Metal azo pigments

Patent metadata

Field	Value
Publication number	US-10059844-B2
Application number	US-201715463174-A
Country	US
Kind code	B2
Filing date	Mar 20, 2017
Priority date	Mar 23, 2016
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

The novel yellow metal azo pigments based on at least two metal azo compounds which differ at least in the type of metal have both improved dispersion properties and improved color strengths and are of excellent suitability for pigmentation of pigment preparations for a broad field of use.

First claim

What is claimed is:

1. Metal azo pigments comprising:
a) at least two metal azo compounds which differ at least in the type of metal and which each contain
structural units of the formula (I), or the tautomeric forms thereof,

in which
R 1 and R 2 are each independently OH, NH 2 or NHR 5 ,
R 3 and R 4 are each independently ═O or ═NR 5 , and
R 5 is hydrogen or alkyl, and

metal ions comprising Zn 2+ and/ Cu 2+ metal ions, and optionally at least one further metal ion Me, where Me is a di- or trivalent metal ion other than Zn 2+ and Cu 2+ ,
with the proviso that the amount of Zn 2+ and Cu 2+ metal ions together is 95 to 100 mol % and, if used, the amount of di- or trivalent metal ions other than Zn 2+ and Cu 2+ is 0 to 5 mol %, based in each case on one mole of all metal ions in the metal azo pigment, and
where the molar ratio of Zn 2+ to Cu 2+ metal ions in the metal azo pigment is 199:1 to 1:15, and

b) at least one compound of the formula (II)

in which R 6 is hydrogen or alkyl.

2. The metal azo pigments according to claim 1 , wherein:
the molar ratio of Zn 2+ to Cu 2+ metal ions in the metal azo pigment is 19:1 to 1:1,
R 5 is hydrogen or C 1 -C 4 -alkyl, and
R 6 is hydrogen, or C 1 -C 4 -alkyl, or C 1 -C 4 -alkyl mono- or polysubstituted by OH.

3. The metal azo pigments according to claim 2 , wherein:
R 1 and R 2 are OH;
R 3 and R 4 are ═O;
R 6 is hydrogen;
components a) and components b) are present together in the form of adducts;
the amount of Cu 2+ and Zn 2+ metal ions together is 100 mol %, based on one mole of all metal ions;
the molar ratio of Zn 2+ to C 2+ metal ions in the metal azo pigment is 9:1 to 2:1;
1.0 to 2.0 mol of compounds of the formula (II) is present per mole of structural units of the formula (I); and
the pigments have a specific surface area of 90 to 150 m 2 /g.

4. The metal azo pigments according to claim 1 , wherein components a) and components b) are present together in the form of adducts.

5. The metal azo pigments according to claim 1 , wherein:
R 1 and R 2 are OH,
R 3 and R 4 are ═O, and
R 6 is hydrogen.

6. The metal azo pigments according to claim 1 , wherein:
the metal ions comprise the Zn 2+ and Cu 2+ metal ions and the at least one further metal ion Me, where Me is a di- or trivalent metal ion selected from the group consisting of Ni 2+ , Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Yb 2+ , Yb 3+ , Er 3+ , Tm 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ , Y 3+ , Sc 3+ , Ti 2+ , Ti 3+ , Nb 3+ , Mo 2+ , Mo 3+ , V 2+ , V 3+ , Zr 2+ , Zr 3+ , Cd 2+ , Cr 3+ , Pb 2+ , Ba 2+ , and
the amount of Zn 2+ and Cu 2+ metal ions together is 95 to less than 100 mol % and the amount of the di- or trivalent metal ions other than Zn 2+ and Cu 2+ is up to 5 mol %, based in each case on one mole of all metal ions in the metal azo pigment.

7. The metal azo pigments according to claim 6 , wherein the at least one further metal ion Me, is selected from the group consisting of Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Yb 3+ , Er 3+ , Tm 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ , Y 3+ .

8. The metal azo pigments according to claim 1 , wherein the amount of Cu 2+ and Zn 2+ metal ions together is 100 mol %, based on one mole of all metal ions.

9. The metal azo pigments according to claim 1 , wherein 0.05 to 4 mol of compounds of the formula (II) is present per mole of structural units of the formula (I).

10. The metal azo pigments according to claim 1 , wherein the pigments have a specific surface area of 20 to 200 m 2 /g.

11. The metal azo pigments according to claim 1 , wherein the pigments produce an x-ray diffractogram wherein, between the interplanar spacings of d=14.7 (±0.3) Å and d=11.8 (±0.3) Å, the x-ray diffractograms have at least one signal S having an intensity I which exceeds the background value by 3 times the square root of this value.

12. A process for producing the metal azo pigments according to claim 1 , the process comprising contacting:
a compound of the formula (III), or tautomers thereof,

in which
X is an alkali metal ion,
R 1 and R 2 are each independently OH, NH 2 or NHR 5 ,
R 3 and R 4 are each independently ═O or ═NR 5 , and
R 5 is hydrogen or alkyl,

with at least one compound of the formula (II)

in which R 6 is hydrogen or alkyl,

simultaneously or successively with at least one zinc salt and at least one copper salt and optionally with at least one further metal salt of a di- or trivalent metal other than zinc and copper, where 0.06 to 0.995 mol of at least one zinc salt, 0.005 to 0.94 mol of at least one copper salt, and, if used, 0.05 to 0 mol of at least one further metal salt are used per mole of compound of the formula (III), and where the sum total of the molar amounts of these metal salts together is one mole.

13. The process according to claim 12 , wherein:
X is a sodium or potassium ion;
R 5 is hydrogen or C 1 -C 4 -alkyl;
R 6 is hydrogen or C 1 -C 4 -alkyl, or C 1 -C 4 alkyl mono- or polysubstituted by OH, and
the at least one further metal salt of a di- or trivalent metal is selected from the group of Ni 2+ , Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Yb 2+ , Yb 3+ , Er 3+ , Tm 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ , Y 3+ , Sc 3+ , Ti 2+ , Ti 3+ , Nb 3+ , Mo 2+ , Mo 3+ , V 2+ , V 3+ , Zr 2+ , Zr 3+ , Cd 2+ , Cr 3+ , Pb 2+ and Ba 2+ salts.

14. Pigment preparations comprising the at least one metal azo pigment according to claim 1 and at least one auxiliary and/or additive selected from the group consisting of surface-active agents, surface-covering agents, bases and solvents, and optionally at least one further pigment.

15. The pigment preparation according to claim 14 , wherein the pigment preparation comprises C.I. Pigment Green 36 and/or C.I. Pigment Green 58.

16. A process for producing a pigment preparation comprising the at least one metal azo pigment according to claim 1 , the process comprising mixing and/or grinding the at least one metal azo pigment with at least one auxiliary and/or additive selected from the group consisting of surface-active agents, surface-covering agents, bases and solvents, and optionally with at least one further pigment.

17. A colour filter, photoresist, printing ink or liquid-crystal display comprising the at least one metal azo pigment according to claim 1 .

18. A photoresist comprising the at least one metal azo pigment according to claim 1 , one or more photocurable monomers, and one or more reaction photoinitiators and optionally one or more binders or dispersants and/or solvents.

19. A process for producing colour filters for liquid-crystal displays with the photoresist according to

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Linke Frank
• Borst Hans-Ulrich
• Endert Sabine

Classifications

• G02F1/133516

  Methods for their manufacture, e.g. printing, electro-deposition or photolithography · CPC title

• G03F7/105

  having substances, e.g. indicators, for forming visible images · CPC title

• C09D11/037

  characterised by the pigment · CPC title

• C09D11/322

  Pigment inks · CPC title

• G03F7/32

  Liquid compositions therefor, e.g. developers · CPC title