JPS5912697B2 - Method for producing crude organic pigment - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing organic pigments.

During the pigment manufacturing process, for example by melting or calcination methods or by methods in organic solvents, many organic pigments are often obtained in a physical form that is not suitable for pigment use.

Some of their drawbacks are too large particle size, uneven and defective crystal shape and excessive tendency to agglomerate.
These materials that are unsuitable for their end use are commonly referred to as crude pigments. They require post-processing to make them usable. A number of methods are known from the literature for reducing the particle size of pigments to desired values, and these do not necessarily lead to uniform particle sizes, but rather a particle size distribution over a certain particle size range. can get.

One method is to mill the crude pigment in the presence of inorganic water-soluble salts and organic liquids [eg, US Pat. Nos. 2,556,728 and 2,556,730].

When carrying out this method, large excesses of salt and long processing times (approximately 1 to 3 days) must be tolerated. The second method consists of stirring a foamable mixture consisting of a crude organic pigment, a water-soluble inorganic salt and an organic liquid (see Pelkey Patent Specification No. 621,890).

The equipment used is a high speed stirred mill capable of grinding the crude pigment in about 60 minutes. 90 However, due to the necessity of using a well-flowable mixture, this can only be carried out with very highly diluted pigments, and such dilution has a negative impact on the space-time yield. give. Grinding of the crude pigment by kneading it with a small amount of organic liquid, optionally in the presence of grinding aids (e.g. 35 sodium chloride) in a discontinuous kneader is also described [U.S. Pat. 2, 982, No. 66].

The required time is 30-180 minutes. Combination methods (for example ball milling followed by kneading in the presence of inorganic water-soluble salts and organic solvents) are also described [DE 1,919,496].

Although 10 to 30 hours are required in a ball mill, an additional approximately 15 to 120 minutes of kneading is required.
The disadvantages of the above methods, which are effective only with regard to the reduction of particle size, are firstly the long residence times and, moreover, the particle size range of the pigments obtained is very wide, the crystalline form is very heterogeneous and the individual The problem is that the crystals are very irregular.

Furthermore, mixtures of deformed crystals may be obtained even if this method is possible. The next negative property of the pigment particles produced is a high tendency to agglomerate, which is incompatible with the properties required of organic pigments, such as fluidity, dispersibility,
Adversely affects color strength, light fastness and climate fastness.

Therefore, due to the above-mentioned drawbacks, it is necessary not only to grind to the required particle size, but also to narrow the particle size distribution as much as possible and obtain a very uniform and well-shaped crystalline form, which is different from the hitherto known pigments. There was a need for a process that would provide pigments with improved properties in use by comparison.

Surprisingly, in a mixture of an organic pigment, an inorganic or organic salt that is water-soluble or soluble in an aqueous acid or base, and an organic or inorganic solvent that does not significantly dissolve said pigment or salt, 10 seconds in a continuously running kneading device with spatially separate means for adding liquid.
3 over a period of 15 minutes (preferably 20 seconds to 6 minutes)
Applying a shear gradient of 00 to 5000/sec (preferably 5
00 to 5000/s) and the amount of solvent is selected such that the energy expended by kneading is 1.7 to 6 KWh per kg of pigment treated, e.g. fluidity, dispersion, etc. Pigments are obtained whose properties as mentioned above, such as properties, are improved compared to pigments prepared according to the literature.

The amount of salt used is 0 with respect to 1 part by weight of the pigment used.
．． It is 1 to 20 parts by weight. Continuous kneading devices suitable for the method according to the invention are, for example, two-screw and four-screw kneaders and one-screw kneaders capable of carrying out vibratory movements.
It is a screw kneading machine.

For example, Metsaas, Warner, and Fridera (
Messrs. WernerandPfleidere
r) ZSK-53 type pearl kneading screw 1 is mentioned, and its kneading device is shown in FIGS. 1 and 3.

A more detailed description of the kneading screws is given in the literature [German Patent Specifications Nos. 862,668 and 94].
No. 0,109].

The temperature in at least part of the kneading zone is between 120 and 350
It is a mixed C (for example, 160 to 280 is C).

Suitable solvents are those with a boiling point above 140° C. and are liquid under crosstalk conditions. Particularly suitable solvents are those which are at least slightly soluble in water or dilute aqueous acids or bases, such as polyhydric aliphatic alcohols such as ethylene glycol, propylene glycol or glycerin, ethanolamine, phenol, aniline, polyethylene glycol, These include propylene glycol, polyethylene glycol and monoesters and monoethers of polypropylene glycol, polyethylene amines, N-alkylated and N-hydroxyalkylated polyethylene imines, and the like. Mention should also be made of silicone oils, phosphoric acid amides and esters, and salt melts of salts and salt mixtures, such as aluminum chloride or zinc chloride. Examples of suitable inorganic and organic salts are sodium chloride, potassium chloride, sodium sulfate, zinc chloride, aluminum chloride, aluminum sulfate, calcium carbonate, sodium acetate, potassium sodium chlorite, calcium acetate or sodium citrate.

Examples of suitable organic pigments are those based on azo, anthraquinone, azaporphin, thioindigo or polycyclics, and those based on quinacritone, dioxazine, naphthalene-tetracarboxylic acid or perylenetetracarboxylic acid, and dye lakes, such as those with sulfonic acid groups and / or Ca. Mg and A1 lakes, many of which have e.g. color index 2
It is known from the edition. The process is particularly suitable for the production of phthalocyanine pigments, such as unhalogenated, partially halogenated or perhalogenated vat and nickel phthalocyanine pigments.

Particularly suitable solvents are polyhydric alcohols and their partial ethers, as well as aniline and nuclear-alkylated and N
- alkylated aniline. Sodium chloride is particularly suitable as salt.

Next, the present invention will be specifically explained using examples. A shear gradient of about 300-5000/sec was applied in each example process. Example 1 Metsaas, Stuttgart
12 kg/h of copper phthalocyanine crude pigment produced by the phthalic anhydride monourea method in the presence of nitrobenzene in a ZSK-53V type kneading screw manufactured by Werner & Freidera and having a copper phthalocyanine purity of 95%. and 60 kg/h of crushed rock salt were fed.

The kneading apparatus is shown in FIG. approximately 8.8 kg/hour of diethylene glycol is fed into the feed orifice 1;
4.5k9/h diethylene glycol was then fed into feed orifice 2. The shaft speed of the kneading screw is 2.
95 rpm was adjusted and the main amount of diethylene glycol was adjusted so that the power exerted by the device was 26 KW. The screw was cooled over its length with 75° C. water at a total inflow rate of 800 l/h. The temperature of the exiting kneaded material was 120°C, while the temperature in the kneading zone was between 160°C and 200°C. The effluent 1009 milled material was stirred with water at 80° C. until the sodium chloride was completely dissolved, and the product was then filtered and washed free of salt.

The compressed cake was dried at 70-80°C in a circulating air drying chamber. The pigments obtained in this way, all of which are of type B, are
It exhibited high color strength and brightness, as well as fluidity and excellent dispersibility after being added into an offset binder on a plate mill or into a toluene gravure printing binder.

The pigments can also be used for aqueous formulations (for example for textile printing), in which case the dispersion does not have to be passed through a dispersion kneader, but only needs to be added with stirring using a solubilizer.

Example 2 Phthalic anhydride/urea was added in the presence of nitronbenzene in a ZSK-53V kneading screw at Metsers-Werner und Freidera, Stuttgart, equipped with a kneading device as shown in FIG. 10 containing about 70% copper phthalocyanine produced by a calcination method
．． 2k9/hour copper phthalocyanine crude pigment and 411<
9/hour of rock salt was fed.

Approximately 5.9 k9/hr diethylene glycol was metered in via feed nozzle 1, 0.935 kg/hr was metered in through nozzle 2, and 1.25 kg/hr was metered in through nozzle 2.
/hour was metered in via nozzle 3. The screw shaft speed was adjusted to 295 revolutions per minute and the main amount of diethylene glycol was readjusted so that the force exerted by the kneading screw was 28 KW. 80'C of inflow rate of 7001/hour through the device over its length
of water. The temperature of the kneaded material exiting was 155°C. The effluent 1009 kneaded material is boiled for 1 hour with 3 kg of 5% strength hydrochloric acid, the product is filtered hot and rinsed with hot 5% strength hydrochloric acid, and the compacted cake is washed free of acid. Washed and dried at 70-80°C.

The type B copper phthalocyanine pigment thus obtained had properties similar to those described in Example 1. Example 3 12.2 with chlorine content of 47-48%
k9/hour crude polychloro monocopper phthalocyanine and 37
K9/h of NaCl was fed into a kneading screw as described in Example 1.

Approximately 8.2 kg/h of diethylene glycol was fed through nozzle 1, 0.4 kg/h was fed through nozzle 2, and 0.661<9/h of diethylene glycol was fed through nozzle 3. The apparatus was operated at 295 revolutions per minute and the main amount of diethylene glycol was chosen such that the force exerted by the kneading screw was 21 KW. The first half of the kneading device was cooled with 80°C water at an inflow rate of 2551/h and the other half was cooled with 3101/h water.
Cooled with 85° C. water at an inflow rate of /h.

The temperature of the kneaded material flowing out was 150°C. The kneaded material was processed as in Example 1.

The green pigments produced in this way were highly suitable for coloring paints and for producing printing inks. Example
4 3.4 kg/h of crude copper monochloro-copper phthalocyanine pigment and 17 kg/h of sodium chloride were fed into a kneading apparatus as described in Example 2.

Approximately 3.2 kg/h of diethylene glycol was fed through nozzle 1, 0.4 kg/h of diethylene glycol was fed through nozzle 2, and 1.06 kg/h of diethylene glycol was fed through nozzle 3.
The shaft speed of the screw was 295 revolutions/minute. The main amount of glycol (nozzle 1) has a healing power of 20.5
Adjusted to be KW. The device was cooled over its length with 14° C. water at a total inflow of 70,011/hr. The kneaded material was processed as in Example 1. The pigments produced in this way were entirely of the alpha type and were very suitable for pigmentation purposes.

Example 5 3.1 kg/h pigment lead, color index 16
6 (This is about 20 to 70μ in length and 2p in manufacturing.
(obtained in a bundle of needles having a thickness of ) and 16 k9/h of sodium chloride were fed into a kneading apparatus as described in Example 1.

Approximately 2.4 kg/h diethylene glycol was metered in through nozzle 1 and 1081<g/h diethylene glycol was metered in through nozzle 2. The shaft speed of screw 1 was adjusted to 295 revolutions per minute, and the main amount of diethylene glycol (nozzle 1
) was readjusted so that the kneading force exerted by the screw was 17 KW. The screw was cooled over its entire length with 85°C water at an inflow rate of 500 l/h. The temperature of the effluent milled material was 140°C and was processed as described in Example 1. The pigment thus obtained exhibits high color strength as well as good brightness and good fastness to light and climate when it is added to an alkydal solution, and it is very suitable for use in an automotive solution. It was suitable for Example
67.5 kg/h crude perylenetetracarboxylic acid diimide, 0.7 k9/h dodecylamine and 37 kg/h
of sodium chloride was fed into a kneading apparatus as described in Example 1.

Approximately 5.0 kg/h diethylene glycol is metered through feed orifice 1, and 2.24 k/h
g/h diethylene glycol was metered in via nozzle 2. Adjust the shaft speed to 295 revolutions per minute,
Then, the main amount of diethylene glycol (nozzle 1) was readjusted so that the kneading force exerted by the screw was 19 KW. The screw was cooled over its entire length with a total inflow of 75°C water of 500 l/hr. The temperature of the effluent milled material was 130°C and it was treated as described in Example 1. The pigment thus obtained had a valuable reddish-purple shade and exhibited a very high color strength when it was added to an alkydal lacquer. Example 7
In the same manner as in Example 5, but using aniline instead of diethylene glycol as the solvent, high color intensity,
A pigment with great brightness and very good fastness properties was obtained.

[Brief explanation of the drawing]

1 to 3 are drawings of a kneading device for carrying out the method of the invention. 1, 2, 3... Supply nozzle.

Claims (1)

[Claims] 1 For liquid addition in a process for producing organic pigments using inorganic salts or organic salts that are soluble in water or soluble in water or bases and organic or inorganic solvents that do not significantly dissolve the organic pigment or the salt. in a continuously running kneading apparatus with spatially separated means of 10 seconds to 15 seconds.
into the pigment-salt-solvent mixture over a period of 300 to 5 minutes.
A method for producing organic pigments, characterized in that a shear gradient of 0.000/sec is applied and the amount of solvent is selected such that the force exerted by kneading is 1.7 to 6 KWh per kg of treated pigment.