JPH09227791A - New crystal type monoazo lake pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new pigment having a specific chemical structure and crystal form, excellent in clearness, coloring power and luster, showing a hue close to a barium lake pigment, not having a toxicity, and useful for coloring a plastic and for a printing ink, a paint, etc. SOLUTION: This new crystal type monoazo lake pigment is strontium bis 4-chloro-3-methyl-1-[(2-naphthol-1-yl) azo] benzene-6-sulfonate} of the formula and constituted by a crystal form having a strong diffraction intensity at 5.4 deg. angle of diffraction in an X ray diffraction chart (2θ±0.2 deg.;Cu-κα ) and weak intensities at 7.1 deg., 9.3 deg., 11.7 deg., 14.1 deg., 21.7 deg. and 24.8 deg.. The pigment is obtained e.g. by dripping a diazotizing liquid of 1-amino-3-methyl-4-chlorobenzene-6-sulfonic acid into a coupler liquid of 2-naphthol, adjusting the liquid to pH 9 after the completion of the reaction, adding an aqueous strontium salt solution and then an aqueous solution of a polyoxyethylene alkyl ether, agitating at 90 deg.C for 3hr, filtering while the reaction mixture is hot, an drying the residue at 50 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to sharpness, coloring power,
Excellent in gloss, printing ink, paint, plastic colorant,
The present invention relates to a novel red-based monoazo lake pigment that is used for stationery and the like.

[0002]

2. Description of the Related Art Conventionally, red pigments include C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 48: 1, barium lake pigments have been used in large quantities, but these pigments contain barium metal which is toxic, so regulations are tightened and their use is being limited in some applications. .

As a red pigment which replaces the barium lake pigment, there is a structural formula (1)

[0004]

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Monoazo lake pigments represented by are known. This pigment has, for example, structural formula (2)

[0006]

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A structural formula (3) obtained by coupling reaction of a diazo component obtained by diazotizing an amine represented by the formula at 5 ° C. or lower with a coupler component obtained by dissolving β-naphthol in an aqueous solution of caustic soda. )

[0008]

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It was obtained by adding an aqueous solution of a strontium salt to a suspension of the monoazo dye represented by the formula (1) to form a lake.

The conventional monoazo lake pigment represented by the structural formula (1) thus obtained has a strong diffraction intensity at the diffraction angle (2θ ± 0.2 °; Cu-Kα) 4.7 ° in the X-ray diffraction pattern. However, it has a medium diffraction intensity at 9.4 °, 14.1 °, 26.0 °, 5.1 °, 7.6 °, 21.0.
It has relatively weak diffraction intensities at °, 23.4 °, 25.4 ° and 26.8 °.

[0011]

However, the crystalline form having the above X-ray diffraction pattern (hereinafter referred to as α form)
When used as a printing ink or paint, the monoazo lake pigment of No. 1 was inferior in sharpness, tinting strength and gloss, and was not practical as a coloring agent for plastics.

The problem to be solved by the present invention is to provide a structural formula having a novel crystal form which is excellent in sharpness, coloring power and gloss when used as a printing ink or paint and which is also highly practical as a coloring agent for plastics. It is to provide a monoazo lake pigment represented by (1).

[0013]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made structural formula (1)

[0014]

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As a result of extensive studies on the method of pigmentation of the monoazo lake pigment represented by the formula (1), when the pigment is heat-treated under a specific condition, a new crystal having a different X-ray diffraction pattern and having excellent sharpness, tinting strength, gloss, etc. It has been found that a pigment of a type can be obtained, and the present invention has been completed.

That is, according to the present invention, in order to solve the above problems, the diffraction angle (2θ ± 0.2 °; C
u-Kα) has a strong diffraction intensity at 5.4 °, 7.1 °,
9.3 °, 11.7 °, 14.1 °, 21.7 ° and 2
Provided is a monoazo lake pigment represented by the above structural formula (1), which has a weak diffraction intensity at 4.8 °.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION X of the monoazo lake pigment of the present invention
Diffraction angle of 7.
The peak heights at 1 °, 9.3 °, 11.7 °, 14.1 °, 21.7 ° and 24.8 ° are 5 to 40% of the peak heights at the diffraction angle of 5.4 °. Is in the range.

The monoazo lake pigment of the present invention is a crystal type (hereinafter referred to as δ type) pigment having an X-ray diffraction pattern which is completely different from that of the α type pigment as described above. The monoazo lake pigment of the present invention is prepared, for example, by adding an aqueous solution of a strontium salt to a suspension of the monoazo dye represented by the structural formula (3) obtained in the same manner as in the prior art to form a lake, and in the presence of a nonionic surfactant. It can be manufactured by heat treatment at 80 to 90 ° C. The monoazo lake pigment of the present invention is prepared by synthesizing a monoazo dye represented by the structural formula (3) in the presence of a nonionic surfactant, adding an aqueous solution of a strontium salt to form a lake, and heat-treating at 80 to 90 ° C. Can also be manufactured by.

Examples of the nonionic surfactant used in producing the monoazo lake pigment of the present invention include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl amines and polyoxyethylene fatty acid amides. Etc., and the amount thereof is generally preferably in the range of 3 to 100% by weight with respect to the pigment, and particularly preferably in the range of 3 to 20% by weight in consideration of quality at the time of use. .

[0020]

EXAMPLES Hereinafter, using Examples, Comparative Examples and Test Examples,
The present invention will be described in more detail, but the present invention is not limited by these examples. In addition, "part" and "%" in the examples are based on weight unless otherwise specified.

<Example 1> 1-amino-3-methyl-4
-Chlorobenzene-6-sulfonic acid 17.7 parts with water 25
After being dispersed in 0 part, 16.8 parts of 20% hydrochloric acid was added,
14.2 parts of 40% sodium nitrite aqueous solution was added dropwise at -5 ° C to diazotize to obtain a diazo solution.

Next, 12.1 parts of β-naphthol was added to 60 parts.
A coupler solution was obtained by dissolving in 400 parts of water and 19.2 parts of a 25% aqueous sodium hydroxide solution at a temperature of ° C. This coupler solution was cooled to 20 ° C., the above diazo solution was added dropwise to the coupler solution while stirring, and the coupling reaction was terminated by stirring at 15 ° C. for 60 minutes to obtain a suspension of monoazo dye.

5% hydrochloric acid was added dropwise to this suspension to adjust the pH to 9.0. Then, a solution prepared by dissolving 16.1 parts of strontium chloride hexahydrate in 100 parts of water was added, and further,
A solution prepared by dissolving 3.8 parts of polyoxyethylene alkyl ether (“Emulgen 147” manufactured by Kao Corporation) in 200 parts of water was added, and then heated to 90 ° C. over 75 minutes,
The mixture was stirred at the same temperature for 180 minutes, filtered while hot, and the residue was washed with water. The washed residue was dried at 50 ° C. for two days and nights and then pulverized to obtain 34.4 parts of yellowish red monoazo lake pigment powder.

With respect to the pigment thus obtained, a diffraction state by Cu-Kα ray irradiation was recorded by a powder X-ray diffraction method using an X-ray diffractometer "RINT1100" manufactured by Rigaku Denki Co., Ltd. The results are shown. This pigment has a diffraction angle (2θ ± 0.2 in the X-ray diffraction pattern of FIG. 1).
.Degree .; Cu-K.alpha.) Having a strong diffraction intensity at 5.4.degree.
It had weak diffraction intensities at 1 °, 9.3 °, 11.7 °, 14.1 °, 21.7 ° and 24.8 °.

The X-ray diffractometer was set as follows. Power consumption: 40 KV, 30 mA Sampling angle: 0.020 ゜ Divergence / scattering slit: 1 ゜ Receiving slit: 0.30 mm Scanning speed: 8 ゜ / min

<Example 2> 1-amino-3-methyl-4
-Chlorobenzene-6-sulfonic acid 17.7 parts with water 25
After being dispersed in 0 part, 16.8 parts of 20% hydrochloric acid was added,
14.2 parts of 40% sodium nitrite aqueous solution was added dropwise at -5 ° C to diazotize to obtain a diazo solution.

Next, 12.1 parts of β-naphthol was added at 60 ° C.
Was dissolved in 400 parts of water and 19.2 parts of a 25% caustic soda aqueous solution, and then 1.6 parts of polyoxyethylene alkylamine (“TAMNS-10” manufactured by Nikko Chemicals Co., Ltd.) was added to obtain a coupler solution. Add this coupler solution to 2
After cooling to 0 ° C., the above diazo solution was added dropwise to the coupler solution with stirring, and the coupling reaction was terminated by stirring at 15 ° C. for 60 minutes to obtain a monoazo dye suspension.

5% hydrochloric acid was added dropwise to this suspension to adjust the pH to 9.0. Next, a solution prepared by dissolving 16.1 parts of strontium chloride hexahydrate in 100 parts of water was added, heated to 90 ° C. over 75 minutes, stirred at the same temperature for 180 minutes, and filtered while hot, and the residue was washed with water. Washed. The washed residue was dried at 50 ° C. for two days and nights and then pulverized to obtain 34.0 parts of yellowish red monoazo lake pigment powder.

With respect to the thus-obtained pigment, the diffraction state by Cu-Kα ray irradiation was recorded by the powder X-ray diffraction method in the same manner as in Example 1. As a result, the diffraction angle was the same as in Example 1. It had almost the same diffraction intensity.

Comparative Example 1 Red monoazo lake pigment powder 33 was prepared in the same manner as in Example 1 except that polyoxyethylene alkyl ether (“Emulgen 147” manufactured by Kao Corporation) was not used. .1 part was obtained.

With respect to the pigment thus obtained, the diffraction state by Cu-Kα ray irradiation was recorded by the powder X-ray diffraction method in the same manner as in Example 1, and the results are shown in FIG.
This pigment has a diffraction angle (2θ) in the X-ray diffraction diagram of FIG.
± 0.2 °; Cu-Kα) has a strong diffraction intensity at 4.7 °, medium diffraction intensity at 9.4 °, 14.1 °, 26.0 °, and 5.1 °. , 7.6 °, 21.0 °, 23.
It had relatively weak diffraction intensities at 4 °, 25.4 ° and 26.8 °.

<Test Example 1> (Ink test) 0.5 part of the pigment obtained in each of the Examples and Comparative Examples and an ink varnish (“MG manufactured by Dainippon Ink and Chemicals, Inc.”
-63 varnish ") was applied at a load of 150 pounds using an automatic Hoover Mahler and kneaded three times at 100 revolutions to prepare an ink. This was used as a dark color ink, and was color-printed on art paper using a small rotary printing machine (Pulfow printing machine). The saturation (C *) of the obtained color-developed paper was measured by a spectrophotometer (Datacolor International
Spectra Flash (SP by lor International)
ECTRAFLASH) 500 ") and gloss (60 °) were measured with a haze gloss meter (manufactured by BYK-Gardner Inc.), and the results are shown in Table 1.

Separately from this, 0.1 part of any of the pigments obtained in each of the examples and comparative examples, 2.0 parts of titanium oxide ("Taipec R-550" manufactured by Ishihara Sangyo Co., Ltd.) and ink varnish (large) "MG-63" manufactured by Nippon Ink Chemical Co., Ltd.
1.3 parts of "varnish") was applied with an automatic Hoover Mahler under a load of 150 pounds and kneaded three times at 100 revolutions to prepare an ink. Using this as a light-colored ink, draw it with a spatula on the color-developed paper and measure the density with a Gretag densitometer (GRETAG (GRET
"D186" manufactured by AG), and the results are shown in Table 1.

[0034]

[Table 1]

From the results shown in Table 1, it is clear that the hue of the ink using the pigment of the example is excellent in gloss and density as compared with the ink using the pigment of the comparative example.

<Test Example 2> (Plastic coloring test) 4 parts of any of the pigments obtained in each Example and Comparative Example, zinc stearate (“SZ200” manufactured by Sakai Chemical Industry Co., Ltd.)
0 ") Dry color consisting of 4 parts was mixed with 4000 parts of polyethylene (" Hi-Zex2100J "manufactured by Mitsui Petrochemical Co., Ltd.) and an injection molding machine (" PS60E9A type "manufactured by Nissei Plastic Co., Ltd.) was used.
A flat plate was prepared under the conditions of a molding temperature of 240 ° C. and a residence time of 5 minutes.

Chroma (C *) and tinting strength of this flat plate were measured by the spectrophotometer used in Test Example 1. The results are shown in Table 2.

[0038]

[Table 2]

From the results shown in Table 2, the hue of the plastic using the pigment of the example is higher in saturation, excellent in sharpness and excellent in coloring power than the plastic using the pigment of the comparative example. It is clear that

[0040]

Industrial Applicability The monoazo lake pigment having the δ-type crystal form of the present invention is excellent in sharpness, tinting strength and gloss when used for coloring plastics, printing inks and paints.

The monoazo lake pigment having a δ-type crystal form of the present invention has a hue similar to that of a conventionally known barium lake pigment, and is barium metal which is laked with strontium and is toxic like a barium lake pigment. Therefore, it is extremely useful as a substitute for barium lake pigment.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction pattern (2θ ± 0.2 °; Cu-Kα) of the monoazo lake pigment (δ type) of the present invention obtained in Example 1.
It is.

FIG. 2 shows X of the monoazo lake pigment (α type) obtained in Comparative Example.
It is a line diffraction diagram (2θ ± 0.2 °; Cu-Kα).

Claims (2)

[Claims] 1. A diffraction angle (2θ ±
0.2 °; Cu-Kα) has a strong diffraction intensity at 5.4 °, 7.1 °, 9.3 °, 11.7 °, 14.1 °, 2
Structural formula (1) characterized by having a weak diffraction intensity at 1.7 ° and 24.8 ° Monoazo lake pigment shown by. 2. A diffraction angle (2θ ± 0.2 °; Cu-K
α) 7.1 °, 9.3 °, 11.7 °, 14.1 °, 2
The respective peak heights at 1.7 ° and 24.8 ° are 5 to 40% of the peak height at the diffraction angle of 5.4 °.
The monoazo lake pigment according to claim 1, which is in the range of