CS239444B1 - A method of micronizing beta modification of copper phthalocyanine - Google Patents

Abstract

A method for micronizing beta modification of copper phthalocyanine, in which an aqueous suspension of beta modification of copper phthalocyanine with a concentration of 50 to 300 g/l is milled in the presence of 2 to 30 g of a compound of the formula R,-C (CH2)n-SO θΚ ® , and where R, is alkyl or alkonyl with the number of carbon atoms from 1 to 6, n ■ 2 to 4, M ■ Na or K, at a temperature of 20 to 80 °C and at a pH of 7 to 10. The surfactants used do not need to be removed after micronization and do not affect the further processing of copper phthalocyanine.

Description

The invention relates to a process for the micronization of crude or purified phthalocyanine by a beta modification medium, wherein the micronization product is particularly suitable for further processing to the final form intended for pigmentation of intaglio bars.

Copper phthalocyanine and e-industry produce in the shoe modification, an unpigmented state, and crystals of velikoatoch up to 100 μη. Crude copper phthalocyonine particles are pounded to a pigment size, which is a prerequisite for successful application. This is done by melting the aicronization, which produces the pigment form of copper phthalocyonin shoe modification with a mean primary particle size of about 0.05 µm. From a coloristic point of view, this size of baseball is optimal.

The micronization of copper phthalocyanine is carried out, for example, by grinding in the presence of an organic solvent (U.S. Pat. Nos. 2,556,726, 2,556,728, 2,556,730), or in aqueous suspensions (U.S. Pat. Nos. 2,816,115, 3,999,862) utilizing e.g. bead mills, optionally in the presence of surfactants, (U.S. Pat. No. 3,775,149). Pigmented beta form can also be obtained by aicronization in knots (U.S. Patent No. 2,982,666).

The pigment form of the beta modification of phthalocyanine can often be further processed after aicronization according to the particular application requirements for the resulting commercial product.

This further treatment is, however, fundamentally influenced by the micronization process and, in particular, by the surfactants which are used in the alkanolization process in an alkali process. For example, commonly used surfactants based on formaldehyde condensation products with 1- or 2-naphthalenesulfonic acid, or on eulfonated phenol, creaol and formaldehyde condensates, cannot be used in micronizing copper phthalocyanine if the final form intended for pigmentation of gravure inks. In this case, these excipients negatively affect the application properties of the final product.

In general, excipients used in micronizing copper phthalocyanine with the cell:

a) it can be removed before further processing (ie after micronization), or - if not removed, b) it must not adversely affect both the further processing of micronized copper phthalocyanine to the final form and the application properties of the resulting product.

Research has now found that micronization of copper phthalocyanine beta modification can be carried out by the process of the present invention using surfactants which do not have to be removed after micronization prior to further processing and which do not adversely affect further processing of micronized copper phthalocyanine, such as pigment preparations intended for the production of gravure inks.

The method for micronizing a copper phthalocyanine beta modification according to the invention is characterized in that an aqueous suspension of copper phthalocyanine beta modification at a concentration of 50 to 300 g / l mill in a bead mill in the presence of 2 to 30 g / l of a compound of the formula.

(AND)

N.

wherein H 1 is an unsaturated or saturated alkyl having a carbon number of 13 to 2 ', R _2' 3 'arylalkyl having a carbon number of 1 to 6, n = 2 to 4, M = Na or K, at 20 to 80 ° C and at .

pH 7-10.

According to the present invention, the crude copper phthalocyanine beta modification can be micronized made, for example, by a continuous process from phthalic anhydride, urea and cuprous chloride (U.S. Patent No. 177,268, 210,288). Advantageously, copper phthalocyanine produced by a continuous process and further purified, for example using dilute sulfuric acid, can be used, whereby a raw material having a content of 92 to 99% by weight is obtained for micronization. copper phthalocyanine.

Aqueous suspensions of 50 to 300 g / l of copper phthalocyanine and 2 to 30 g / l of a compound of formula (I), which may be, for example, N-methyl-N-, are prepared from crude or purified copper phthalocyanine. (2-sodium trimethylsulfonate) -8-hepta-decenecarboxamide, N-propyl-N- (2-sodium trimethylsulfonate) -hexsecenecarboxamide, etc.

The aqueous suspension of copper phthalocyanine and the surfactant of formula (1) is micronized by grinding, e.g., in pearl dispersants, to the appropriate pigment particle size. Micronization is carried out at a temperature of 20 to 80 ° C and a pH in the range of 7 to 10.

The micronization process of the present invention produces copper phthalocyanine beta of the desired particle size, wherein the micronization product, i.e. aqueous dispersion of copper phthalocynin, can be directly used for further pigment processing and preferably to a final form suitable for pigmenting intaglio inks, e.g. in accordance with the procedure The surfactant of the formula (1) present in the copper phthalocyanine dispersion has no adverse effect on the further processing of the dispersion or on the application properties of the product. The surfactants used for micronization according to the invention are biodegradable so that their presence in the waste water is not ecologically harmful.

The examples below illustrate embodiments of the invention.

He did

A vertical laboratory bead mill (vessel diameter 0.078 m, disc diameter 0.060 m) was charged with 145 ml of water, 1.8 g of N-methyl-N- (2-sodiumethylsulfonate) -8-heptadecenecarboxamide and was run under stirring at 300 rpm 26 g of copper phthalocyanine (98.0%) were gradually added over 2 minutes. Thereafter, 130 ml of ballotin having a glass bead diameter of about 0.7 mm was added to the mill over a period of 3 minutes. Micronization was then performed at 2000 rpm. The temperature of the mixture was maintained at 40 ° C, the pH of the dispersion was 7.8. Dispersion samples were taken during micronization and the size and distribution of primary copper phthalocyanine particles were evaluated using an OEM-100 electron microscope. The results (logarithmic-normal distribution parameters) are given in Table I.

Table 1

Evaluation of particle size in micronization (μη).

Time (h) Modal size Median ^X -.x tp P 0.00 9.07 »10 ^-2 9,86.10 ^-2 0.37 2.89 0.185 0.25 8,12.10 ^-2 8,58.10 ^-2 0.33 3.03 0.204 1.00 6,88.10 ^-2 7,95.10 ^-2 0.29 2.60 1,786 2.00 5,37.10 ^-2 6,74.10 ^-2 0.24 2.61 0.219 3.50 4,18.10 ^-2 5,77.10 ^-2 0.23 2.61 0.188

^X max ³ maximum particle size tp = shape distance (distance / width) p - polydispersity

From Table 1 it is evident that in about 3 hours, the micronization will reduce the mean particle size to about 0.05 μ », which is the desired value.

The dispersion after micronization was separated from the ballotin, and then it was subjected to the procedure of US. of the author's certificate No. 234 629 processed into the final form intended for the production of gravure inks:

A solution of 12.0 g of oleic acid diethanolamide in 24 g of ethanol was added to the dispersion. The mixture was stirred for 10 minutes, then heated to 85 ° C and acidified to pH = 1.5 with hydrochloric acid. The mixture was stirred at 85 ° C for 60 minutes. The product was then filtered off, washed with water and dried at 90 ° C.

The resulting pigment preparation was evaluated in a rotogravure barium, the product being easily dispersed and the test prints having satisfactory coloristic parameters.

The pigment preparation prepared by the above process from the dispersion obtained by micronizing copper phthalocyanine in the presence of the formaldehyde condensation product with 2-naphthalenesulfonic acid was coloristically unsatisfactory in the intaglio ink.

Example 2

In a horizontal bead mill type KDL Special 0.6 L VA Bachofen, 1.5 kg copper phthalocyanine suspended in 8.5 L water was micronized in the presence of 0.06 kg N-ethyl-N- (2-sodiumethylsulfonate) -8-heptadecenecarboxamide . A mean particle size of copper phthalocyanine of 0.04 to 0.06 μη was achieved at 2 passes of the slurry through the mill at a peripheral wheel speed of 15 m / s. The dispersion was then processed in an analogous manner to that of Example 1. The product was fully suitable for the preparation of intaglio ink.

Claims (1)

WHERE TO INVENT THE INVENTION A method of micronizing a copper phthalocyanine beta modification in the presence of a surfactant, characterized in that an aqueous suspension of copper phthalocyanine beta modification at a concentration of 50 to 300 g / l is ground in the presence of 2 to 30 g / l of a compound of the formula alkenyl having a carbon number of 1 to 6, n = 2 to 4, M = Na or K, at a temperature of 20 to 80 ° C and a pH of 7 to 10.