JPS647108B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention produces copper phthalocyanine having an ε-type X-ray diffraction spectrum in a pure, inexpensive and safe manner.
Concerning a method for manufacturing on an industrial scale in a non-polluting process. Pure ε-type copper phthalocyanine has a more reddish color tone than α-type copper phthalocyanine, is clear and has high coloring power, and is more stable against crystal dislocation, so it is considered to be a copper phthalocyanine with extremely desirable properties. It is evaluated. Although various methods for producing ε-type copper phthalocyanine have been proposed, all of them have been extremely unsatisfactory from the viewpoint of industrial production methods for obtaining pure ε-type copper phthalocyanine. For example, British Patent No. 1411880, Japanese Patent Publication No. 52-6300, Japanese Patent Publication No. 52-6301, which uses α-type or γ-type copper phthalocyanine that has undergone a pigmentation process as a raw material to undergo crystal rearrangement to ε-type. Even though the described method yields pure ε-type copper phthalocyanine, it is unavoidable that the cost is extremely high, and the crude β-type copper phthalocyanine can be converted into ε-type copper phthalocyanine.
It is not possible to obtain pure ε-type copper phthalocyanine using the method described in German Patent No. 1,181,248, which causes crystal rearrangement in the form. The method of synthesizing ε-type copper phthalocyanine from the beginning using phthalic anhydride or phthalodinitrile as a starting material is considered to be an advantageous method, but it is possible to synthesize phthalodinitrile, urea, and copper salt in a molten state using a co-kneader, etc. The method described in US Pat. No. 3,051,721, in which the reaction is carried out under high shear force, is extremely difficult to control because the reaction is completed in an extremely short period of time, and there is only a viscosity state during which high shear force can be applied. It's strange and impractical. Furthermore, the method described in Japanese Patent Publication No. 40-2780, in which raw materials such as phthalic anhydride or phthalodinitrile are added little by little using molten urea as a solvent, does not produce stable ε-type crystals and is extremely inefficient. This is also not practical. The only special method is to synthesize ε-type copper phthalocyanine in one step by heating and stirring phthalic anhydride, urea, copper salt, and a reaction catalyst in nitrobenzene as a solvent in the presence of a condensation reaction product of copper phthalocyanine sulfochloride and an amine. Although the method described in 1973-39325 is considered to be of industrial value, the drawback of this method is that pure ε-type copper phthalocyanine cannot be obtained using solvents other than nitrobenzene. That is,
The combination of the type of solvent used in the reaction and the type of amine used in the production of the condensation reaction product of copper phthalocyanine sulfochloride, which is a crystal system modifier, and an amine will affect the purity of the resulting ε-type copper phthalocyanine and the reaction. The combination that has an extremely large effect on the yield and provides a high yield of pure ε-type copper phthalocyanine is the combination of nitrobenzene solvent and dehydroabiethylamine in the method of JP-A-53-39325 mentioned above, and the combination that uses nitrobenzene Even if it is, the yield is extremely low with other combinations, or it can only be obtained by mixing with the β type. However, nitrobenzene is highly toxic, and its industrial use as a solvent poses serious problems in terms of occupational safety and health, and it is not practical because treatment of industrial wastewater requires a large amount of cost. Moreover, since the crystalline modifier used is directly mixed into the final product, highly oil-soluble compounds such as the condensate of copper phthalocyanine sulfochloride and dehydroabiethylamine may affect the bleed resistance of the pigment. This is not desirable as it will cause a loss. The present inventors used an alkylbenzene as a solvent, which has low toxicity from the standpoint of occupational safety and health and does not cause pollution problems like nitrobenzene or chlorinated solvents, and has no practical problems with bleed resistance, and is a pure ε-type solvent. As a result of intensive research on a method to obtain copper phthalocyanine stably and in high yield, which exhibits an X-ray diffraction spectrum of
In the alkylbenzene solvent method, a condensation reaction product of copper phthalocyanine sulfochloride, which has low oil solubility, and an aromatic amine is used as a crystal system modifier, and a pre-produced ε having a specific surface area of 35 m ² /g or less by the BET method is used. The objective was achieved by adding a certain amount of copper phthalocyanine crude pigment as seed crystals from the beginning. The crystalline modifier used in the method of the present invention is a compound represented by the following general formula (), (In the formula, Pc represents a metal or metal-free phthalocyanine residue, M represents a hydrogen atom, an alkali metal atom, or an ammonium group, and R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkanol represents a group, x and y represent a number from 0 to 4, z represents a number from 1 to 4, but x,
The sum of y and z is in the range of 1 to 4. ) Particularly preferred is one in which Pc is copper phthalocyanine. This compound can be produced by a conventional method in which crude copper phthalocyanine is treated with chlorosulfonic acid and thionyl chloride, and the resulting copper phthalocyanine sulfochloride is reacted with an aromatic amine. Aromatic amines used include aniline,
o,p-toluidine, o,m,p-chloroaniline, o,m,p-bromoaniline, o,p-anisidine, 2,4-dichloroaniline, 3,5-dichloroaniline, 2,4- dibromoaniline,
Examples include 3,5-dibromoaniline and 2,4-xylidine, with aniline being particularly useful. The number of substituents is 0 to 4 for x and y, respectively;
Although z is 1 to 4 and the sum of x, y, and z is 1 to 4, it is particularly preferable that x, y are close to 0 and z is 1 to 2. The crude ε-type copper phthalocyanine pigment used as a seed crystal may be pure ε-type copper phthalocyanine with a specific surface area of 35 m ² /g or less by the BET method, or it may be obtained by drying and pulverizing the produced pigment into powder. The reaction solution containing the produced pigment can also be used as it is. The alkylbenzene used as a solvent needs to be inactive in the reaction system under the reaction conditions of 150 to 200°C for 3 to 8 hours in the production method of the present invention, so an alkylbenzene with a boiling point of 150 to 250°C is used. . Specific examples include isopropylxylene, diisopropyltoluene, t-aluminumbenzene, t-hexylbenzene, 2-ethylhexylbenzene, and mixtures having a boiling point range such as Solbetsuso 150 may also be used. The amount used is 2 to 5 by weight based on the phthalocyanine ring-forming organic compound.
Double the amount is appropriate. The organic compounds capable of forming a phthalocyanine ring used in the method of the present invention include conventionally known phthalic acid, phthalic anhydride, phthalimide, phthalic diamide, phthalamic acid, o-cyanobenzoic acid, phthalodinitrile, etc. However, phthalic anhydride is particularly preferred. Copper compounds include anhydrous cuprous chloride, anhydrous cupric chloride, copper oxide, cuprous oxide, copper hydroxide, copper sulfate, etc.
A compound conventionally known as a copper atom supplying compound for copper phthalocyanine is used in an amount of about 0.9 to 1.05 moles per 4 moles of the phthalocyanine ring-forming organic compound. As for the reaction catalyst, any conventionally known catalyst can be used, but ammonium molybdate or molybdenum oxide is useful, and the amount used is 0.01 to 0.03 mol per 4 mol of the phthalocyanine ring-forming organic compound. is appropriate. It is particularly important that the amounts of the crystal modifier and the ε-type copper phthalocyanine seed crystals be within a specific range based on the balance between the two, and this range is specified as follows. In other words, when the horizontal axis (X) is the proportion of the crystalline modifier used in relation to the phthalocyanine ring-forming organic compound and the vertical axis (Y) is the proportion of the ε-type copper phthalocyanine seed crystal used, the point is A(X=
4.0%, Y=6.0%) and point B (X=4.0%, Y=10%)
The range sandwiched between the straight line connecting point A (X=4.0%, Y=6.0%) and point C (X=10%, Y=6.0%) (however, X≧4.0%, Y≧6.0%) is the usable range, and the ratio of both compounds can be freely selected within this range. However, using more than necessary is not only wasteful, but especially an excess of crystalline modifiers will not have a positive effect on the bleed resistance of the final product, so the amount used should be kept to the minimum necessary. Usually, in the case of standard quality, both the crystalline modifier and the ε-type copper phthalocyanine seed crystal are used at a ratio of 6%, or 5% of the former and 6% of the latter. Needless to say, the amount can be increased or decreased as appropriate depending on factors such as the type of crystalline modifier, reaction conditions, and reaction equipment. When both compounds are used outside the specified range, β-type or π-type, or mixed crystals of these and ε-type are often obtained.
It is not possible to stably obtain the desired copper phthalocyanine that also has pure ε-type crystals. For the synthesis reaction, a reaction vessel equipped with a large and highly efficient stirrer is used, and the cold raw materials are added and heated to 150°C to 200°C for 3 to 8 hours.
It is done in a very ordinary way to keep time. The crystal system modifier and the ε-type seed crystal can be added at any time when the temperature is below 130°C, and it is convenient to add them from the beginning. The ε-type copper phthalocyanine obtained by the method of the present invention usually has a specific surface area of 35 m ² /g or less by the BET method, and can be used as a pigment as it is.
By performing a grinding treatment to make the primary crystals smaller by a known method described in US Pat. No. 2,556,730, US Pat. The ε-type copper phthalocyanine obtained by the method of the present invention is useful for coloring synthetic or natural polymeric substances, other organic compounds, or inorganic substances.
It is also extremely useful as a coloring agent for printing inks and paints. Next, the present invention will be explained with reference to Examples. In each example, both % and parts represent weight % and parts by weight. Example 1 A glass autoclave was equipped with a stainless steel thermal reflux condenser kept at 90°C, and 120 parts of phthalic anhydride, 156 parts of urea, 20.3 parts of anhydrous cuprous chloride, 0.8 parts of ammonium molybdate, and Tarsia were added. Add 300 parts of lyhexylbenzene and stir to obtain 7.4 parts of ε-type copper phthalocyanine crude pigment powder with a specific surface area of 24.5 m ² /g by the BET method and expressed by the formula (). Add 6.0 parts of the compound and raise the temperature to 110°C for 30 minutes.
After keeping at the same temperature for 30 minutes, the temperature was raised to 165℃ in 1 hour.
The mixture was stirred at the same temperature for 4 hours. During the reaction, operate the pressure regulating valve attached to the tip of the reflux condenser to reduce the internal pressure to 3.0.
I made sure not to exceed Kg/cm ² . After cooling, filter, thoroughly wash with methanol, stir and disperse in 3,000 parts of water, add 170 parts of 35% hydrochloric acid, stir at 90°C for 2 hours, filter, thoroughly wash with water, and dry at 80°C. did. 114 parts of beautiful copper phthalocyanine showing a pure ε-type X-ray diffraction spectrum was obtained. The specific surface area of this pigment determined by the BET method was 20.3 m ² /g. Example 2 Into the same reactor used in Example 1, 120 parts of phthalimide, 104 parts of urea, 27.2 parts of cupric chloride,
0.8 parts of ammonium molybdate and 300 parts of diisopropyltoluene were added and stirred. Next, Example 1
By the same operation as above, add the solution containing the ε-type copper phthalocyanine produced at the time the reaction is completed in an amount such that the content of ε-type copper phthalocyanine is 12 parts,
Furthermore, 12 parts of a compound represented by formula (), was added and then operated in the same manner as in Example 1 to obtain pure ε
Copper phthalocyanine showing X-ray diffraction spectrum of type
Obtained 122 copies. The specific surface area of this pigment determined by the BET method was 28.6 m ² /g. Example 3 120 parts of phthalic anhydride, 156 parts of urea, 32.2 parts of anhydrous copper sulfate, 0.8 parts of ammonium molybdate, and 300 parts of 2-ethylhexylbenzene were added to the same reactor as used in Example 1, and stirred. 7.2 parts of ε-type copper phthalocyanine crude pigment powder obtained in Example 2, formula () 7.2 parts of a compound represented by was added. 110℃ in 30 minutes
Stir at the same temperature for 30 minutes, then stir for 1 hour.
The temperature was raised to 180°C, and the mixture was further stirred at the same temperature for 4 hours.
The gas generated during the reaction was released to the outside of the system by opening the pressure regulating valve at the tip of the reflux condenser. 109 parts of copper phthalocyanine having a pure ε-type X-ray diffraction spectrum was obtained by processing in the same manner as in Example 1. BET of this pigment
The specific surface area determined by the method was 18.5 m ² /g. Example 4 120 parts of phthalimide, 104 parts of urea, 19.7 parts of copper hydroxide, 0.8 parts of ammonium molybdate, and 150,300 parts of sorbet were added to the same reactor as used in Example 1 and stirred. Similarly obtained, ε
Completion of synthesis reaction solution containing 12 parts of type copper phthalocyanine and formula () 9.6 parts of a compound represented by was added. By operating in the same manner as in Example 3, 108 parts of copper phthalocyanine exhibiting a pure ε-type X-ray diffraction spectrum was obtained. The specific surface area of this pigment as measured by the BET method was 17.8 m ² /g. Examples 5-10 The operation of Example 1 was repeated by changing the amounts of the crystalline modifier and the ε-type copper phthalocyanine crude pigment powder.

[Table] In all cases, copper phthalocyanine exhibiting a pure ε-type X-ray diffraction spectrum was obtained. Comparative Examples 1-8 For comparison, the operation of Example 1 was repeated by changing the amounts and ratios of the crystalline modifier and the ε-type copper phthalocyanine crude pigment powder outside the scope of the claims.

[Table] In either case, copper phthalocyanine exhibiting a pure ε-type X-ray diffraction spectrum was not obtained. Reference example ε-type copper phthalocyanine crude pigment obtained in Example 1
Add 225 parts and 1600 parts of crushed common salt to a double-arm kneader, and further add 230 parts of diethylene glycol.
After grinding at 80° to 90°C for 6 hours, wash with hot water,
Wash thoroughly with water, dry at 80℃, and use BET.
Beautiful blue pigment with a specific surface area of 68m ² /g by method
Obtained 220 copies. 2.0 parts of this pigment was placed in a glass bottle containing 40 parts of glass beads with a diameter of 1 mm, and 7 parts of melamine-alkyd baking paint varnish and 4 parts of xylene were added.
After running the paint shaker for 1 hour, 27 parts of the same melamine-alkyd varnish was added and running for another 10 minutes, and the glass beads were strained through a wire mesh to obtain a blue primary color paint. Three parts of this primary color paint and five parts of a white paint of the same type containing 30% titanium white were mixed well with a glass rod to make a blue paint. Separately, a blue paint was obtained in exactly the same manner using α-type copper phthalocyanine prepared through crystal stabilization treatment using a known method for paint use. When both were applied side by side on a glass plate and baked at 120°C for 30 minutes, the paint using the pigment of the present invention obtained in Example 1 had a more reddish hue and was clearer.
The coloring power was also approximately 30% higher. In addition, 1.0 part of the pigment of Example 1 was kneaded with 1.6 parts of resin varnish for lithographic ink on a Hubermaller for 3 cycles at 100 revolutions to make an ink, and an untreated α
When a type of copper phthalocyanine pigment was used and spread on paper next to an ink obtained in the same manner, it was found that, as in the case of paint, the ink using the pigment according to the present invention had a redder tone, clearer color, and higher coloring power. The results showed that.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between changes in the proportions of an ε-type copper phthalocyanine crude pigment used as a seed crystal and a crystalline modifier, and the crystal type of the produced copper phthalocyanine.

Claims (1)

[Claims] 1. When synthesizing copper phthalocyanine by heating and stirring an organic compound capable of forming a phthalocyanine ring, urea, a copper compound, and a reaction catalyst in an alkylbenzene solvent with a boiling point of 150 to 250°C, the following formula () shown in (In the formula, Pc represents a metal or metal-free phthalocyanine residue, M represents a hydrogen atom, an alkali metal atom, or an ammonium group, and R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkanol group) , x and y each represent a number from 0 to 4, z represents a number from 1 to 4, but the sum of x, y and z is in the range from 1 to 4.) As a crystal system modifier and a seed crystal specific surface area
The weight ratio of the ε-type copper phthalocyanine crude pigment of 35 m ² /g or less to the organic compound that can form a phthalocyanine ring, and the usage ratio of the crystalline modifier is plotted on the horizontal axis (X), and the ε-type copper phthalocyanine crude pigment is used. If the ratio is plotted on the vertical axis (Y), point A (X = 4.0
%, Y=6.0%) and point B (X=4.0%, Y=10%)
The range sandwiched between the straight line connecting point A (X=4.0%, Y=6.0%) and point C (X=10%, Y=6.0%) (however, X≧4.0%, Y≧ 6.0%) A method for producing ε-type copper phthalocyanine.