DE2256544A1 - COPPER PHTHALOCYANINE PIGMENT AND METHOD FOR MANUFACTURING IT - Google Patents

Description

PATENT LAWYERS DR.-ING. H. FIMCKE

DIPL .-! N G. H BOHR 1 7th NOV. 1972

DIPL-ING S. STAEGER MÖNCHEN 5 MOLLERSTR. 31

Imperial Chemical Industries Limited, London, Great Britain

Copper Phthalocyanine Pigment and Process for its production

The invention relates to new copper phthalocyanine pigments, which are suitable for solvent systems.

-2-22565U

It is known to use copper phtheloeyanine as Figment ill solvent systems, eg paint * or printing inks based on an organic liquid resin binder is ground, but the time sum elections of crude copper phthalocyanine to a sufficient Pigeentform is over moderately long · (lower crude copper a copper is to be understood that still no Pigmentierungsbehandlung like BB Bald ode with a Saia * "processing ψι one y fas te with a ßJnire) · It has now been found that such long times for grinding can be considerably shortened without the de? Bisperaion may affect wew * one instead of, raw copper phthalocyanine elm votm. «Ü & lfttl? · Phthalocyanine vfjpweMftt * ·! t # iliif4l «a sjure» and / or

so that 20 M «100 woUto *> Qwwm Wf IQO phthalocyanine molecules are present, that is, every copper phthalocyanine molecule on average

9QtItWI * t t

- ■ * "" ■ /. 2.2565A4

Although copper phthalocyanine rail; a small amount of carboxylic acid "and / or Cai ^ oBjmi & gruppen" already in US Pat. No. 2,805,957 ", these in turn contain only 2 to 15 such groups per 100 ICupferphthalocjaniijmoleküle, and such modified copper phthalocyanines show no significant advantages over copper phthaloeyanine itself with regard to the time it takes to produce the pigment » properties in solvent systems.

According to the invention, a caper phthalocyanine would be used suggested that 20 to 100 carboxylic acid and / or Carbon arid groups on 1OvO Kopferpthalocyeninmolekiile contains ;.

Another hot feature of the invention is a Procedure for the production of jferphthalocyanine with the specified amounts of carboxylic acid and / or Carbonamidgruj) pen proposed, which consists in that iaan a mixture of Hithalsäiareanhydrid, 3? Rimellitic anhydride or smiaellitic acid, Urea and copper (II) chloride in one organic Solvents such as nitrobenzoi, eerosin or trichlorobenzene heated, the trimellitic anhydride or the CDrrunellitic acid in an amount of 5 to 25 mol% refer to all anhydrides or

«. / 4. -. 3098 ^ 1 / 10.91

Anhydrides and acids is used.

Dae inventive method can in the normal manner for the production of copper phthalocyanine conditions are preferably carried out at a temperature between 150 ° and 200 ⁰ C, the reaction mixture is preferably a catalyst for the reaction, for example Hatriummolybdat contains. At the end of the reaction, the mixture can be poured into water containing sulfuric acid, whereupon the mixture is heated and. the crude, modified Eupf erphthalocyanine filtered off, washed with water

and is dried. But it is also possible to remove the solvent by steam distillation. before the raw pigaent is filtered off and dried.

In a preferred embodiment of the invention, the Eupferphthalocyanin contains 30 to 60 carboxylic acid » and / or carbonamide groups on 100 Eupferphthalocyanine » molecules.

They invented copper phthalocyanines with Carboxylic acid and / or carbonamide groups can be processed into the pigaent form, while in an organic liquid in the presence of a

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Dispersant and / or a resin binder, which is preferably soluble in the organic liquid, are ground. As examples of Organic liquids can be aliphatic hydrocarbons, including petroleum fractions and aromatic hydrocarbons such as toluene and xylene. Preferred dispersants are used the condensates of polyesters containing hydroxyl groups, such as polyhydroxystearic acid, with dyes that contain reactive halogen atoms, such as ζ · Β ·! Eris (trichloromethyl) phthalocyanine, such as them in German patent application P 22 06 611 · 1 of the applicant are described in fs? ag @. As Ears « binders that can be used e.g. those in paint and

commonly used, "for example Alkylhsrsse, Ilelamine formaldehyde resins and metal resinates such as Zinc or caloium resinate «in carrier ·

The organic liquid dispersion obtained can be converted into a paint or printing ink by mixing them with the components commonly used in the manufacture of such paints will.

In the following, the invention is purely by way of example

309821/10 * 1 - 6 -

225654A

explained in more detail using an exemplary embodiment » the specified parts and percentages being based on weight.

example

A mixture of 1260 parts of phthalic anhydride, 182 parts of trimellitic anhydride (10 mol% based on the total amount of anhydride), 330 parts of anhydrous copper (II) chloride, 14 parts of sodium molybdate, 770 parts of urea and 3935 parts of 1,2,4-trichlorobenzene is 30 minutes stirred at 150 ^° C. under reflux. Bern reaction mixture is added rapidly to a slurry of 1540 parts of urea in 4535 parts of 1,2,4-trichlorobenzene, wherein the temperature drops to 110 ⁰ C. You temperature of the reaction mixture then Wirde while 195 Hinuten to 170 ° C brought, held there 90 Hinuten while 45 Hinuten brought to 190 ⁰ C and held for 90 finally Hinuten to 190 ⁰ C. The reaction mixture is cooled, poured into 12,000 parts of water containing 1,194 parts of sulfuric acid and then heated ^{to 95 ° C. for 4 hours.} The precipitated solid is then filtered off, washed with water and then dried.,

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The product obtained is a. modified copper phthalocyanine with 40 carboxylic acid and / or carbonamide groups per 100 Eupferphthalocyaninmoleldile.

The control pigments were analogous

A) a crude copper phthalocyanine, the 1 260 Parts of phthalic anhydride and 182 parts of trimellitic anhydride have been replaced by 1 400 (Delle phthalic anhydride, and

B) a copper phthalooyanine with 12 carboxylic acid and / or Carbonamide groups on 100 phosphorus phthalocyanine molecules (according to US Pat. No. 2,805,957), the 1,260 parts of phthalic anhydride and 182 parts Parts trimellitic anhydride by 1,358 parts, phthalic anhydride bnr · 55 parts® trimellitic anhydride were replaced,

By optically exploiting a solution to the connection According to this example in sulfuric acid, it was found that its inherent color number is 88.4% that of a analogous solution of the control compound A, while the inherent color number of the control compound B was 93.4% that of control A compound.

A mixture of 724 parts of the compound according to

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this example, 160 parts of a condensate of polyhydroxystearic acid and copper tris (chloromethyl) phthalocyanine (produced according to example 3 of German patent application P 22 06 611.1), 128 parts of zinc resinate and 988 parts of a petroleum fraction boiling between 100 and 120 ° 0 becomes 96 Hours worked in a laboratory ball mill, whereby a liquid, deflocculated dispersion of the modified copper phthalocyanine pigment results This dispersion does not contain any particles that are larger than 3 μ, the greater number of the particles has a particle size of less than 1 μ. This dispersion is then incorporated into an engraving color, which is then used to print on paper.

For comparison, a mixture of 640 parts of the control compound A (this amount is inherent Color number according to the 724 parts of the invention Compound equivalent), 160 parts of the described condensate of polyhydroxystearic acid, 128 parts Zinc resinate and 1,072 parts of the same petroleum fraction (to achieve the same total dispersion amount) Processed analogously in the ball mill for 216 hours, with a sample being taken after the first 96 hours. Portions of the dispersions obtained after 96 hours and after 216 hours are analogously in engraving inks

309821/1091 ~ ⁹ ~

incorporated, and swar such that the weight ratio the dispersion and the binder of the paint is the same as in the case of the engraving with the one according to the invention Link. The colors obtained are then printed on paper »

A mixture of 685 parts is also used for comparison of the control compound JJ (this amount is the inherent color number after the 724 parts of the invention Compound equivalent), 160 parts of the condensate of polyhydroxystearic acid, 128 parts of zinc resinate and T 027 parts of the same petroleum fraction (to achieve the same total dispersion amount) 96 hours processed analogously in the ball mill. The dispersion obtained is incorporated into an engraving paint, in such a way that the weight ratio of the dispersion to the binder is the same as in the other colors «, then paper is printed with the color.

The color strength of the viex printed products is then assessed. The relative color strengths in comparison with the color strength of the color with the control compound A ₁ which was milled for 216 hours are as follows:

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Printing with a compound according to the invention

(Grinding time at 96 hours) 105

Bridge with control connection B

(Payment time 96 hours) β?

Print with control connection A

(Grinding time 96 hours) 77

Print with control connection A

(Payment time 216 hours) 100

If one converts these relative color strengths, so that it is based on (in each case the same quantities of compounds and not on the same inherent color values are, the result for the compound according to the invention is still a ratio of 93 * die is significantly higher than the ratio for the control compound A after a grinding time also of 96 hours.

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Claims (1)

Claims 1. Copper phthalocyanine, characterized in that there are 20 to 100 carboxylic acid "" and / or carbonamide groups for every 100 Jöipfer phthalocyanine molecules " 2, Enpferphthalocyanin according to claim 1, characterized in that there are 30 to 60 carboxylic acid and / or, Carbonamide groups on 100 copper phthalocyanine molecules contains. 3, a method for producing a copper phthalocyanine according to claim 1, characterized in that a mixture of phthalic anhydride, trimellitic anhydride odea? iPrimellitic acid ©, urea and cupric chloride is heated in an organic solvent, the used. Amount! Trimellitic anhydride or 3? rimellitic acid based on 5 to 25 mol% on the total amounts of anhydrides or anhydrides and acids used. 4, dispersion of a copper phthalocyanine according to claim or 2 in an organic liquid with one in it dissolved dispersant. - 12 309821/1091 Dispersion according to Claim 4, characterized in that a condensate of polyhydroxysteeric acid is used as the dispersant with Eupfer-tris (chloriaethyl) - phthalocyanine is used. PATENT LAWYERS INt-HIG. H. flKCL, D'Pl.-IHG. H. BOHI CS StAlSUt 309821/1091