DE1195710B - Process for the production of a recrystallization-resistant copper phthalocyanine pigment which is predominantly in the alpha form - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C09b

German class: 8 m -13

Number: 1195 710

File number: F 29888IV c / 8 m

Filing date: November 20, 1959

Opening day: July 1, 1965

Since the discovery that metal-free and metal-containing phthalocyanines have different physical properties There are numerous methods of transforming each shape became known to each other. The purpose of such conversion processes is to improve the application properties of the pigment dyes.

Among the metal-containing phthalocyanines, the chlorine-free copper phthalocyanine has excellent properties Lightfastness and the clarity of the color shade found particularly widespread application. Among these properties, the brilliance and, moreover, especially the color strength, are very extensive bound to the physical or crystallographic form of copper phthalocyanine and thus from depends on the type of manufacturing or conversion process.

The known processes for the preparation of chlorine-free copper phthalocyanine generally give a crude product, which is known as the /? form and which is due to the coarsely crystalline, weakly colored Structure not yet suitable as a pigment. This fact has to develop very much Numerous and different procedures led to the formation or conversion to a The purpose of pigment dye is to meet the ever increasing demands in this field. Acid pasting or dissolving of the crude product (/ S-form) in sulfuric acid leads to different results Concentration on the more finely divided "form (see British patent specification 711 677 and Fiat FINAL report, 1313, Vol. 3, pp. 446 to 448).

The form obtainable in this way is, however, especially when used in organic dye binders or diluents not resistant to recrystallization, d. H. the crystals become coarser on contact with organic solvents or thinners after prolonged storage, being a conversion to the more stable / 5 modification takes place with a coarser particle size and lower color strength.

Another process for converting the crude, coarsely crystalline / 5 form into the finely crystalline «form consists in grinding with grinding substrates in the absence of organic liquids (USA.Patent 2 402 167). The grinding of raw copper phthalocyanine or «-Cu-phthalocyanine with Salts in the presence of organic liquids leads to the process of US A. Pat. 2,556,730 and 2,645,643 as well as the German patent 846 757 to a very finely crystalline, coloring Process for the production of a recrystallization-resistant, predominantly in the α-form present copper phthalocyanine pigment

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Named as inventor:

Dr. Hans Raab, Cologne-Stammheim;

Dr. Reinhold Hörnle, Cologne-Flittard

valuable ^ modification. Especially when used

fine grinding substrates according to the process of US Pat. No. 2,669,569 are said to be made from the paste with acid unstable "form a stable" form can be obtained (column 3, lines 52 to 55). at After this treatment, a change in the color of the pigment to greenish blue was noticed, which, based on previous experience, allows the conclusion that here, too, predominantly /? - form and not the «-form arises.

When simply marrying the «or / S modification of Cu phthalocyanine with a number of organic liquids, for example aromatic or aliphatic hydrocarbons, a ^ modification with good properties is also obtained (U.S. Patent 2,556,726).

The conversion of the «form of Cu phthalocyanine by kneading with salt in the presence of each according to the progress of the process, differently dosed amounts of organic solvents should result in a solvent-resistant / 3-modification ' (U.S. Patent 2,486,304).

An amorphous form of the modification is obtained from the aqueous dispersion by mixing a finely crystalline form of the with an organic, water-insoluble liquid while stirring «Modification (U.S. Patent 2,540,775).

When grinding metal-containing phthalocyanines with grinding substrates and solid hydrocarbons one gets from the «- to ^ - modification (German Patent Specification 1,015,556).

The tendency of metal-containing phthalocyanine pigments to crystallize is said to be based on a special Procedure can also be remedied in that one

509 598/338

the crystals can be added to the grinding or kneading obtained by acid pasting.

Phthalocyanine pigments initially by contact with Preferably, a crude product is ground which

Organic solvents enlarged and caked on by phthalonitrile, sodium sulfate

finally by means of dry milling again and copper (I) salt has been obtained.

crushed (U.S. Patent 2,486,351). 5 When processing in a ball mill, care must be taken

In further processes it is recommended to ensure the crystalline, that the consistency of the grinding mixture

The tendency of phthalocyanine dyes to become sated by remaining powdery if possible, d. i.e. that the

intimate mixing with small amounts of zinc, aluminum grinding mixture does not become sticky. Usually

minium, titanium, or iron phthalocyanine too offset proportion of »organic auxiliaries«

wrestling (see French patent specification 1,145,176). io at 0.5 to 20%> calculated on the total amount

In addition, processes have become known through grinding or kneading mixing. In many cases

Mixing of chlorine-containing phthalocyanines in the preferred range is 1 to 2% organic

Phthalocyanine pigments or by using auxiliaries «.

of chlorinated phthalyl compounds as early as the _ The process enables the recrystallization

Production of the phthalocyanines, the inherent authenticity, largely in the form of the modification

shafts, including the ability to crystallize, to present pigment in technically more favorable

improve (French patents 1,116,429 time to get. In many cases, a grinding or

and 1 091 466). Kneading time from 2 to 50 hours. Of course

Common to all of these known processes is that they can be milled for any length of time, with the fact that the crude phthalocyanine pigment is first separated from the reaction mixture or recrystallization-resistant form obtained during the general no further conversion of the reaction mixture obtained. As is known, the process basically requires neither an increase in temperature, the only one of interest in the present case, nor a cooling of the grinding copper phthalocyanine produced by removing apparatus. In the course of the grinding, in particular neither phthalic anhydride or phthalonitrile in large ball mills, self-solvents often occur in the presence of suitable copper heating of the ground material of up to 70 to 80 ^D C compounds. When using phthalo instead. This increase in temperature has no post-dinitrile, there is still the possibility of partially influencing the properties or yields of the baking process without solvents, whereby the process product; On the other hand, however, it would not be necessary as a diluent for the grinding process,
Avoid an excessive increase in the temperature of an anhydrous inorganic salt, ζ. B. are: advantageously hydrocarbons, such as gasoline, sodium sulfate or table salt, is also used. But also naphthalene or preferably xylene

When working up for the purpose of the later halogenated hydrocarbons, such as chloroform or conversion of the crude ^ -modification into a 35 chlorobenzene; Alcohols, such as butanol or chloroethylfärberisch more suitable form, proceed as follows, alcohol; Phenols such as phenol or cresols; Ketones "that you can mix the raw melt with water, usually under like acetone; Carboxylic acids, such as formic acid or the addition of hydrochloric or sulfuric acid, and acetic acid; Acid amides, e.g. B. dimethylformamide; separating the dye by filtration. The nitrile like acetonitrile; Nitro compounds, ζ. Β, obtainable crude product is then a salt grinding 4 ° nitrobenzene; Amines such as aniline; Ether, such as anisole; or other conversion measures according to an or ester, such as butyl acetate.
subject to the procedures described above. The in

It has now been found that a proportion of salt which is soluble in industrial water can be washed out with

very easy to carry out process a water, optionally with the addition of acid, before

Recrystallization-resistant, predominantly in the 45 added sulfuric acid or hydrochloric acid, are removed.

«-Form present copper phthalocyanine pigment. This washout can already take place in the grinding vessel itself

if you are introduced to the manufacture of copper, whereupon you put the product on a

Sucks off phthalocyanine by baking phthalonitrile filter suction filter and then washes it out,

in the presence of copper salts and inorganic As far as the "organic auxiliaries" are not

Salts accumulating bakery crude product without separation 50 are also removed when washing with water,

the crude pigment with such organic these can either by distilling off with

Grind liquids and / or solids or water vapor before sucking off the reaction material

kneaded, which removed for the conversion of modifications or when drying the suctioned, with

metal-containing phthalocyanine pigments are used; water-washed filter material is evaporated,

who are. 55 The advantage of the method according to the invention lies

The following are the aforementioned once in the considerably simplified technical

organic liquids or solids of the single procedure, which in a single operation to

for the sake of it called "organic aid". a recrystallization-resistant product that

The method can expediently only in this way according to the best previously known methods

carry out that one can achieve the cooled raw baking 60 several operations. It is

product in the form of an easily divisible mass but also surprising that after this process

is present, in a suitable device, for example at all the «modification arises after from

It was wisely known in a ball mill, a pan mill or the above-mentioned literature that

a kneading apparatus, with the organic aid in the salt grinding of copper phthalocyanine

ground or kneaded, the organic auxiliary 65 raw products in the presence of organic liquids

medium or mixtures of different such or solids exclusively or at least at least

Aids already at the beginning of the grinding or mainly the / S modification, which is greener

Kneading, or at any other stage of the process, is created.

The end products which can be produced by the method according to the invention are predominantly in the form the «modification. The proportion varies depending on the type of "organic aids" selected / J modification generally between 5 and 30%. Here, however, it must be taken into account that at almost all known processes always contain mixtures of various modifications of the metal-containing phthalocyanine pigments develop.

IO

example 1

100 g of phthalonitrile, 24 g of copper (I) chloride and 400 g of sodium sulfate (anhydrous) are ground and intimately mixed and then heated to a temperature of 155 ° C in a suitable drying oven. the The temperature then rises by itself to 200 to 220 ° C. After cooling, 240 g of the Reaction mass is poured into a ball mill with a capacity of 51, which contains 6 kg of steel balls. After still 4 g of n-butanol have been added, the mixture is milled for 50 hours.

Then the mill is filled with hot water, run again briefly and the Separate the contents of the grinder from the balls using a coarse sieve. After filtering, wash out with water and drying at 50 ° C. gives a strongly colored, crystallization-resistant copper phthalocyanine which consists of almost 100% of the «-form.

Example 2

23 g of phthalonitrile, 5.5 g of copper (I) chloride and 92 g of sodium chloride are ground and mixed and, as described in Example 1, brought to implementation. The implementation mass is after Cool in a ball mill of 21 content with the addition of 2 g of xylene ground for 50 hours. the Customary work-up yields a copper phthalocyanine, 95% of which consists of the «form.

If, in this example, corresponding or comparable amounts are used instead of xylene Gasoline, chloroform, chlorobenzene, butanol, chloroethyl alcohol, phenol, cresols, acetone, formic acid, Acetic acid, dimethylformamide, acetonitrile, nitrobenzene, aniline, anisole, butyl acetate and ground 25 to 30 hours, you will get similar or equally good results.

Example 3

Used as an “organic auxiliary” instead of the n-butanol used in Example 1 Naphthalene and the ground reaction mass is subjected to suction and washing a steam distillation to remove the naphthalene, one also obtains copper phthalocyanine, which is almost 100% the «modification.

Example 4

350 g of a reaction mass prepared as in Example 1 are mixed with 70 g of dimethylformamide and g of water are kneaded in a Werner and Pfleiderer kneading apparatus of 11 content. During the During the kneading process, the temperature rises to 45 ° C. After a kneading time of 2 hours, the mass is with rinsed g of water from the kneader and, after adding a lot of hot water, filtered, washed and then dried at 50 ° C. 58 g of copper phthalocyanine are obtained, 55% of which comes from the «form consists.

Claims (3)

Patent claims: 1. Process for the production of a recrystallization-resistant, predominantly in the α-form present copper phthalocyanine pigment, characterized in that the in the production of copper phthalocyanine by baking phthalonitrile in the presence of copper salts and inorganic salts accruing crude baking product without separation of the raw pigment with such organic liquids and / or solids or ground Kneaded for the conversion of modifications of metal-containing phthalocyanine pigments have been used. 2. The method according to claim 1, characterized in that one grinds a crude product, obtained by baking phthalonitrile, sodium sulfate and copper (I) salt. 3. The method according to claim 1 and 2, characterized in that the organic liquids Hydrocarbons, preferably xylene, are used. Considered publications:
U.S. Patent Nos. 2,524,672, 2,540,775. 509 598/338 6.65 © Bundesdruckerei Berlin