JPH032911B2 - - Google Patents

Description

[Detailed description of the invention]

The method of the present invention relates to a method for producing copper phthalocyanine and/or its derivatives useful as dyes and pigments. In general, the most well-known method for producing copper phthalocyanine is to synthesize it by heating phthalic anhydride and/or its derivatives, copper compounds, and urea in the presence of a catalyst in an inert reaction medium.
It is usually called the urea method or the Weiler method and is widely practiced industrially. Molybdenum compounds are effective and commonly used as catalysts. In this urea method, the raw material is conventionally added to a mixture of phthalic anhydride and/or its derivatives and a solvent, either as a catalyst powder or as a slurry in which the catalyst powder is suspended together with a copper compound in an inert reaction medium. Then, urea was added to cause a reaction. We conducted a detailed study on this reaction and found that copper compounds have a high dissolution rate in urea, but the dissolution rate of molybdenum compounds such as ammonium molybdate used as catalysts in urea is quite low, indicating that they are not uniformly dispersed in the reaction mixture. I found it difficult. Therefore, it was necessary to increase the amount of catalyst used in the copper phthalocyanine synthesis reaction, which was considered to be the cause of a decrease in yield and variation in quality. As a result of intensive studies to overcome these drawbacks in the use of catalysts, the present inventors conducted a copper phthalocyanine synthesis reaction using a melt obtained by dispersing or dissolving a molybdenum compound used as a catalyst in urea in advance. When this process was carried out, the dispersibility of the catalyst was improved, and the amount of catalyst was reduced to about 1/10 to 1/100 of the conventional method, and surprisingly, the yield was reduced to 1/10.
The present invention was completed by discovering that the amount increased by ~3 mol%. That is, the method of the present invention involves reacting phthalic acid and/or its derivatives, urea and/or urea derivatives, and a copper compound in the presence of an inert reaction medium and a catalyst to produce copper phthalocyanine and/or its derivatives. In this method, a molybdenum compound is predispersed or dissolved in urea, and a melt obtained is used as a catalyst, and 0.003 to 0.05% in terms of ammonium molybdate (based on phthalic acid and/or its derivatives (in terms of phthalic anhydride): The present invention relates to a method for producing copper phthalocyanine and/or its derivatives, characterized in that the reaction is carried out using the same). The present inventors proposed a method of using a melt of a copper compound, urea, and a molybdenum compound as a catalyst prior to the method of the present invention (Japanese Patent Application No. 55-99870
issue). However, when using cuprous chloride, which is generally used as a copper compound because it is cheap,
The above-mentioned melt is highly corrosive and corrodes general-purpose corrosion-resistant metal materials such as stainless steel and Hastelloy. Therefore, the melting container and piping require expensive special materials such as glass lining, which is expensive. In contrast, the method of the present invention is extremely advantageous because it is not corrosive to the above-mentioned general-purpose metals. Examples of the molybdenum compound used in the catalyst of the present invention include ammonium molybdate, sodium molybdate, ammonium phosphomolybdate, and molybdenum oxide, but ammonium molybdate is generally used.
Although the molybdenum compound may have a commercially available particle size, it is preferable to finely grind it in terms of dispersibility and solubility. In the method of the present invention, a melt is prepared by dispersing or dissolving the molybdenum compound in urea, and various methods can be used for the treatment. For example, (1) a method of adding a molybdenum compound to molten urea and dispersing or dissolving it; (2) a method of mixing urea and a molybdenum compound in powder form and melting them at the same time; (3) a method of (1) above with a relatively low melting point; Examples include a method of adding a predetermined amount of urea and a molybdenum compound to the obtained melt and dispersing or dissolving it. Usually, methods (1) and (3) are used. The urea used in this case can be used alone, but it may also be mixed with urea derivatives such as biuret, triuret or cyanuric acid. The amount of urea derivative mixed is usually 50%.
It is preferable that The amount of urea when preparing the above melt is about 1.7 times or more, generally 2 times to 100 times, and usually 4 times to 30 times as much as the molybdenum compound. If the amount is less than about 1.7 times, the molybdenum compound becomes difficult to dissolve.
This is not preferable because the fluidity becomes poor. In the present invention, the object of the present invention can generally be achieved by dispersing the molybdenum compound in molten urea, but it is preferable to completely dissolve the molybdenum compound in urea. The dissolution time varies depending on the type of molybdenum compound and the temperature, but usually for ammonium molybdate it is about 5
30 minutes or more for molybdenum oxide.
The longer the urea melting time, the more urea will be decomposed, so it is not preferable to melt the urea for too long.
Generally, 48 hours or less is preferable. In the present invention, the temperature when dispersing or dissolving the molybdenum compound in urea is higher than the melting point, generally 128 to 160°C, preferably 130 to 140°C.
Note that when a molybdenum compound is dissolved in urea, it is known from X-ray diffraction results that a portion of the molybdenum compound reacts with urea and changes into another molybdenum compound. When dispersing or dissolving this molybdenum compound in urea, it can be carried out under atmospheric pressure, in an inert gas atmosphere such as nitrogen, or under pressure. The urea melt containing the molybdenum compound thus obtained can be used as a catalyst for the copper phthalocyanine synthesis reaction in liquid form or in solid form, such as powder or granules after cooling. When the catalyst of the present invention is used in the above reaction, the reaction rate of the copper phthalocyanine synthesis reaction increases by 10 to 20%, compared to the 0.5 to
0.05% (converted to ammonium molybdate,
0.003% against phthalic acid and/or its derivatives (in terms of phthalic anhydride, hereinafter the same amount of catalyst used)
Even if the reaction rate is reduced to , the reaction rate hardly decreases. Therefore, the amount of the catalyst used in the present invention is generally smaller than that used in the copper phthalocyanine synthesis reaction.
0.003%, usually selected from 0.003-0.5%. However, in order to further enhance the effects of the present invention,
It is preferred to use an amount of the catalyst according to the invention of 0.003 to 0.05%, especially 0.01 to 0.05%, which increases the yield of copper phthalocyanine by 1 to 3% compared to conventional methods. When the catalyst of the present invention is used in an amount greater than 0.05%, the reaction rate increases, but the yield decreases to that of the conventional method. In the method of the present invention, examples of phthalic acid and/or phthalic acid derivatives used in the copper phthalocyanine synthesis reaction include phthalic acid, phthalic anhydride,
Compounds with unsubstituted benzene nuclei such as ammonium phthalate, phthalamic acid or phthalimide, or compounds in which the benzene nucleus of these compounds is a halogen atom such as a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; other nitro groups, carboxyl groups, Examples include phthalic acid derivatives substituted with one or more sulfonic acid groups, aryl groups, and the like. Generally, phthalic anhydride and phthalimide are used. In the method of the present invention, the urea or urea derivative used in the copper phthalocyanine synthesis reaction includes:
Examples include urea, biuret, triuret, and cyanuric acid. The amount of urea and/or urea derivative used, including the urea content contained in the catalyst of the present invention, is usually 1.5 to 3.5 times the mole of phthalic acid and/or phthalic acid derivative. In the method of the present invention, the copper compounds used in the copper phthalocyanine synthesis reaction include known compounds such as cuprous chloride, copper oxide, copper hydroxide, copper phthalate, copper acetate, cupric chloride, copper sulfate, etc. However, cuprous chloride, which is inexpensive and industrially easily available, is usually used. The amount of the copper compound used is 20 to 30 mol % based on phthalic acid and/or phthalic acid derivative. Although the copper phthalocyanine synthesis reaction in the method of the present invention can be carried out in the absence of a solvent, it is preferably carried out in the presence of an inert reaction medium. Examples of the inert reaction medium used in the method of the present invention include known inert organic solvents with relatively high boiling points used in the synthesis reaction of copper phthalocyanine, specifically nitrobenzene, dichlorobenzene, trichlorobenzene, and chlorotoluene. , aromatic compounds such as isopropylbenzene, diisopropylbenzene, diisopropylxylene, t-butylbenzene, naphthalene, chlornaphthalene, isopropylnaphthalene, or octane, nonane,
Examples include aliphatic compounds such as decane and kerosene. Of course, two or more of these may be used in combination. The amount of solvent used is generally about 1.5 to 4 times the amount of the phthalic acid derivative. The copper phthalocyanine synthesis reaction in the method of the present invention can be carried out under the same conditions as conventional synthesis conditions. Generally, a reactor is charged with urea, a melt of urea, a phthalic acid derivative such as phthalic anhydride or phthalimide, and an inert reaction medium, including, for example, cuprous chloride, a molybdenum compound, and the reaction temperature
The reaction is carried out at a temperature of 140 to 230°C, preferably 170 to 200°C, and a reaction pressure of normal pressure to 20 kg/cm ² G, preferably 1 to 10 kg/cm ² G. When using a pressurized reaction, the generated carbon dioxide, ammonia, and the vapor of an inert reaction medium are used, and the pressure is adjusted by providing a gas outlet in the reactor and releasing a portion of the generated gas. be able to. At that time, ammonia in the released gas is subjected to an imidization reaction, for example, ammonia in the gas and phthalic anhydride are combined at 130 to 230°C, 1 to 20 kg/
It can be used to react with cm ² G to form phthalimide. It is preferable to carry out the reaction under pressure because it has the effect of suppressing the decomposition of ureas and reducing the loss of phthalic anhydride or its derivatives accompanying the generated gas. Next, the method of the present invention will be explained with reference to Examples, but the present invention is not limited to the following Examples. In addition, "%" in this specification represents "% by weight" unless otherwise specified, and "parts" means "parts by weight".
represents. Example 1 (1) Preparation of catalyst 150 parts of urea was melted by heating, and 11.1 parts of ammonium molybdate was dissolved in the melted material over about 5 minutes while stirring. After dissolving, the mixture was maintained at 132 to 135°C for 5 hours, and then the melt was cooled to room temperature, solidified, and pulverized. The amount of melt or catalyst obtained was 148 parts. (2) Copper phthalocyanine synthesis reaction: 200 ml of phthalimide in a glass autoclave.
parts, 204 parts of urea, 33.6 parts of cuprous chloride, 0.54 parts of the catalyst
parts (0.02% converted to ammonium molybdate)
phthalimide) and 340 parts of t-butylbenzene were charged, and the mixture was heated and reacted at 175 to 195°C for 4.5 hours with stirring. Reduce the pressure inside the autoclave to 3Kg/
The opening of the outlet valve was adjusted to maintain the pressure at cm ² G, and the generated reaction gas was discharged. The time until the end of reaction gas generation in this reaction (actual reaction time) is
It took 4.0 hours. After recovering the reaction product or solvent t-butylbenzene by distillation under reduced pressure, the residue was washed with about 7 times the amount of hot water and filtered, then washed with about 7 times the amount of 2% sulfuric acid, washed with water, and dried. As a result, 190 parts of crude copper phthalocyanine with a purity of 7% was obtained. The yield was 94 mol%. (3) Experiment on the influence of the amount of catalyst added Using the catalyst of Example (1) above,
The following procedure was carried out in the same manner as in Example (2) above, except that in (2), the catalyst amount was changed to 0.001, 0.005, 0.01, 0.04, 0.08, 0.1, and 0.15% of phthalimide in terms of ammonium molybdate. The results shown in Table 1 were obtained. In the table, the amount of catalyst added and the yield are shown in the same units as in this example.

[Table] That is, the limiting value of the catalyst amount of the present invention is “0.003
A very critical yield drop was observed around ~0.05%. Comparative example 1 200 parts of phthalimide, 204 parts of urea, cuprous chloride
33.6 parts, ammonium molybdate 0.3 parts (0.15%
phthalimide) and 340 parts of t-butylbenzene were charged into a glass autoclave.
The reaction was carried out at 3 Kg/cm ² G for 5.5 hours with stirring.
The time until the end of reaction gas generation in this reaction is
It took 5.0 hours. The reaction product was treated in the same manner as in Example 1 to obtain 184 parts of crude copper phthalocyanine with a purity of 97%. The yield was 91 mol%. In addition, the amount of ammonium molybdate added was 0.02
% (relative to phthalimide), the reaction time was 6.0 to 7.0 hours. The reaction gas generation completion time in this reaction was 5.5 to 6.5 hours, and the reaction time varied. The yield was 91 mol%. Example 2 (1) Catalyst Preparation 125 parts of urea was melted by heating, and 15 parts of ammonium molybdate was dissolved in this melt over about 5 minutes while stirring. After dissolving, the mixture was maintained at 132 to 135°C for 5 hours, and then the melt was cooled to room temperature, solidified, and pulverized. The amount of the catalyst obtained was 116 parts (containing 12.9% ammonium molybdate). (2) Copper phthalocyanine synthesis reaction The copper phthalocyanine synthesis reaction was carried out in the same manner as in Example 1, except that 0.311 parts of the catalyst (0.02% phthalimide in terms of ammonium molybdate) was used, and the same reaction gas generation completion time was used. Obtained, purity 97
% crude copper phthalocyanine was obtained. The yield is
It was 95 mol%. Example 3 0.155 parts of the catalyst obtained in Example 2 (0.01% to phthalimide in terms of ammonium molybdate), 200 parts of phthalimide, 204 parts of urea, 1st chloride
A glass autoclave was charged with 33.6 parts of copper and 340 parts of t-butylbenzene, and reacted at 175 to 202°C for 5.0 hours. The pressure inside the autoclave is 3Kg/cm ²
The opening degree of the autoclave outlet valve was adjusted so as to maintain the temperature at G. It took 4.5 hours to complete the reaction gas generation in this reaction. The reaction product was post-treated in the same manner as in Example 1 to obtain 191 parts of crude copper phthalocyanine with a purity of 97%. Yield is 94.5
It was in mol%. Example 4 (1) Catalyst Preparation 125 parts of urea was melted by heating, and 12.2 parts of molybdenum trioxide was stirred and dissolved in the melt over 30 to 40 minutes. After dissolving, the mixture was maintained at 132 to 135°C for 5 hours, cooled to room temperature, solidified, and pulverized. The amount of catalyst obtained is
114 parts (13.15% as ammonium molybdate)
Contains). (2) Copper phthalocyanine synthesis reaction Copper phthalocyanine synthesis reaction was carried out in the same manner as in Example 1 except that 0.304 parts of the catalyst (0.02% ammonium molybdate to phthalimide) was used, and the time until the end of reaction gas generation was 4.0 hours and the purity was 192 parts of 97% crude copper phthalocyanine were obtained. The yield was 95 mol%. Example 5 0.311 parts of the catalyst obtained in Example 2 (0.02% in terms of ammonium molybdate) (phthalic anhydride +
A glass autoclave was charged with 61.6 parts of 4-chlorophthalic anhydride, 150 parts of phthalic anhydride, 244 parts of urea, 33.4 parts of cuprous chloride, and 420 parts of t-butylbenzene. The reaction was carried out at ~195°C for 6 hours. The pressure inside the autoclave is 3
The opening degree of the outlet valve was adjusted to maintain the pressure at Kg/cm ² G. The time required for completion of reaction gas generation in this reaction was 5.5 hours. The reaction product was post-treated in the same manner as in Example 1 to obtain 193 parts of crude monochlorocopper phthalocyanine with a purity of 97%. The yield was 91 mol%. Comparative Example 3 150 parts of phthalic anhydride, 4-chlorophthalic anhydride
A glass autoclave was charged with 61.6 parts of urea, 244 parts of urea, 33.4 parts of cuprous chloride, and 0.04 parts of ammonium molybdate (0.02% vs. (phthalic anhydride + 4-chlorophthalic anhydride)), and heated at 175 to 195°C, 3 kg/ ^cm2
G for 8 hours. The reaction product was post-treated in the same manner as in Example 1 to obtain 167 parts of crude monochlorocopper phthalocyanine with a purity of 96%. The yield was 78 mol%. Example 6 The same procedure as in Example 1 was carried out except that ammonium phosphomolybdate was used instead of ammonium molybdate, and similar results were obtained. Example 7 (1) Catalyst Preparation 104 parts of urea was melted by heating, and 12.2 parts of molybdenum trioxide powder was added to the melt and stirred for about 5 minutes to fully disperse it. The obtained melt was cooled, solidified, and pulverized. The amount of catalyst obtained was 113.9 parts (containing 13.15% in terms of ammonium molybdate). (2) Copper phthalocyanine synthesis reaction Copper phthalocyanine synthesis reaction was carried out in the same manner as in Example 1 except that 0.304 parts of the catalyst (0.02% ammonium molybdate to phthalimide) was used, and the time until the end of reaction gas generation was 4.0 hours and the purity was 186 parts of 97% crude copper phthalocyanine were obtained. The yield was 92 mol%.

Claims (1)

[Claims] 1. Phthalic acid and/or its derivatives, urea and/or
Alternatively, in a method for producing copper phthalocyanine and/or derivatives by reacting a urea derivative and a copper compound in the presence of an inert reaction medium and a catalyst, a melt obtained by dispersing or dissolving a molybdenum compound in urea in advance is used. Copper phthalocyanine and/or characterized in that the reaction is carried out using 0.003 to 0.05% in terms of ammonium molybdate (in terms of phthalic acid and/or its derivatives (in terms of phthalic anhydride)) as a catalyst. A method for producing its derivatives. 2. The method according to claim 1, wherein the molybdenum compound is ammonium molybdate. 3 The amount of urea relative to the molybdenum compound is approximately 1.7
The method according to claim 1, wherein the amount is more than twice as large. 4 The amount of urea relative to the molybdenum compound is about 2 to
10. The method of claim 1, which is approximately 100 times as large. 5. The method according to claim 1, wherein the dispersion or dissolution temperature is 128 to 160°C. 6. The method according to claim 5, wherein the dispersion or dissolution temperature is 130 to 140°C.