JPH0157150B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing β-type crystalline copper phthalocyanine. More specifically, the present invention relates to a method for producing β-type crystal copper phthalocyanine by dry-pulverizing crude copper phthalocyanine in the absence of a grinding aid and immersing it in a crystallization solvent. Crude copper phthalocyanine obtained by synthesis generally has coarse primary particles and exhibits only low tinting strength even when dispersed in a vehicle, and therefore must be made into fine particles before use. When this crude copper phthalocyanine is ground in a ball mill or vibration mill without using a grinding aid, it gradually becomes amorphous and the X-ray diffraction diagram of CuKα shows 2Θ±0.2 degrees =
The peak area representing the β-type crystal form at 18.1° and 18.4° decreases, and the peak area representing the α-type crystal form at 2Θ±0.2° = 15.6° and 16.6° increases relatively.
The more pulverization is performed, the stronger the cohesive force becomes, and even when dispersed in a vehicle, only extremely low coloring power is exhibited. However, when this pulverized pigment is immersed in a crystallization solvent such as xylene, it transforms into the β form and loosens again. The method of producing β-type copper phthalocyanine by dry grinding crude copper phthalocyanine in the absence of grinding aids and immersing it in a crystallization solvent does not use grinding aids such as inorganic salts or high boiling point solvents. This saves resources,
This is an advantageous method from the standpoint of energy conservation. However, if crude copper phthalocyanine is dry-pulverized alone and immersed in a crystallization solvent, crystals grow excessively and become coarse particles again. As a result of intensive research into additives during dry grinding that suppress excessive crystal growth, the present inventors added a compound represented by the following general formula () to crude copper phthalocyanine in an amount of 0.5 to 20% by weight. %, it was discovered that a versatile β-type crystalline copper phthalocyanine with high tinting power could be obtained.
The present invention has now been accomplished. That is, the present invention involves the following steps: (a) Adding 0.5 to 20% by weight of a compound represented by the following general formula () to crude copper phthalocyanine, [Symbols in the formula are the same as above] (b) If the areas of the peaks in the X-ray diffraction diagram representing the α-type and β-type are Sα and Sβ, then Sβ/Sα+
Dry grinding until Sβ≦0.6; (c) immersing the pulverized product in a crystallization solvent to substantially completely transform it into the β-type crystal form. This is what we provide. Crude copper phthalocyanine can be produced using phthalic anhydride or its derivatives, urea and a copper source, or phthalodinitrile or its derivatives and a copper source (for example, ammonium molybdate, tetrachloride). titanium, etc.) in an organic solvent at 120 to 270°C,
It is preferably produced by reacting at 170 to 230°C for 2 to 10 hours, preferably 3 to 7 hours, under normal pressure or increased pressure. In step (a) above, if the amount added to the crude copper phthalocyanine is less than 0.5% by weight, excessive crystal growth cannot be suppressed and a pigment with high tinting power cannot be obtained. Moreover, if it is added in an amount exceeding 20% by weight, the transition to the β-type crystal form is slow and it is not economical. Dry pulverization in step (b) can be carried out, for example, by pulverizing in a ball mill, vibration mill, attritor, or other pulverizer, using a jacket so that the pulverizing temperature is below 100°C, preferably below 80°C; Alternatively, cool by pouring water directly onto the crusher. Grinding at 100° C. or higher is not desirable because copper phthalocyanine transforms into a β-type crystal form and does not become fine even when immersed in a crystallization solvent in step (c). After the step (b), if Sβ/Sα+Sβ>0.6, the pulverization step is insufficient to obtain a pigment with high tinting power. In the X-ray diffraction diagram, the α-type crystal form had peaks at 2Θ±0.2 degrees = 15.6° and 16.6°, and the β-type crystal form had peaks at 2Θ±0.2 degrees = 18.1° and 18.4°. In the step (c), the amount of the pulverized material obtained in the step (b) above is 1 to 100 times the amount (weight) of the pulverized material.
It is immersed in a crystallization solvent and treated until it transforms into the β-type crystal form. Crystallization solvents include benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, ethanolamine,
Aniline, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichloroethylene, tetrachloroethylene, cellosolve acetate, butyl acetate, etc. are used. Note that water, alcohol, and other non-crystallizing solvents can be used together as a solvent, but they are used within a range that does not inhibit the transition to the β-type crystal form. Treatment is carried out by refluxing at the boiling point of the system or by stirring at any temperature at which the system remains in a liquid phase, or by immersion without stirring. Normal processing time
It takes about 0.5 to 8 hours. After steps (a) to (c), the pigment is isolated if necessary. Usually, the slurry after step (c) is isolated as a pigment by filtration, drying, or distillation. Of course, it is also possible to use it as it is for paints, printing inks, etc. without isolation. When the copper phthalocyanine pigment obtained according to the present invention is dispersed in a vehicle, it becomes a paint, printing ink, etc. that has a bright red color and has high adhesion. Next, the present invention will be explained with reference to Examples and Comparative Examples.
In the examples, "part" and "%" indicate parts by weight and weight %. In addition, production examples are shown for some of the compounds represented by the general formula (). Production Example 1 Anthraquinone-2-carboxylic acid was heated and stirred with equimolar thionyl chloride in benzene under reflux for 1 hour to synthesize a chlorinated product, and after the reaction was completed, the compound was reacted with an amine to obtain the compound of formula (1). Ta. Production Example 2 When diphenyl-amine-2-carboxylic acid obtained by Ulmann condensation of O-chlorobenzoic acid and aniline is dehydrated and ring-closed in concentrated sulfuric acid, it is heated at 100°C for 3 hours to produce acridonesulfonic acid. I got it. Production Example 3 In Production Example 2, instead of O-chlorobenzoic acid, 2,4
-dichlorobenzoic acid and m instead of aniline
- An acridone derivative obtained by using phenoxyaniline was produced and subjected to reaction treatment in the same manner as in Production Example 2 to obtain acridon sulfonic acid. The obtained acridonsulfonic acid was dissolved or uniformly dispersed in water or a dilute alkaline solution, calcium chloride was added, and the resulting precipitate was separated to obtain a calcium salt of acridonsulfonic acid. Adding various amines instead of the above metal chlorides,
Compounds represented by (4) and (5) were obtained. Production Example 4 3,6-
Dichlorophenothiazine was obtained. Compounds (9) and (10) were obtained by reacting 3,6-dichlorophenothiazine with equimolar strength of sulfuric anhydride in an organic solvent such as ether. The compounds shown in (9) and (10) were also obtained by using chlorosulfonic acid instead of sulfuric anhydride to obtain phenothiazine chlorosulfonic acid and then hydrolyzing it. . Production Example 5 2-phenylcarbamoylphenoxazine obtained by heating equimolar amounts of 2-amino-4-phenylcarbamoylphenol and catechol to 200 to 210°C in a closed tube is treated in the same manner as in Production Example 4 to obtain a fluorine. Enoxazine sulfonic acid was obtained. Production Examples 6 to 8 Obtained by heating a combination mixture of 4-nitro, 4-diethylsulfamoyl and 4-chloro substituted O-phenylenediamine and equimolar amounts of catechol to 200 to 210°C in a closed tube. The dihydrophenazine derivative was reacted with chlorosulfonic acid and further reacted with an amine to obtain the following dihydrophenazine derivative. Production Examples 9 to 11 Dihydrophenazine obtained in Production Examples 6 to 8 was oxidized with a weak oxidizing agent such as iron chloride to obtain phenazine. Phenazine was treated in the same manner as the acridone derivatives in Production Examples 2 and 3 to obtain the following compounds. Production Examples 16-18 Substituted or unsubstituted benzene and phthalic anhydride were mixed in the presence of anhydrous aluminum chloride for about 70 min by a conventional method.
The substituted O-benzoylbenzoic acid obtained by heating to 120°C was heated in concentrated sulfuric acid to obtain the following anthraquinone derivative. The above anthraquinone was treated in the same manner as the acridone derivatives of Production Examples 2 to 4 to obtain the following compounds. Example 1 The following formula (1) obtained in Production Example 1 was added to 95 parts of crude copper phthalocyanine produced by the urea method. 5 parts of the compound represented by was added and pulverized with an attritor for 1 hour. At this time, the β-type crystal content determined from the X-ray diffraction diagram was 31%. 5 parts of the obtained pulverized material was poured into 100 parts of xylene, immersed at room temperature for 3 hours, filtered, replaced with methanol, and dried. This pigment has 100% transition to the β-type crystal form in the X-ray diffraction pattern, and the specific surface area of this pigment is 74
m ² /g, and when dispersed in a rosin-modified phenol resin type varnish using a Huber Muller, an oil ink with a bright red color and high tinting power was obtained. X-ray diffraction conditions are Target-Cu, Filter-Ni,
Voltage−30KV, Current−40mA, Count Full
Scall−20000cps, Time Const.−1sec.,
Scanning Speed-4゜/min, Chart Speed-4
cm/min, Divergence Slit−1°, Receiving Slit
-0.3mm, Detector-GMC. Comparative Example 1 Oil ink was obtained in the same manner as in Example 1, except that the compound shown in Example 1 was not added and 0.4 part was used. Pigments obtained without additives and with 0.4 parts added (specific surface area, respectively)
35, 40m ² /g) had significant crystal growth and exhibited extremely low tinting strength with oil ink. Comparative Example 2 An oil ink was obtained in the same manner as in Example 1 except that the amount of the compound shown in Example 1 was 25 parts. The pigment obtained by this method (specific surface area 16 m ² /g) does not undergo 100% β-type crystal transformation,
It was highly agglomerated and showed only low tinting strength with oil ink. Comparative Example 3 In Example 1, the pulverization time was 10 minutes, and the β-type crystal content was 65%. When this pulverized pigment (specific surface area: 45 m ² /g) was made into an oil ink in the same manner as in Example 1, it exhibited low tinting power because the particles were coarse. Example 2-43 An oil ink was obtained using the compounds shown in Table 1 in the same manner as in Example 1 using the added amounts, crystallization solvent, and crystallization temperature conditions shown in Table 2. All of these exhibited bright red color and high coloring power.

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Claims (1)

[Claims] 1 (a) 0.5 to 20% by weight of a compound represented by the following general formula () is added to crude copper phthalocyanine, and the compound represented by the general formula () is prepared. [In the formula, A and B are respectively -CO-, -NH-, -
N=, -S-, X is a halogen atom, a nitro group, a methoxy group, a phenoxy group, a methyl group,
Represents a substituent selected from a phenylcarbamoyl group or a phenylsulfamoyl group substituted or unsubstituted with a methyl group or a halogen atom, and Y represents a substituent shown in the following (a) to (i),
m represents 0 to 2, and n represents 0 to 4 (however, both m and n are not 0). (a) [Formula] (R ₁ and R ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ₁ and R ₂ are nitrogen,
Indicates a heterocycle containing an oxygen or sulfur atom. ) (b) [Formula] (R ₃ represents a hydrogen atom, a nitro group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.) (c) [Formula] (R ₄ represents a hydrogen atom, a carbon number 1 ~4 alkyl group, _R5 is an alkylene or arylene group having 1 to 20 carbon atoms substituted or unsubstituted with nitrogen, oxygen or sulfur atom,
R ₆ and R ₇ are each a hydrogen atom and have a carbon number of 1 to 20
a substituted or unsubstituted alkyl group, or
R ₆ and R ₇ represent a heterocycle containing a nitrogen, oxygen or sulfur atom. ) (d) −SO ₃ H (e) −SO ₃ M ₁ (M ₁ represents an alkali metal or alkaline earth metal.) (f) −SO ₃ HNR ₈ R ₉ R ₁₀ (R ₈ and R ₉ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or nitrogen in the formula in R ₈ and R ₉ , respectively;
Indicates a heterocycle containing an oxygen or sulfur atom. R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) (g) [Formula] (R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. _{R 12}
is an alkylene or arylene group having 1 to 20 carbon atoms substituted or unsubstituted with a nitrogen, oxygen or sulfur atom, R ₁₃ and R ₁₄ are each a hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or R ₁₃ , R ₁₄ in the formula, nitrogen, oxygen,
Or it shows a heterocycle containing a sulfur atom. ) (h) (i) −COOM ₂ (M ₂ represents an alkali metal or an alkaline earth metal.) (b) When the areas of the peaks in the X-ray diffraction diagram representing α-type and β-type crystal forms are Sα and Sβ, Sβ /
A method for producing a copper phthalocyanine pigment, characterized in that it is dry-pulverized until Sα+Sβ≦0.6, and (c) the pulverized product is immersed in a crystallization solvent to substantially completely transform it into a β-type crystal form. . 2. At least one crystallization solvent selected from benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, ethanolamine, aniline, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichloroethylene, tetrachloroethylene, cellosolve acetate, and butyl acetate. A method for producing a copper phthalocyanine pigment according to claim 1 using the following.