JPH0154373B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The method of the present invention relates to a method for producing copper phthalocyanine and/or derivatives useful as dyes and pigments.

In general, the most well-known method for producing copper phthalocyanine is to synthesize phthalic anhydride and/or its derivatives, a copper compound, and urea by heating in the presence of a catalyst in an inert reaction medium. This method is widely practiced industrially and is usually called the urea method or Weiler method.

In this urea method, urea, a copper compound and/or a catalyst are conventionally added to a reactor in the following manner. That is, in a reactor filled with a mixture of phthalic anhydride and/or its derivatives and a solvent, urea in solid or molten liquid form and a copper compound and catalyst in powder form or slurry suspended in an inert reaction medium are added.
Each is added.

In this case, cuprous chloride is generally used as the copper compound, but it can be added to the reactor as a powder or as a slurry suspended in an inert medium. The difference in specific gravity between the active reaction medium and cuprous chloride (inert reaction medium 0.8 to 1.4, cuprous chloride approximately 4.1) is large and may accumulate on the bottom of the reactor or block the cuprous chloride slurry transport pipe. In order to avoid such problems, powder of 100 mesh or less is usually used.
However, when this cuprous chloride powder is handled industrially, such as when it is put into a storage tank, cuprous chloride dust is generated, absorbs moisture from the air, and is partially hydrolyzed, producing irritating hydrogen chloride. It has drawbacks such as generating gas, contaminating the working environment, and corroding parts of the equipment.

On the other hand, urea is usually produced by heating and melting industrial granules.
It is fed to the reactor in liquid form. In the past, it was used to feed the reactor in its solid form, but because it requires a long melting time, this practice is now only done on a very small scale.

However, urea has a melting point (132-133℃)
Above 15% of ammonia is extremely easy to decompose.
It is difficult to suppress decomposition unless under special conditions such as under pressure of Kg/cm ² G or more (140°C). Therefore, it is necessary to limit the melting time to a short time and suppress the decomposition of urea as much as possible.

Specifically, a predetermined amount of urea is heated and melted for each reaction and immediately supplied to the reactor. In this way, since urea easily decomposes above its melting point,
Since batches of several reactions cannot be stored in liquid form, it is time-consuming and productivity is extremely low.

The present inventors conducted extensive research to overcome the above-mentioned drawbacks regarding the method of supplying cuprous chloride and urea to a reactor, and as a result, discovered the following fact. Copper compounds, such as cuprous chloride, dissolve very easily in molten urea, so it is not necessary to use fine powders of less than 100 mesh as in the conventional method of dispersing them in an inert reaction medium, but in the form of flakes (3 mm
20mmφ), bead-like or block-like particles with large particle size can be used. Therefore, there is no fear of dust generation as in the conventional method.

Moreover, the melting point of urea made by melting cuprous chloride is about 20-133°C, compared to 132-133°C for urea alone.
The temperature has dropped by 30℃ to 100-110℃.

The present inventors maintained a melt obtained by dissolving cuprous chloride in urea at around its melting point for more than 24 hours, and then used the melt to carry out a synthetic reaction of copper phthalocyanine or its derivatives. The reaction proceeded extremely smoothly. In fact, surprisingly, compared to the conventional method (a method in which cuprous chloride is slurried in an inert medium and then fed to the reactor), the yield is the same or higher, and the reaction rate is actually faster, with a shorter reaction time. It was possible to reduce the time by about 20%. Furthermore, the present invention was achieved based on the groundbreaking discovery that dissolving a catalyst together with a copper compound in urea can reduce the amount of catalyst and at the same time further improve the yield.

That is, the method of the present invention is a method for producing copper phthalocyanine and/or a derivative thereof by reacting phthalic acid and/or a derivative thereof, urea, and a copper compound in the presence of a catalyst. A molybdenum compound and urea or a mixture of urea and urea derivatives are melted, the resulting melt is maintained at a temperature above the melting point and below 130°C for 0.5 hours or more, and the resulting melt is treated as a catalytic amount containing phthalate. The present invention relates to a method for producing copper phthalocyanine and/or its derivatives, characterized in that the reaction is carried out using 0.003 to 0.05% of the acid and/or phthalic acid derivative.

In the present invention, urea or urea and a urea derivative, a copper compound or a copper compound, and a catalyst may be substantially melted before carrying out the copper phthalocyanation reaction, and various methods can be employed for this treatment. For example, (1) a method in which a predetermined amount of a copper compound and a catalyst are added to molten urea or urea and a urea derivative and stirred to melt, in other words, dissolve the copper compound or urea and a urea derivative; A method of mixing a urea derivative, a copper compound, and a catalyst in powder form and melting them at the same time, (3) a method in which a predetermined amount of urea or urea and a urea derivative and a copper compound are added to the melt as obtained in (1), which has a relatively low melting point. and a method of adding and dissolving a catalyst respectively. In general, (1)
Or method (3) is adopted. At this time, the copper compound is easily dissolved in liquid urea and is added to the solution and becomes uniform within a few minutes, whereas a catalyst such as ammonium molybdate requires 10 to 20 minutes to completely dissolve in liquid urea. To dissolve a copper compound and a catalyst in liquid urea, either one may be dissolved first, but in general, in order to suppress the decomposition of urea as much as possible, the copper compound is dissolved first, and then the catalyst is dissolved. is preferable.

The above treatment method or the method for holding the generated melt is carried out in the atmosphere or in an inert gas atmosphere. Preferably, when only the copper compound is melted, it may be in the atmosphere, but the copper compound and the catalyst When performing the melting treatment, a method in which the atmosphere is shut off under an inert gas atmosphere such as nitrogen is particularly preferred in order to maintain a high reaction rate of the copper phthalocyanation reaction.

The melt produced by the above treatment method is maintained at a temperature above its melting point, usually 100 to 130°C, preferably 100 to 110°C, and even if kept at that temperature for 24 hours or more, there will be no hindrance in the subsequent copper phthalocyanation reaction. No, but generally 0.5 to 48 hours, usually 1
Holds for ~24 hours. If the holding temperature of the melt increases, the yield will actually decrease, which is not preferable.

The thus obtained urea or urea and urea compound, copper compound, and catalyst melt may be used in the next copper phthalocyanine synthesis reaction in liquid form, but it is necessary to solidify the melt before converting it into powder or granules. The same reaction can also be carried out using

Usually, it is industrially advantageous to subsequently use the melt in liquid form in the same reaction. It is also possible to generate the melt in advance in a reactor, and then charge a predetermined amount of other raw materials and an inert reaction medium to carry out the reaction.

When the copper compound and catalyst are dissolved in urea or urea and urea derivative, the amount of urea or urea and urea derivative used may be a part or the entire amount of the predetermined amount used in the subsequent copper phthalocyanine synthesis reaction. In order to avoid troublesome process operations, it is preferable to use a predetermined amount of the entire amount. In the method of melting a copper compound and urea or urea and a urea derivative, the amount of urea or urea and a urea derivative used is preferably about three times or more that of the copper compound.

Further, when the catalyst is melted with urea or urea and urea derivative together with copper compound, the ratio of copper compound and urea or urea and urea derivative to the amount of catalyst may be less than the predetermined amount required for copper phthalocyanation reaction. For example, when ammonium molybdate (NH ₄ ) ₆ M ₀₇ O ₂₄ ·4H ₂ O is used as a catalyst and cuprous chloride CuCl is used as a copper compound, the amounts of urea and cuprous chloride to be used relative to the catalyst are preferably may be ammonium molybdate: urea: cuprous chloride = 1: about 1.7 or more: about 0.5 or more. but,
In this case, the remaining urea or urea, urea compound, and copper compound can be added separately in liquid form or, if necessary, in solid form during the copper phthalocyanine synthesis reaction.

Therefore, many advantages of the method of the present invention can be listed as follows. That is, the dissolution of a copper compound in liquid urea is endothermic, but in the method of the present invention, the copper compound is dissolved in urea before the copper phthalocyanine synthesis reaction step, so that the powdered copper compound is dissolved in the copper phthalocyanine synthesis reaction step. There is no endotherm at the initial stage of the reaction unlike in the conventional method of adding , and the reaction time can be shortened by the amount of endotherm.

In addition, the reaction rate of the copper phthalocyanine synthesis reaction is approximately
Since it is 20% larger, reaction time can be further shortened and productivity can be expected to improve.

Furthermore, when the copper phthalocyanine synthesis reaction is performed using a melt of a copper compound, such as cuprous chloride, and a catalyst with liquid urea under an inert gas, the reaction rate increases by 10 to 20%. , the catalyst amount usually used is 0.4-0.05% (for phthalic acid derivatives) to 0.003
It was found that even if the reaction rate was reduced to 10%, the reaction rate did not decrease, but rather the yield increased by 1 to 2%, a surprising effect.

Phthalic acid and/or phthalic acid derivatives used in the method of the present invention include, for example, phthalic acid, phthalic anhydride, ammonium phthalate, phthalamic acid, or phthalimide, which are unsubstituted benzene nuclei, or compounds in which the benzene nucleus of these compounds is a chlorine atom. ,
Examples include halogen atoms such as bromine atoms; alkyl groups such as methyl and ethyl groups; and phthalic acid derivatives substituted with one or more nitro groups, carboxyl groups, aryl groups, and the like.

Generally, phthalic anhydride and phthalimide are used.

Urea or urea derivatives used in the method of the invention include urea, biuret, triuret, and cyanuric acid. Urea can be used as it is, but urea derivatives such as Biuret may be used in combination with urea. Usually up to 50% may be mixed. The amount of urea or urea derivative used is usually per mole of phthalic acid and/or phthalic acid derivative.
It is 1.5 to 3.5 times the mole.

The copper compounds used in the method of the present invention include:
Known compounds include cuprous chloride, copper oxide, copper hydroxide, copper phthalate, copper acetate, cupric chloride, copper sulfate, etc., but usually cuprous chloride is inexpensive and easily available industrially. Copper is used. The copper compound can also be used in the form of flakes, beads or blocks of relatively large particle size.

The amount of the copper compound used is 20 to 30 mol % based on phthalic acid and/or phthalic acid derivative.

Examples of the catalyst used in the method of the present invention include molybdenum compounds such as ammonium molybdate, ammonium phosphomolybdate, and molybdenum oxide, and ammonium molybdate is usually used.

The amount of catalyst used is preferably 0.003 to 0.05%. Within this range, the yield improves by 1 to 2%.

In the method of the present invention, the copper phthalocyanine synthesis reaction can be carried out in the absence of a solvent, but 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. , isopropylbenzene, diisopropylbenzene, diisopropylxylene, t-butylbenzene, naphthalene, chlornaphthalene, isopropylnaphthalene, or other aromatic compounds such as 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.

In addition, in the method of the present invention, the synthesis reaction of copper phthalocyanine can be carried out based on conventional reaction methods. Generally, a reactor is charged with, for example, a melt of cuprous chloride and a catalyst with urea, a phthalic acid derivative such as phthalic anhydride or phthalimide, and an inert reaction medium, and the reaction temperature is 140-230°C, preferably 170~200℃, reaction pressure normal pressure~20Kg/ ^cm2
G, preferably 1 to 10 Kg/cm ² G. When using a pressurized reaction, the pressure is adjusted by using the generated carbon dioxide gas, ammonia, and the vapor of the inert reaction medium, and by providing a gas outlet in the reactor and releasing a part of the generated gas. be able to.
At that time, the ammonia in the released gas is used in an imidization reaction, for example, a reaction in which ammonia in the gas and phthalic anhydride are reacted at 130 to 230°C and 1 to 20 kg/cm ² G to form phthalimide. Can be done. 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.

As described above, the method of the present invention can bring about many industrial effects such as the following.

Namely, (1) Since the copper compound can be used in the form of large-sized flakes, beads, lumps, etc., there is very little dust generation, the working environment is significantly improved compared to the conventional method, and there is almost no corrosion of the equipment. It disappears. (2)
The yield (relative to phthalic acid and/or phthalic acid derivatives) is the same or higher, and the reaction rate is approximately 20%.
As the size increases, productivity is improved by shortening the reaction time. (3) The melting point of urea and copper compounds, as well as the catalyst, is 100 to 106°C, which is lower than the melting point of urea.
Therefore, it is possible to maintain the liquid state for more than 24 hours, simplifying operations and improving productivity. (4) When using a melt of urea, a copper compound, and a catalyst, the amount of catalyst can be reduced to about 1/10 to 1/100 compared to the conventional method, and the yield is increased by about 1 to 2 mol%. do.

Next, the method of the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples. In addition, in this specification, "%" represents "weight %" unless otherwise specified.

Example 1 (Amount of catalyst used: 0.02% vs. phthalimide) 204 parts of urea was heated and melted, and then nitrogen gas was gently passed through it to form flakes (1 to 7 mm).
φ, thickness 0.2-1.0 mm) Dissolve 33.6 parts of cuprous chloride and 0.04 parts of ammonium molybdate (0.02% vs. phthalimide).

After dissolution, hold at 110-115°C for 10 hours. At this time, the freezing point of this melt was 105°C.

This melt, 200 parts of phthalimide, and 340 parts of tert-butylbenzene were charged into a glass autoclave, and heated and stirred at 175 to 200°C for 5.5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 5.0 hours.

After first recovering the solvent tert-butylbenzene from the reaction product by distillation under reduced pressure, the residue in the can was washed with hot water, filtered, pickled, and dried to obtain 190 parts of crude copper phthalocyanine with a purity of 97%. The yield was 94 mol% (based on theory).

Example 2 (Amount of catalyst used: 0.005% vs. phthalimide) 204 parts of urea was heated and melted, and then nitrogen gas was gently passed through it to form cuprous chloride flakes.
33.6 parts, ammonium molybdate 0.01 parts (0.005
% versus phthalimide).

After dissolution, hold at 110-115°C for 10 hours. At this time, the freezing point of this melt was 105°C.

This melt, 200 parts of phthalimide, and 340 parts of tert-butylbenzene were charged into a glass autoclave, and heated and stirred at 180 to 200°C for 5.5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 5.0 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 188 parts of crude copper phthalocyanine with a purity of 98%. The yield was 94 mol% (based on theory).

Comparative Example 1 (Using normal reaction method, catalyst usage amount: 0.02% phthalimide) 200 parts of phthalimide, 204 parts of urea, cuprous chloride
33.6 parts, ammonium molybdate 0.04 parts (0.02
% vs. phthalimide) and tert-butylbenzene
Fill 340 parts into a glass autoclave, 175~
The mixture was heated and stirred at 200° C. and 3 Kg/cm ² G for 6.0 to 7.0 hours.
The reaction gas generation completion time in this reaction is 5.5~
It took 6.5 hours. Reaction times were highly variable.

Thereafter, the same treatment as in Example 1 was carried out to obtain 184 parts of crude copper phthalocyanine with a purity of 97%. The yield was on average 91.0 mol% (based on theory).

Change the amount of catalyst used to 0.005% vs. phthalimide,
The same method as above was carried out except that the reaction conditions were changed to 180-210°C, 3 Kg/cm ² G, and 8.0 hours, but the reaction gas generation time was 7.5 hours, and the yield was 75.0 mol%.

Comparative example 2 (only urea and cuprous chloride are melted, the amount of catalyst used is
0.005% to phthalimide) 204 parts of urea is heated and melted, and then 33.6 parts of cuprous chloride flakes are dissolved therein.

After dissolution, hold at 110-115°C for 10 hours. At this time, the freezing point of this melt was 105°C.

This melt, 200 parts of phthalimide, 0.01 part of ammonium molybdate (0.005% to phthalimide), and 340 parts of tert-butylbenzene were charged into a glass autoclave, and heated and stirred at 175 to 200°C for 6.0 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 5.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 175 parts of crude copper phthalocyanine with a purity of 98%. Yield is 87.7
It was mol% (vs. theory).

Comparative Example 3 (Same method as Example 1, but the amount of catalyst used was
0.15% phthalimide) 204 parts of urea is heated and melted, and then nitrogen gas is gently passed through it to form cuprous chloride flakes.
33.6 parts, ammonium molybdate 0.3 parts (0.15%
(anti-phthalimide).

After dissolution, hold at 110-115°C for 10 hours. At this time, the freezing point of this melt was 106°C.

This melt, 200 parts of phthalimide, and 340 parts of tert-butylbenzene were charged into a glass autoclave, and heated and stirred at 175 to 195°C for 5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 4.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 186 parts of crude copper phthalocyanine with a purity of 97%. The yield was 92 mol% (based on theory).

Example 3 (When phthalic anhydride was used instead of phthalimide in Example 1) Same as Example 1 except that 201 parts of phthalic anhydride and 245 parts of urea were used instead of 200 parts of phthalimide in Example 1. I did it and got exactly the same results.

Example 4 [Using monochlorophthalic anhydride and phthalic anhydride (this mixture is referred to as a phthalic acid derivative) as a phthalic acid derivative, catalyst usage amount 0.02% vs. phthalic acid derivative] 244 parts of urea was heated and melted, and then this cuprous chloride in the form of flakes while gently passing nitrogen gas through it.
33.4 parts, ammonium molybdate 0.04 parts (0.02
% vs. phthalic acid derivatives). 110~ after dissolving
Hold at 115°C for 10 hours.

This melt and 61.6 parts of 4-chlorophthalic anhydride,
Fill a glass autoclave with 150 parts of phthalic anhydride and 420 parts of tert-butylbenzene and heat to 175-195℃.
The mixture was heated and stirred for 6.0 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 5.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 191 parts of crude monochlorocopper phthalocyanine with a purity of 97%.
The yield was 90 mol% (based on theory).

Comparative Example 4 (Carried out using a conventional reaction method, using the same amounts of raw materials, catalyst, and solvent as in Example 4) 61.6 parts of 4-chlorophthalic anhydride, phthalic anhydride
150 parts, urea 244 parts, flaked cuprous chloride 33.4 parts
0.04 parts of ammonium molybdate (0.02% vs. phthalic acid derivative) and 420 parts of tert-butylbenzene were charged into a glass autoclave and heated at 175 to 195°C.
The mixture was heated and stirred for 8.0 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 7.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 167 parts of crude monochlorocopper phthalocyanine with a purity of 96%.
The yield was 78 mol% (based on theory).

Example 5 [In the present invention, cupric chloride is used instead of cuprous chloride as the copper salt, and a phthalic acid derivative is used at a catalyst usage rate of 0.02%.] 204 parts of urea is heated and melted, and then nitrogen gas is slowly added to it. Anhydrous cupric chloride 45.7
part, and 0.04 part ammonium molybdate (0.02% to phthalate derivative). 110-115℃ after dissolution
Hold for 10 hours. The freezing point of this melt was 97°C.

To this melt, 200 parts of phthalimide and 340 parts of tert-butylbenzene were added to a glass autoclave, and the mixture was heated and stirred at 175 to 195°C for 5.0 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 4.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 184 parts of crude copper phthalocyanine with a purity of 97%. The yield was 91 mol% (versus theory).

Comparative Example 5 (Carried out using the conventional reaction method, using the same amounts of raw materials, catalyst, and solvent as in Example 5) 200 parts of phthalimide, 204 parts of urea, 45.7 parts of anhydrous cupric chloride, 0.04 ammonium molybdate (0.02% to phthalic acid derivative) and 340 parts of tert-butylbenzene were charged into a glass autoclave.
The mixture was heated and stirred at ~195°C for 7.5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 7.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 176 parts of crude copper phthalocyanine with a purity of 97%. The yield was 87 mol% (vs. theory).

Comparative Example 6 The same procedure as in Comparative Example 5 was conducted except that the amount of ammonium molybdate added was changed to 0.3 parts (0.15% to phthalic acid derivative), and 174 parts of crude copper phthalocyanine with a purity of 97% was obtained. Ta. The yield was 86 mol% (based on theory).

Example 6 [In the present invention, copper sulfate and a catalyst usage amount of 0.02% (based on phthalic acid derivatives) are used instead of cuprous chloride as the copper salt] 204 parts of urea is heated and melted, and then nitrogen gas is slowly added to it. Dissolve 54.2 parts of anhydrous copper sulfate and 0.04 parts of ammonium molybdate (0.02% to phthalate derivative) while passing through the solution. After dissolution, hold at 110-115°C for 10 hours. The freezing point of this melt was 97°C.

To this melt, 200 parts of phthalimide and 340 parts of tert-butylbenzene were added to a glass autoclave, and the mixture was heated and stirred at 175 to 195°C for 5.0 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 4.5 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 176 parts of crude copper phthalocyanine with a purity of 97%. The yield was 87 mol% (vs. theory).

Comparative Example 7 (Carried out using the conventional reaction method, using the same amounts of raw materials, catalyst, and solvent as in Example 6) 200 parts of phthalimide, 204 parts of urea, anhydrous copper sulfate
54.2 parts, ammonium molybdate 0.04 parts (0.02
% vs. phthalic acid derivatives), tert-butylbenzene 340
Fill a glass autoclave with 175~195
The mixture was heated and stirred at ℃ for 7.5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G.

Thereafter, the same treatment as in Example 1 was carried out to obtain 145 parts of crude copper phthalocyanine with a purity of 97%. The yield was 72 mol% (based on theory).

Comparative Example 8 The same procedure as Comparative Example 6 was carried out except that the amount of ammonium molybdate added in Comparative Example 7 was changed to 0.4 parts (0.2% to phthalic acid derivative).
167.5 parts of 97% crude copper phthalocyanine were obtained. The yield was 83 mol% (based on theory).

Example 7 [In the present invention, cuprous chloride and a catalyst usage amount of 0.02% (based on phthalic acid derivatives) are used as the copper salt, and a part of the melt containing the catalyst prepared in advance is added] 39 parts of urea 11.7 parts of anhydrous cuprous chloride was heated and melted, and then nitrogen gas was gently passed through it.
23.4 parts of ammonium molybdate (0.02% to phthalic acid derivative) is dissolved with stirring. 115-122℃ after dissolution
Hold for 10 hours. The freezing point of this melt was 95°C.

A glass autoclave was charged with 0.13 parts of this melt [containing 0.04 parts of ammonium molybdate (0.02% to phthalic acid derivatives)], 200 parts of phthalimide, 204 parts of urea, 33.6 parts of cuprous chloride, and 340 parts of tert-butylbenzene. The mixture was heated and stirred at 175-200°C for 5.5 hours. At this time, the opening degree of the autoclave outlet valve was adjusted so that the pressure inside the reactor was maintained at 3 kg/cm ² G. The reaction gas generation completion time in this reaction was 5.0 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain 190 parts of crude copper phthalocyanine with a purity of 97%. The yield was 94 mol% (based on theory).

Claims (1)

[Scope of Claims] 1. A method for producing copper phthalocyanine and/or its derivatives by reacting phthalic acid and/or its derivatives, urea and a copper compound in the presence of a catalyst, wherein the copper compound, molybdenum as a catalyst The compound and urea or a mixture of urea and urea derivatives are melted, and the resulting melt has a melting point of 130 or higher.
℃ or below for more than 0.5 hours, and the resulting melt is
A method for producing copper phthalocyanine and/or its derivatives, characterized in that the reaction is carried out using a catalyst amount of 0.003 to 0.05% based on phthalic acid and/or phthalic acid derivatives contained therein. 2. The method according to claim 1, wherein the molybdenum compound is ammonium molybdate.