JPS5825698B2 - Ganryōso Seibutsu Oyobi Sono Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel azo pigment composition containing an acetoacetylaryl acid compound and a method for producing the same.

The usefulness of organic pigments depends on a number of complexly interrelated properties of the pigment, such as its degree of dispersion, rate of development of color intensity, and crystallization stability in organic solvents.

Also, the properties of paints or inks containing these pigments are highly influenced by the properties of the pigments used.

The color stability, ie the resistance to setting and color lifting under various forcing conditions, as well as the rheology of the pigment-containing medium, therefore varies depending on the nature of the pigment used.

It is already known that one or more of the above-mentioned properties can be significantly improved by adding various substances to pigments, such as rosin and its derivatives and long-chain aliphatic amines and their salts. be.

More recently, British Patent No. 1,139,294 describes pigments with the following formula: (wherein X1 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; , represents an aryl group or an aryl group containing a substituent, zl represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and A1 represents an alkyl group, an alkenyl group, or a substituted alkyl group having more than 10 carbon atoms, or a secondary It represents an alkyl group having an amino group or a tertiary amino group as a substituent, and nl represents an integer.

) A dispersible composition containing an azoacylamide represented by the following is disclosed.

The key point of the above-mentioned known azo additives is that they have both aliphatic properties and basic properties.

However, the present inventors have discovered that when certain acidic azo compounds are used as a minor component of an azo pigment-azo dye composition, the properties of the pigment are improved and an excellent pigment composition can be obtained.

The pigment composition of the present invention is characterized by significantly improved color strength compared to conventional pigment compositions, but also has improved properties such as transparency and gloss, making it excellent.

Furthermore, the present inventors have also found that similar improvements can be made by using known additives such as rosin or long-chain aliphatic amines in addition to the above-mentioned acidic azo compounds.

Specifically, the present invention provides the following formula (Ia): A-(-N=N-B)p (Ia) [wherein A is a 3,3'-dichlorodiphenyl group or the following formula: (in the formula , X represents a chlorine atom, a methyl group or a methoxy group), and B represents a group represented by the following formula: represents the group,
Q represents a tolyl group), p represents 1 or 2], and an azo pigment represented by the following formula ■b= (wherein, T is -C00H1-CH2C00H1-CH2CH2C
■H1-CH2S03H or Z represents a hydrogen atom when T represents -CH25O3H or -COOH; otherwise represents -COOH; A and p have the meanings already expressed above); 1 to 10% by weight of the represented compound.

A represents a substituted phenyl group or a substituted diphenyl group, and has a group that does not provide water solubility as a substituent.

Groups that do not impart water solubility refer to groups that do not impart water solubility at all or rarely impart water solubility to the molecules to which they belong; examples include chlorine atom, methyl group, methoxy group,
It is a nitro group.

Specifically, A is 4-chloro-2-nitroaniline,
4-Methyl-2-nitroaniline, 2-methoxy-4-
It is a group derived from nitroaniline or 3,3'-dichlorobenzidine.

Preferred pigment components of the compositions of the invention are azo pigments, such as azoacylacetoarylamide pigments or pyrazolone pigments.

The above-mentioned pigments include, for example, those obtained by coupling a diazonium compound derived from an amine listed in Group (1) below with an acetoacetarylamide compound listed in Group (2).

Group...Amine: 4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 3.3'-Schiff benzidine, 4-methoxy-2-nitroaniline Group ■: Acetoacetarylamide acetate Acetanilide Acetoaceto-m-xylidide, Acetoaceto-〇-chloranilide, Acetoaceto-
〇-anisidide acetoaceto=5-chloro-2,4-
Dimethoxyanilide, acetoaceto-2,5-dimethoxyanilide, acetoaceto-2,5-dimethoxy-4-
Chloranilide Acetoaceto-0-toluicide Acetoaceto p-toluicide The present invention further relates to a method for producing a pigment composition as described above.

The method for producing the novel pigment composition according to the present invention is as follows: one or more diazo compounds or tetraazo compounds derived from amines represented by the following formula (1): A (NH2)I) (II) are added under aqueous conditions to the following formula: ■: BH (IID) The coupling reaction is carried out together with one or more of the first coupling components represented by the following formula (■) and 1 to 10% by weight of the second coupling component represented by the following formula (■).

Examples of the compounds represented by formula (2) include the following.

2-acetoacetyl-amino-ethane-1-sulfonic acid acetoacetylaminosuccinic acid α-acetoacetyl-aminoglutaric acid α-acetoacetyl-amino-β-phenylpropionic acid acetoacetylaminoacetic acid Among the above, preferred are: Acetoacetylaminoacetic acid.

The compound represented by formula (a) is produced by a known method.

As one of them, a compound represented by the following formula (■: (wherein T and Z have the meanings already expressed above) or an alkali metal salt thereof, and a diketene or the following formula: %formula% (in the formula , R4 represents an alkyl group having 1 to 4 carbon atoms.

) There is a method of reacting with a compound represented by

Among the above reactions, it is advantageous to react the amine of formula (1), preferably its alkali metal salt, with diketene.

Most preferably, a free acid represented by the formula (■) is first reacted with an alkali metal hydroxide in an aqueous medium to form the formula (
An alkali metal salt of the compound represented by V) is prepared, and then diketene is added to a solution of the alkali metal salt, preferably by cooling, so that the reaction temperature is 50°C or less, preferably 20°C.
This is a method of adding while maintaining the temperature between 40°C and 40°C.

After completion of the reaction, any convenient method may be used to isolate the compound represented by the formula (low).

The production of the pigment composition according to the invention may optionally be carried out in stages.

That is, for example, a diazo compound or a tetraazo compound derived from an amine represented by formula (II) is first
Coupling with a coupling component represented by formula (5), then adding a compound represented by formula (5), and further coupling with a diazo compound or tetraazo compound derived from an amine represented by formula (II) One example is the method.

Additionally, a diazo compound or a tetrazo compound derived from an amine represented by formula (II) and a diazo compound or tetraazo compound derived from an amine represented by formula (II) and
A coupling component represented by ID is coupled, and then a compound represented by formula (V) and a diazo compound or tetraazo compound derived from an amine represented by formula (II) are separately coupled. The method of adding the product obtained in this process is a similar two-step process.

It goes without saying that in the above two-step method, the reaction order of the two coupling components may be reversed.

That is, prior to coupling the coupling component represented by formula (IIN) diBH with the diazo compound or tetraazo compound, the compound represented by formula (5) is derived from the amine represented by formula (II). It is also possible to react with a diazo compound or a tetraazo compound.

Even more preferable and convenient than the above methods is the mixed coupling technique.
This is the manufacturing method of the present invention using ``Nique''.

This is the combination of the coupling component represented by the formula ■ and the formula ([0
A mixture with a coupling component represented by the formula (II
) is a method of coupling with a diazo compound or a tetraazo compound derived from an amine represented by:

In order to use the compound represented by formula (5) in the production of a pigment composition, it is necessary to use the compound represented by formula (5) in an amount of 1 to 10, based on the total amount of coupling components.
Use in heavy weight quantities.

However, it is more preferable to use the compound represented by formula (2) in an amount of 2 to 8 weight percent of the total amount of coupling components.

In each of the various methods for producing the pigment compositions of the present invention as described above, the coupling reaction is carried out at a reaction temperature of, for example, -10 to 50°C and an acidic pH value, for example, a pH of 1 to 6.
done under value conditions.

A convenient method for isolating the coupling product after completion of the coupling is to raise the temperature of the coupling product mixture to, for example, 80 to 100°C, filter it, and then dry the resulting composition. .

The composition of the product of the process of the invention depends on the nature of the azo component and the coupling component used as starting materials.

Preferred examples are listed below.

The following substituent atoms or substituents: A diazo compound derived from an amine benzene having a chlorine atom, a nitro group, a methyl group, or a methoxy group, and a coupling component represented by the formula (A) and a coupling component represented by the formula (IID). Coupling with a mixture of components.

This reaction produces the following components: 1) A compound of the following formula (VD: A-N2N-B (Vll), where X has the following substituent atom or group: chlorine atom, nitro group, methyl group or methoxy group represents a phenyl group, B
has the same meaning as above.

) and 2) a composition containing a compound represented by the following formula: (wherein R, T and Z each have the meanings expressed above).

To give yet another preferred specific example, it is possible to combine a tetraazo component derived from a diamine represented by the following formula (I) with a coupling component represented by the formula (■) and a mixture of coupling components represented by the formula (I[D). This is a reaction that couples with

Depending on this reaction, the following components: 1) a compound of the formula IX: in which B, T and Z have the meanings already given above; and 2) a compound of the formula X: in which: B has the meaning already given above) and 3) a composition containing a compound of the following formula xI: (wherein Z has the meaning already given above) It will be done.

Further, a method of obtaining a pigment component as a mixture by using one or both of a diazo compound derived from an amine represented by the formula (It) and a compound represented by a weapon is also a specific example of the present invention.

For example, one type of diazo compound derived from an amine represented by formula (II) and two different types of coupling components represented by formula ([I), namely, a compound represented by BH and a compound represented by B'H. There are methods of coupling compounds according to the invention.

The pigment composition obtained by this method contains all or part of the compounds listed below.

The types of compounds included vary depending on the reaction method used.

Compound represented by formula (IX) Compound represented by formula (X) Compound formula represented by formula (XI): Compound formula represented by B-N=N-A-N=N-B': B'-N A compound represented by the formula: Represents something other than what B in the formula represents, as shown in the definition of B.

) Also included in the present invention are a method of incorporating an azo derivative obtained by simultaneous coupling of several mixtures of compounds represented by general formula (I), and a pigment composition obtained by that method. It is.

Among the monoazo pigments &-N=N-H, azoacylacetoarylamide pigments are preferred.

This pigment contains, for example, a diazo component of 4-chloro-2-nitroaniline or 4-methyl-2-nitroaniline and acetoacetarylamides, such as acetoacetanilide, acetoaceto-〇-toluiside, acetoaceto-〇-chloroanilide. , acetoaceto-m-xylidide or acetoaceto-4-chloro-2,4-dimethoxyanilide.

Examples of group B include a series of acetoacetoarylamides or 1-, which optionally have one or more substituents of groups that do not confer water solubility, such as halogen atoms, nitro groups, methyl groups, or methoxy groups. Examples include arylpyrazol-5-ones.

In the production of the pigment composition according to the invention, a certain amount of
It is usually advantageous to add, for example, from 1 to 40 parts by weight, calculated on the total weight of the composition, of one or more agents that improve the application properties of the pigment.

Examples of such modifiers include rosin, rosin amines, resin acid zinc/calcium salts, and especially amines or derivatives thereof, preferably aliphatic amines having 1 to 20 carbon atoms, amine salts, or amine oxides. Can be mentioned.

The above amines may be primary, secondary or tertiary.

More preferred are primary amines having long chain alkyl groups, such as oleylamine, stearylamine, cyclohexylamine, 3-dimethylamino-propylamine, 3-dimethylamino-propylamine,
Tetradecylamino-propylamine, 3-(2'-undecylamino)-pendylamine or 3-(2'-pentadecylamino)-propylamine, and optionally carboxylic acid salts of the amines mentioned above, preferably Examples are acetate or oleate.

The pigment composition of the present invention has excellent applicability.

When the pigment compositions of the present invention are used in ink and paint media, the degree of coloration, gloss and clarity are improved over those of the prior art, and the stability of color in solvents is improved.

Color stability in a solvent refers to the ability of a pigment to retain its color intensity when stored in a solvent, particularly an aliphatic or aromatic hydrocarbon.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

"Parts" in the examples indicate "parts by weight" unless otherwise specified.
The relationship between "1 part" and "capacity part" is "kilogram" and "
The relationship is similar to that of liter.

Furthermore, the pigment composition of the present invention described in the following examples is almost the same as the base pigment and exhibits a yellowish color.

Example 1 A coupling component solution was prepared by dissolving 203.3 parts of acetoacetanilide and 11.0 parts of acetoacetylaminoacetic acid in a solution consisting of 87.3 parts of sodium hydroxide and 2000 parts of water.

200 parts of this coupling component solution was added to 1500 parts of water and 18 parts of sodium acetate hydrate in a coupling reaction vessel.
．． 0 parts of an aqueous solution.

Next, glacial acetic acid was added to the resulting solution to adjust the pH of the solution to 4.
It was set to 5 to 5.0.

The remaining coupling component solution used above was put into the above coupling reactor, and at the same time, a solution of tetraazotide of 3,3'-dichlorobenzidine separately prepared as follows was added, and the pH was adjusted to 4.5-5. The coupling reaction was carried out at 5.0.

The tetraazo component used above was produced by the following method.

3. 145.2 parts of 3'-dichlorobenzidine (calculated as dihydrochloride) in 300 parts of water and 198 parts of ION hydrochloric acid.
．． Stir with 5 parts by volume and add 82.2 parts of sodium nitrite.
A solution prepared by dissolving 1 part in 200 parts of water was added, and then impurities were removed from the tetraazotized 3,3-dichlorobenzidine solution using activated carbon.

The slurry pigment obtained by coupling was heated to 95°C.
and held at that temperature for 30 minutes.

Next, it was filtered, washed until it contained no inorganic acid salts, and dried at a temperature of 50°C.

The pigment composition thus obtained is used in an oil-based ink.
Pigment Yellow 12
ow 12) showed superior transparency and degree of coloration.

The standard pigment Pigment Yellow 12 used as a control was produced in the same manner as in this example, using an equimolar amount of acetoacetanilide instead of the acetoacetylaminoacetic acid used in this example.

Further, the pigment obtained in this example could be dispersed in the medium of nitrocellulose or gravure photographic printing ink by high-speed stirring.

The obtained ink exhibited a higher degree of coloring, better gloss, and color stability than when Pigment Yellow 12, which is included in the color index, was used.

The comparison was made as follows.

The ink containing 30 parts pigment was passed through a three-roll mill once lightly and twice heavily, and subsequently diluted to 15 parts pigment, giving a pigment to binder ratio of 1:2.2.

The ink was applied onto the paper using a steel plate blade.

The degree of coloration was determined by visually evaluating the control and test inks.

Transparency was measured. Transparency was determined by applying the ink on a bright and dark paper with black and white stripes and visually evaluating the transparency from above the painted ink.

Example 2 An aqueous slurry containing 359.5 parts of pigment was produced in the same manner as in Example 1.

To this slurry was added 89.9 parts of a solution of octadecylaminopropylamine diacetate.

The slurry was then heated to a temperature of 95°C and held at this temperature for 30 minutes.

The temperature was lowered to 70°C and the pH was subsequently adjusted to 10-11.

The product was separated, washed and dried at a temperature of 50°C.

The pigment composition obtained in this example had better properties than the pigment Pigment Yellow 12 in the Color Index (treated with occudecylaminopropylamine diacetate in the same manner as in this example). Indicates the degree of coloration.

Example 3 A pigment aqueous slurry was prepared in the same manner as in Example 2, and
The subsequent treatments were carried out in almost the same manner, but in this example, octadecylaminopropylamine diacetate was treated at a temperature of 95°C.
This differs from Example 2 in that it was added to the slurry after it had been heated to .

The resulting slurry was cooled to a temperature of 70°C and the pH was again adjusted to 1.
After adjusting to 0 to 11, it was filtered and dried in the same manner as in Example 2.

The pigment obtained in this example was found in a gravure photographic ink medium (for publication), compared to Pigment Yellow 12 (treated in the same manner as in this example) in the color index used as a control. It showed a better degree of coloration.

Example 4 In the same manner as in Example 1, a solution of a tetraazo compound was obtained from 145.2 parts of 3,3'-dichlorobenzidine (the amount calculated as its dihydrochloride).

Furthermore, in the same manner as in Example 1, this tetraazotide and
A coupling reaction was performed using a coupling component solution prepared by dissolving 207.6 parts of acetoacetanilide and 6.8 parts of acetoacetylaminoacetic acid in a solution consisting of 87.3 parts of sodium hydroxide and 2000 parts of water. .

The obtained slurry pigment was heated to a temperature of 95°C, and
It was held at this temperature for minutes.

A solution of octadecylaminopropylamine diacetate was then added and the pH was finally adjusted to 10.

The product was filtered, washed and dried at a temperature of 50°C, and the resulting pigment was stirred at high speed to form a gravure photographic medium (
However, the obtained colored body was prepared in the same manner as in this example using acetoacetanilide instead of acetoacetylaminoacetic acid, and was dispersed in the color index used as a control. It exhibited a coloring degree superior to that of Pigment Yellow 12.

Example 5 In the same manner as in Example 1, a solution containing a tetraazo component was produced from 145.2 parts of 3,3'-dichlorobenzidine (the amount calculated as the dihydrochloride).

Further, in the same manner as in Example 1, this tetraazo component solution, 237.2 parts of acetoaceto-m-xylidide, and 10.4 parts of acetoacetylaminoacetic acid were dissolved in a solution consisting of 68.9 parts of sodium hydroxide and 3000 parts of water. A coupling reaction was performed using the coupling component solution prepared in the above manner.

The resulting slurry was heated to a temperature of 95°C and maintained at this temperature for 2 hours.

The product was then separated, washed and dried at a temperature of 50°C.

The obtained product and the standard pigment Pigment Yellow 13 in Color Index produced in the same manner as in this example.
As a result of comparing the two in a lithographic printing ink medium, it was found that the pigment composition obtained in this example had stronger coloring and greater transparency.

Example 6 An aqueous slurry was prepared from 392.8 parts of pigment in the same manner as in Example 5, and heat treated.

Next, Rosin Amine D (Rosin Amine D)
D) (This is RICH2NH2 (where W represents a group based on an abiethyl structure).

) is the trade name of the type of amine represented by ]19.6
was added in the form of its acetate solution to the slurry obtained above and the pH was adjusted to 10.

The product was separated, washed and dried at a temperature of 50°C.

The product obtained in this example and Pigment Yellow 13 in the color index subjected to the same treatment as in this example
(Control) in a lithographic printing ink medium, the results showed that the coloring degree and transparency when the product of this example was used was superior.

Example 7 3,3'-dichlorobenzidine 1 was prepared in the same manner as in Example 1.
A solution containing the tetraazotide was prepared from 45.2 parts (amount calculated as its dihydrochloride).

Separately, 219.9 parts of 3-methyl-1-p-tolyl-5-pyrazolone and 10 parts of acetoacetylaminoacetic acid
．． A coupling component solution was prepared by dissolving 8 parts in a solution consisting of 67.6 parts of sodium hydroxide and 1600 parts of water.

Next, coupling was performed in the same manner as in Example 1.

The slurry obtained above was heated to a temperature of 95°C and kept at this temperature for 30 minutes.

The product was oven separated, washed and dried at a temperature of 50°C.

The pigment obtained in this example and the standard orange pigment obtained by the same method as in this example using an equimolar amount of tolylmethylpyrazolone in place of the acetoacetylaminoacetic acid used in this example. As a result of a comparative test in a lithographic printing ink, it was found that the pigment composition of this example had better gloss and transparency.

Example 8 An aqueous slurry containing 375.8 parts of pigment was produced in the same manner as in Example 7.

The slurry was heated to a temperature of 95° C. and 18.8 parts of rosin amine D was then added in the form of an acetate solution.

Heating of the slurry was continued and maintained at a temperature of 95° C. for 30 minutes, after which its pH was adjusted to 10.

The product was filtered, washed and dried at a temperature of 50°C.

The pigment composition obtained in this example exhibited properties similar to those obtained in Example 7, but was even easier to disperse into a lithographic varnish.

The ink was applied onto the paper with a steel blade.

Transparency was measured in the same manner as in Example 1.

Glossiness was visually evaluated.

Example 9 115.4 parts of acetoaceto-〇-chloroanilide and 3.1 parts of acetoacetylaminoacetic acid were mixed with 2 parts of sodium hydroxide.
A coupling component solution was prepared by dissolving in a solution consisting of 7.3 parts and 2000 parts of water.

31.7 parts of sodium acetate hydrate was added to the above solution and the pH of the mixture was adjusted to 6.9 using acetic acid.

The generated slurry and 4- produced as follows
Coupling was performed using a solution of chloro-2-nitroaniline diazotide.

The diazo component was produced as follows.

96.6 parts of 4-chloro-2-nitroaniline, 200 parts of water
1 part and 118.6 parts by volume of ION hydrochloric acid were stirred, and a solution obtained by dissolving 39.2 parts of sodium nitrite in 150 parts of water was added thereto, and then from the obtained solution containing the diazotide, Impurities were removed using activated carbon.

The slurry obtained by coupling was heated to a temperature of 70°C and maintained at this temperature for 30 minutes.

The product is washed door to door until it contains no inorganic acid salts,
Then, it was dried at a temperature of 50°C.

The resulting pigment composition exhibited excellent coloration and transparency and gloss in oil-based ink media and in the media of decorative paints based on soybean oil pen querite alkyd resins.

Coloring using this pigment composition was carried out using a pigment of a color index standard pigment produced in the same manner as in Example 1 using an equimolar amount of acetoaceto-〇-chloroanilide in place of acetoacetylaminoacetic acid in Example 1. This was more advantageous than coloring using Yellow 3.

Example 10 An aqueous slurry containing 215 parts of pigment was prepared in the same manner as in Example 9.

The resulting slurry was heated to a temperature of 70°C and held at this temperature for 30 minutes.

Next, to this slurry, rosin amine O [this is Fe
-CH2NH2 (wherein R1 represents a group based on an abiethyl structure).

) is the trade name of the compound represented by

) A solution of 10.8 parts of acetate was added.

The pH of the resulting mixture was adjusted to 10, the solid product was filtered out, washed and dried at a temperature of 50°C.

The pigment composition obtained in this example exhibited almost the same properties as the pigment composition of Example 9, but was easier to disperse in an alkyd resin medium.

Example 11 114 parts of acetoacetanilide and 3.5 parts of acetoacetylaminoacetic acid were mixed with 30.8 parts of sodium hydroxide and 2 parts of water.
A coupling component solution was prepared by dissolving it in a solution consisting of 1,000 parts.

To this solution was added 21.8 parts of sodium acetate hydrate, followed by adjusting the pH of the mixture to 6.9 using acetic acid.

Separately, 98.0 parts of 4-methyl-2-nitroaniline was stirred with 200 parts of water and 135 parts by volume of ION hydrochloric acid,
To this was added 46 parts of sodium nitrite dissolved in 150 parts of water.
8 parts of diazotide of 4-methyl-2-nitroaniline was prepared by adding 8 parts and removing impurities from the resulting mixture with activated carbon; using this and the previous coupling component solution, Coupled.

After the coupling was completed, the resulting slurry was heated to a temperature of 70°C and kept at this temperature for 30 minutes.

Next, the slurry was separated and the resulting solid was washed until it was free of inorganic acid salts and dried at a temperature of 50°C.

The pigment composition prepared in this example was significantly superior to the standard pigment Pigment Yellow 1 in terms of color strength, gloss and transparency in the ink medium.

Moreover, this excellent degree of coloration was demonstrated even in a decorative alkyd resin medium.

Example 12 An aqueous slurry containing 217.3 parts of pigment was produced in the same manner as in Example 11.

The resulting slurry was heated to a temperature of 70°C and kept at this temperature for 30 minutes.

A solution of 10.9 parts of Rosinamine D acetate was then added to the slurry.

The pH of the mixture was adjusted to 10, and the resulting slurry was sent door to door to separate and collect the solid content, which was washed and further heated to a temperature of 5.
It was dried at 0°C.

The pigment composition obtained in this example exhibited excellent coloration, gloss, and transparency in oil-based ink media and decorative alkyd media.

Examples 13 and 14 Examples were carried out using an equimolar amount of acetoacetyl-2-amino-sulfoethane or an equimolar amount of acetoacetylaminosuccinic acid in place of the acetoacetylaminoacetic acid used in Example 5. Production was carried out in the same manner as in No. 5.

Both of the two pigment compositions thus obtained exhibited excellent transparency and gloss in the oil-based ink medium.

Example 15 The same production as in Example 2 was carried out except that in place of acetoacetylaminoacetic acid in the coupling component solution used in Example 2, an equimolar amount of acetoacetyl α-aminoglutaric acid was used.

The product of this example exhibited excellent clarity and gloss in the oil-based ink medium.

Example 16 In the same manner as in Example 1, a tetraazo component solution was prepared from 145.2 parts of 3,3'-dicyclobenzidine (the amount calculated as the dihydrochloride).

Apart from this, acetoaceto-〇-toluicide 219.0
A coupling component solution was prepared by dissolving 11 parts of acetoacetylaminoacetic acid and 90 parts of sodium hydroxide in 1500 parts of water.

Next, a coupling reaction was performed using the above two solutions.

The resulting slurry was heated to a temperature of 50°C and kept at this temperature for 30 minutes.

Subsequently, the mixture was separated, and the resulting solid was washed until it contained no inorganic acid salts, and further dried at a temperature of 50 to 55°C.

The product obtained in this example is superior to the product prepared similarly to this example by replacing the acetoacetylaminoacetic acid of this example with an equimolar amount of acetoaceto-o-toluiside in an oil-based ink medium. It exhibited excellent gloss and transparency.

Example 17 The same procedure as in Example 11 was carried out except that 85 parts of soluble acetate of octadecylaminopropylamine was added when the slurry was heated to a temperature of 95°C.

The temperature of the resulting slurry was maintained at 95° C. for 30 minutes, and the pH of mixture (7) was adjusted to 10.5.

Next, the mixture was washed from house to house until it contained no inorganic acid salts, and further dried at a temperature of 55°C.

The pigment composition obtained in this example and a pigment composition prepared in the same manner using an equimolar amount of acetoacetyl-o-toluiside in place of the acetoacetylaminoacetic acid of this example were used for gravure photographic printing. As a result of comparison in the ink medium, it was found that the pigment composition of this example showed a superior degree of coloring. Instead of α-acetoacetylamino-β-
This was carried out using 16.5 parts of phenylpropionic acid.

The product obtained in this example exhibited properties similar to those of Example 5.

Example 19 A similar production as in Example 1 was carried out using, in place of the acetoacetanilide of Example 1, a mixture of 102 parts of acetoacetanilide and 110 parts of acetoaceto-〇-toluide.

As a result of testing in gravure photographic printing ink, it was found that the product was produced in the same manner as in this example using either acetoacetanilide or acetoaceto-〇-toluide in an equimolar amount instead of acetoacetylaminoacetic acid in this example. The product obtained in this example is
It was found that the degree of coloration and gloss were improved.

Example 20 A diazo component manufactured in the same manner as in Example 9 using 94.0 parts of 2-nitro-4-methoxyaniline instead of 4-chloro-2-nitroaniline used in Example 9, Further, a coupling component prepared from 112.9 parts of acetoacetyl-0-anisidide and 3.1 parts of acetoacetylaminoacetic acid was used.

As a result of dispersing the product of this example in a face for lithographic printing, the obtained face was prepared using the same molar amount of acetoacet-〇-anisidide in place of the acetoacetylaminoacetic acid of this example. It was superior in coloration and gloss to products produced in a similar manner.

Example 21 The same production as in Example 9 was carried out using a coupling component prepared from 114.3 parts of acetoaceto-m-xylidide and 3.1 parts of acetoacetylaminoacetic acid.

Testing of the product obtained in this example by dispersing it in an oil-based ink or decorative alkyd paint medium revealed that the product of this example contained acetoacetylaminoacetic acid in an equimolar amount of acetoacetate-m- Compared to the product prepared in the same manner as in this example except for the substitution with xylidide, it showed better coloration intensity, purity of shade, gloss, clarity and stability of brilliance in the above tests.

Claims (1)

[Claims] Primary formula (Ia) A − (−N=N−B) p (I a )
[Wherein, A represents a 3,31-dichlorodiphenyl group or a group represented by the following formula: (wherein, X represents a chlorine atom, methyl group, or methoxy group), and B represents the following formula: (wherein, Q represents a phenyl group or a phenyl group substituted with a methyl group, a methoxy group and/or a chlorine atom,
q represents a tolyl group), p represents 1 or 2], and an azo pigment represented by the following formula I
b= (wherein, T is -COOH1-CH2COOH, -CH2CH2C
0OH. -CH2503H or Z represents a hydrogen atom when T represents -CH25O3H or -COOH, otherwise represents -COOH, A and p have the meanings already expressed above) A pigment composition containing 1 to 10% by weight of a compound. 2 Under aqueous conditions, the following formula ■: A (NH2)l) (II) [wherein A is a 3,3 dichlorodiphenyl group or the following formula: (wherein,
X represents a chlorine atom, a methyl group, or a methoxy group), p represents 1 or 2] and one or more amine diazo compounds or tetraazo compounds represented by the following formula , B is the following formula: (wherein, Q represents a phenyl group or a phenyl group substituted with a methyl group, a methoxy group and/or a chlorine atom, and q
represents a group represented by the following formula: (represents a tolyl group)] and the following formula: (wherein, Z represents T represents -CHdiSO3H or -COOH) The following formulas (Ia) and (Ib): A- (-N=N-B,lp(Ia)) and a compound represented by (wherein A, B, T, Z and p have the meanings already given above) A method for producing a pigment composition.