Iron blue pigment, process for making the same and use

• US 4,378,995 A
• Filed: 10/06/1981
• Issued: 04/05/1983
• Est. Priority Date: 10/10/1980
• Status: Expired due to Term

• Current Assignee: Degussa AG (Rag-Stiftung)
• Original Assignee: Degussa AG (Rag-Stiftung)
• Inventors: Schaefer, Hans, Reinhardt, Helmut, Gratzfeld, Everhard, Clausen, Eva
• Primary Examiner(s): Morris, Theodore
• Application Number:
  US06/309,425
• Time in Patent Office: 546 Days
• Field of Search: 106/304, 106/171, 106/22, 106/20, 106/15.05, 423/367
• US Class Current: 106/15.05
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09C 1/26 Iron blues

Abstract

Iron blue pigment (DIN 55 906) is produced by white paste precipitation and subsequent oxidation of the white paste. Alakli or alkali metal ions i.e. sodium and potassium ions, cyanide or complex iron cyanide ions and iron ions are used as raw materials. The iron blue pigment according to the invention is characterized by a potassium content of 0.5-4.5% by weight, preferably 0.5-2.0% by weight, a sodium content of 0.2-1.0% by weight, an ammonium content of 2.0-4.5% by weight, preferably 3.0-4.5% by weight, a coloring power in accordance with DIN 53 204 and DIN 53 234 of 5-15% above the Vossen Blue 705 Standard and the following color intervals (determined in accordance with DIN 53 204 and DIN 53 234 in conjunction with DIN 6174, in relation to Vossen Blue 705 as standard):

ΔL: -0.7 to -1.5

Δa: -0.5 to 1.5

Δb: -0.6 to -2.3

ΔC: +0.5 to 2.0

In order to save potassium ions, the white paste precipitation of the iron blue pigment according to the invention is carried out in two phases, potassium ions being used as alkali ions in the first phase and sodium ions in the second phase. After removal of the reaction salts and addition of ammonium salts, the white paste suspension thus obtained is aged and subsequently oxidized to iron blue pigment by known methods. The iron blue pigment can be used as a pigment for the production of printing inks, colored paints, colored varnishes and as coloring agents for fungicides.

Claims

1. Iron blue pigment, characterized by a potassium content of 0.5-4.5% by weight, a sodium content of 0.2-1.0% by weight, an ammonium content of 2.0-4.5% by weight, a coloring power in accordance with DIN 53 204 and DIN 53 234 of 5-15% above the Vossen Blue 705 Standard and the following color intervals determined in accordance with DIN 53 204 and DIN 53 234 in conjunction with DIN 6174, in relation to Vossen Blue 705 as standard:

Δ

L;

-0.7 to -1.5

Δ

a;

-0.5 to 1.5

Δ

b;

-0.6 to -2.3

Δ

C;

0.5 to 2.0

2. Iron blue pigment according to claim 1 having a potassium content of 0.5-2.0% by weight and an ammonium content of 3.0-4.5% by weight.

3. In the process for the production of the iron blue pigment in accordance with claim 1 by means of white paste precipitation followed by oxidation of the white paste, the improvement which comprises carrying out the white paste precipitation with alkali metal ions, cyanide or complex iron cyanide ions and iron ions in two phases, adding potassium ions as alkali metal ions in the first phase of the white paste precipitation and sodium ions as alkali metal ions in the second phase, diluting the white paste suspension thus obtained with water, decanting the supernatant solution, adding ammonium salts, heating and maintaining the suspension at the boiling point thereof, cooling the suspension, adding inorganic salts in the form of an aqueous solution and oxidizing agents in the form of an aqueous solution and, after oxidation, separating the iron blue pigment from the solution.

4. The process according to claim 3 wherein precipitation of the white paste is effected by the simultaneous or successive introduction in the first phase of aqueous potassium ferrocyanide solution and iron (II) sulfate solution into a vessel with water under constant stirring, followed by the simultaneous or successive introduction under constant stirring in the second phase of sodium ferrocyanide solution and the same aqueous iron (II) sulfate solution as in the first phase.

5. The process according to claim 3 wherein the white paste precipitation is effected by the simultaneous introduction in the first phase into a reaction vessel under constant stirring of an aqueous hydrocyanic acid solution, an aqueous iron (II) sulfate solution and an aqueous potassium hydroxide solution, followed in the second phase by the simultaneous addition of an aqueous sodium hydroxide solution and the same aqueous iron (II) sulfate solution as in the first phase.

6. The process according to claim 3 wherein the white paste precipitation is effected by the simultaneous introduction in the first phase into a reaction vessel with water under constant stirring of an aqueous iron (II) sulfate solution and an aqueous potassium cyanide solution, followed in the second phase with continued stirring by the simultaneous addition of an aqueous sodium cyanide solution and the same aqueous iron (II) sulfate solution as in the first phase.

7. The process according to claim 3 wherein the white paste precipitation is effected by the simultaneous or successive introduction in the first phase under constant stirring into a vessel containing water in which necessary FeSO₄ has been dissolved, of an aqueous iron (II) sulfate solution and an aqueous potassium sulfate solution, followed in the second phase under continued stirring by the simultaneous or successive introduction of an aqueous sodium ferrocyanide and sodium sulfate solution and the same iron (II) sulfate solution as in the first phase.

8. The process according to claim 3 wherein the white paste precipitation is effected by the simultaneous introduction in the first phase, under constant stirring, into a reaction vessel containing an aqueous hydrocyanic acid solution of an aqueous iron (II) sulfate solution and a potassium carbonate solution, followed in the second phase by the simultaneous addition of an aqueous sodium carbonate solution and the same aqueous iron (II) sulfate solution as in the first phase.

9. The process which comprises utilizing the iron blue pigment according to claim 1 for the production of printing inks, colored paints, colored varnishes and coloring agents for fungicides.

10. A printing ink containing the iron blue pigment according to claim 1.

11. A colored paint containing the iron blue pigment according to claim 1.

12. A colored varnish containing the iron blue pigment according to claim 1.

13. A fungicide containing as coloring agent the iron blue pigment according to claim 1.