JPS59155467A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE:To obtain the titled pigment which has a shade of yellow and causes less bronzing, by dry-crushing crude copper phthalocyanine in the absence of a crushing aid, crushing it in the presence of a crystallizing solvent and further dispersing it in the presence of mechanical energy. CONSTITUTION:99.5-85wt% crude copper phthalocyanine and 0.5-15wt% at least one compd. selected from those of formulas I and II [wherein CuPC is copper phthalocyanine residue; R1 is H, a 1-4C alkyl; A is a 2-6C alkylene; R2, R3 are each a 1-20C alkyl, a 3-12C alkoxyalkyl, a 6-8C cycloalkyl, or R2 and R3 may form an N-contg. 5-, 6- or 7-membered heterocyclic ring when combined together; Q is (substd.) benzene, (substd.) naphthalene; n is 1-6] are dry-crushed to a size satisfying the formula III (wherein Salpha and Sbeta are a peak area of X-ray diffraction pattern in alpha type and beta type crystal form, respectively). 1-10wt% crystallizing solvent is added to the crushed product to completely convert the alpha type crystal into beta type crystal. The resulting product is immersed in a solvent in the presence of machanical energy to produce the titled pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing β-type crystalline copper phthalocyanine. More specifically, crude copper phthalocyanine is dry-milled in the absence of a milling aid, and then milled in the presence of a crystallization solvent in an amount that allows the milled product to maintain dry powder properties, resulting in β-type crystals. The present invention relates to a method for producing a υβ-type crystalline copper phthalocyanine pigment by taking it out in the form of υβ type crystal and dispersing it in a solvent in the presence of mechanical energy.

The crude copper phthalocyanine obtained by synthesis generally has coarse primary particles and exhibits only low tinting strength even when dispersed in a vehicle, so it must be made fine. The process of refining crude copper phthalocyanine to a particle size suitable for use as a pigment is called pigmentation. Methods of pigmentation include dissolving it in sulfuric acid and re-precipitating it to make it fine.
There is a method of miniaturization using mechanical energy.

In order to obtain β-type crystalline copper phthalocyanine, a method of grinding using mechanical energy is generally used2, but industrially, inorganic salts and a binder such as ethylene glycol are used to produce copper phthalocyanine using a kneader or the like. There are methods of pulverizing with a device, and methods of adding a small amount of an inorganic salt and a crystallization solvent such as xylene and pulverizing with a device such as a ball mill.

All of these methods use a grinding aid other than the crushed material during grinding, but from the standpoint of resource conservation, it is preferable not to use a grinding aid.

In the method of grinding in the absence of a grinding aid, as the crude copper phthalocyanine becomes finer, its crystal form changes from the β-type crystal form to the α-type crystal form, resulting in strong agglomeration. It has no use as a. Therefore, this strongly aggregated copper phthalocyanine containing a mixture of α-type crystal form and β-type crystal form is immersed in a crystallization bath agent such as xylene, and the α-type crystal part is transformed into β-type crystal form and dispersed. let me,
A method is used to obtain a copper phthalocyanine pigment suitable as a pigment (JP-A-50-157419, JP-A-52-69435).

However, the β-type crystalline copper phthalocyanine pigment obtained by this method undergoes crystal growth when dispersed in a crystallization solvent, and the crystal shape is acicular crystals with a large ratio of major axis to minor axis.゛The disadvantage is that only β-type crystalline copper phthalocyanine can be obtained, which has a reddish hue and a large amount of bronze.

The present inventors have conducted intensive research on a method of obtaining a product with a yellowish hue and little bronze formation by grinding crude copper phthalocyanine in the absence of a grinding aid and treating it with a solvent. By adding a crystallization solvent of The present inventors have discovered that it is possible to obtain a copper phthalocyanine pigment with low taste and low bronzing, leading to the present invention.

That is, the present invention is a method for producing a copper phthalocyanine pigment, which comprises the following steps (a) to C).

(a) Made by ffl = Phthalonanine 99.5-85
M Ryu % fz and at least one compound selected from the following general formulas (1) and (b) 0.5 to 153r amount ratio, the area of the peak of the X-ray diffraction diagram representing the α-type and β-type crystal forms If Sα and Sβ are Sβ/Sα+S
Dry grinding with an ox so that β≦06, 1 [In the formula, CuPC is copper phthalocyanine residue 7L, R1 is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, A
is a linear or branched alkylene group having 2 to 6 carbon atoms, R2 and R3 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 3 to 12 carbon atoms; An alkyl group or a cycloalkyl group having 6 to 8 carbon atoms, or a 5-, 6-, or 7-membered heterocycle containing a nitrogen atom (one oxygen atom, sulfur atom, or other ), Q is a benzene ring or a nantarene ring which may have a substituent, and n is an integer from 1 to 6] (b) For the pulverized product 1 to 10 weight ratio is added, and the pulverization is continued until the pulverized material completely transforms into the β type. (C) (b) Step T Soak in the presence of.

Crude copper phthalocyanine and soybean are produced by using phthalic anhydride or its derivatives, urea and a copper source, or by using phthalic anhydride or its derivatives and a copper source (for example, ammonium molybutate, titanium chloride, etc.) in an organic solvent at 120 to 270°C, preferably 1
It is produced by reacting at 230° C. for 2 to 10 hours, preferably 3 to 7 hours, under normal pressure or increased pressure.

The compound of general formula (1), which is a derivative, can be obtained by reacting a chlorosulfonated product of copper phthalocyanine with an amine component. Examples of amine components include piperidinomethylamine, dimethylaminoethylamine, diethylaminoethylamine, dinotylaminopropylamine, diethylaminepropylamine, dinotylaminopropylamine, piperidinoethylamine, piperidiethylamine, morpholinoethylamine, Peridinoethylamine, pibecorinopropylamine, diethylaminohexylamine, diethylaminoethoxypropylamine, diethylaminebutylamine, dimethylaminoamylamine, NXN-methyl-lauryl-aminopropylamine, 2-ethylhexylaminoethylamine, stearylaminoethylamine , oleyl-minoethylamine, and the like.

The compound of general formula (b), which is a derivative, can be obtained by reacting a chloromethylated product of copper phthalocyanine with a compound having a phthalimide group or a naphthalimide group.

(a) The amount of the compound added to the step is 0.5 to 1.
If the weight range is less than 0.5, the crystal growth in step (C) will be excessive and only a pigment with low coloring power will be obtained, and if it exceeds 15 weight, the crystal growth in step (C) will be excessive. Does not disperse easily.

Dry pulverization in the process is carried out, for example, by pulverizing in a vibrating mill, attritor, or other pulverizer, using a jacket so that the pulverizing temperature is below 100°C, preferably below 80°C, or directly. Cool by pouring water over the grinder.

(a) (After ID process, Sβ/Sα-1-3β>0.6
In this case, the grinding process does not sufficiently refine the particles, making it impossible to obtain pigments with high coloring power. In addition, in the X-ray diffraction diagram, the peaks at θ ± 0.2 degrees = 15.6 degrees and 16.6 degrees are 9 for the α type crystal form, and 2θ ± 0.2 degrees = 18 for the β type crystal form.
The peaks were taken at 1° and 18.4°.

Step (b) is a step in which pulverization is continued in the presence of a crystallization solvent in a range [ffl] in which the pulverized product can maintain all the characteristics of a dry powder. β in a liquid phase filament where there is sufficient crystallization solvent
When the pigment is transformed, it undergoes a β transformation and is simultaneously dispersed with crystal growth, becoming acicular crystals with a large ratio of the long axis to the short axis of the primary particle of the pigment, but to the extent that the pulverized product can maintain the characteristics of a dry powder. When β-transition is carried out in the presence of a crystallization solvent, crystal growth does not occur, and therefore, the result is a strongly agglomerated pulverized pigment without being dispersed.

(b) Crystallization M agents used in the process include benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, hydrinodine, zincylformamide, dimethylsulfoquine, N-methylpyrrolidone, trichloroethylene, tetrachloroethylene, cellosolve acetate, butyl acetate, etc. The amount added is 1 to 1 for the pulverized material.
If the amount is less than 10% by weight, crystal transition to the β type will not occur, and if it exceeds 10% by weight, the pulverized product will not be able to maintain the properties of dry powder.

Step (C) is a step of dipping and dispersing the fine, strongly agglomerated pulverized pigment in β-type packed crystal form obtained in step (b). Because the copper phthalocyanine pigment has already transformed into the β-type crystal form, it does not cause excessive crystal growth even when dispersed in a crystallization solvent, and it forms rice-grain-like crystals with a small ratio of the major axis to the minor axis of the -order particles. I can do 9 things. (c) Mechanical energy equipment used in the step includes a sand mill, etc., and the strongly agglomerated pulverized pigment is dispersed by the mechanical energy of the sand mill and the dispersion force of the solvent. It should be noted that in the absence of mechanical energy sufficient to immerse the crushed face i knee 1 into the solvent 7 will not disperse.

In addition to the solvent used in step (b), the solvent used in step (C) includes alcohols such as methanol, ethanol, butanol, propyl alcohol, and isopropyl alcohol.

The pigment dispersion obtained in step (C) can of course be used as a solvent base, or it can be filtered and used as a solvent base, or the pigment can be isolated by drying, distillation, etc. You may also use it.

The σβ-type copper phthalocyanine pigment obtained by the present invention is a β-type crystalline copper phthalocyanine pigment that has a yellowish hue and has a high tinting power and is less likely to generate bronze. Used as a pigment for paints, printing materials, etc.

The present invention will be explained below based on Examples and Comparative Examples.

``Part'' and ``%'' in the item indicate the weight of the cuff.

Example 1 5 parts of a compound expressed by the following formula was added to 95 parts of phase steel phthalonanine, and the mixture was pulverized with an attritor for 1 hour. At this time, the content of the β-type crystal form determined from the X-ray diffraction pattern was 31 Da. Next, 5 parts of xylene was added, and pulverization was continued for 15 minutes.The content of the β-type crystal form determined from the Xi diffraction pattern at this time was 10.0%.

10 parts of the obtained r+ 7j pulverized product was added to 30 parts of xylene and dispersed in a sand mill for 2 hours. Methanol was added to the obtained xylene paste, and the paste was replaced with methanol and dried.

Electron micrographs show that the secondary particles of this pigment are grain-like, and when dispersed in a resin-type varnish using a Zuber-Mahler, it produces a yellowish hue with a small amount of frozen bronze. This is an oil ink with great coloring power.

X-ray diffraction conditions are Target-CuXFilter-N
i, Voltage-30KVXCurrent-4
'OmAXCogtFul] 5call-20,
000cpsXTime Con5t, -l se
c,,5cannjn'g 5peed-4'7-m1
nXChart 5peed -4cm/minXD
ivergence S 1it-10Receivi
ng S lit -0.3mm, Detector
-G, MC is there.

Comparative Example 1 150 parts of xylene was added to 10 parts of the pulverized material whose β-type crystal content determined from the X-ray diffractogram in Example 1 was 31%, and the mixture was immersed at room temperature. 150 parts of xylene was added to 10 parts of xylene and dispersed in a sand mill while immersed at room temperature, and then each was replaced with methanol and dried and pulverized. All the pigments obtained from the dispersion show needle-like crystals when viewed with an electron microscope.
・Compared to the oil ink obtained in Example 1, the oil ink dispersed in the resin-type varnish was developed using a mala, and the color was reddish and the appearance of bronze was thicker. Ta.

Example 2 2.5 parts of a compound expressed by the following formula was added to 975 parts of crude 'RM7 talocyanine, and the mixture was ground with an attritor for 1 hour.

The β-type crystal content determined from the X-ray diffraction diagram at this time was 31%.

Then 5 parts of Nakasolef were added and milling was continued for 15 minutes. The β-type crystal content determined from the X-ray diffraction diagram at this time was 100%. 10 parts of the obtained pulverized material was added to 30 parts of methanol and dispersed in a sand mill for 2 hours. The resulting methanol paste was dried and the pigment isolated.

Similar to Example 1, when this material is seen in an electron microscope photograph, its -
The secondary particles are rice grain-like, and when dispersed in a resin-type varnish using a Zuber muller, an oil ink with a clear yellowish hue and high tinting power with little bronzing was created.

patent applicant Toyo Ink Manufacturing Co., Ltd.

Claims (1)

[Scope of Claims] 1. A method for producing a copper phthalocyanine pigment, which comprises the following steps (a) to C). (a) Crude copper phthalocyanine 99.5-85 M
t % and at least one f-hybrid compound selected from the following general formulas (1) and (n) in a weight ratio of 0.5 to 15,
When the areas of the peaks of the X-ray diffraction diagram representing the α-type and β-type crystal forms are Sα and Sβ, Sβ/Sα+Sβ≦0
[In the formula, CuPC is a copper phthalocyanine residue, R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is a linear or branched 2 to 6 carbon atom. An alkylene group having a carbon atom, R2 and R3 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxynalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 6 to 8 carbon atoms. A 5-, 6-, or 7-membered heterocycle containing a nitrogen atom by the group or R2 and R3 (which may contain one nitrogen atom, sulfur atom, or one other nitrogen atom as a ring member) ), Q is a benzene group or a naphthalene group which may have a substituent, and n is an integer of 1 to 6.] (b) Adding a weight-grading solvent of 1 to 10 to the pulverized material, Grinding is continued until the pulverized material completely transforms into the β form, and (e) the pulverized material obtained in step (b) is immersed in a solvent in the presence of mechanical energy. 2 Benzene, toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichloroethylene, tetrachloroethylene, cellosolve acetate and butyl acetate are selected as the crystallization bath agent used in the above step ('b). A method for producing a copper phthalocyanine pigment according to claim 1, using at least one of the following. 3 Benzene as a solvent used in the above step (C),
Toluene, xylene, chlorobenzene, nitrobenzene, tetrahydrofuran, pyridine, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, trichloroethylene, tetrachloroethylene, cellosolve acetate, butyl acetate, methanol, ethanol, butano-
2. A method for producing a copper phthalocyanine pigment according to claim 1 or 2, using at least one selected from the group consisting of copper phthalocyanine pigments, propatool, and inglobanol.