JPS6049227B2 - Method for producing a new crystalline ρ-type copper phthalocyanine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a reddish blue copper phthalocyanine pigment having a novel crystalline form.

Specifically, the present invention involves reacting phthalonitrile and ammonia in an ethylene glycol solvent, and then
A divalent silver salt and, if necessary, ethylene glycol are added to this reaction product at 0°C or below, and then this mixture is reacted under certain conditions to produce a copper phthalocyanine pigment having a new crystal form. An object of the present invention is to provide a manufacturing method. Copper phthalocyanine pigments are organic pigments with a beautiful blue hue and excellent properties such as heat resistance, chemical resistance, and light resistance, and are widely used as coloring agents for paints, printing inks, resin coloring, etc. It is used. Copper phthalocyanine is a polymorphic isomer, and so far Alhaa (α)
Crystal forms such as type, beta (β) type, gamma (γ) type, delta (σ) type, pi (π) type, and chi-(x) type have been reported in various literatures.

These differ in hue, solvent resistance, and
They have different heat resistance and other physical properties, and their uses are also becoming different. Among these crystal forms, the α type (organic solvent unstable type) is used industrially as a reddish blue pigment, and the β type (organic solvent stable type) is used industrially as a greenish blue pigment and is widely used in the pigment field. It is used. The present invention provides a method for producing a copper phthalocyanine pigment having a new crystalline form, which is different from the crystalline copper phthalocyanine reported above.

In addition, this new crystalline copper phthalocyanine pigment has a unique hue, and even compared to conventional α-type copper phthalocyanine pigments, it has a much redder hue and clarity, making it suitable for industrial use. The inventors of the present invention have discovered that the present invention is also valuable, and have completed the present invention. This new crystal form is named the rho (ρ) type. Regarding this new crystal form of ρ-type copper phthalocyanine, the present inventors filed a patent application in
As detailed in the specification of No. 57, this crystalline form of copper phthalocyanine has a CuK
X-ray analysis using alpha rays reveals approximately 8.6 degrees, 17.2 degrees, 18.3 degrees, 23.2 degrees, 25.3 degrees, 26.5 degrees,
X showing strong line at flag angle 20 which corresponds to 28.8 degrees
It has a crystal structure with a line diffraction pattern, and the conventionally known α type,
It was recognized that it is a new crystal form different from the β type, γ type, δ type, π type and X type.

This ρ-type copper phthalocyanine is unstable in organic solvents because it transforms to the β-type when boiled in a benzene or toluene solvent.

The ρ-type copper phthalocyanine pigment obtained by the method of the present invention and having a new crystalline form is characterized by a unique and excellent hue.

This hue is a blue with a strong reddish tinge, and the saturation is high.
When compared with α-type copper phthalocyanine pigments, it exhibits a much redder tinge. Therefore, in recent years, there has been a strong demand for a clear reddish blue color, and this new crystalline pigment satisfies this demand and is extremely useful when used in textile printing, resin coloring, printing ink, etc. It is useful for For example, as shown in the examples below, polyvinyl chloride resin colored using this ρ-type copper phthalocyanine pigment,
Compared to polyvinyl chloride resin colored using α-type copper phthalocyanine pigment, the resin is colored with a unique blue color that is clearer and has a much more reddish tinge.

Furthermore, the light resistance, weather resistance, and heat resistance of this p-type copper phthalocyanine are as excellent as those of conventional crystal forms. The present invention is thus industrially extremely useful.
- Provides a method for producing a ρ-type copper phthalocyanine pigment having a novel crystalline form. When producing copper phthalocyanine from phthalonitrile, the present invention performs a heating reaction of phthalonitrile and ammonia in an ethylene glycol solvent at a temperature of 50 to 150°C as a first operation, and as a second operation, At a temperature below °C, a divalent copper salt and, if necessary, ethylene glycol are added to the above reaction product, and then, as a third operation, the obtained mixture is added to the phthalonitrile used as the starting material on the horizontal axis. In Figure 1, where the weight ratio X of the ethylene glycol used in the mixture to the weight of is taken, and the holding temperature T°C is plotted on the vertical axis, CA) X = 3.5, T = 90, and (B) X = 2,
To T=9 (C) X=2, T=60. ．． (D)X=8,T
= 60, heat and hold for at least 2 hours at a temperature within a range corresponding to the composition of the mixture, and finally, as a fourth operation, 60 to 1
This is a method for producing a novel crystalline ρ-type copper phthalocyanine, which is characterized by heating at a temperature of 50° C. to complete reaction 7. Thus, the present invention involves thermally reacting phthalonitrile and ammonia in ethylene glycol, and
A divalent copper salt and, if necessary, ethylene glycol are added to the above reaction product at a temperature below °C, and then the resulting mixture is heated and held within a specific temperature range corresponding to its composition for a certain period of time or more. This is a method for producing a new crystalline ρ-type copper phthalocyanine, which is performed by completing the copper phthalocyanine synthesis reaction.

Conventionally, a method has been reported in which copper phthalocyanine is obtained by heating phthalonitrile and ammonia in ethylene glycol and then adding a copper salt.

For example, in the invention of JP-A-48-10127, phthalonitrile and ammonia are heated in a hydrophilic organic solvent, then a copper salt is added, and the reaction is heated at a temperature of 80 to 140°C to form an organic solvent unstable type. The aim is to produce a copper phthalocyanine pigment.

The specification of the same issue describes examples in which ethylene glycol, methanol, and isopropanol were used as solvents, so it is clear that the use of hydrophilic solvents was only considered, and that the reaction All temperatures are 1
It is pointed out that it is carried out at temperatures of 0 to 1100C, and is not carried out at all below 100C. Furthermore, while the invention of the same title is aimed at directly producing a copper phthalocyanine pigment that no longer requires pigmentation,
The purpose of the present invention is to produce copper phthalocyanine having a new crystalline form, and the purpose of the present invention is clearly different. In fact, the inventor of the present application conducted a follow-up experiment on the example in the same issue and found that the crystal form of the copper phthalocyanine obtained was a crystal form close to the γ type, and was not the new crystal form obtained in the present application. Further, the copper phthalocyanine obtained in the same issue is found to have a much more yellow tinge than the acid paste product from the crystals in the hue test described in the same issue. On the contrary, the copper phthalocyanine obtained by the present invention has a much more reddish color than the acid-based product, and there is a noticeable difference in quality. (See Comparative Example 1) In addition, the present inventor has already reported in JP-A-50-10320 that phthalonitrile and ammonia are heated in ethylene glycol at 50 to 100 °C, then a copper salt is added, A method is disclosed for preparing organic solvent labile copper phthalocyanine pigments by holding at a temperature of -80°C for at least one hour and then reacting at 100-160°C.

However, this method is also aimed at producing copper phthalocyanine pigments with a fine particle size industrially and safely in a short period of time and in high yield, and the purpose of this method is to produce copper phthalocyanine pigments with a novel crystalline form in an industrial manner. The purpose is different from the manufacturing method. Also,
The crystal form of the copper phthalocyanine obtained in the same issue is also close to the γ type, and the copper phthalocyanine obtained in the present application cannot be obtained, and there is also a noticeable difference in hue. (See Comparative Example 3) The present invention will be explained in more detail below. The raw material used in this invention is phthalonitrile and the solvent is specified as ethylene glycol.

In order to synthesize the novel crystalline form of copper phthalocyanine according to the present invention, the solvent is an important factor, and the use of ethylene glycol is an essential condition. Novel crystal forms of copper phthalocyanine cannot be synthesized using solvents other than ethylene glycol, such as hydrophilic organic solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, and glycerin. Furthermore, in the present invention, ammonia is used.

The copper salt used in the present invention must be a divalent copper salt, such as cupric chloride, cupric acetate, cupric bromide, etc.
Particularly preferred is cupric chloride. Cuprous chloride, cuprous bromide
Monovalent copper salts such as copper cannot be used because they hardly produce ρ-type copper phthalocyanine. The particle size of the copper salt used is preferably as fine as possible, particularly preferably about 60 mesh or less. The amount of copper salt used is in the range of 0.9 mol to 1.1 mol per 4 mol of phthalonitrile. Next, a method of implementing the present invention will be explained.

In the present invention, first, as a first operation, phthalonitrile and ammonia are sufficiently heated and reacted in ethylene glycol.

At this time, sodium methylate may be added,
Also, it may not be added. The amount of ethylene glycol used at this time is 1 to 4 parts by weight per 1 part by weight of phthalonitrile. In addition, the amount of ammonia used is
It is 1 to 3 times the mole per mole of phthalonitrile. The heating temperature in this case is 50 to 150°C, preferably 60 to 130°C. Heating time is 1 to 7 hours. Next, as a second operation, a divalent copper salt and, if necessary, ethylene glycol are added to the reaction product thus obtained.

A feature of the present invention is that a divalent copper salt is also added to the reaction product obtained by heating phthalonitrile and ammonia in ethylene glycol at a temperature of 50°C or less.

The temperature at which this copper salt is added is important, and it is necessary to perform the addition at 50°C or lower, preferably from 20 to 40°C. 50℃
When performing the above process, it is not possible to obtain a new crystalline ρ-type copper phthalocyanine with high purity.

Furthermore, it has been found that good results can be obtained in carrying out the present invention if the mixture obtained when the copper salt is added is prepared into a paste that is as finely and uniformly dispersed as possible.

The following method may be used to obtain such a paste-like mixture. That is, when adding a copper salt in a reaction vessel equipped with a normal stirrer, it is preferable to add the copper salt in the form of a solution prepared by dissolving the copper salt in ethylene glycol.
0 Stir and mix evenly. It is also preferable to add the copper salt in advance in a premixing tank equipped with a mixer and disperser. Examples of such a mixing and dispersing machine include Homomixer (Tokushu Kika Kogyo), Vistar (Nippon Senzo Kikai), colloid mill, ball mill, attritor, sand mill, high-speed stirrer, and the like. In this case, the copper salt may be added in the form of a powder or a solution in ethylene glycol. In addition, after dispersing the reaction product obtained by heat-reacting phthalonitrile and ammonia in ethylene glycol using these dispersers, a solution of copper salt dissolved in ethylene glycol is prepared in a reaction vessel equipped with a normal stirrer. It may be added in the form of
Then, as a third operation, the mixture thus obtained is heated and held for at least 2 hours at a certain temperature depending on the amount of ethylene glycol used in the mixture.

That is, in the third operation, (A)X= in FIG.
3.5, T=90, (B)X=2, T=90, (C)X
The mixture is heated at a temperature according to the amount of ethylene glycol used in the mixture so that it is within the range surrounded by the straight line connecting the four points: = 2, T = 60, (D)X = 8, T = 60. Retained. As is clear from FIG. 1, the holding temperature used in the present invention is in the range of 60 to 90°C, and the amount of ethylene glycol in the mixture is 2 parts by weight of phthalonitrile used as the starting material. The holding temperature and the amount of ethylene glycol used are not independent of each other, but are closely related to each other, and the amount of ethylene glycol used depends on the holding temperature. For example, when the holding temperature is 80°C, the amount of ethylene glycol used is 2 to 5 times the amount of phthalonitrile, and when the holding temperature is 65°C, the amount of ethylene glycol used is 2 to 5 times the amount of phthalonitrile. It is 7 times the amount. In this case, if the heating and holding temperature is 60°C or lower, the holding time will be very long, which is industrially undesirable; It is not preferable because it cannot be obtained with high purity.

Furthermore, the holding time in this third operation varies depending on conditions such as the amount of ethylene glycol used, the type of copper salt, and the holding temperature, but requires 2 hours or more.
In particular, when the holding temperature is below 70°C, the holding time is 8
More than 1 hour, preferably 1 hour or more, 70 to 4 hours are required.
At 800C, it takes 3 hours or more, preferably 4 hours or more. Even when a holding temperature exceeding 80° C. is employed, it takes 2 hours or more, preferably 3 hours or more.
Furthermore, it should be noted that when the temperature approaches the upper limit of 90° C., although the holding time is shortened, it becomes difficult to perform a safe operation to obtain the ρ type with high purity. Therefore, it is preferable that the holding time be within 3 hours or longer. By carrying out such appropriate heating and holding operations, it is possible to obtain a new crystal form of ρ-type copper phthalocyanine. When the retention time is insufficient,
New crystalline forms cannot be obtained with high purity. Finally, as a fourth operation, the mixture thus heated and maintained is heated in a temperature range of 60 to 150°C to complete the reaction.

In this case, the reaction may be completed by heating at a temperature range of 60 to 90°C for a certain period of time or more, and then heating at the same temperature to complete the reaction. , After heating and holding for more than a certain period of time, the temperature is raised to 90~
The reaction may be completed by heating at a temperature of 150°C.

Copper phthalocyanine is produced when heated and held for a long time in the temperature range of 60 to 90℃, but then
The reaction may be completed by heating to 0°C. If the synthesis temperature is 60° C. or lower, the reaction rate is slow, which is industrially unfavorable. If the synthesis temperature is 150° C. or higher, copper phthalocyanine is produced in a crystal form other than the new crystal form, which is undesirable.

The present invention can be carried out batchwise, semi-continuously, or continuously. After such a reaction, copper phthalocyanine with a new crystal form is obtained by filtration, washing with water, and drying, but when treated with a dilute acid or dilute alkaline solution, a red color with an even clearer new crystal form is obtained. A strong copper phthalocyanine is obtained.

The new crystal form of copper phthalocyanine thus obtained is already very fine crystals with a particle size of about 0.05 to 0.5 μm, and moreover, the particle size is extremely uniform.

Moreover, although copper phthalocyanine is a fine particle, it is extremely soft and can be easily dispersed in a color vehicle without the need for enormous mechanical energy or long kneading. It has excellent dispersibility. Thus, according to the method of the present invention, a new crystalline form of copper phthalocyanine can be produced, and moreover, it can be obtained in the form of fine particles and in a soft form.

Therefore, it can be used as a pigment as it is without any post-processing operations such as micronization or pigmentation. In addition, the new crystalline copper phthalocyanine pigment obtained by the present invention is a blue pigment with an extremely strong reddish tint, so it is useful as a coloring agent for textile printing, resin coloring, printing ink, paint, etc. It is something.

Examples are shown below to explain the present invention in detail, but
The invention is not limited within the scope of these examples.

Hereinafter, part J indicates part by weight. Example 1 Part of ethylene glycol, 5 parts of ammonia, and phthalonitrile 3C5 were added to a 300 cc capacity four-neck cylindrical round-bottomed flask equipped with a stirrer, a cooler, a thermometer, and a gas blowing tube, and the mixture was stirred. The reaction mixture was heated at 110'C for 3 hours while further blowing in ammonia.

Next, the mixture was cooled while stirring, and at 25°C, a solution of 7.8 parts of anhydrous cupric chloride dissolved in the ethylene glycol mark was gradually added to the obtained reaction product, and further,
Stir well for about 6 minutes at 30°C. The resulting mixture was then heated to 75°C over about 6 minutes, kept at 75°C for 7 hours, and then heated at 100°C for 4 hours to complete the reaction.

After the reaction was completed, the filter cake was cooled, filtered through p-filtering, washed with methanol, and boiled in a 2% aqueous solution of hydrochloric acid.
After thorough washing with water, the product was placed in a vacuum dryer for 90 minutes.
Washed with 0C. The product obtained in this way is
It was a bright blue copper phthalocyanine pigment, and the yield was 87%. X-ray analysis This copper phthalocyanine pigment was λ=1.5418A. X-ray analysis using CuKα rays of U shows approximately 8.6 degrees, 17.2 degrees, and 1 degree as shown in Figure 2.
8.3 degrees, 23.2 degrees, 25.3 degrees, 26.5 degrees, 28
．． It was a crystalline copper phthalocyanine having an X-ray diffraction pattern showing a peak at Black angle 20, which corresponds to 8 degrees.

This X-ray diffraction pattern was clearly different from that of any other known crystalline form of copper phthalocyanine, and was a completely new crystalline form of copper phthalocyanine. Particle size measurement using an electron microscope with a magnification of 15,000 times shows that the major axis is 0.05 to . 0.2μ, minor axis 0.02-0.05
The particles were very fine, about μ in size, and the particles were uniform with little variation.

In addition, FIG. 3 shows an electron micrograph of this copper phthalocyanine. Dispersibility Test 0.5 y of the obtained ρ-type copper phthalocyanine pigment was laminated with 1 y of printing varnish No. 4 using a Huber Muller at a bond load of 150 for 100 rotations x 3 times.

The dispersibility was also measured by placing the resulting paste on a grindmeter with a depth of 0 to 25 μm, and observing the streaks produced by stretching it with a scraper. This sample had no streaks at all and was very soft and easily dispersible. 0.5 y of the ρ-type copper phthalocyanine pigment obtained in the hue test and 1 y of printing varnish No. 4 were combined using a Huber Muller with a load of 150 bond and 100 rotations x 3 times.

Separately, the same operation was performed on α-type copper phthalocyanine pigments, which are considered to have a reddish tinge among commercially available products, and the two types of kneaded paste were spread side by side on white paper, and the top color and bottom color were colored. compared. It was observed that the color of the paste using the ρ-type copper phthalocyanine pigment obtained in the present invention was much reddish blue, deep, clear and beautiful. Next, 0.2 g of the obtained ρ-type copper phthalocyanine pigment was mixed with 0.5 q of castor oil using a Huber mala with a load of 150 bond and 100 revolutions x 1.
After setting up the line, titanium oxide 2.0y and castor oil 0
．． 5y was added and 100 rotations x 2 lines were combined.

NC Lacquer 20f was added to the resulting paste and mixed in a glass container to prepare a colored paint.The colored paint was spread onto art paper to a thickness of 4 mils using an applicator. On the other hand, the same procedure was performed on α-type copper phthalocyanine pigments that are thought to have a reddish color among the five commercially available products, and after the coated surface had dried, the color of these two types of samples was measured using a spectrophotometer.

The results are shown in Table 1. From Table 1, it can be seen that the p-type copper phthalocyanine pigment is a bright blue pigment with a stronger reddish tinge than the α-type copper phthalocyanine pigment.

Even when compared visually, it was observed that the sample using the p-type copper phthalocyanine pigment had a slightly reddish blue color and a unique, beautiful hue. Polyvinyl chloride resin coloring reagent ρ-type copper phthalocyanine pigment obtained 0.2y1 Polyvinyl chloride 50y1 Dioctyl phthalate 25y1 Calcium stearate 1y1 Mono-di-n-butyltin dilaurate 1y1 Mono-di-n-butyltin maleate 1g on a roll mill at 145 After kneading for 5 minutes at ℃, heat press to 17℃.
Preheat at 0℃ for 1 minute to 150k9/Cdll7O'C
Pressure molded for 2 minutes and colored blue, thickness 0.55?
I made a sheet.

On the other hand, the same procedure was performed on α-type copper phthalocyanine pigments, which are considered to have a reddish color among commercial products, and the reflected and transmitted colors of these two types of sheets were measured using a spectrophotometer. The results are shown in Table 2. From Table 2, it can be seen that the sheet using ρ-type copper phthalocyanine is colored and molded in a beautiful blue color that is much more reddish than that of α-type copper phthalocyanine.

Visually, it was observed that the sheet made using ρ-type copper phthalocyanine had a unique and beautiful blue color with a much reddish tinge in both the reflected and transmitted colors. From these results, the obtained copper phthalocyanine is a copper phthalocyanine pigment having a strikingly new crystal form,
Moreover, it was shown to have very excellent pigment properties.

Example 2 120 parts of ethylene glycol, 7 parts of ammonia and 45 parts of phthalonitrile were added to the same 300 cc four-necked flask as used in Example 1, and the temperature was raised while stirring, and the temperature was raised to 110°C while further blowing in ammonia. The mixture was reacted for 3 hours.

Next, it was cooled with stirring, and a solution prepared by dissolving 10.4 parts of anhydrous cupric chloride in ethylene glycol was gradually added to the obtained reaction product at 25 °C, and then heated to 30 °C. Stir well for about 6 minutes at 35°C. Then,
The resulting mixture was heated to 80°C and
After heating and maintaining for an hour, the temperature was raised to 100°C, and heated at 100°C for 5 hours to complete the reaction. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a copper phthalocyanine product. The yield was about 88%. X-ray analysis of this product revealed that it was a new crystalline form of ρ-type copper phthalocyanine, and the particle size was fine 5. It was soft and had good dispersibility, and the hue was clear and reddish blue, making it suitable for use as a pigment. If it was, it would have been very good. Example 3 Add 10 parts of ethylene glycol, 8 parts of ammonia and phthalonitrile (a) to the same 300cc four-necked plastic bottle as used in Example 1, raise the temperature while stirring, and raise the temperature to 100°C while further blowing in ammonia. The reaction was carried out for 5 hours.

Next, it was cooled while stirring, and a solution prepared by dissolving 13 parts of anhydrous cupric chloride in 4 parts of ethylene glycol was gradually added to the obtained reaction product at 25°C, and further,
Stir well at 30-35°C. The resulting mixture was then heated to 85°C and heated at 85°C for 1 hour to complete the reaction. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a copper phthalocyanine product. The yield was about 90%. X-ray analysis of this product revealed that it was a new crystalline form of ρ-type copper phthalocyanine, and the particle size was fine, soft and well-dispersed, and the hue was clear and reddish blue, making it possible to use it as a pigment. Yang He was very good. Example 4 Same 300 as used in Example 1
Ethylene glycol 9 in a cc 4 flask? , 8 parts of ammonia, 3 parts of sodium methylate, and (1) part of phthalonitrile were added, and the temperature was raised while stirring, and the temperature was increased to 1 at 70°C.
Allowed time to react.

Next, it was cooled while stirring, and a solution prepared by dissolving 7.8 parts of anhydrous cupric chloride in 60 parts of ethylene glycol was gradually added to the obtained reaction product at 25°C, and further,
The mixture was stirred well for about 6 minutes at 30-35°C. Then, the temperature of the obtained mixture was raised to 65°C, and the reaction was completed by heating at 65°C three times. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a copper phthalocyanine product. The yield was about 82%. X-ray analysis of this product revealed that it was a new crystalline form of ρ-type copper phthalocyanine, and its particle size was fine, soft and well-dispersed, and its hue was clear and reddish blue, making it useful as a pigment. If it was, it would have been very good. Example 5 Add 1 ethylene glycol to the same 300 cc four flasks used in Example 1.
(4) parts, 8 parts of ammonia and (4) parts of phthalonitrile were added, the temperature was raised while stirring, and the mixture was allowed to react at 100°C for 1 hour while further blowing in ammonia.

Next, the obtained reaction product was cooled while stirring, and at 25°C, a solution prepared by dissolving 13 parts of anhydrous cupric chloride in the ethylene glycol mark was gradually added, and the mixture was further cooled for 3
Stir well for about 12 minutes at 0-35. The resulting mixture was then heated to 70°C and heated at 70°C for 2 hours to complete the reaction. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a copper phthalocyanine product.

The yield was about 85%. X-ray analysis of this product revealed that it was a p-type copper phthalocyanine with a new crystalline form, and the particle size was fine, soft, and had good dispersibility, and the hue was clear and reddish blue, and it was used as a pigment. The case was very good. Example 6 Add 9 parts of ethylene glycol, 5 parts of ammonia, and 9 parts of phthalonitrile to the same 300cc four flasks used in Example 1, raise the temperature while stirring, and then raise the temperature to 110°C while blowing in ammonia. The mixture was allowed to react for 3 hours.

Next, it was cooled while stirring, and the obtained reaction product was transferred to a 500 cc container equipped with a homomixer.
While stirring well, at 25°C, a solution prepared by dissolving 7.8 parts of anhydrous cupric chloride in 105 parts of ethylene glycol was gradually added to the solution for 30 to 35 minutes. Stir well for about 1 minute at C. Then, the resulting mixture is passed through an Ikari-type stirrer,
The mixture was transferred to a 500 cc cylindrical round bottom flask equipped with a condenser and a thermometer, the temperature was raised to 65°C, and the reaction was completed by heating at 65°C for one hour. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a copper phthalocyanine product. The yield was about 84%. X-ray analysis of this product revealed that it was a new crystalline form of ρ-type copper phthalocyanine, which was fine in particle size, soft and well-dispersed, and had a clear, reddish blue color that could be used as a pigment. If it was, it would have been very good. Example 7 Add 12 parts of ethylene glycol, 7 parts of ammonia and 1 part of phthalonitrile to the same 300 cc four flasks used in Example 1, raise the temperature while stirring, and heat at 100°C for 30 minutes while blowing in ammonia. Allowed time to react.

Next, the reaction product was cooled while stirring, and a solution of 10.4 parts of anhydrous cupric chloride dissolved in ethylene glycol was gradually added to the obtained reaction product at 25°C.
The mixture was stirred well for about 60 minutes at 35°C. Then, the temperature of the obtained mixture was raised to 75 °C, and the temperature was maintained at 75 °C for 1 hour, and then the temperature was raised to 120 °C, and the reaction was completed. , the same work-up as in Example 1 was carried out to obtain the copper phthalocyanine product. The yield was about 91%. X-ray analysis of this product revealed that it was a new crystalline form of ρ-type copper phthalocyanine, the particle size was fine, it was soft and had good dispersibility, and its hue was clear and reddish blue, making it suitable for use as a pigment. It was very good when used. Comparative Example 1 25.6 parts of phthalonitrile and ethylene glycol saturated with ammonia) 19? was added and reacted at 100°C for 5 hours, then cooled to room temperature, the reaction solution was transferred to a reaction vessel at normal pressure, and cuprous chloride 5. Aqueous solution was added thereto, and the mixture was reacted at 100 to 110°C for 7 hours.

The crystalline form of copper phthalocyanine obtained in this way is
When analyzed with X-rays, the Black angle 520- has a strong peak at about 6.8 degrees, a moderate peak at about 15.6 degrees, and a peak at about 24 degrees.
It is a crystalline type that shows several broad moderate peaks at 28 degrees, and the Black angle 2θ is a strong peak at about 8.6 degrees, about 17.2 degrees, 18.3 degrees, and 23.2 degrees. ,2
This is different from the crystalline form of ρ-type copper phthalocyanine, which exhibits moderate θ degree peaks at 5.3 degrees, 26.5 degrees, and 28.8 degrees. Next, by the method described in Example 1, a hue test and a PVC coloring test were conducted. Comparing copper phthalocyanine obtained by this method and ρ-type copper phthalocyanine, the hue of copper phthalocyanine obtained by this method is yellowish blue, whereas p-type copper phthalocyanine has a strong reddish hue. The color was tinged with blue, and a remarkable difference in hue was observed. Furthermore, regarding colored PVC sheets, the color of the sheet using copper phthalocyanine obtained by this method is yellowish blue, whereas the color of the sheet using ρ-type copper phthalocyanine is reddish. The color was tinged with blue, and again, a remarkable difference was observed. Comparative Example 2 Using 6.7 parts of cupric chloride instead of cuprous chloride,
The reaction was otherwise carried out in the same manner as in Comparative Example 1.

When the obtained crystal form of copper phthalocyanine was analyzed by X-ray, the Black angle 2θ showed a strong peak at about 6.8 degrees, and a strong peak at about 1
It was in a crystal form showing a medium peak at 5.6 degrees and several broad peaks at about 24 to 28 degrees, and was different from the crystal form of ρ-type copper phthalocyanine. Moreover, the hue of this copper phthalocyanine was much more yellowish blue than that of p-type copper phthalocyanine, and a remarkable difference was observed. Comparative Example 3 According to the method of Example 10 of JP-A-50-1032 Gin Specification, 3α-phthalonitrile, 1 part of sodium methylate,
55 parts of ammonia and 150 parts of ethylene glycol
After reacting at a temperature of 120°C for 1 hour, 7.4 parts of cupric chloride was added at 55°C, heated and maintained at 75-80°C for 1 hour, and then reacted at 120°C for 2 hours.

X-ray analysis of the crystal form of the copper phthalocyanine obtained showed that the Black angle was 20 degrees, a strong P3. It was in a crystal form showing a medium peak at about 15.6 degrees and several broad peaks at about 24 to 28 degrees, and was different from the crystal form of ρ-type copper phthalocyanine. Moreover, the hue of this copper phthalocyanine was much more yellowish blue than that of the ρ-type copper phthalocyanine, and a remarkable difference was observed. Comparative Example 4 The temperature at the time of adding the copper salt in Example 1 was set to 25°C.
The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 60'C instead of .

X-ray analysis of the crystal form of the copper phthalocyanine obtained revealed that the Black angle was 20 degrees, a strong peak at about 6.8 degrees, and a strong peak at about 15 degrees.
．． It was in a crystal form showing a medium peak at 6 degrees and several broad peaks at about 24 to 28 degrees, and was different from the crystal form of p-type copper phthalocyanine. Moreover, the hue of this copper phthalocyanine was much more yellowish blue than that of the ρ-type copper phthalocyanine, and a remarkable difference was observed.

[Brief explanation of the drawing]

Figure 1 shows the relationship between the amount of ethylene glycol used in the mixture obtained in the second operation of the present invention and the holding temperature. Weight ratio of ethylene glycol used
The vertical axis represents the holding temperature T°C.

Claims (1)

[Claims] 1. When producing copper phthalocyanine from phthalonitrile, as a first operation, phthalonitrile and ammonia are heated in an ethylene glycol solvent at a temperature of 50 to 150°C, and as a second operation, a reaction is performed at a temperature of 50°C or less. A divalent copper salt and, if necessary, ethylene glycol are added to the above reaction product at the salinity, and then, as a third operation, the obtained mixture is plotted on the horizontal axis in terms of the weight of the phthalonitrile used as the starting material. The weight ratio of the ethylene glycol used in the mixture is taken as X, and the vertical axis is the holding temperature T°C.
In the figure, (A) X=3.5, T=90, (B) X=
2, T=90, (C)X=2, T=60, (D)X=8
, T = 60, and heated and held for at least 2 hours at a temperature within a range corresponding to the composition of the mixture, and finally, as a fourth operation, 60 ~
A method for producing a novel crystalline ρ-type copper phthalocyanine, which comprises heating at a temperature of 150°C to complete the reaction.