JP2003073582A - Solid solution of acetanilide benzimidazolone-type azo pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an azo pigment having high chroma and transparency and developing a desired hue within the range from yellow to orange by a simple method without mixing different pigments for toning. SOLUTION: The new solid solution of azo pigment is composed of two kinds of acetanilide benzimidazolone-type azo pigments having yellow and orange color, respectively. A desired hue can be developed within the range from yellow to orange by selecting the mixing ratio of these pigments.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel acetanilide benzimidazolone type azo pigment solid solution comprising two specific types of pigments.

[0002]

2. Description of the Related Art Azo pigments have been widely used since ancient times and are said to account for half of the amount of organic pigments produced at present. Azo pigments have a clear hue and a large tinting strength, and their color tones range from yellow to purple. In general, pigments often have different hues even if they have the same chemical composition but different crystal forms. Therefore, in order to obtain a desired hue, a toning step of mixing two or more kinds of pigments having different hues is required. Usually, when different kinds of pigments are mixed and toned, the hue of the pigment after the toning changes continuously according to the hue of each contained pigment and the content ratio of each pigment, but the mere physical Since it is a mixture, there are problems that the colors are often separated due to aggregation and that the saturation and the transparency are lowered.

[0003]

The object of the present invention is to provide high saturation, excellent transparency, and within the range of yellow to orange,
It is an object of the present invention to provide a novel azo pigment that can develop a desired hue by a simple method without mixing different pigments for toning.

[0004]

The present invention provides the following formula (I):
The above-mentioned problems have been solved by providing an acetanilide benzimidazolone-based azo pigment solid solution comprising a pigment (a) represented by the following formula and a pigment (b) represented by the following formula (II).

[0005]

[Chemical 3] Formula (I)

[0006]

[Chemical 4] Formula (II)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The acetanilidebenzimidazolone type azo pigment solid solution of the present invention comprises a yellow pigment (a) represented by the above formula (I) and an orange pigment (a) represented by the above formula (II). It consists of b). Hereinafter, "acetanilide benzimidazolone-based azo pigment solid solution of the present invention" is "pigment solid solution of the present invention", "yellow pigment (a) represented by formula (I)" is "pigment (a)", The "orange pigment (b) represented by the formula (II)" is abbreviated as "pigment (b)".

The pigment solid solution of the present invention is characterized in that its hue can be continuously changed from yellow to orange by changing the component ratio of the pigment solid solution. Therefore, it is not necessary to mix different pigments for toning, and the saturation is high and the transparency is excellent. The pigment (a), which is a component of the pigment solid solution of the present invention, has a crystal structure in which the X-ray diffraction angle 2θ has a maximum peak at (26.1 ± 0.2) °, and the pigment ( b) has a crystal structure in which the X-ray diffraction angle 2θ has a maximum peak at (27.4 ± 0.2) °.

It is generally known that the crystal structure of a solid solution continuously changes as the ratio of the components constituting the solid solution changes. MiXed Crystals, Springer-Verlag, Be
On page 210 of rlin, Heidelberg, New York, Tokyo, 1984, it can be said that the crystal lattice constant of cubic solid solution generally follows Vegard's law, which linearly changes in proportion to the change in the ratio of solid solution constituents. Have been described.

The crystal structure of the pigment solid solution of the present invention is continuously changed by changing the ratio of the components constituting the solid solution, that is, the ratio of the pigment (a) and the pigment (b).
Such a continuous change in the crystal structure with a change in the ratio of the solid solution constituents is observed by powder X-ray diffraction measurement. The position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention (X-ray diffraction angle 2θ) is the position of the maximum peak in the powder X-ray diffraction of pigment (a) by changing the ratio of the constituents ( It continuously changes between 26.1 ± 0.2) ° and (27.4 ± 0.2) ° which is the position of the maximum peak in the powder X-ray diffraction of the pigment (b).

Assuming that the change in the position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention changes linearly and continuously according to the above-mentioned Vegard's law, the pigment (a) X
The position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention consisting of mol% and the pigment (b) (100-X) mol% is theoretically {(27.4-0.013).
X) ± 0.2} °.

The present inventors have made the following findings as a result of examining how the crystal structure of the pigment solid solution of the present invention changes with the change in the ratio of the solid solution constituents. 1) The powder X-ray diffraction pattern of the pigment solid solution of the present invention is similar to the powder X-ray pattern of the host pigment. 2) The plurality of peak positions appearing by powder X-ray diffraction of the pigment solid solution of the present invention continuously change depending on the ratio of the pigment (a) and the pigment (b), but the magnitude of change in the X-ray diffraction angle 2θ. , And the direction of the change should be different for each peak. 3) Despite the phenomenon of the previous section, pigment (a) Xmol
% And the measured position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention consisting of the pigment (b) (100-X) mol%, the X-ray diffraction angle 2θ when it is assumed that the above-mentioned Vegard's law is established. , {(27.4-0.013X)
Although it does not exactly match ± 0.2} °, {(27.
4−0.013X) ± 0.3} °, and they should be almost the same. 4) The slight deviation between the measured position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention described in the preceding paragraph and the position of the maximum peak when the above-mentioned Vegard's law is assumed to be formed is the production of the solid solution. Caused by the method or crystal growth treatment method. 5) The hue of the pigment solid solution of the present invention continuously changes in the range from yellow to orange in accordance with the change in the position of the maximum peak in powder X-ray diffraction.

From the above findings, the relationship between the position of the maximum peak in the powder X-ray diffraction of the pigment solid solution of the present invention and the ratio of the pigment (a) and the pigment (b) constituting the pigment solid solution is as follows:
It has a substantially linear relationship, and by controlling the ratio of the pigment (a) and the pigment (b), it is clear that the pigment solid solution of the present invention having a desired hue can be obtained within the range from yellow to orange. It was

The pigment solid solution of the present invention can be produced by a known method for producing an organic pigment solid solution. A general method for producing an organic pigment solid solution is roughly classified into a dissolution precipitation method, a synthesis method, and a grinding method. The pigment solid solution of the present invention can be produced by any of the methods, but in the present invention, it is preferable to use a dissolution precipitation method which can obtain a pigment solid solution having high crystallinity.

Regarding the dissolution precipitation method, JP-A-5-3395 is used.
Japanese Patent Laid-Open Publication No. H8-8128 discloses a method in which a plurality of pigments are dissolved in sulfuric acid and then dropped into water to precipitate a pigment solid solution.
In JP120189, a method of dissolving a plurality of pigments in alkaline dimethylsulfoxide and then neutralizing or dropping the pigment in alcohol to precipitate a solid solution of the pigment is disclosed in JP-A-2-229867. A method in which a pigment is heated and dissolved in nitrobenzene and then cooled to precipitate a solid solution of the pigment is disclosed in JP-A-7-196939, t-.
After dissolving multiple pigments with butoxycarbonyl groups in a non-polar solvent such as toluene or diphenyl ether,
A method for depositing a pigment solid solution by heat treatment is described.

The pigment solid solution prepared by the dissolution precipitation method as described above often has fine crystals, and the powder X-ray pattern derived from the crystal structure may not always be clearly observed. The pigment solid solution of the present invention can be grown in a state of being dispersed in a solvent by heating while stirring to increase the particle diameter of the pigment solid solution crystal. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, isobutanol, and ethylene glycol monobutyl ether, aromatic solvents such as toluene, xylene, and nitrobenzene, ethyl acetate, butyl acetate, 2-ethoxyethyl acetate, etc. It is preferable to use an aprotic polar solvent such as the ester, dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, and the heating temperature is preferably 50 ° C. or higher. The required particle diameter of the pigment varies depending on its application, but the primary particle diameter of the pigment used as a coloring material for printing ink, paint, plastic, etc. is generally several tens to several hundreds nm.

The powder X-ray diffraction pattern of the crystal-grown pigment solid solution of the present invention is similar to the powder X-ray diffraction pattern of the solid solution matrix pigment (a) or pigment (b). The peak position is pigment (a)
Alternatively, unlike each peak position of the pigment (b), the peaks are continuously shifted depending on the ratio of the pigment (a) and the pigment (b), and the shift width of the X-ray diffraction angle 2θ at each peak position and the shift direction are peaks. Different for each.

Pigment (a) X mol%, and pigment (b)
The pigment solid solution of the present invention consisting of (100-X) mol% has an X-ray diffraction angle 2θ of {(27.4-0.013X) ±.
It has a crystal structure showing a maximum peak in the range of 0.3} °, and by changing the charging ratio of the pigment (a) and the pigment (b), from (26.1 ± 0.3) ° to ( 27.4 ± 0.
Within the range of 3) °, a desired hue of yellow to orange can be obtained.

In addition, the pigment solid solution of the present invention has higher saturation and excellent transparency as compared with the toned products of general yellow azo pigments, and also has light resistance, heat resistance and solvent resistance. Are better. Taking advantage of these features, the pigment solid solution of the present invention can be widely used for applications such as traffic paints, automobile paints, printing inks, and plastic colorants.

[0020]

The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, "part" and "%"
Represents "parts by mass" and "% by mass", respectively.

(Example 1) As a pigment (a), "Symuler FastYell" manufactured by Dainippon Ink and Chemicals, Inc.
ow 4192 ") (C.I. Pigment Yel
low 154) 10.6 parts, and as a pigment (b), "Symuler Fa" manufactured by Dainippon Ink and Chemicals
st Orange 4183H "(C. I. Pigm
ent Orange 36) 1.6 parts at 95 ° C. at 0 ° C.
It was dissolved in 300 ml of concentrated sulfuric acid. The solution was added dropwise to 1000 parts of ice water with stirring to precipitate an acetanilide benzimidazolone azo pigment solid solution. The precipitated solid solution of pigment was suction filtered and washed with water until the washing liquid became neutral. The obtained water-containing pressed cake was dispersed in 3000 parts of water and stirred at room temperature for 2 hours. After suction filtration and washing with water, 1
It was dried by heating at 30 ° C. for 2 hours. Further, the mixture was refluxed in 200 ml of isobutanol for 4 hours with stirring to perform crystal growth treatment. After cooling, the pigment solid solution was suction filtered, washed with methanol and water in this order, and the obtained water-containing pressed cake was
It was dried by heating at 30 ° C. for 2 hours to obtain 11.2 parts of an orange yellow pigment. In this case, the charging ratio (X) of the pigment (a) is 8
It is 7.5 mol%.

The results of elemental analysis of the obtained acetanilide benzimidazolone azo pigment solid solution are shown below.
The figures in parentheses are theoretical values. It is generally known that the error range of the elemental analysis measurement value of the fluorine-containing compound is ± 0.4% with respect to the theoretical value, and all the measurement values are within this error range. C: 52.4% (52.8%) H: 3.4% (3.4%) N: 17.3% (17.6%)

Table 1 shows the results of the powder X-ray diffraction analysis of the obtained acetanilide benzimidazolone azo pigment solid solution. However, the analysis by powder X-ray diffraction is CuK
"Wide-angle X-ray measuring device manufactured by Rigaku Corporation using α radiation
RINT type "was used. The 2θ measurement error is ± 0.
It is 2 °.

[0024]

[Table 1]

In addition, the pigment (a) ("Symuler F
Table 2 shows the result of the analysis by powder X-ray diffraction of "ast Yellow 4192").

[0026]

[Table 2]

From the results shown in Tables 1 and 2, it is found that the powder X-ray diffraction pattern of the acetanilide benzimidazolone azo pigment solid solution is similar to the powder X-ray diffraction pattern of the pigment (a) as the host pigment. Further, from Table 1, X of acetanilide benzimidazolone type azo pigment solid solution was obtained.
The line diffraction angle 2θ is {(27.4-0.013X) ± 0.
It is understood that the crystal structure has a maximum peak at 3} ° = (26.26 ± 0.3) ° (X = 87.5).

Example 2 In Example 1, 10.6 parts of pigment (a) was 9.1 parts, 1.6 parts of pigment (b) was 3.1 parts, and the crystal growth treatment time was 4 hours. In the same manner as in Example 1 except that the time was changed to 2 hours, 11.6 parts of a yellowish orange pigment was obtained. In this case, the charging ratio (X) of the pigment (a) is 75 mol%.

The results of elemental analysis of the obtained acetanilide benzimidazolone azo pigment solid solution are shown below.
The figures in parentheses are theoretical values. The elemental analysis measurement value is within an error range of ± 0.4% with respect to the theoretical value. C: 51.9% (52.2%) H: 3.4% (3.4%) N: 17.6% (18.0%) Obtained acetanilide benzimidazolone azo pigment solid solution powder X Table 3 shows the results of the analysis by line diffraction.

[0030]

[Table 3]

From the results shown in Tables 2 and 3, it is found that the powder X-ray diffraction pattern of the acetanilide benzimidazolone azo pigment solid solution is similar to the powder X-ray diffraction pattern of the host pigment (a). Further, from Table 3, X of acetanilide benzimidazolone type azo pigment solid solution was obtained.
The line diffraction angle 2θ is {(27.4-0.013X) ± 0.
It can be seen that the crystal structure has a maximum peak at 3} ° = (26.43 ± 0.3) ° (X = 75).

Example 3 In Example 1, 10.6 parts of pigment (a) was added to 9.1 parts, 1.6 parts of pigment (b) was added to 3.1 parts, and 4 parts in 200 ml of isobutanol were added. The crystal growth treatment performed for 7 hours was performed in 200 ml of m-xylene.
11.7 parts of a yellowish orange pigment was obtained in the same manner as in Example 1 except that the time was changed. In this case, the charging ratio (X) of the pigment (a) is 75 mol%.

The results of elemental analysis of the obtained acetanilide benzimidazolone azo pigment solid solution are shown below.
The figures in parentheses are theoretical values. The elemental analysis measurement value is within an error range of ± 0.4% with respect to the theoretical value. C: 51.9% (52.2%) H: 3.4% (3.4%) N: 17.8% (18.0%) Obtained acetanilide benzimidazolone azo pigment solid solution powder X Table 4 shows the results of the analysis by line diffraction.

[0034]

[Table 4]

From the results shown in Tables 4 and 2, the powder X-ray diffraction pattern of the acetanilide benzimidazolone azo pigment solid solution was similar to that of the pigment (a) as the host pigment. Further, from Table 4, X of acetanilide benzimidazolone type azo pigment solid solution was obtained.
The line diffraction angle 2θ is {(27.4-0.013X) ± 0.
It can be seen that the crystal structure has a maximum peak at 3} ° = 26.43 ± 0.3 ° (X = 75).

The acetanilide benzimidazolone azo pigment solid solutions obtained in Examples 2 and 3 had the same charging ratio (X) of the pigment (a) of 75 mol%, and the crystal growth treatment solvent was Although different, it can be seen from the results of Table 3 and Table 4 that the actually measured positions of the maximum peaks in the powder X-ray diffraction coincide with each other within the error range.

Example 4 Dimethyl Sulfoxide 30
To 0 ml, 3.0 parts of pigment (a), and pigment (b) 9.
3 parts was added, and the mixture was heated under reflux with stirring to dissolve. After allowing to cool, the deposited precipitate was filtered off, the filtrate was poured into 1 l of water while stirring, and the precipitated orange acetanilidebenzimidazolone-based azo pigment solid solution was suction-filtered. The pigment solid solution was washed with methanol and water in this order, and the obtained water-containing pressed cake was dried by heating at 130 ° C. for 2 hours,
4.2 parts of a yellowish orange pigment are obtained. Pigment (a) in this case
The preparation ratio (X) is 25 mol%.

The results of elemental analysis of the obtained acetanilide benzimidazolone azo pigment solid solution are shown below.
The figures in parentheses are theoretical values. The elemental analysis measurement value is within an error range of ± 0.4% with respect to the theoretical value. C: 50.4% (50.1%) H: 3.4% (3.2%) N: 19.1% (19.5%) Obtained acetanilide benzimidazolone azo pigment solid solution powder X Table 5 shows the results of the analysis by line diffraction.

[0039]

[Table 5]

Further, the pigment (b) ("Symulator F
Table 6 shows the results of analysis by powder X-ray diffraction of "ast Orange 4183H").

[0041]

[Table 6]

From the results of Tables 5 and 6, it is found that the powder X-ray diffraction pattern of the acetanilide benzimidazolone azo pigment solid solution is similar to the powder X-ray diffraction pattern of the pigment (b) which is the host pigment. Further, from Table 5, X of acetanilide benzimidazolone type azo pigment solid solution was obtained.
The line diffraction angle 2θ is {(27.4-0.013X) ± 0.
It can be seen that the crystal structure has a maximum peak at 3} ° = 27.08 ± 0.3 ° (X = 25).

The novel pigment solid solution of the present invention comprising the pigment (a) and the pigment (b) is a known pigment solid solution production method,
For example, it can be easily produced by a dissolution precipitation method, and the hue can be continuously changed in the range from yellow to orange by changing the charging ratio of the pigment (a) and the pigment (b). Therefore, without causing color separation due to aggregation, which often occurs in the conventional method of mixing different pigments and toning, it is a simple method and excellent in saturation and transparency,
An acetanilide benzimidazolone azo pigment solid solution having a desired hue is obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Maki             2-7-15-402 Fujisaki, Narashino City, Chiba Prefecture (72) Inventor Yoshitomo Yonehara             1-1-1 Senari, Sakura City, Chiba Prefecture

Claims (2)

[Claims] 1. A pigment (a) represented by the following formula (I):
An acetanilide benzimidazolone-based azo pigment solid solution comprising a pigment (b) represented by the following formula (II). [Chemical 1] Formula (I): Formula (II) 2. A pigment (a) Xm represented by the above formula (I).
ol% and the pigment (b) represented by the above formula (II).
The X-ray diffraction angle 2θ of the pigment solid solution composed of (100-X) mol% is {(27.4-0.013X) ± 0.3} °.
The acetanilide benzimidazolone azo pigment solid solution according to claim 1, which has a crystal structure showing a maximum peak at 1.