JP2002161215A - gamma TYPE-LIKE METAL PHTHALOCYANINE COMPOSITION AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a γ type-like metal phthalocyanine composition having excellent solvent resistance without performing a specific stabilization, utilizable as a pigment, etc., and to provide a method for producing the same. SOLUTION: This γ type-like metal phthalocyanine composition comprises a metal phthalocyanine diphenylamide derivative represented by general formula (1) (M is a metal such as copper, nickel, cobalt, iron or the like; n is an integer of 1 or 2). The method for producing they type-like metal phthalocyanine composition is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a γ-type metal phthalocyanine composition having excellent solvent resistance without special stabilization and usable as a pigment composition.

[0002]

BACKGROUND OF THE INVENTION Metal phthalocyanines are the most important pigments in industry. Among them, copper phthalocyanines have a beautiful blue hue and are excellent in various properties such as heat resistance, chemical resistance, light resistance, etc., and are mainly used as blue pigments for coatings, printing inks, resin coloring, etc. Widely used. Hereinafter, copper phthalocyanines will be described in detail by way of example. Copper phthalocyanine is known to have many crystal forms having different physical properties, hue, coloring power, etc., and as pigments, other than α-type and β-type which are industrially used, γ-type, δ-type, ε type, π type, χ
Type, ρ type, etc. are reported. It is known that α-type copper phthalocyanine exhibits a reddish blue color, β-type exhibits a greenish blue color, and γ-type exhibits an intermediate color. However, the γ-form has a crystal structure similar to the α-form, is a metastable crystal form like the α-form, and gradually transitions to a stable β-form in an organic solvent, and thus is not often used as a pigment. Was.

For the purpose of improving the stability of this γ-type copper phthalocyanine, Japanese Patent Application Laid-Open No. 53-71130 discloses a copper similar to γ-type by adding a sulfonated copper phthalocyanine derivative in the presence of a halogenated phthalic acid derivative. A method for producing phthalocyanine is disclosed. Patent No. 6
No. 91708 discloses a method for producing γ-type copper phthalocyanine by treating copper phthalocyanine with sulfuric acid at a high temperature to produce copper phthalocyanine-sulfate, and then hydrolyzing with sodium hydroxide. However, these methods are industrially disadvantageous because sulfonation or sulfuric acid treatment of copper phthalocyanine requires treatment of waste acid.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a γ-type metal phthalocyanine composition which is excellent in solvent resistance without special stabilization and can be used for pigments and the like. It is still another object of the present invention to provide an industrially easy production method of the metal phthalocyanine composition similar to the γ-type.

[0005]

Means for Solving the Problems The inventor of the present invention has a general formula (1)

[0006]

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(Wherein M represents a metal such as copper, nickel, cobalt, iron and the like, and n represents an integer of 1 or 2), and contains a metal phthalocyanine diphenylamide derivative and is similar to γ-type metal phthalocyanine It has been found that the composition has excellent solvent resistance without special stabilization.

Further, phthalic acid or a phthalic acid derivative,
In a method for producing a metal phthalocyanine in which a metal compound and a urea compound are reacted, it has been found that by adding trimellitic acid diphenylamide or a derivative thereof, a metal phthalocyanine composition similar to the γ-type can be produced, and the present invention has been completed. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The metal phthalocyanine composition similar to γ-type in the present invention is a metal phthalocyanine containing metal phthalocyanine diphenylamide represented by the general formula (1). Its content is 3.2 to 14 mol%, preferably 4 to 1 mol% based on the main metal phthalocyanine.
2 mol%. The metal phthalocyanine composition,
2θ = 6.9 ° and 15.7 °, 23.7 °, 24.8
°, 25.8 °, 26.8 ° have X-ray diffraction peaks,
3 shows an X-ray diffraction spectrum similar to the γ-type crystal form. FIG. 1 shows an example. FIG. 2 shows an X-ray diffraction spectrum of a γ-type copper phthalocyanine crystal, which was reprinted from the report of Sekiguchi et al., Page 499 of Industrial Chemistry, Vol. 70, No. 4, (1967).

The central metal of the metal phthalocyanine diphenylamide includes copper, nickel, cobalt, iron and the like, which may be the same as or different from the central metal of the main metal phthalocyanine.

The method for producing a metal phthalocyanine composition similar to γ-type according to the present invention can be carried out, for example, by adding phthalic acid or a phthalic acid derivative, a metal compound in the presence of trimellitic anhydride diphenylamide or a derivative thereof or a metal phthalocyanine diphenylamide. And a method of reacting a urea compound if necessary. In the present invention, examples of the trimellitic acid diphenylamide and derivatives thereof include compounds represented by the following general formula.

General formula (2)

[0013]

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(Wherein R ₁ and R ₂ each independently represent a carboxylic acid group, an alkoxycarbonyl group, a carbamoyl group, a carboxylate group or a nitrile group. A ring is formed between R ₁ and R ₂ to form an imide or an acid anhydride. Examples of a method for producing these trimellitic acids and derivatives thereof include a method of reacting a compound such as trimellitic anhydride chloride with diphenylamine.

The phthalic acid or phthalic acid derivative used in the present invention is widely known as a compound forming a copper phthalocyanine ring. Phthalic acid derivatives include phthalic acid salts, phthalic anhydride, phthalimide, phthalamic acid and its salts or esters, phthalic acid esters,
Phthalonitrile and the like can be mentioned. However, when phthalonitrile is used as a reaction raw material, a urea compound and a catalyst are not required, but it is expensive and highly toxic, so that special equipment is required for handling.

The metal compound used in the present invention includes:
Examples thereof include metals such as copper, nickel, cobalt, and iron, and metal salts of these metals. Examples of copper compounds include copper halide, copper oxide, copper phosphate, copper nitrate, copper hydroxide, copper acetate, copper sulfate, and the like, with copper (I) chloride being most preferred. Metal compounds such as nickel, cobalt and iron include, similarly to copper salts, halides, oxides, hydroxides, phosphates, nitrates, acetates, sulfates and the like of each metal, and chlorides are most preferred. Examples of the urea compound include urea, biuret, and triured. Generally, urea is used, but urea or triuret may be used.

In the present invention, a catalyst usually used for synthesizing metal phthalocyanine can be used. Examples include ammonium molybdate, molybdic acid,
There are molybdenum compounds such as ammonium phosphomolybdate and molybdenum oxide, tungsten compounds such as ammonium tungstate and ammonium phosphotungstate, arsenic vanadium compounds, boric acid, and titanium, tin and antimony halides or oxyhalides. Ammonium acid is the best. The use amount of these catalysts is usually 0.1 to
2% by weight is preferred.

The production method of the present invention can be carried out using the same reaction apparatus and reaction procedure as used for producing ordinary metal phthalocyanine. An organic solvent may or may not be used for the reaction, but the color tone of the resulting metal phthalocyanine composition is preferably clear when an organic solvent is used, since it is clearer. Examples of the organic solvent to be used include alkylbenzene, nitrobenzene, alkylnaphthalene, chloronaphthalene, naphthalene, paraffin, naphthene, kerosene, trichlorobenzene, and sulfolane. Alkylbenzene is preferred because of easy handling.

The reaction temperature at the time of production of the present invention is the same as that of the usual synthesis reaction of metal phthalocyanine,
0 ° C. is preferred.

The use amount of trimellitic acid diphenylamide or a derivative thereof in the present invention is 0.8 to 3.5 mol% based on phthalic acid or a phthalic acid derivative.
Preferably it is 1-3 mol%. 0.8mo used
If it is less than 1% or more than 3.5 mol%, a metal phthalocyanine composition similar to γ-type cannot be obtained. The amount of each reaction raw material used in the present invention is no different from the usual synthesis conditions of metal phthalocyanine, the molar ratio of urea / phthalic acid or phthalic acid derivative is 2 to 4, and the ratio of metal compound / phthalic acid or phthalic acid derivative is The molar ratio is preferably from 0.2 to 0.3. Further, a surfactant, ammonium chloride or the like may be added to suppress aggregation of the metal phthalocyanine.

[0021]

EXAMPLES Examples and production examples will be described below. However, the present invention is not limited to these. In each case, unless otherwise specified, “parts” means “parts by weight” and “%” means “% by weight”.

Production Example 1 21.1 parts of trimellitic anhydride chloride, 17.1 parts of diphenylamine, and 78.1 parts of Hisol P (alkylbenzene, manufactured by Nippon Petrochemical) were placed in a reactor equipped with an air-cooled tube for 150 parts.
The mixture was reacted at a temperature of 2 ° C. for 2 hours, filtered, washed with hexane and dried to obtain 33.8 parts of diphenylamide trimellitic anhydride.

Example 1 4.2 parts of trimellitic anhydride diphenylamide obtained in Production Example 1, 178.2 parts of phthalimide, 170 parts of urea
Parts, copper (I) chloride 30.3 parts, ammonium molybdate 0.1 part, ammonium chloride 18 parts
06 parts, a pressure of 2.5 kg / cm ² and a reaction at 190 ° C. for 4.5 hours.
After heating and stirring for 2 hours, the mixture was filtered, washed with warm water and dried to give a blue product 1
59 parts were obtained. When the mass spectrum of the obtained product was measured, M / Z = 772 together with a large signal of unsubstituted copper phthalocyanine having M / Z = 577.
A signal corresponding to copper phthalocyanine diphenylamide was observed. When the X-ray diffraction of the obtained product was measured, it showed a spectrum similar to that of γ-type copper phthalocyanine.

This gamma-type similar copper phthalocyanine composition 1
Was added to 50 parts of ortho-xylene and stirred at 140 ° C. for 3 hours. This was filtered, washed and dried to recover a copper phthalocyanine composition. The X-ray diffraction of the product remained similar to the γ-type, and no change was observed in the particle size, indicating that the copper phthalocyanine composition similar to the γ-type was excellent in solvent resistance. Was done.

Example 2 12.6 parts of trimellitic anhydride diphenylamide obtained in Production Example 1, 174.6 parts of phthalimide, urea 172
Parts, copper (I) chloride 30.3 parts, ammonium molybdate 0.1 part, ammonium chloride 18 parts
06 parts, a pressure of 2.5 kg / cm ² and a reaction at 190 ° C. for 4.5 hours.
After heating and stirring for 2 hours, the mixture was filtered, washed with warm water and dried to give a blue product 1
61 parts were obtained. In the mass spectrum of the obtained product,
The signal of one adduct of diphenylamide group and the signal of two adducts were observed together with the signal of unsubstituted copper phthalocyanine, and the X-ray diffraction was measured. The result was the same as that of the product obtained in Example 1. A diffraction spectrum similar to that of γ-type copper phthalocyanine was shown. This γ-type similar copper phthalocyanine composition was heat-treated in ortho-xylene in the same manner as in Example 1, but no change was observed in the crystal type and particle size, indicating that the solvent resistance was excellent. .

Example 3 In Example 1, 179.4 parts of phthalic anhydride were used in place of 178.2 parts of phthalimide, and 170 parts of urea were added to 23 parts of phthalimide.
The same reaction and post-treatment were carried out except that the amount was changed to 0 parts, to obtain 158 parts of a blue product. In the mass spectrum of the obtained product, a signal of an adduct of one diphenylamide group was observed together with a signal of unsubstituted copper phthalocyanine, and X-ray diffraction was measured. Similar to the product, it showed a diffraction spectrum similar to that of γ-type copper phthalocyanine. The copper phthalocyanine composition similar to the γ-form was heat-treated in ortho-xylene in the same manner as in Example 2, but no change was observed in the crystal type and the particle size, indicating that the solvent resistance was excellent. .

Example 4 12.6 parts of trimellitic anhydride diphenylamide obtained in Production Example 1, 174.6 parts of phthalimide, 330 urea
Parts, 72.8 parts of cobalt chloride hexahydrate, 0.9 part of ammonium molybdate, 18 parts of ammonium chloride, 324 parts of Hisol P, a pressure of 2.5 kg / cm ² , and 5 parts at 200 ° C.
After reacting for 2 hours, the solvent was distilled off under reduced pressure,
After heating and stirring at 2 ° C. for 2 hours, the mixture was filtered, washed with warm water and dried to obtain 155 parts of a blue product. In the mass spectrum of the obtained product, a signal of one adduct of diphenylamide group and a signal of two adducts were observed together with the signal of unsubstituted cobalt phthalocyanine, and X-ray diffraction was measured. Similar to the product obtained in Example 1, it showed a diffraction spectrum similar to that of γ-phthalocyanine. This γ-type similar cobalt phthalocyanine composition,
Heat treatment was performed in orthoxylene in the same manner as in Example 1.
No change was observed in the crystal form and the size of the particles, indicating that the solvent resistance was excellent.

Comparative Example 1 In Example 1, 178.2 parts of phthalimide was changed to 180 parts without using trimellitic anhydride diphenylamide,
169 parts of urea were changed to 169 parts, and the other parts reacted similarly.
Work-up gave 166 parts of a blue product. When the X-ray diffraction of the obtained product was measured, it showed a diffraction spectrum corresponding to β-type copper phthalocyanine.

Comparative Example 2 In Example 1, 3.2 parts of trimellitic anhydride diphenylamide was changed to 3.2 parts, and 178.2 parts of phthalimide was changed to 178.7 parts. 157 parts of the product were obtained. When the X-ray diffraction of the obtained product was measured, it showed a diffraction spectrum corresponding to β-type copper phthalocyanine as in the product obtained in Comparative Example 1.

Comparative Example 3 In Example 1, 4.2 parts of trimellitic anhydride diphenylamide was used as 21 parts, and 178.2 parts of phthalimide was used as 1 part.
The reaction and post-treatment were carried out in the same manner as in the above except that the amount was 71 parts and 173 parts were urea, and 162 parts of a blue product were obtained. When the X-ray diffraction of the obtained product was measured, it showed a diffraction spectrum corresponding to β-type copper phthalocyanine as in the product obtained in Comparative Example 1.

Comparative Example 4 The same reaction and post-treatment were carried out as in Preparation Example 1 except that aniline (9.4 parts) was used instead of diphenylamine (17.1 parts) to obtain 26.5 parts of trimellitic anhydride anilide. The procedure of Example 2 was repeated, except that 10.6 parts of trimellitic anhydride diphenylamide was used instead of 12.6 parts of trimellitic anhydride anilide. Was. In the mass spectrum of the obtained product, a signal of one adduct of an anilide group and a signal of two adducts of the anilide group were observed together with a signal of unsubstituted copper phthalocyanine. When X-ray diffraction was measured, Similar to the product obtained in Comparative Example 1, a diffraction spectrum corresponding to β-type copper phthalocyanine was shown.

Comparative Example 5 The same reaction and post-treatment were carried out except that 10.1 parts of cyclohexylamine was used in place of 17.1 parts of diphenylamine in Production Example 1, to obtain 25.9 parts of cyclohexylamide trimellitic anhydride. . 9. cyclohexylamide trimellitic anhydride obtained in Example 2 instead of 12.6 parts of diphenylamide trimellitic anhydride
The same reaction and post-treatment were carried out except for using 8 parts to obtain 160 parts of a blue product. In the mass spectrum of the obtained product, a signal of one adduct of cyclohexylamide group and a signal of two adducts were observed together with the signal of unsubstituted copper phthalocyanine. And a diffraction spectrum corresponding to β-type copper phthalocyanine.

Comparative Example 6 The reaction was carried out in the same manner as in Preparation Example 1 except that 25.2 parts of di-n-octylamine was used instead of 17.1 parts of diphenylamine, followed by filtration and concentration to obtain di-n-trimellitic anhydride.
-Octylamide 40.1 parts were obtained. The procedure of Example 1 was repeated, except that 12.6 parts of trimellitic anhydride diphenylamide was used and 15.3 parts of trimellitic anhydride di-n-octylamide obtained were used. 159 parts were obtained. In the mass spectrum of the obtained product, except for the signal of unsubstituted copper phthalocyanine, no signal of the di-n-octylamide group adduct was observed, and the X-ray diffraction was measured. The corresponding diffraction spectrum was shown.

[0034]

According to the present invention, it is possible to provide a metal phthalocyanine composition similar to γ-type which is excellent in solvent resistance without special stabilization and can be used for pigments and the like, and is industrially easy and advantageous. Can be manufactured by the method.

[Brief description of the drawings]

FIG. 1 shows an X-ray diffraction spectrum of a metal phthalocyanine composition containing metal phthalocyanine diphenylamide.

FIG. 2 shows an X-ray diffraction spectrum of a γ-type copper phthalocyanine crystal.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hatsuo Hondo 1-2-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Kawasaki Chemical Industry Co., Ltd. (72) Inventor Atsushi Endo 2-3-3 Kyobashi, Chuo-ku, Tokyo No. 13 Inside Toyo Ink Manufacturing Co., Ltd. (72) Inventor Tetsuya Kaneko 2-13-13 Kyobashi, Chuo-ku, Tokyo F-term inside Toyo Ink Manufacturing Co., Ltd. 4C050 PA12

Claims (2)

[Claims] 1. A γ-type metal phthalocyanine composition comprising a metal phthalocyanine diphenylamide derivative represented by the following general formula (1). General formula (1) (In the formula, M represents a metal such as copper, nickel, cobalt, and iron, and n represents an integer of 1 or 2.) 2. The process for producing metal phthalocyanine by reacting phthalic acid or a phthalic acid derivative, a metal compound and a urea compound, wherein trimellitic acid diphenylamide or a derivative thereof is added. A method for producing a metal phthalocyanine composition similar to γ-type.