JP6281345B2 - Azo pigment and method for producing the same - Google Patents

Description

  The present invention relates to an azo pigment and a method for producing the same.

An azo pigment is a compound obtained by reacting a diazotized aromatic amine as a base component with a coupler component. Among them, a naphthol AS pigment is a printing ink, plastic, It is used as a colorant in various fields such as textile printing, electrophotographic printing, color toner, inkjet ink, and color filter.

Among the naphthol AS pigments, C.I. I. Pigment Red 269 is attracting particular attention as a pigment for color toners and inkjet inks because of its bluish red hue that satisfies Japan color, high tinting strength, sharpness, water resistance, and the like. As pigments for color toners and inkjet inks, coloring power, sharpness, water resistance, light resistance, high purity, and high yields are required. In order to reproduce a vivid color tone when performing the above, high transparency of the pigment is required.
C. I. As a method for synthesizing Pigment Red 269, methods described in Patent Document 1 and Patent Document 2 are known.
However, C.I. produced by these known methods. I. The half-width of the peak near the diffraction angle 2θ = 13.0 ° by powder X-ray diffraction of Pigment Red 269 is large, and using this pigment to create a master batch as a raw material for color toner, There was a tendency for the ink to become opaque during heat-kneading, and for the inkjet ink prepared using this pigment to have a dispersed particle size that would become enlarged or unstable when stored for a long period of time. This is C.I. I. It is known that the pigment red 269 crystal is unstable to heat, and is caused by receiving a thermal history and growing the crystal after long-term storage. Therefore, C.I. I. Pigment Red 269 is in demand.

JP 2004-123866 A JP-A-11-272014

The present invention solves the problems of the related art, has high crystal thermal stability, and does not become opaque by crystal growth during heating. I. An object of the present invention is to provide CI Pigment Red 269 and a manufacturing method thereof.

As a result of intensive investigations, the present inventors have found that C.I. I. It has been found that CI Pigment Red 269 can solve the above problems, and has led to the present invention.
That is, an embodiment of the present invention is an X-ray powder diffraction diagram represented by a diffraction intensity with respect to a diffraction angle 2θ measured by CuKα rays.
A peak indicating the maximum diffraction intensity within the range of 2θ = 13.0 ± 0.5 °, A
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.5 ° or more.
The point where 2θ is the minimum diffraction intensity within the range of Ax or more and Ax + 1.5 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.45 or more and 0.69 or less . I. It is related with pigment red 269.

An embodiment of the present invention is a C.I. I. A method for producing CI Pigment Red 269, which includes a step of treating with a water-soluble organic solvent during a coupling reaction. I. The present invention relates to a method for producing CI Pigment Red 269.

An embodiment of the present invention is a C.I. I. A method for producing CI Pigment Red 269, which includes a step of performing a solvent salt milling process. I. The present invention relates to a method for producing CI Pigment Red 269.

Also, an embodiment of the present invention provides at least the C.I. I. The present invention relates to a pigment red 269 and a coloring composition comprising a dispersion medium.

According to the present invention, the thermal stability of pigment crystals increases, so that a color toner having high transparency and an inkjet ink having good dispersion stability can be produced. I. Pigment Red 269 and a method for manufacturing the same are provided.

1 shows C.I. produced in Example 8. FIG. I. It is a powder X-ray diffraction pattern of pigment red 269 (pigment H). FIG. 2 is a schematic view of a powder X-ray diffraction diagram according to the present invention.

Hereinafter, the present invention will be described in detail. Note that “CI” in this specification means a color index (CI).

<C. I. Pigment Red 269>
C. in the present invention. I. Pigment Red 269 is a powder X-ray diffraction diagram indicated by a diffraction intensity with respect to a diffraction angle 2θ measured by CuKα ray.
A peak indicating the maximum diffraction intensity within the range of 2θ = 13.0 ± 0.5 °, A
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.5 ° or more.
The point where 2θ is the minimum diffraction intensity within the range of Ax or more and Ax + 1.5 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.96 or less.

The X-ray diffraction spectrum measurement method is as follows.
Device: Rigaku MiniFlex II
X-ray source: CuKα
Voltage: 30kV
Current: 15 mA
Measurement range: 3.0 ° to 35.0 °
Step angle: 0.02 °

[Half width]
From this measurement result, the peak half width was obtained by performing data processing under the following conditions. Here, the half-value width is a Bragg angle value defined by a peak width at an intensity position that is ½ of the X-ray diffraction intensity at a certain 2θ peak.

The half width was obtained as follows. Smooth the obtained diffraction data by B-spline method (
xthreshold = 1.5). In the vicinity of the target peak value (2θ = 13.0 ± 0.5 °), the peak indicating the maximum diffraction intensity is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.5 ° or more.
The point where 2θ is the minimum diffraction intensity within the range of Ax or more and Ax + 1.5 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
Fx−Ex was defined as the half width of A (Δ2θ).

The half width (Δ2θ) obtained here corresponds to the size of the crystallite (= crystallinity). The larger the crystallite and the higher the crystallinity, the smaller the half width.

If the half-value width is 0.96 or less, the inventors have high thermal stability of pigment crystals, and can produce color toners having high transparency, inkjet inks having good dispersion stability, and the like.
. I. It was found that it becomes Pigment Red 269. Further, when the half width is 0.70 or less, C.I. can produce a color toner having higher thermal stability of the pigment crystal, higher transparency, and ink jet ink having better dispersion stability. I. Pigment Red 26
9 can be obtained.

[C. I. Production of Pigment Red 269]
C. I. Pigment Red 269 (Chemical Formula (1)) can be produced by a known azo pigment synthesis method. Specifically, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (chemical formula (2)) as a coupler component and 3-amino-4-methoxybenzanilide as a base component It can be produced by subjecting a diazonium salt obtained by diazotizing (Chemical Formula (3)) to a coupling reaction. C. of the present invention. I. Pigment Red 269 can be produced by treating with a water-soluble organic solvent during the coupling reaction.
Chemical formula (1)

Chemical formula (2)

Chemical formula (3)

Specifically, N- (5-chloro-2-methoxyphenyl) -3- is a coupler component.
It is obtained by diazotizing acid precipitation slurry obtained by neutralizing a basic solution containing hydroxy-2-naphthamide or a basic solution containing a coupler component with an acid and 3-amino-4-methoxybenzanilide as a base component. A solution containing the diazo component is coupled. In this case, it can be produced by adding a water-soluble organic solvent to any one or more of a solution containing a coupler component, an acid for neutralizing it, and a solution containing a diazo component. According to our study, C.I. I. It is considered that the crystal form of Pigment Red 269 is determined when the crystal is formed. In a system containing no organic solvent, C.I. I. Pigment Red 269 produces a large number of fine and unstable crystals and agglomerates strongly, which rapidly grows when subjected to heat and causes low heat resistance. Even if the solvent treatment is performed after the coupling is completed, the aggregated unstable crystals at the center of the pigment remain and it is difficult to improve the heat resistance. On the other hand, when a coupling reaction is carried out in a system containing the water-soluble organic solvent of the present invention, the system has a small amount of pigment dissolving ability when crystals are formed. I. Pigment Red 269 crystals are produced, and C.I. I
. Pigment Red 269 can be obtained.

  A solution containing a coupler component can be prepared by adding N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, which is a coupler component, to a heated basic aqueous solution. Moreover, you may melt | dissolve by mixing water, a water-soluble organic solvent, a coupler component, and a base at room temperature (about 10 to 30 degreeC). The dissolution temperature varies depending on the amount and type of the water-soluble organic solvent to be added, the amount of water, the type and amount of the base, but is about 15 to 50 ° C. when the water-soluble organic solvent is included. When no water-soluble organic solvent is contained, the temperature is 80 to 95 ° C.

  As the base, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide can be dissolved in water, and an acid in a solution containing an acid aqueous solution or a diazo component described later can be dissolved. Any base can be used as long as it does not produce an insoluble salt upon neutralization, but sodium hydroxide or potassium hydroxide is preferably used from the viewpoints of cost, coupler component solubility, waste liquid treatment, and the like.

(Water-soluble organic solvent)
As the water-soluble organic solvent that can be used, any water-soluble organic solvent may be used as long as it can be freely mixed with water. Specifically, dimethyl sulfoxide, N, N-dimethylformamide, etc. Aprotic polar solvent, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, dihydric alcohols such as ethylene glycol, diethylene glycol and polyethylene glycol, methanol, ethanol, Monohydric alcohols such as isopropanol are preferably used.
In particular, among the above water-soluble organic solvents, dimethyl sulfoxide, cyclic ethers, ketones, and dihydric alcohols are preferable, and ketones and dihydric alcohols are more preferable. When ketones are used, the pigment is obtained with good purity, and when dihydric alcohols are used, the pigment is obtained with good yield. When a solvent having a high boiling point is used, the solvent may remain in the pigment to some extent, but this is not a problem as long as the purpose of use is not adversely affected.

  The amount of water-soluble organic solvent added depends on the type of water-soluble organic solvent, but when added to any solution containing a coupler component, aqueous acid solution, or solution containing a diazo component, It is desirable to add 1% to 50%, more desirably 2 to 40%, and even more desirably 3 to 30%. When the amount of the solvent added is less than 1%, the effect due to the addition of the solvent may not be obtained. On the other hand, if it exceeds 50%, primary particles of the pigment grow and heat resistance is improved, but excessive crystal growth may cause a decrease in transparency.

Moreover, you may use for this coupling what reacted this solution with acid aqueous solution, and acidified the coupler component. The acid used in the acid aqueous solution may be any acid as long as it dissolves in water, but it is preferable to use either hydrochloric acid or acetic acid, or a mixture of hydrochloric acid and acetic acid. Further, acid precipitation may be performed by adding a water-soluble organic solvent to the acid aqueous solution. As the water-soluble organic solvent, any organic solvent may be used as long as it can be freely mixed with water, and an organic solvent that can be used for the solution containing the coupler component is preferably used.

A solution containing a diazo component can be obtained by diazotizing 3-amino-4-methoxybenzanilide which is a base component. A known method can be used as the diazotization method. For example, diazotization can be carried out by adding hydrochloric acid to a reslurry of the base component in ice water and dissolving it, and then adding sodium nitrite. Moreover, you may add a water-soluble organic solvent to the solution containing a diazo component. As the water-soluble organic solvent, any organic solvent may be used as long as it can be freely mixed with water, and an organic solvent that can be used for the solution containing the coupler component is preferably used.

  Examples of the coupling method include reverse coupling, forward coupling, and acid precipitation forward coupling, and any method can be used. Particularly preferred is an acid precipitation coupling in which an effect can be obtained even with a small amount of solvent.

As a method of reverse coupling, a known method can be used, and a method of adding a solution containing a coupler component to a solution containing a diazo component can be mentioned. Coupling temperature is 0-5
0 ° C. is desirable, particularly from 10 to 30 from the viewpoint of alteration of the diazo component, suppression of decomposition, and reaction rate.
° C is desirable. A buffer may be added in advance to the solution containing the diazo component. Any kind of buffer solution may be used as long as it has a buffer capacity, but an acetic acid-sodium acetate aqueous solution is preferably used. When adding a buffer solution, the pH of the solution containing the diazo component is 3.0.
˜6.5 or less is desirable. From the viewpoint of improving the reaction rate and heat resistance, it is preferable to heat the slurry after coupling as necessary.

As a method of acid precipitation normal coupling, a known method can be used, and an acid precipitation coupler slurry is obtained by reacting a solution containing a coupler component with an acid aqueous solution, and then a coupling reaction with a solution containing a diazo component. The method of letting it be mentioned. The temperature of the acid aqueous solution during acid precipitation can be selected arbitrarily, but it is preferably 0 to 10 ° C. from the viewpoint of reaction rate. From the viewpoint of improving the reaction rate and heat resistance, the acid precipitation coupler slurry is preferably heated as necessary before adding the solution containing the diazo component. However, since the diazo component is easily altered and decomposed when the temperature becomes too high, the temperature of the acid precipitation coupler slurry during the coupling reaction is preferably 50 ° C. or lower. The pH of the acid precipitation coupler slurry before adding the solution containing the diazo component is preferably 2-6.
When the pH is less than 2, the reaction rate after adding the solution containing the diazo component is extremely slow, and when the pH exceeds 6, the diazo component is easily deteriorated, which is not preferable. Any acid can be used as the acid used for adjusting the pH as long as it dissolves in water, but it is preferable to use either hydrochloric acid or acetic acid, or a mixture of hydrochloric acid and acetic acid. The acid may be added in advance by using an acid used for acid precipitation in excess of the equivalent of the base of the solution containing the coupler component, or may be added in advance when the base is dissolved, or may be added to the diazo solution. A necessary amount may be added later to the coupler slurry after acid precipitation. Moreover, it is preferable to heat the slurry after coupling as needed from a viewpoint of reaction rate improvement and heat resistance improvement.

(Different raw materials)
In addition, C.I. I. In producing Pigment Red 269, C.I. I. Pigment Red 2
Different raw materials for producing an azo compound different from 69 may be added. The azo compound that is a different component is not particularly limited, but C.I. I. It is preferable in terms of transparency that the pigment red 269 and the base portion or the coupler portion have the same structure.

Any different raw material for producing the different component can be used as long as it reacts with the diazo component or the coupler component to become an azo compound.

《Heterogeneous coupler》
Examples of the heterogeneous coupler component that reacts with the diazo component to form an azo compound include the general formula (1
) And other naphthol derivatives such as β-naphthol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-6-sulfonic acid and the like.

General formula (1)

General formula (2)

(In general formula (1), R ₁ represents a hydrogen atom, a benzimidazolone group, an alkylaminoalkyl group, or a group represented by general formula (2)).
(In the general formula (2), R _{2 to} R ₆ are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, trifluoromethyl group, nitro group, carbonyl group, sulfone group, carbamoyl group, sulfamoyl group. Represents a nitrile group or a benzoylamino group,
In R _{2 to} R ₆ , adjacent groups may be bonded to each other to form a ring. )

《Heterogeneous base》
Examples of the heterogeneous base component that reacts with the coupler component to become an azo compound include the general formula (3
).

General formula (3)

(In the general formula (3), R _{7 to} R ₁₁ are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, trifluoromethyl group, nitro group, carbonyl group, sulfone group, carbamoyl group, sulfamoyl group. Represents a nitrile group or a benzoylamino group, and R _{7 to} R ₁₁ may be bonded to each other to form a ring.

The order in which the azo pigments that are different components are produced is the same as before,
Any of them after generation may be used. When the azo pigment as the main component and the azo pigment as the dissimilar component are produced at the same time, when using the dissimilar base component, diazotize simultaneously with the main base component, and when using the dissimilar coupler component, mix with the main coupler component. It can be carried out by dissolving simultaneously.
These different raw materials are composed of 1 to 30 mol% of the azo pigment as a different component relative to the whole azo pigment.
It is preferable to add so that it may produce | generate in the range of 5-20%, and it is preferable to add so that it may produce | generate especially in 5 to 20% of range.

(Additive)
When manufacturing an azo pigment, various additives can be added as needed. The type of additive that can be used is not particularly limited, but it is preferable to add either a surfactant or a pigment derivative, and it is particularly preferable in terms of transparency to add a surfactant.

When an additive is used when producing an azo pigment, the additive may be used in addition to a solution containing a coupler component, a solution containing a diazo component or an acid solution for acid precipitation in advance. It may be used in addition to the slurry. When adding to a solution containing a coupler component, it may be added before the coupler is dissolved, or may be added after acid precipitation.

<Surfactant>
As the surfactant, an anionic, nonionic or amphoteric surfactant can be preferably used. When adding a surfactant to a solution containing a coupler component, an anionic or amphoteric surfactant is preferred. In the case of adding a surfactant to an acid solution for acid precipitation or an acid precipitation coupler slurry, a nonionic surfactant can also be suitably used.

Anionic surfactants include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyls. Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid Examples include esters and polyoxyethylene glycerol fatty acid esters.

Examples of amphoteric surfactants include betaine, sulfobetaine, alkylbetaine, and alkylamine oxide.

Nonionic surfactants include 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 fatty acid ester And polyoxyethylene fatty acid ester polyoxyethylene alkylamine.

These may be used alone or in combination. When combining a surfactant, a surfactant selected from the above can be freely selected, but a combination of an amphoteric surfactant and an anionic surfactant is preferably used. Moreover, these can be used in 0.1-10 weight% with respect to the total weight of a pigment composition, Preferably it is 0.5-5 weight%.

<Pigment derivative>
Examples of the pigment derivative include compounds represented by the following general formulas (4) to (6).

General formula (4)

P- [X _1- (Y ₁ ) _k ] _m

(In the formula, P represents an organic dye residue.
X ₁ is a direct bond connecting P and Y ₁ , —O—, —S—, —CO—, —SO ₂ —, —NR ₁₂ —,
_{-CONR 12 -, - SO 2 NR} 12 -, - NR 12 CO -, - NR 12 SO 2 -, 1~12 carbon atoms
Linear or branched alkylene groups, or alkyl groups, amino groups, nitro groups,
A benzene residue or triazine residue which may be substituted with any one of a hydroxyl group, an alkoxy group and a halogen atom, or a linking group formed by linking two or more of these linking groups (
Here, R ₁₂ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group).
Y ₁ represents —NR ₁₃ R ₁₄ , —SO ₃ · M / j, or —COO · M / j,
R ₁₃ and R ₁₄ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₃ and R ₁₄ together. And represents an optionally substituted heterocyclic group containing a nitrogen, oxygen or sulfur atom, and 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, and j represents the valence of M.
k represents an integer of 1 or 2, and m represents an integer of 1 to 4. )

General formula (5)

_{Q- [X 2 - (Y 2} ) k] m

(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 ₁₂ —, —CONR ₁₂ —.
, —SO ₂ NR ₁₂ —, —NR ₁₂ CO—, —NR ₁₂ SO ₂ —, a linear or branched alkylene group having 1 to 12 carbon atoms, or an alkyl group, amino group, nitro group, hydroxyl group, alkoxy group , A benzene residue or triazine residue which may be substituted with any one of a halogen atom and a trifluoromethyl group, or a linking group formed by linking two or more of these linking groups (wherein R ₁₂ represents Represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group).
Y ₂ represents —NR ₁₃ R ₁₄ , —SO ₃ · M / j, or —COO · M / j,
R ₁₃ and R ₁₄ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₃ and R ₁₄ together. And represents an optionally substituted heterocyclic group containing a nitrogen, oxygen or sulfur atom,
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, and j represents the valence of M. k represents an integer of 1 or 2, and m represents an integer of 1 to 4. )

General formula (6)

(In the formula, R represents a triazine residue.
X ₃ to X ₅ are each independently a direct bond connecting R and any of Y ₃ to Y ₅ , —O—, —
S -, - CO -, - SO 2 -, - NR 12 -, - CONR 12 -, - SO 2 NR 12 -, - NR 12
CO—, —NR ₁₂ SO ₂ —, a linear or branched alkylene group having 1 to 12 carbon atoms,
Alternatively, it represents a benzene residue which may be substituted with any of an alkyl group, amino group, nitro group, hydroxyl group, alkoxy group and halogen atom, or a linking group formed by linking two or more of these linking groups. (Wherein R ₁₂ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group).
Y ₃ represents —NR ₁₃ R ₁₄ , —SO ₃ · M / j, or —COO · M / j, each of R ₁₃ and R ₁₄ independently represents a hydrogen atom or an optionally substituted alkyl group. Represents an optionally substituted alkenyl group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group containing a nitrogen, oxygen or sulfur atom together with R ₁₃ and R ₁₄ ; ,
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, and j represents the valence of M.
Y ₄ and Y ₅ are each independently the same as Y ₃ , or may be an alkyl group, amino group, nitro group, hydroxyl group, alkoxy group, halogen atom, trifluoromethyl group, or substituted. It represents one of phenyl groups.
p, q, and r each independently represent an integer of 1 or 2. )

Here, examples of the organic dye residue in P include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, and the like. Anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, porphyrin dyes, phthalocyanine dyes Examples thereof include dyes and metal complex dyes.

Examples of the linear or branched alkylene group having 1 to 12 carbon atoms in X _{1 to} X ₃ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group. Group, dexylene group, undecylene group, dodexylene group and isomers thereof.

Moreover, as an alkyl group which may be substituted in R < ₁₃ > -R < ₁₄ >, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group is used as a skeleton, In which one hydrogen of the above may be substituted with any one of an amino group, a hydroxyl group, chlorine, bromine, a sulfone group, and a nitro group.

Moreover, as an alkenyl group which may be substituted in R < ₁₃ > -R < ₁₄ >, a vinyl group, 2
-Propenyl group is used as a skeleton, and one of those hydrogens may be substituted with any of amino group, hydroxyl group, chlorine, bromine, sulfone group and nitro group.

Examples of the optionally substituted phenyl group in R _{13 to} R ₁₄ include a phenyl group, a methylphenyl group, a dimethylphenyl group, a methoxyphenyl group, a nitrophenyl group, a hydroxyphenyl group, a chlorophenyl group, and an aminophenyl group. Can be mentioned.

In addition, the heterocyclic group which may be substituted with R ₁₃ and R ₁₄ and containing a nitrogen, oxygen or sulfur atom includes an azolidine ring, oxolane ring, thiolane ring, azole ring, oxol ring, thiol ring Azinan ring, oxane ring, thiane ring, pyridine ring, lactam ring,
Examples include a pyrazole ring, an imidazole ring, an oxazole ring, a benzimidazolone ring, and the like.

Moreover, as a 1-3 valent metal ion in M, lithium, sodium, potassium,
Examples include magnesium, calcium, strontium, barium, aluminum, vanadium, copper, and iron.

Examples of ammonium ions in which at least one of M is substituted with an alkyl group include dimethylammonium, ethylmethylammonium, diethylammonium, trimethylammonium, triethylammonium, dimethylpropylammonium, diethylpropylammonium and the like.

These may be used alone or in combination. And these are
It can be used in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the pigment composition.

  The following compounds etc. are mentioned as an example of General formula (4).

The following compounds etc. are mentioned as an example of General formula (5).

The following compounds etc. are mentioned as an example of General formula (6).

The above-mentioned compounds (1) to (8) can be produced by a method known in the industry, for example, JP 2010-19590.
6 can be produced.

(Solvent salt milling process)
C. produced by the above production method I. C. Pigment Red 269 is subjected to a solvent salt milling treatment, so that C.I. I. Pigment Red 269 can be obtained.

The method for producing the solvent salt milled pigment of the present invention is C.I. I. A mixture containing CI Pigment Red 269, grinding aid, and water-soluble organic solvent is mechanically kneaded with a kneader or the like, and then poured into water to form a slurry, which is then filtered, washed with water, and dried. Manufactured by.

The grinding aid used at the time of kneading is preferably a water-soluble inorganic salt and is not particularly limited as long as it dissolves in water. For example, metal chloride such as salt (sodium chloride), chloride Examples thereof include potassium, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, and mixtures thereof. Sodium chloride is preferably used from the viewpoint of price.

The particle diameter of the water-soluble inorganic salt used in the present invention is not particularly limited, but is water-soluble with a volume-based median particle diameter (D50) of 1 to 50 μm and a 95% particle diameter (D95) of 80 μm or less. Inorganic salts are desirable. The particle diameter of the water-soluble inorganic salt can be determined using a dry-type laser diffraction particle size distribution analyzer.

The water content is also important as the quality of the water-soluble inorganic salt. Industrial average salt usually contains 1.0% by weight or more of water, and if salt with a water content of 1.0% by weight or more is pulverized as it is without drying, adhesion of the crushed water-soluble inorganic salt It is strong and often hardens immediately if left unattended. The water-soluble inorganic salt is preferably dried to a water content of 0.5% by weight or less, more preferably 0.3% by weight or less. Particularly preferably, the water-soluble inorganic salt is sintered at a high temperature so that the water content is 0.2% by weight or less.

The amount of water-soluble inorganic salt used is C.I. I. It is preferable that it is 1-30 weight part of water-soluble inorganic salt with respect to 1 part of pigment red 269, and 5-15 weight part of water-soluble inorganic salt is more preferable.

The water-soluble organic solvent used in the present invention is intended to increase the grinding effect by accelerating the pigment crystal stabilization by wetting the mixture of the crude organic pigment and the water-soluble inorganic salt into a dough having an appropriate hardness. However, it is preferably a water-soluble organic solvent having a high viscosity such as ethylene glycol, diethylene glycol, or polyethylene glycol.

The amount of water-soluble organic solvent used varies depending on the amount of water-soluble inorganic salt. I. CI Pigment Red 269 is generally 0.1 to 5 parts by weight, preferably 1 to 2 parts per 1 part by weight.
Parts by weight.

Examples of water-soluble organic solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl 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, low Molecular weight polypropylene glycol, aniline, pyridine, tetrahydrofuran,
Dioxane, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methyl Examples thereof include a solvent having a hydroxyl group such as pyrrolidone, a carbonyl group, a carboxyl group, an amide group, and a hetero atom. If necessary, two or more of these water-soluble organic solvents may be mixed and used.

As a device for mechanically kneading the kneaded mixture, a kneader, a planetary mixer, a trimix (manufactured by Inoue Seisakusho), a two-roll, a three-roll, a multi-axis roll, an extruder, a KRC kneader (Kurimoto Steel Works) Manufactured), Miracle KCK (manufactured by Asada Tekko Co., Ltd.) and the like, but are not particularly limited, as long as mechanical shearing force can be efficiently applied to the kneaded material, regardless of batch type or continuous type. Can be used.

The temperature at which the kneaded mixture is mechanically kneaded is not particularly limited.
It is preferable to process at 120 degreeC, and it is more preferable to process at 70-90 degreeC. 12
When the temperature exceeds 0 ° C., C.I. I. The crystal growth of CI Pigment Red 269 is promoted, the primary particle diameter becomes coarse, and the colored composition becomes opaque. Further, when the temperature is lower than 40 ° C., it is difficult to remove the thermal energy generated during kneading, and the operation such as reducing the mechanical energy applied, reducing the processing amount of the kneaded mixture, or reducing the viscosity of the kneaded mixture, or A combination of these actions is required and productivity is reduced.

C. after kneading I. Pigment Red 269 is processed by a conventional method. That is, the kneaded composition is treated with water or an aqueous mineral acid solution, filtered, washed with water, and the pigment is isolated, dried and pulverized to obtain a higher thermal stability. I. Pigment Red 269 can be obtained.

<Coloring composition>
The azo pigment produced by the production method of the present invention is excellent in the thermal stability of crystals, and has the characteristics of excellent coloring power and sharpness. Therefore, it can be suitably used for printing ink, plastic, textile printing, inkjet ink, electrophotographic printing, color toner, color filter and the like.

According to the present invention, at least C.I. I. The pigment red 269 and the coloring composition containing the dispersion medium are specifically various dispersions such as printing ink, coating composition, plastic coloring composition, toner, etc., but the coloring composition of the present invention. Things are not limited to that.
Here, the printing ink represents all printing inks such as offset ink, gravure ink, flexo ink, and ink for inkjet.

For offset ink, depending on the application and drying method, sheet-fed ink, offset rotary ink,
Newspaper ink, UV ink, and the like can be cited as main ones, but the present invention is not limited to these.

The offset ink of the present invention is a C.I. I. Pigment Red 269 and a vehicle for offset ink as a dispersion medium can be mixed and dispersed. Vehicles for offset ink include, for example, rosin-modified phenolic resins, petroleum resins, alkyd resins, or resins such as these dry oil-modified resins, and vegetable oils such as linseed oil, tung oil, soybean oil, and n-paraffin as necessary. , Isoparaffin, aromatech, naphthene, α-olefin and the like, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight), resin: vegetable oil: solvent = 10-50 The range of wt%: 0-30 wt%: 20-60 wt% is preferred. In the offset ink, known additives such as an ink solvent, a dryer, a leveling improver, a thickener, and a pigment dispersant can be appropriately blended as necessary.

The gravure ink or flexographic ink of the present invention is a C.I. I. Pigment Red 269 and a gravure ink vehicle or a flexo ink method vehicle as a dispersion medium can be mixed and dispersed. The vehicle is composed of a resin and a solvent, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight). Resin: solvent = 5-5
The range of 0% by weight: 50 to 95% by weight is preferable.

Examples of the resin include gum rosin, wood rosin, tall oil rosin, calcified rosin,
Lime rosin, rosin ester, maleic resin, gilsonite, dammar, shellac,
Polyamide resin, vinyl resin, nitrocellulose, cyclized rubber, chlorinated rubber, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resin, chlorinated polypropylene resin, urethane resin, polyester resin, styrene resin, styrene acrylic resin, Examples include alkyd resins. Examples of the solvent include hydrocarbon solvents such as n-hexane, toluene and chlorobenzole, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol and glycerin, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, Examples thereof include ester solvents such as ethyl lactate and ethyl acetoacetate, ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and ethyl ether, and water.

For gravure ink or flexographic ink, if necessary, for example, barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate, and other extender pigments. As an adjunct
Known additives such as a plasticizer, an ultraviolet ray inhibitor, an antioxidant, an antistatic agent, and a pigment dispersant can be appropriately blended.

The ink-jet ink of the present invention is a C.I. I. Pigment Red 269 and a vehicle for inkjet ink as a dispersion medium can be mixed and dispersed. A vehicle for inkjet ink is composed of a resin, an activator, and a solvent, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight), resin: solvent = 1-10% by weight: 90. A range of ˜99% by weight is preferred. Examples of the resin include resins that are soluble in water such as acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluororesin, and water-dispersible emulsions or colloidal dispersion resins. These resins are added with neutralizing agents such as ammonia, amines and inorganic alkalis as required. Examples of the solvent include water, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, and substituted pyrrolidone. Also, alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of accelerating the drying property of the ink-jet ink. Also, alcohols such as glycerin can be used to suppress drying at the head. Further, an antiseptic, a penetrating agent, a chelating agent, and an anionic, nonionic, cationic, zwitterionic activator and pigment dispersant can be added to the ink-jet ink in order to improve the dispersion stability of the pigment.

The paint of the present invention is a C.I. I. Pigment Red 269 can be produced by mixing and dispersing a paint vehicle as a dispersion medium. The paint vehicle consists of a resin and a solvent, and the mixing ratio thereof is based on the total weight of the vehicle components (100% by weight).
Resin: solvent = 5 to 45% by weight: 55 to 95% by weight is preferable.

Examples of the resin include nitrocellulose, alkyd resin, aminoalkyd resin, acrylic resin, aminoacrylic resin, urethane resin, polyvinyl acetal resin, epoxy resin, polyester resin, vinyl chloride resin, vinylidene fluoride resin, vinyl fluoride resin, Examples include polyethersulfone resins and silicone resins. Solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ethers / alcohols, ethers / esters organic solvents, water, etc. Can be mentioned.

Other organic pigments such as barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate and the like are within the range not inhibiting the effect of the present invention. In addition to extender pigments, curing agents as auxiliary agents,
Curing accelerators, flame retardants, anti-settling agents, anti-sagging agents, film-forming aids, preservatives, silane coupling agents, anti-foaming agents, antifoaming agents, viscosity modifiers, leveling to improve coating adhesion Agent, ultraviolet absorber, infrared absorber, antifreeze agent, plasticizer, pH adjuster, antibacterial agent, light stabilizer, matting agent,
Known additives such as an antioxidant, a pigment dispersant, and a pigment derivative can be appropriately blended.

The plastic composition of the present invention has C.I. I. Pigment Red 269 can be manufactured by mixing and dispersing a plastic resin as a dispersion medium. Plastic resins include polypropylene, polyethylene, ethylene / propylene copolymer, α-olefin and acrylic acid or maleic acid copolymer, ethylene / vinyl acetate copolymer, ethylene and acrylic acid or maleic anhydride copolymer. Polyolefin resins such as polymers, vinyl resins such as polyvinyl chloride and polyvinyl acetate, acetal resins such as formal resins and butyral resins,
Acrylic resins such as polyacrylonitrile and methacrylic resins, polystyrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers, polyester resins such as polyethylene terephthalate and polycarbonate, nylons such as 6-nylon, unsaturated polyester resins, epoxy resins, urea There are resin, melamine resin, cellulose resin and the like.

The plastic includes other organic pigments, inorganic pigments, waxes or derivatives thereof, heavy metal deactivators, alkali metal, alkaline earth metal, or zinc metal soap, hydrotalcite, as long as the effects of the present invention are not impaired. Nonionic surfactants, cationic surfactants, anionic surfactants, antistatic agents composed of amphoteric surfactants, flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylene bisalkylamides And various additives for known polymers such as antioxidants, ultraviolet absorbers, processing aids, fillers, pigment dispersants, pigment derivatives and the like. In order to satisfy the required quality and coloring workability, the pigment is dispersed in advance with these components to obtain a powdery dry color, granular bead color, liquid paste color, etc., and then mixed with the resin. May be. Moreover, what is called a masterbatch which is comprised from a pigment, a plastics, and other said additive and contains a pigment in high concentration may be manufactured, and resin may be colored using a masterbatch. Further, the plastic dispersion of the present invention may be used as a toner.

The toner of the present invention is a C.I. I. Pigment Red 269, which includes a binder resin as a dispersion medium. As the binder resin, for example, a vinyl resin such as styrene-acrylic resin, a polyester resin, an epoxy resin, or a hybrid resin obtained by bonding them can be used. In addition, the toner may contain components such as a wax component, a charge control material, and a fluidizing agent.

Specific examples of the wax component include petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and petrolatum, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, and polyethylene. Polyolefin waxes and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof, which include oxides, block copolymers with vinyl monomers, and graft-modified products. . Also included are alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, fatty acid amides, fatty acid esters, hydrogenated castor oil and derivatives thereof, vegetable waxes, and animal waxes. These can be used alone or in combination.

Examples of the charge control agent include monoazo metal compounds, boron compounds, quaternary ammonium salts, calixarene, silicon compounds, aromatic hydroxycarboxylic acids, metal salts thereof, anhydrides, ester bodies, and the like. Examples of the fluidizing agent include silica, titania, alumina, and the like.

As a toner production method, a melted binder resin and a pigment are kneaded and dispersed, and then pulverized to a desired particle size, a so-called pulverization method, suspension polymerization method, emulsion polymerization aggregation method, dissolution suspension method, ester Examples thereof include a chemical toner system represented by an elongation polymerization method and the like, which produces toner particles by a chemical method under a wet condition.

EXAMPLES Hereinafter, although the manufacturing method of this invention is demonstrated by an Example, this invention is not limited to these. In Examples and Comparative Examples, “part” represents “part by mass” unless otherwise specified.

<Production of pigment / pigment composition>
(Example 1) Production method of pigment A As a base component, 24.2 parts of 3-amino-4-methoxybenzanilide was added to 294 parts of water and stirred to prepare a suspension, and further 137 parts of ice was added. The temperature was adjusted to 5 ° C. or lower.
31.6 parts of 35% -hydrochloric acid was added thereto, and stirred for 30 minutes. Thereafter, 7.1 parts of sodium nitrite was added to 14 parts of water, an adjusted aqueous solution was added, and the mixture was stirred for 1 hour for diazotization. 2 parts of sulfamic acid was added to the reaction mixture to eliminate nitrous acid. 25
A buffer solution composed of 36.5 parts of a% -aqueous sodium hydroxide solution, 36.5 parts of ice, and 37.7 parts of 80% -acetic acid was added to prepare a solution containing a diazo component.

On the other hand, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide as a coupler component was added to a mixed solution of 66.8 parts of water and 66.8 parts of dimethyl sulfoxide.
4 parts were added and stirred and suspended for 15 minutes. 25% aqueous sodium hydroxide solution 32.
6 parts were added and the mixture was further stirred for 30 minutes, and 66.8 parts of water was added to make a coupler solution. This solution was added to the solution containing the diazo component over 20 minutes to carry out a coupling reaction.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C. and stirred for 30 minutes, followed by filtration and washing with water to obtain a pigment press cake. The press cake was dried at 90 ° C. for 18 hours and then pulverized to obtain 55.5 parts of Pigment A.
Example 1 is a reference example.

(Example 2) Production method of Pigment B Except for adding 33.4 parts of dimethyl sulfoxide to a solution containing a diazo component before coupling, 55.0 parts of Pigment B were added in the same manner as in Example 1. Obtained.
Example 2 is a reference example.

(Example 3) Production method of pigment composition C 2.3 parts of sodium di-2-ethylhexyl sulfosuccinate was added to an aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of dimethyl sulfoxide) before adding the coupler component. 57.9 parts of pigment composition C was obtained in the same manner as in Example 1, except that
Example 3 is a reference example.

(Example 4) Production method of pigment D 55.8 parts of pigment D were obtained in the same manner as in Example 1 except that 120 parts of acetone was added instead of adding dimethyl sulfoxide.

(Example 5) Production method of pigment E 54.7 parts of pigment E was obtained in the same manner as in Example 4 except that 80 parts of acetone was added to the solution containing the diazo component before coupling.

(Example 6) Production method of pigment composition F Into a solvent aqueous solution (mixture of 66.8 parts of water and 120 parts of acetone) before adding the coupler component, 0.6 part of dimethyldodecylbetaine and sodium alkylbenzenesulfonate (Co., Ltd.) 56.8 parts of pigment composition F was obtained in the same manner as in Example 4 except that 2.9 parts were added.

(Example 7) Production method of pigment G 54.1 parts of pigment G were obtained in the same manner as in Example 1 except that 66.8 parts of methyl ethyl ketone was added instead of adding dimethyl sulfoxide.

(Example 8) Production method of pigment H Before the coupling, 54.2 parts of pigment H was obtained in the same manner as in Example 7, except that 33.4 parts of methyl ethyl ketone was added to the solution containing the diazo component. It was.

(Example 9) Production method of pigment composition I To a solvent aqueous solution (mixture of 66.8 parts of water and 66.8 parts of methyl ethyl ketone) before adding the coupler component, sodium alkylbenzene sulfonate (manufactured by Teika Co., Ltd .: Teica Power BN2060) ) 56.4 parts of pigment composition I were obtained in the same manner as in Example 7, except that 3.9 parts were added.

(Example 10) Production method of pigment J 55.8 parts of pigment J were obtained in the same manner as in Example 1 except that 66.8 parts of tetrahydrofuran was added instead of adding dimethyl sulfoxide.
Example 10 is a reference example.

(Example 11) Production method of pigment K 54.9 parts of pigment K was obtained in the same manner as in Example 10, except that 33.4 parts of tetrahydrofuran was added to the solution containing the diazo component.
Example 11 is a reference example.

(Example 12) Production method of pigment composition L The same method as in Example 10 except that 0.6 parts of dimethyldodecylbetaine and 1.7 parts of sodium dodecylbenzenesulfonate are added to the aqueous solvent solution before adding the coupler component. In this way, 56.9 parts of pigment composition L were obtained.
Example 12 is a reference example.

(Example 13) Production method of pigment M 57.6 parts of pigment M were obtained in the same manner as in Example 1 except that 66.8 parts of diethylene glycol was added instead of adding dimethyl sulfoxide.

(Example 14) Production method of pigment N Before the coupling, 57.5 parts of pigment N was obtained in the same manner as in Example 13, except that 33.4 parts of diethylene glycol was added to the solution containing the diazo component. It was.

(Example 15) Production method of pigment composition O Except for adding 2.3 parts of dimethyldodecylbetaine to an aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of diethylene glycol) before adding the coupler component, In the same manner as in Example 13, 59.7 parts of Pigment Composition O was obtained.

(Example 16) Production method of pigment P 58.0 parts of pigment P were obtained in the same manner as in Example 1 except that 170 parts of ethylene glycol was added instead of adding dimethyl sulfoxide.

Example 17 Production Method of Pigment Q 56.7 parts of Pigment Q was obtained in the same manner as in Example 16 except that 130 parts of ethylene glycol was added to the aqueous acetic acid solution.

(Example 18) Production method of pigment composition R In a solvent aqueous solution (mixture of 66.8 parts of water and 170 parts of ethylene glycol) before adding the coupler component, 0.2 part of dimethyldodecylbetaine and 70% polyoxyethylene alkyl 60.3 parts of pigment composition R was obtained in the same manner as in Example 16 except that 3.0 parts of potassium ether phosphate (manufactured by Kao Corporation: Electro Stripper F) was added.

(Example 19) Production method of pigment S 54.5 parts of pigment S was obtained in the same manner as in Example 1 except that 66.8 parts of polyethylene glycol having an average molecular weight of 300 was added instead of adding dimethyl sulfoxide. .

(Example 20) Production method of pigment T Prior to coupling, pigment T was prepared in the same manner as in Example 19, except that 33.4 parts of polyethylene glycol having an average molecular weight of 300 was added to the solution containing the diazo component. 55.6 parts were obtained.

(Example 21) Production method of pigment composition U Into an aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of polyethylene glycol having an average molecular weight of 300) before adding the coupler component, 0.2 part of dimethyldodecylbetaine 57.6 parts of pigment composition U were obtained in the same manner as in Example 19, except that 2.1 parts of sodium di-2-ethylhexyl sulfosuccinate was added.

(Example 22) Production method of pigment V As a base component, 24.2 parts of 3-amino-4-methoxybenzanilide was added to 294 parts of water and stirred to prepare a suspension, and further 137 parts of ice was added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% -hydrochloric acid was added thereto, and stirred for 30 minutes. Thereafter, 7.1 parts of sodium nitrite was added to 14 parts of water, an adjusted aqueous solution was added, and the mixture was stirred for 1 hour for diazotization. 2 parts of sulfamic acid was added to the reaction mixture to eliminate nitrous acid, thereby preparing a solution containing a diazo component.
Further, 33.7 parts of 80% -acetic acid aqueous solution and 550 parts of water were placed in a coupling tank and stirred to obtain an aqueous acetic acid solution.

On the other hand, 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide was added as a coupler component to a mixed solution of 66.8 parts of water and 66.8 parts of dimethyl sulfoxide for 15 minutes. Stir and suspend. Thereto was added 32.6 parts of a 25% aqueous sodium hydroxide solution, and the mixture was further stirred for 30 minutes, and 66.8 parts of water was added to make a coupler solution. This solution was added to a coupling tank in which an acetic acid aqueous solution was stirred over 30 minutes to cause acid precipitation, thereby obtaining an acid precipitation coupler slurry. While stirring the acid precipitation coupler slurry, the solution containing the diazo component was added over 20 minutes.
After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 1 hour. The slurry was further heated to 50 ° C. and stirred for 30 minutes, followed by filtration and washing with water to obtain a pigment press cake. The press cake was dried at 90 ° C. for 18 hours and then pulverized to obtain 54.8 parts of Pigment V.
Example 22 is a reference example.

(Example 23) Production method of pigment W 54.9 parts of pigment W were obtained in the same manner as in Example 22 except that 33.4 parts of dimethyl sulfoxide was added to an aqueous acetic acid solution.
Example 23 is a reference example.

(Example 24) Production method of pigment composition X To a solvent aqueous solution (mixture of 66.8 parts of water and 66.8 parts of dimethyl sulfoxide) before adding the coupler component, sodium di-2-ethylhexyl sulfosuccinate 2.3 57.8 parts of pigment composition X were obtained in the same manner as in Example 22 except for adding parts.
Example 24 is a reference example.

Example 43 Method for Producing Pigment AQ Instead of using 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide as a coupler component, N- (5-chloro-2 Example except that 31.8 parts of -methoxyphenyl) -3-hydroxy-2-naphthamide and 1.6 parts of N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthamide are used. In the same manner as in Example 22, 55.7 parts of pigment AQ was obtained.
Example 43 is a reference example.

(Example 44) Manufacturing method of pigment AR N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2 as a coupler component
-Instead of using 33.4 parts of naphthamide, N- (5-chloro-2-methoxyphenyl)
31.8 parts of 3-hydroxy-2-naphthamide and N-[(2,3-dihydro-2-oxo-1H-benzimidazole) -5-yl] -3-hydroxy-2-naphthalenecarboxamide 1.6 54.1 parts of pigment AR was obtained in the same manner as in Example 5 except that the parts were used.

(Example 45) Manufacturing method of pigment AS N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2 as a coupler component
-Instead of using 33.4 parts of naphthamide, N- (5-chloro-2-methoxyphenyl)
In the same manner as in Example 8, except that 31.8 parts of 3-hydroxy-2-naphthamide and 1.6 parts of N- (2-methyl-5-chlorophenyl) -3-hydroxy-2-naphthamide were used, 55.1 parts of pigment AS were obtained.

Example 46 Method for Producing Pigment AT Instead of using 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide as a coupler component, N- (5-chloro-2 -Methoxyphenyl) -3-Hydroxy-2-naphthamide 31.8 parts and N- (2-methyl-5-chlorophenyl) -3-hydroxy-2-naphthamide 1.6 parts, but using Example 11 In this way, 54.9 parts of pigment AT were obtained.
Example 46 is a reference example.

Example 50 Method for Producing Pigment AX Instead of using 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide as a coupler component, N- (5-chloro-2 -Methoxyphenyl) -3-hydroxy-2-naphthamide 31.8 parts and N-phenyl-3-hydroxy-2-naphthamide 1.3 parts except that AX 54. 6 parts were obtained.
Example 50 is a reference example.

(Example 53) Manufacturing method of pigment composition BA 58.3 parts of pigment composition BA was prepared in the same manner as in Example 10 except that 2.9 parts of compound (2) was added during the preparation of a solution containing a coupler component. Got.
Example 53 is a reference example.

(Example 55) Production method of pigment composition BC 59.5 parts of pigment composition BC in the same manner as in Example 16 except that 2.9 parts of compound (4) was added during preparation of a solution containing a coupler component. Got.

(Example 57) Production method of pigment composition BE 57.8 parts of pigment composition BE in the same manner as in Example 4 except that 2.9 parts of compound (6) was added during preparation of a solution containing a coupler component. Got.

(Example 58) Production method of pigment composition BF To the slurry before heating to 50 ° C after coupling, 2.9 parts of compound (7) dissolved in hydrochloric acid was added, and then the pH was adjusted to 7 with an aqueous sodium hydroxide solution. Example 7 except for adjusting to
In the same manner as above, 57.8 parts of pigment composition BF was obtained.

(Example 59) Manufacturing method of pigment composition BG To the slurry before heating to 50 ° C after coupling, 2.9 parts of compound (8) dissolved in hydrochloric acid was added, and then the pH was adjusted to 7 with an aqueous sodium hydroxide solution. 58.0 parts of pigment composition BG were obtained in the same manner as in Example 10 except that the amount of the pigment composition BG was adjusted.
Example 59 is a reference example.

(Example 60) Production method of pigment BH A kneaded material having the following composition was put into a 300 volume part kneader and kneaded at a rotation speed of 60 rpm and a processing temperature of 50 ° C for 7.5 hours.
Pigment M obtained in Example 13 25 parts Sodium chloride 220 parts Diethylene glycol 27 parts The kneaded product obtained here is taken out in 1000 parts of 70 ° C water, stirred for 1 hour with heat, filtered, washed and dried at 90 ° C for 18 hours. And pulverized to obtain 23.2 parts of pigment BH.

Example 61 Production Method of Pigment BI Example 5 and Example 5 except that the amount of acetone added to the solution containing the coupler component is changed to 250 parts and the amount of acetone added to the solution containing the diazo component is changed to 250 parts. In the same way, 55.1 parts of pigment BI were obtained.

(Example 62) Production method of pigment BJ 55.3 parts of pigment BJ were obtained in the same manner as in Example 22 except that 120 parts of acetone was added instead of adding dimethyl sulfoxide.

(Example 63) Production method of pigment BK Before the coupling, 55.4 parts of pigment BK was obtained in the same manner as in Example 62, except that 80 parts of acetone was added to the solution containing the diazo component.

(Example 64) Method for producing pigment composition BL Into an aqueous solvent solution (mixture of 66.8 parts of water and 120 parts of acetone) before adding the coupler component, 0.6 parts of dimethyldodecylbetaine and sodium alkylbenzenesulfonate (Co., Ltd.) (Taika Power: BN2060) Pigment composition BL (56.4 parts) was obtained in the same manner as in Example 62 except that 2.9 parts were added.

(Example 65) Production method of pigment BM 55.3 parts of pigment BM were obtained in the same manner as in Example 22 except that 66.8 parts of methyl ethyl ketone was added instead of adding dimethyl sulfoxide.

(Example 66) Manufacturing method of pigment BN 55.3 parts of pigment BN were obtained by the same method as Example 65 except adding 33.4 parts of methyl ethyl ketone to the acetic acid aqueous solution.

(Example 67) Pigment composition BO production method Sodium alkylbenzene sulfonate (Taika Power BN2060, manufactured by Teika Co., Ltd.) was added to a solvent aqueous solution (mixed solution of 66.8 parts of water and 66.8 parts of acetone) before adding the coupler component. 57.7 parts of pigment composition BO was obtained in the same manner as in Example 65 except for adding 3.9 parts.

(Example 68) Production method of pigment BP 55.1 parts of pigment BP was obtained in the same manner as in Example 22 except that 66.8 parts of tetrahydrofuran was added instead of adding dimethyl sulfoxide.
Example 68 is a reference example.

(Example 69) Production method of pigment BQ 55.2 parts of pigment BQ was obtained in the same manner as in Example 68 except that 33.4 parts of tetrahydrofuran was added to the acetic acid aqueous solution.
Example 69 is a reference example.

Example 70 Production Method of Pigment Composition BR Into an aqueous solvent solution (a mixture of 66.8 parts of water and 66.8 parts of tetrahydrofuran) before adding the coupler component, 0.6 part of dimethyl dodecyl betaine and sodium dodecylbenzenesulfonate 58.0 parts of pigment composition BR was obtained in the same manner as in Example 68 except that 1.7 parts were added.
Example 70 is a reference example.

(Example 71) Production method of pigment BS 57.0 parts of pigment BS was obtained in the same manner as in Example 22 except that 66.8 parts of diethylene glycol was added instead of adding dimethyl sulfoxide.

(Example 72) Production method of pigment BT 57.9 parts of pigment BT was obtained in the same manner as in Example 71 except that 33.4 parts of diethylene glycol was added to the aqueous acetic acid solution.

(Example 73) Production method of pigment composition BU Except for adding 2.3 parts of dimethyldodecylbetaine to an aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of diethylene glycol) before adding the coupler component, In the same manner as in Example 71, 59.8 parts of pigment composition BU was obtained.

(Example 74) Production method of pigment BV 57.7 parts of pigment BV were obtained in the same manner as in Example 22 except that 170 parts of ethylene glycol was added instead of adding dimethyl sulfoxide.

(Example 75) Production method of pigment BW 57.3 parts of pigment BW was obtained in the same manner as in Example 74 except that 130 parts of ethylene glycol was added to the aqueous acetic acid solution.

(Example 76) Production method of pigment composition BX 0.2 parts of dimethyl dodecyl betaine and 70% polyoxyethylene alkyl were added to a solvent aqueous solution (mixture of 66.8 parts of water and 170 parts of ethylene glycol) before adding the coupler component. 60.1 parts of pigment composition BX were obtained in the same manner as in Example 74, except that 3.0 parts of potassium ether phosphate (manufactured by Kao Corporation: Electro Stripper F) was added.

Example 77 Production Method of Pigment BY 54.9 parts of Pigment BY were obtained in the same manner as in Example 22 except that 66.8 parts of polyethylene glycol having an average molecular weight of 300 was added instead of adding dimethyl sulfoxide. .

(Example 78) Production method of pigment BZ 54.6 parts of pigment BZ was obtained in the same manner as in Example 77, except that 33.4 parts of polyethylene glycol having an average molecular weight of 300 was added to the acetic acid aqueous solution.

(Example 79) Production method of pigment composition CA Into an aqueous solvent solution (a mixture of 66.8 parts of water and 66.8 parts of polyethylene glycol having an average molecular weight of 300) before adding the coupler component, 0.2 part of dimethyldodecylbetaine 57.7 parts of pigment composition CA were obtained in the same manner as in Example 77 except that 2.1 parts of sodium di-2-ethylhexyl sulfosuccinate was added.

Example 80 Method for Producing Pigment CB Instead of using 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide as a coupler component, N- (5-chloro-2 Pigment CB 57.1 in the same manner as in Example 71 except that 30.9 parts of -methoxyphenyl) -3-hydroxy-2-naphthamide and 1.5 parts of 3-hydroxy-2-naphthalenecarboxamide were used. Got a part.

(Example 81) Production method of pigment CC N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2 as a coupler component
-Instead of using 33.4 parts of naphthamide, N- (5-chloro-2-methoxyphenyl)
3-hydroxy-2-naphthamide 30.1 parts and N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthamide 1.6 parts and N- (2-methyl-5-chlorophenyl) ) 58.1 parts of pigment CC were obtained in the same manner as in Example 74 except that 1.6 parts of -3-hydroxy-2-naphthamide was used.

(Example 82) Method for producing pigment composition CD N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2 as a coupler component
-Instead of using 33.4 parts of naphthamide, N- (5-chloro-2-methoxyphenyl)
In the same manner as in Example 77 except that 32.4 parts of 3-hydroxy-2-naphthamide and 0.9 part of N- [3- (diethylamino) propyl] -3-hydroxy-2-naphthamide were used, the pigment 54.1 parts of composition CD were obtained.

Example 83 Method for Producing Pigment Composition CE Instead of using 24.2 parts of 3-amino-4-methoxybenzanilide as a base component, 23.5 parts of 3-amino-4-methoxybenzanilide and sulfanilic acid 0 55.0 parts of pigment composition CE were obtained in the same manner as in Example 62 except that 0.5 part was used.

(Example 84) Manufacturing method of pigment composition CF Add 2.9 parts of compound (1) to the coupler slurry after acid precipitation, and after stirring for 8 hours after coupling, adjust pH to 7 with aqueous sodium hydroxide solution Except that, 58.5 parts of pigment composition CF was obtained in the same manner as in Example 65.

(Example 85) Production method of pigment composition CG Add 2.9 parts of compound (3) to the coupler slurry after acid precipitation, and after stirring for 8 hours after coupling, adjust pH to 7 with aqueous sodium hydroxide solution Except that, 59.3 parts of pigment composition CG was obtained in the same manner as in Example 71.

(Example 86) Manufacturing method of pigment composition CH Add 2.9 parts of compound (5) to the coupler slurry after acid precipitation, and after stirring for 8 hours after coupling, adjust the pH to 7 with aqueous sodium hydroxide solution Except for this, 58.0 parts of pigment composition CH was obtained in the same manner as in Example 77.

(Example 87) Manufacturing method of pigment composition CI A sodium alkylbenzenesulfonate (manufactured by Teika Co., Ltd .: Teica Power BN2060) was added to an aqueous solvent solution (mixed solution of 66.8 parts of water and 66.8 parts of diethylene glycol) before adding the coupler component. ) 60.8 parts of pigment composition CI were obtained in the same manner as in Example 80 except that 3.9 parts was added.

(Example 88) Manufacturing method of pigment composition CJ Except adding 0.8 part of dimethyl dodecyl betaine to the aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of diethylene glycol) before adding the coupler component. In the same manner as in Example 80, 57.7 parts of pigment composition CJ was obtained.

(Example 89) Manufacturing method of pigment composition CK Implemented except adding 0.8 part of dimethyldodecylbetaine to an aqueous solvent solution (mixture of 66.8 parts of water and 66.8 parts of diethylene glycol) before adding the coupler component. In the same manner as in Example 87, 61.6 parts of pigment composition CK was obtained.

(Example 90) Method for producing pigment composition CL Sodium alkylbenzene sulfonate (Taika Power BN2060, manufactured by Teika Co., Ltd.) was added to an aqueous solvent solution (mixed solution of 66.8 parts of water and 170 parts of ethylene glycol) before adding the coupler component. 60.2 parts of pigment composition CL was obtained in the same manner as in Example 81 except that 3.9 parts was added.

(Example 91) Production method of pigment composition CM Example except that 0.8 part of dimethyldodecylbetaine is added to an aqueous solvent solution (mixture of 66.8 parts of water and 170 parts of ethylene glycol) before adding the coupler component. In the same manner as in 81, 56.9 parts of pigment composition CM was obtained.

(Example 92) Production method of pigment composition CN Example except that 0.8 part of dimethyldodecylbetaine is added to an aqueous solvent solution (mixed liquid of 66.8 parts of water and 170 parts of ethylene glycol) before adding the coupler component. In the same manner as in 90, 61.1 parts of pigment composition CN was obtained.

Example 93 Method for Producing Pigment Composition CO Sodium alkylbenzenesulfonate (Taika Co., Ltd.) was added to an aqueous solvent solution (a mixture of 66.8 parts of water and 66.8 parts of polyethylene glycol having an average molecular weight of 300) before adding the coupler component. Manufactured by: TAIKE POWER BN2060) 61.0 parts of pigment composition CO was obtained in the same manner as in Example 82 except that 3.9 parts were added.

Example 94 Method for Producing Pigment Composition CP 0.8 parts of dimethyl dodecyl betaine was added to an aqueous solvent solution (a mixture of 66.8 parts of water and 66.8 parts of polyethylene glycol having an average molecular weight of 300) before adding the coupler component. 58.1 parts of pigment composition CP was obtained in the same manner as in Example 82 except for adding.

Example 95 Method for Producing Pigment Composition CQ 0.8 parts of dimethyl dodecyl betaine was added to an aqueous solvent solution (a mixture of 66.8 parts of water and 66.8 parts of polyethylene glycol having an average molecular weight of 300) before adding the coupler component. 63.1 parts of pigment composition CQ was obtained in the same manner as in Example 93 except for adding.

Example 96 Method for Producing Pigment Composition CR Example 89 is the same as Example 89 except that the slurry containing the diazo component added to the acid precipitation coupler slurry and stirred for 1 hour is heated to 90 ° C. and stirred for 30 minutes. In the same manner, 61.8 parts of pigment composition CR was obtained.

(Example 97) Method for producing pigment composition CS Example 92 except that the slurry containing the diazo component added to the acid precipitation coupler slurry and stirred for 1 hour while stirring the acid precipitation coupler slurry was heated to 90 ° C and stirred for 30 minutes. In the same manner, 61.5 parts of pigment composition CS was obtained.

Example 98 Method for Producing Pigment Composition CT Example 95 except that the slurry containing the diazo component added to the acid precipitation coupler slurry and stirred for 1 hour while stirring the acid precipitation coupler slurry was heated to 90 ° C. and stirred for 30 minutes. In the same manner, 63.7 parts of pigment composition CT was obtained.

(Example 99) Production method of pigment composition CU 54.3 parts of pigment CU were obtained in the same manner as in Example 65 except that the amount of methyl ethyl ketone added to the solution containing the coupler was 20 parts.
Example 99 is a reference example.

(Example 100) Production method of pigment composition CV 54.5 parts of pigment CV were obtained in the same manner as in Example 65 except that the amount of methyl ethyl ketone added to the solution containing the coupler was 33 parts.

(Example 101) Production method of pigment composition CW 54.8 parts of pigment CW were obtained in the same manner as in Example 65 except that the amount of methyl ethyl ketone added to the solution containing the coupler was 45 parts.

(Comparative example 1) Production method of pigment a 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 294 parts of water and stirred to prepare a suspension, and further 137 parts of ice was added. The temperature was adjusted to 5 ° C. or lower.
31.6 parts of 35% -hydrochloric acid was added thereto, and stirred for 30 minutes. Thereafter, 7.1 parts of sodium nitrite was added to 14 parts of water, an adjusted aqueous solution was added, and the mixture was stirred for 1 hour for diazotization. 2 parts of sulfamic acid was added to the reaction mixture to eliminate nitrous acid. 25
A buffer solution composed of 36.5 parts of a% -aqueous sodium hydroxide solution, 36.5 parts of ice, and 37.7 parts of 80% -acetic acid was added to obtain a solution containing a diazo component.

Meanwhile, a mixture of 133.6 parts of water and 32.6 parts of 25% -aqueous sodium hydroxide solution
During the heating, 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide was added and dissolved as a coupler component. To this was added 66.8 parts of ice and cooled to obtain a coupler solution. This solution was added to the solution containing the diazo component over 20 minutes to carry out a coupling reaction.

  After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C. and stirred for 30 minutes, followed by filtration and washing with water to obtain a pigment press cake. The press cake was dried at 90 ° C. for 18 hours and then pulverized to obtain 55.7 parts of pigment a.

(Comparative Example 2) Method for Producing Pigment b In the same manner as in Example 13, except that the amount of diethylene glycol added to the solution containing the coupler was reduced from 66.8 parts to 6.7 parts, 54.9 parts of Pigment b was added. Obtained.

<Manufacture of coloring composition>
Pigments or pigment compositions A to CW, a to b 4 obtained in Examples 1 to 101 and Comparative Examples 1 to 2
00 parts and 600 parts of a polyester resin as a dispersion medium (trade name: Diacron, manufactured by Mitsubishi Rayon Co., Ltd., glass transition temperature 55 ° C., softening temperature 130 ° C.)
Charged into the kneader of the part, and melt-kneaded at 145 ° C. for 30 minutes, thereby coloring compositions A to CW,
a to b were obtained.

  The pigments and pigment compositions are summarized in Tables 1 to 3.

<Evaluation of pigment or pigment composition>
[Measurement of X-ray diffraction spectrum]
The obtained pigment or pigment composition was subjected to X-ray diffraction spectrum measurement under the following conditions.
Device: Rigaku MiniFlex II
X-ray source: CuKα
Voltage: 30kV
Current: 15 mA
Measurement range: 3.0 ° to 35.0 °
Step angle: 0.02 °

[Half width]
From this measurement result, the peak half width was obtained by performing data processing under the following conditions. Here half width and is at the peak of a 2 [Theta], the diffraction angle value defined by the peak width at an intensity position is half the intensity of the X-ray diffraction intensity.

The half width was obtained as follows. First, the X-ray diffraction intensity of 2θ = x was smoothed by the B-spline method. In the vicinity of the target peak value (2θ = 13.0 ± 0.5 °), the peak indicating the maximum diffraction intensity is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.5 ° or more.
The point where 2θ is the minimum diffraction intensity within the range of Ax or more and Ax + 1.5 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
Fx−Ex was defined as the half width of A (Δ2θ).

The half width (Δ2θ) obtained here corresponds to the size of the crystallite (= crystallinity). The larger the crystallite and the higher the crystallinity, the smaller the half width.

[Transparency evaluation method]
An offset ink was prepared using the pigments or pigment compositions obtained in the examples and comparative examples. Offset ink is 0.5 g of pigment or pigment composition, varnish for offset ink (Tamanol 361 (Arakawa Chemical Industries, Ltd .: rosin modified phenolic resin) 50 parts by weight, linseed oil 20 parts by weight, No. 5 Solvent (Japan Petroleum) Co., Ltd .: Solvent for offset ink) 30 parts by weight added and melted by heating at 200 ° C.) 2.0 g was kneaded by rotating 100 × 4 with a Hoover-Muller with a load of 150 lbs. Obtained.

The offset ink was developed on art paper (Mitsubishi Paper: Tokishi Art Both Sides N), and the transparency was visually evaluated as A to C shown below. In Comparative Example 1, C (reference) was defined as B when the transparency was higher than that of C, and A when markedly highly transparent.

<Evaluation of coloring composition>
[Evaluation method of heat resistance]
About the obtained coloring composition, heat resistance was evaluated.
The polyester resin (trade name: Diacron, manufactured by Mitsubishi Rayon Co., Ltd., glass transition temperature 55 ° C., softening temperature 130 ° C.) and high boiling ester solvent (trade name: Rick Sizer S4)
, Made by Ito Oil Co., Ltd.), mixed at the same weight, diluted varnish heated and melted at 145 ° C. and cooled to room temperature, and the resulting colored composition pulverized was mixed 1: 1 and a load of 150 lbs. A master batch ink was obtained by rotating 100 × 4 with a Hoover Muller to which ink was applied. This masterbatch ink is developed on art paper in the same manner as the offset ink, ◎ if there is no change in transparency compared to the offset ink, ◎ if there is almost no change in transparency, ○ for slightly opaque, x for extremely opaque
It was.

  The evaluation results are shown in Tables 4 and 5.

  As shown in Tables 4 and 5, the pigments obtained in Comparative Examples 1 and 2 have a larger half-value width by X-ray diffraction than the pigments or pigment compositions obtained in Examples 1 to 101, and are colored compositions. It was clarified that when the product was made, the transparency was drastically lowered and the heat resistance was poor.

Claims (4)

In the powder X-ray diffraction diagram indicated by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays,
A peak indicating the maximum diffraction intensity within the range of 2θ = 13.0 ± 0.5 °, A
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.5 ° or more.
The point where 2θ is the minimum diffraction intensity within the range of Ax or more and Ax + 1.5 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.45 or more and 0.69 or less . I. Pigment Red 269. C. I. A method of manufacturing a pigment red 269, C. according to claim 1, further comprising the step of treating with a water-soluble organic solvent during the coupling reaction I. Pigment Red 269 manufacturing method. C. I. A method of manufacturing a pigment red 269, C. according to claim 1 further comprising a solvent salt milling process to step I. Pigment Red 269 manufacturing method. At least, C. according to claim 1, wherein I. Pigment Red 269 and a coloring composition comprising a dispersion medium.