Metal azo pigments

Patent metadata

Field	Value
Publication number	US-10017645-B2
Application number	US-201715463284-A
Country	US
Kind code	B2
Filing date	Mar 20, 2017
Priority date	Mar 23, 2016
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

The novel yellow metal azo pigments based on at least three metal azo compounds which differ at least in the type of metal have 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 three 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 ,
R 5 is hydrogen or alkyl, and

Ni 2+ and Zn 2+ ions and at least one further metal ion Me, where
Me is a di- or trivalent metal ion selected from the group consisting of 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+ , Er 3+ , Tm 3+ , Yb 2+ , Yb 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 2+ , Ti 3+ , Zr 2+ , Zr 3+ , V 2+ , V 3+ , Nb 3+ , Cr 3+ , Mo 2+ , Mo 3+ , Mn 2+ , Cd 2+ and Pb 2+ ,
with the proviso that the amount of Zn 2+ and Ni 2+ ions together is 75 to 99.5 mol % and the amount of metal ions Me is 25 to 0.5 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 Ni 2+ ions in the metal azo pigment is 90:3 to 3:90, 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:
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;
the molar ratio of Zn 2+ to Ni 2+ ions in the metal are pigment is 80:5 to 5:80: and
the pigment comprises 0.05 to 4 mol of compounds of the formula (II) per mole of structural units of the formula (I).

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

4. The metal an pigment according to claim 1 , wherein:
R 1 and R 2 are OH,
R 3 and R 4 are ═O,
R 6 is hydrogen, and
the molar ratio of Zn 2+ to Ni 2+ ions is 60:33 to 33:60.

5. The metal azo pigments according to claim 1 , wherein Me is a di- or trivalent metal ion selected from the group consisting of La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ and Yb 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Y 3+ and Mn 2+ .

6. The metal azo pigments according to claim 1 , wherein 0.5 to 2.5 mol of compound of the formula (II) are present per mole of structural units of the formula (I).

7. The metal azo pigments according to claim 1 , wherein the pigments have a specific surface area of 50 to 200 m 2 /g.

8. The metal azo pigments according to claim 1 , wherein:
components a) and components b) are present together in the form of adducts;
R 1 and R 2 are OH;
R 3 and R 4 are ═O;
R 6 is hydrogen;
Me is selected from the group consisting of La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ and Sr 2+ ;
the molar ratio of Zn 2+ to Ni 2+ ions is 60:33 to 33:60;
1.0 to 2.0 mol of compound of the formula (II) are present per mole of structural units of the formula (I); and
the pigment has a specific surface area of 100 to 150 m 2 /g.

9. 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,

either simultaneously or successively with at least one nickel salt and at least one zinc salt and with at least one further metal salt selected from the group consisting of the 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+ , Er 3+ , Tm 3+ , Yb 2+ , Yb 3+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 2+ , Ti 3+ , Zr 2+ , Zr 3+ , V 2+ , V 3+ , Nb 3+ , Cr 3+ , Mo 2+ , Mo 3+ , Mn 2+ , Cd 2+ and Pb 2+ salts, where 0.03 to 0.95 mol of at least one nickel salt, 0.03 to 0.95 mol of at least one zinc salt and 0.005 to 0.25 mol of at least one metal salt from the abovementioned group are used per mole of compound of the formula (III), and the sum total of the molar amounts of all the metal salts used is 100 mol %.

10. The process according to claim 9 , 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 is selected from the group consisting of La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ and Sr 2+ salts.

11. Pigment preparations comprising the at least one metal azo pigment according to claim 1 and at least one auxiliary and/or additive.

12. The pigment preparation according to claim 11 , wherein the pigment preparation comprises the at least one further pigment, and the at least one further pigment comprises C.I. Pigment Green 36 and/or C.I. Pigment Green 58.

13. 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.

14. A colour filter, photoresist, printing ink, or liquid-crystal display comprising one or more metal azo pigments according to claim 1 .

15. The colour filter, photoresist, printing ink, or liquid-crystal display of claim 14 , wherein the at least one metal azo pigment is a component of a pigment preparation comprising the at least one metal azo pigment, 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.

16. A photoresist comprising one or more metal azo pigments according to claim 1 , one or more photocurable monomers, one or more reaction photoinitiators, and optionally one or more binders or dispersants and/or solvents.

17. The photoresist of claim 16 , wherein the at least one metal azo pigment is a component of a pigment preparation comprising the at least one metal azo pigment, 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.

18. A process for producing colour filters for liquid-crystal displays, the process comprising a) applying the photoresist according to claim 16 to a substrate, b) exposing the photoresist by means of a photomask, c) curing, and d) developing to provide a finished coloured colour filter.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Endert Sabine
• Linke Frank
• Borst Hans-Ulrich

Classifications

• C09B45/22 Primary

  containing other metals · CPC title

• G03F7/2004

  characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light · CPC title

• C09B67/0029

  of monoazo compounds · CPC title

• G03F7/0007

  Filters, e.g. additive colour filters; Components for display devices · CPC title

• G02F1/133514

  Colour filters · CPC title