preferably 10 to 20%. .

  Spray drying methods include atomizer method using centrifugal spraying with a rotating disk, turbine spraying method using a pressurized nozzle, and spraying method using a two-fluid nozzle. The atomizer method has a fine average particle size of the dried pigment and a small particle size distribution width. Therefore, it is preferable. An example of such a spray dryer is a NIRO spray dryer. The drying condition is that the inlet temperature of the water slurry is usually 200 to 350 ° C., the outlet temperature is in the range of 100 to 200 ° C., and the particle size can be adjusted by changing the amount of water slurry supplied, atomizer rotation speed, inlet temperature, and outlet temperature. Can be adjusted.

  Examples of the organic dye that forms the organic dye derivative represented by the general formula (1) used in the present invention include phthalocyanine dyes, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, and diaminodianthraquinone. , Anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinones Dyes such as quinophthalone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes, but dioxazine dyes, phthalocyanine dyes, quinacridone dyes, and anthraquinone dyes are preferable. I. Most preferred are dioxazine dyes having a resin adsorption effect similar to that of the pigment violet 23.

  The anthraquinone that forms the anthraquinone derivative represented by the general formula (2) is an alkyl group such as a methyl group or an ethyl group, an amino group, a nitro group, a hydroxyl group or a methoxy group, an alkoxy group such as an ethoxy group, or a halogen such as chlorine. Anthraquinone which may have a substituent. The triazine that forms the triazine derivative represented by the general formula (3) is 1,3,5-triazine.

  The organic dye derivative represented by the general formula (1), the anthraquinone derivative represented by the general formula (2), and the triazine derivative represented by the general formula (3) of the present invention have specific substitutions for the above organic dye, anthraquinone and triazine. An organic compound into which a group is introduced, and the substituent is, for example, phthalimidomethyl group, 4-nitrophthalimidomethyl group, 4-chlorophthalimidomethyl group, tetrachlorophthalimidomethyl group, (4,6-bis (phthalimidomethylamino) ) -1,3,5-triazine) -2-ylaminomethyl group, carbamoyl group, sulfamoyl group, methylamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, octylamino group, dodecylamino group Group, octadecylamino group, dimethylamino group, diethylamino , Dibutylamino group, dimethylaminopropylamino group, diethylaminopropylamino group, diethylaminoethylamino group, dibutylaminopropylamino group, piperidinomethyl group, dimethylaminomethyl group, diethylaminomethyl group, dibutylaminomethyl group, (4,6-bis (Diethylaminopropylamino) -1,3,5-triazin) -2-yl group, (4,6-bis (diethylaminopropylamino) -1,3,5-triazin) -2-ylamino group, (4- ( Diethylaminopropylamino) -6-hydroxy-1,3,5-triazin) -2-ylamino group, dimethylaminopropylaminosulfonyl group, diethylaminopropylaminosulfonyl group, dibutylaminopropylaminosulfonyl group, morpholinoethylamino Sulfonyl group, dimethylaminopropylaminocarbonyl group, 4- (diethylaminopropylaminocarbonyl) phenylaminocarbonyl group, dimethylaminomethylcarbonylaminomethyl group, diethylaminopropylaminomethylcarbonylaminomethyl group, dibutylaminopropylaminomethylcarbonylaminomethyl group, Sulfonic acid group, sodium sulfonate group, calcium sulfonate group, strontium sulfonate group, barium sulfonate group, aluminum sulfonate group, 4- (aluminum sulfonate group) phenylcarbamoylmethyl group, dodecylammoniosulfonate group, octadecylammoni group Osulfonato group, trimethyloctadecylammoniosulfonato group, dimethyldidecylammoniosulfonato group, carboxylic acid group, 2-a Luminium carboxylato-5-nitrobenzamidomethyl group, and the like.

  In addition, in the triazine derivative represented by the general formula (3), in addition to the above-described substituents which are essential forming elements, for example, a hydroxyl group, an amino group, a methoxy group, an ethoxy group, a phenoxy group, 4-nitrophenylamino And substituents such as a 4-benzaminophenylamino group and 4-aminophenoxy group.

  Examples of the organic dye derivative represented by the general formula (1), the anthraquinone derivative represented by the general formula (2), and the triazine derivative represented by the general formula (3) of the present invention include, for example, JP-B-39-28884 and JP-A-51-51. -18736, 54-62227, 56-32549, 56-81371, 56-118462, 56-166266, 59-96175, 60-88185, 60-98525, 63-305173, JP-A-03-26767, 11-199796 It can manufacture by the method of.

  Specific examples of the organic dye derivative represented by the general formula (1), the anthraquinone derivative represented by the general formula (2), and the triazine derivative represented by the general formula (3) of the present invention are shown below with compound numbers.

  The organic compound selected from the organic dye derivative represented by the general formula (1), the anthraquinone derivative represented by the general formula (2) and the triazine derivative represented by the general formula (3) of the present invention is C.I. I. It is preferable that 0.1%-30% is included with respect to the pigment violet 23. If it is less than 0.1%, it is difficult to obtain the added effect, and if it is 30% or more, the added effect cannot be obtained, and the physical properties of the obtained pigment composition and the organic pigment alone can be obtained. When the difference becomes large and it is used in inks and paints, problems in practical quality may occur.

  The organic compound selected from the organic dye derivative represented by the general formula (1), the anthraquinone derivative represented by the general formula (2) and the triazine derivative represented by the following general formula (3) is C.I. I. The pigment violet 23 may be added when the pigment is made into a pigment form, may be mixed as a water slurry, or may be mixed as a powder after spray drying. If necessary, rosin, resin, surfactant, etc. are added to C.I. I. It may be added to the pigment violet 23.

  C. produced by the method according to the invention. I. The pigment violet 23 can be used for gravure ink, flexo ink, offset ink, paint, inkjet ink, plastic coloring, color filter, color toner, etc., but gravure ink and flexo ink show particularly remarkable effects. For example, when a gravure ink is prepared, the vehicle to be used is not particularly limited, and may contain an auxiliary agent or extender pigment. As one example, gravure ink vehicles include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin ester, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate, ethyl cellulose, chlorinated rubber, cyclized rubber, Ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin, acrylic resin, gilsonite, dammar, shellac, etc., or a mixture of the above resins or a water-soluble resin obtained by water-solubilizing the above resins, or an emulsion resin And hydrocarbons, alcohols, ketones, ether alcohols, ethers, esters, water, and other solvents. Especially in gravure inks, cellulose, urethane resin, polyamide resin, acrylic resin Effect remarkable, high density, high color strength, clear quality is obtained in high gloss.

  C. in the vehicle. I. When the pigment violet 23 is mixed or dispersed, good mixing or dispersion can be performed by using a dissolver, a high speed mixer, a homomixer, a kneader, a flasher, a roll mill, a sand mill, an attritor or the like as a dispersing machine.

  Hereinafter, the present invention will be described in detail with reference to examples and comparative examples according to conventional methods. However, the present invention is not limited to the scope of these examples. In the examples, “parts” represents parts by weight, and “%” represents% by weight.

[Example 1]
C. I. 100 parts of Pigment Violet 23 crude pigment (Sumitomo Chemical First Violet 3R base), 800 parts of sodium chloride and 160 parts of diethylene glycol were charged into a 1000 volume part double arm kneader and kept in a dense lump at 90 ° C. The mixture was kneaded for 5 hours. The obtained kneaded composition was taken out in 5000 parts of water at 70 ° C., stirred for 1 hour with heat, filtered and washed with water to obtain a wet cake in the form of a pigment. 15 parts of this wet cake (in terms of solid content) was added to 85 parts of water and dispersed with a homomixer to obtain a water paste having a solid content concentration of 15%. C. I. The spray amount of Pigment Violet 23 water paste was adjusted using a spray dryer (MOBILE MINER manufactured by NIRO) so that the number of revolutions was 25000 rpm, the inlet temperature was 230 ° C., and the outlet temperature was 105 ° C. I. A dry powder of Pigment Violet 23 was obtained. C. I. Pigment Violet 23 pigment was a hollow spherical particle having an average primary particle of 50 nm, a specific surface area of 87 m ² / g, a powder particle diameter D50 of 10 μm, and a 99% particle diameter D99 of 44 μm.
This C.I. I. In the urethane ink using Pigment Violet 23, dispersibility was good and high density, coloring power, and gloss were exhibited.

[Example 2]
In Example 1, C.I. I. Pigment Violet 23 wet cake 14.25 parts (solid content conversion, 95%) and the above compound (1) 0.75 part (solid content conversion, 5%) as a derivative are added to water 85 parts and dispersed with a homomixer. In the same manner as in Example 1 except that a water paste having a solid content concentration of 15% was used, it was spray-dried. I. A dry powder of Pigment Violet 23 was obtained.
This C.I. I. In the urethane ink using Pigment Violet 23, dispersibility was good and high density, coloring power, and gloss were exhibited.

[Examples 3 and 4]
C. was spray-dried in the same manner except that the derivative was changed to compounds (2) and (3) in Example 2. I. A dry powder of Pigment Violet 23 was obtained.
[Example 5]
In Example 1, spray dried C.I. I. The wet cake of compound (1) was dried in a box dryer at 100 ° C. for 15 hours with 5 parts of dry powder of Pigment Violet 23, and 5 parts of pulverized powder that had been pulverized with a hammer mill were mixed with C.I. I. A dry powder of Pigment Violet 23 was obtained.
This C.I. I. In the urethane ink using Pigment Violet 23, dispersibility was good and high density, coloring power, and gloss were exhibited.

[Example 6]
C. I. Pigment Violet 23 crude pigment (Sumitomo Chemical First Violet 3R base) 95 parts, the previous compound (4) 5 parts, sodium chloride 800 parts, diethylene glycol 160 parts were charged into a 1000 volume parts double arm kneader at 90 ° C. While maintaining a dense lump (dough), the mixture was kneaded for 5 hours. The obtained kneaded composition was taken out in 5000 parts of water at 70 ° C., stirred for 1 hour with heat, filtered and washed with water to obtain a wet cake in the form of a pigment. Thereafter, the same operation as in Example 1 was performed and C.I. I. A dry powder of Pigment Violet 23 was obtained. C. I. Pigment Violet 23 pigment was a hollow spherical particle having an average primary particle of 45 nm, a specific surface area of 90 m ² / g, a powder particle diameter D50 of 11 μm, and a 99% particle diameter D99 of 40 μm. This C.I. I. In the urethane ink using Pigment Violet 23, dispersibility was good and high density, coloring power, and gloss were exhibited.

[Comparative Example 1]
C. I. 100 parts of Pigment Violet 23 crude pigment (Sumitomo Chemical First Violet 3R base), 800 parts of sodium chloride and 160 parts of diethylene glycol were charged into a 1000 volume part double arm kneader and kept in a dense lump at 90 ° C. The mixture was kneaded for 5 hours. The obtained kneaded composition was taken out in 5000 parts of water at 70 ° C., stirred for 1 hour with heat, filtered and washed with water to obtain a wet cake in the form of a pigment. The wet cake was dried with a box dryer at 100 ° C. for 15 hours, and C.V. I. A dry powder of Pigment Violet 23 was obtained. C. I. Pigment Violet 23 powder particles were agglomerated particles having an average primary particle size of 50 nm, a specific surface area of 83 m ² / g, a particle size D50 of 11 μm, and a 99% particle size D99 of 78 μm.
This C.I. I. The urethane ink using Pigment Violet 23 was inferior in dispersibility, and had low density, coloring power, and gloss.
[Comparative Example 2]
In Comparative Example 1, C.I. I. Pigment Violet 23 wet cake 14.25 parts (in terms of solid content) 0.75 parts of the above compound (1) (in terms of solid content) is added to 85 parts of water and dispersed with a homomixer to obtain a solid content concentration of 15%. And then filtered, dried in a box dryer at 100 ° C. for 15 hours, and pulverized by hammer mill. I. A dry powder of Pigment Violet 23 was obtained. This C.I. I. The urethane ink using Pigment Violet 23 was inferior in dispersibility, and had low density, coloring power, and gloss.

[Reference Example 1]
In Example 1, C.I. I. Pigment Violet 23 crude pigment was added to C.I. I. C. Pigment Blue 15: 3 (T99 Crude made by Zhuhai Toyo) I. A dry powder of CI Pigment Blue 15: 3 was obtained. The specific surface area was 71 m ² / g.
[Reference Example 2]
In Comparative Example 1, C.I. I. Pigment Violet 23 crude pigment was added to C.I. I. C. Pigment Blue 15: 3 (T99 Crude made by Zhuhai Toyo) I. A dry powder of CI Pigment Blue 15: 3 was obtained. The specific surface area was 69 m ² / g.
There is almost no difference in specific surface area between Reference Example 1 and Reference Example 2, and C.I. I. Pigment Blue 15: 3 is C.I. I. It was inferred that dry pulverization and aggregation were weaker than those of Pigment Violet 23.

(Evaluation method)
The primary particle diameter is an average of the long diameter in a TEM photograph (H-7650 transmission electron microscope manufactured by Hitachi), the particle diameter of the powder is a laser particle size distribution analyzer (HELOE & RODOS Helos Particle Analyzer), and the powder shape is SEM photograph (JEOL JSM-6700F), specific surface area was measured with a specific surface area measuring device (Mountech Macsorb HM 1208 type).

Dispersibility: C.I. I. 6 parts by weight of dry powder of Pigment Violet 23 was added to 48 parts of urethane resin varnish, 23 parts of MEK, ester and 23 parts of an alcohol solvent, and the mixture was stirred at 2500 rpm for 10 minutes using a high speed mixer as a premix. Measure the remainder. The smaller the value, the better the dispersibility.
Concentration: 225 ml mayonnaise bin with C.I. I. 6 parts by weight of dry powder of Pigment Violet 23, 48 parts of urethane resin varnish, 23 parts of MEK, 23 parts of ester, alcohol solvent, 100 g of 1.2 mmφ glass beads were weighed and dispersed for 60 minutes with a paint conditioner to prepare urethane ink. . The ink is developed on a triacetate film with a # 6 bar coater, and the density is visually evaluated. ○ is high density, × is low density.
Coloring power: A light color ink was prepared by mixing 2 g of urethane ink used for density measurement with 20 g of urethane white ink. Ink was developed on a triacetate film with a # 6 bar coater and measured with a colorimeter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The standard product was set as Comparative Example 1, and the relative coloring power of each Example and Comparative Example 2 was determined from the L value. The higher the value, the higher the coloring power.
Gloss: Measured 60 ° gloss with a gloss meter (VG2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The higher the value, the higher the gloss.

Claims (2)

C. I. A method for producing a violet pigment comprising spray-drying an aqueous slurry of pigment violet 23 , comprising: C.I. I. Water slurry comprising only CI Pigment Violet 23, or C.I. I. Pigment Violet 23 water slurry is C.I. I. An organic compound selected from an organic pigment derivative represented by the following general formula (1), an anthraquinone derivative represented by the following general formula (2), and a triazine derivative represented by the following general formula (3) with respect to CI Pigment Violet 23: A method for producing a violet pigment, comprising spray-drying a water slurry containing 1 to 30% by weight.
_{P- [X 1 - (Y 1} ) l 1] m 1 Equation (1)
(In the formula, P represents an organic dye residue. X ₁ is a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR. _1- , —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a straight chain or branched chain having 1 to 12 carbon atoms A divalent linking group represented by an alkylene group, an alkyl group that can be a divalent or trivalent linking group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a benzene residue optionally substituted with a halogen atom; triazine residue or .Y ₁ is a nitro group or a halogen atom which may be substituted phthalimidomethyl group representing two or more combined linking group of these linking _{groups,, -NR 2 R 3, -SO} 3 · M / N or -COO · M / The stands, R ₂ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group or R ₂ and R _3, Together represents an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom, where M is a hydrogen ion, a 1-3 valent metal ion, or an ammonium having at least one substituted with an alkyl group And n represents the valence of M. l ₁ represents an integer of 1 or 2, and m ₁ represents an integer of ₁ to 4.)
_{Q- [X 2 - (Y 2} ) l 2] m 2 Equation (2)
(In the formula, Q represents an alkyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or an anthraquinone residue optionally substituted with a halogen atom. X ₂ represents a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR ₁ —, —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ is a hydrogen atom, an alkyl group) Represents a hydroxyalkyl group), a divalent linking group represented by a linear or branched alkylene group having 1 to 12 carbon atoms, an alkyl group that can be a divalent or trivalent linking group, an amino group, Y ₂ represents a nitro group, a hydroxyl group, an alkoxy group, a benzene residue or a triazine residue optionally substituted with a halogen atom, or a linking group obtained by combining two or more of these linking groups, Y ₂ being a nitro group or a halogen atom. Put in Which may be phthalimidomethyl group, -NR ₂ R _3, represents -SO ₃ · M / n or -COO · M / n,, R 2 and R ₃ are each independently a hydrogen atom, optionally substituted A good alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or an optionally substituted group containing additional nitrogen, oxygen or sulfur atoms together with R ₂ and R ₃ Represents a heterocyclic ring, M represents a hydrogen ion, a metal ion having 1 to 3 valences or an ammonium ion in which at least one is substituted with an alkyl group, n represents a valence of M. l ₂ is an integer of 1 or 2 M ₂ represents an integer of 1 to 4.)
Formula (3)

(In the formula, R represents a triazine residue. X ₃ to X ₅ are each independently a direct bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —. , —SO ₂ NR ₁ —, —NR ₁ CO—, —NR ₁ SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a straight chain having 1 to 12 carbon atoms. It may be substituted with a divalent linking group represented by a chain or branched alkylene group, an alkyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom that can be a divalent or trivalent linking group. benzene residue or .Y ₃ is a nitro group or a halogen atom which may be substituted phthalimidomethyl group representing two or more combined linking group of these linking _{groups,, -NR 2 R 3, -SO} 3 · M / N or -COO · M / n R ₂ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₂ and R ₃ together. Represents an optionally substituted heterocycle containing further nitrogen, oxygen or sulfur atoms, M represents a hydrogen ion, a 1-3 valent metal ion or an ammonium ion at least one of which is substituted with an alkyl group , N represents the valence of M. Y ₄ and Y ₅ are each independently the same as Y ₃ , or an alkyl group, amino group, nitro group, hydroxyl group, alkoxy group, halogen atom, or substituted And represents an optionally substituted phenyl group, and l ₃ to l ₅ each independently represent an integer of 1 or 2.) The organic compound is an organic dye derivative represented by the general formula (1), and an organic dye residue with P is C.I. I. The method for producing a violet pigment according to claim 1, represented by 23 residues of pigment violet.