Aqueous pigment preparations

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Reexamination Certificate

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C008S094260, C008S094330, C106S420000, C106S447000, C106S453000, C106S460000, C106S476000, C106S479000, C106S480000, C106S493000, C106S494000, C106S495000, C106S496000, C106S497000, C106S498000, C106S499000, C106S823000, C106S031600, C252S008570, C507S117000, C516S909000

Reexamination Certificate

active

06478866

ABSTRACT:

The invention relates to aqueous pigment preparations, to a process for their preparation and to their use for pigmenting natural and synthetic materials.
BACKGROUND OF THE INVENTION
Aqueous pigment preparations are already known from the prior art, for example DE-A 3 231 299, EP-A 816 406 and DE-A 41 25 458.
However, these pigment preparations have certain application disadvantages. The present invention, then, provides aqueous pigment preparations comprising
a) at least one pigment,
b) at least one condensation product based on
A) sulphonated aromatics,
B) aldehydes and/or ketones and optionally
C) one or more compounds selected from the group consisting of unsulphonated aromatics, urea and urea derivatives, and
c) at least one polyetherpolyol having an atmospheric pressure boiling point of greater than 150° C., in particular greater than 250° C.
DETAILED DESCRIPTION OF THE INVENTION
The pigments in the pigment preparations of the invention are not subject to any restriction. They can be organic or inorganic in nature. Suitable inorganic pigments for component a) are for example oxide pigments such as iron oxides, titanium dioxide, nickel oxides, chromium oxides and cobalt blue and also zinc sulphides, ultramarine, sulphides of the rare earths, bismuth vanadate and also carbon black, which is considered a pigment for the purposes of this invention. Particular carbon blacks are the acidic to alkaline carbon blacks obtained by the gas or furnace process and also chemically surface-modified carbon blacks, for example sulpho- or carboxyl-containing carbon blacks.
Suitable organic pigments are for example those of the monoazo, disazo, laked azo, &bgr;-naphthol, Naphthol AS, benzimidazolone, diazo condensation, azo metal complex, isoindolinone and isoindoline series, also polycyclic pigments for example from the phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole series. Suitable pigments also include solid solutions of the pigments mentioned, mixtures of organic and/or inorganic pigments with organic and/or inorganic pigments such as, for example, carbon black coated metal, mica or talc pigments, for example mica CVD-coated with iron oxide, and also mixtures between the pigments mentioned. Other suitable pigments include laked dyes such as Ca, Mg and Al lakes of sulpho- and/or carboxyl-containing dyes.
Particularly preferred pigments from the group of the azo metal complex pigments are pigments of the formula (III) or their tautomeric forms
where
R
1
, R
2
, R
3
and R
4
are independently hydrogen, alkyl, especially C
1
-C
6
-alkyl, cycloalkyl, especially C
5
-C
8
-cycloalkyl, aryl, especially optionally substituted phenyl, aralkyl, especially C
6
-C
10
-aryl-C
1
-C
4
-alkyl, such as benzyl or ethylphenyl, or hetaryl,
Z
1
to Z
4
are independently O or NR
5
, and
R
5
is hydrogen or cyano.
Particularly preferred pigments of the formula (III) conform to the formulae (VIII) and (IX)
especially in the form of their inclusion compounds or intercalation compound, in which case the included compound is preferably a cyclic or acyclic compound, preferably carboxylic or sulphonic acid amides, urea or substituted ureas and also heterocycles, especially 2,4,6-triamino-1,3,5-triazine, acetoguanamine and benzoguanamine.
Suitable salts and complexes for the compounds of the formula (III) are preferably the salts and complexes of mono-, di-, tri- and tetraanions with the metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn. Of particular importance are the nickel salts and complexes and their solid solutions, intercalation and inclusion compounds. Particular preference is given to an inclusion compound, intercalation compound, solid solution of a salt or of a complex of azobarbituric acid, particularly preferably of the azobarbituric acid-nickel-1:1 complex.
Condensation Product of Component b)
Based on it is to be understood as meaning that the condensation product may have been prepared from reactants in addition to A, B and optionally C. However, for the purposes of this application, preference is given to the condensation products prepared only from A, B and optionally C.
For the purposes of this invention, the sulphonated aromatics of component A) also include sulphomethylated aromatics. Preferred sulphonated aromatics are: naphthalenesulphonic acids, phenolsulphonic acids, dihydroxybenzenesulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4′-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl and benzenesulphonic acids.
The aldehydes and/or ketones of component B) are especially aliphatic, cycloaliphatic and also aromatic ones. Preference is given to aliphatic aldehydes, particular preference being given to formaldehyde and to other aliphatic aldehydes having 3 to 5 carbon atoms.
The unsulphonated aromatics of component C) include for example phenol, cresol, 4,4′-dihydroxydiphenyl sulphone or dihydroxydiphenylmethane.
Examples of urea derivatives are dimethylolurea, melamine and guanidine.
The preferred condensation product for component b) is a condensation product based on
A) at least one sulphonated aromatic selected from the group consisting of naphthalenesulphonic acids, phenolsulphonic acids, dihydroxybenzene-sulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4′-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl and benzenesulphonic acids,
B) formaldehyde and optionally
C) one or more compounds selected from the group consisting of phenol, cresol, 4,4′-dihydroxydiphenyl sulphone, dihydroxydiphenylmethane, urea, di-methylolurea, melamine and guanidine.
The preferred condensation product preferably has an average degree of condensation of 1 to 150, particularly preferably from 1 to 20, especially from 1 to 5.
The condensation products of component b) can be used as aqueous solution or as a suspension or as solid for example as powder or granules, preferably as spray-dried powder or granules.
Preferred condensation products of component b) have an inorganic salt content of below 10% by weight, preferably below 5% by weight, especially below 1% by weight, based on the aqueous solution or suspension of the component used or based on the solids of component b) used.
It is likewise preferable to use condensation products of component b) which are low in or free from residual monomer.
By low in monomer is understood a residual monomer content of less than 30% by weight, preferably less than 20% by weight, based on the condensation product, especially <10% by weight, preferably <5% by weight. Residual monomers in this context are the reactants used for preparing the condensation product.
Condensation products of this type which are low in salt and low in residual monomer are known from EP-A 816 406, for example.
The condensation products of component b) can be prepared for example by first preparing the sulphonated aromatics of component A) optionally in a mixture with unsulphonated aromatics of component C) by reacting the parent aromatics with a sulphonating agent, preferably sulphuric acid, especially concentrated sulphuric acid, chlorosulphonic acid, amidosulphonic acid or oleum.
The amount of sulphonating agent used per 1 mol of the parent aromatic of component A) is preferably 0.4 to 3.2 mol, especially 0.8 to 1.6 mol.
This is followed by the condensation with aldehydes and/or ketones of components B), preferably formaldehyde, optionally together with further compounds of component C). The condensation is preferably carried out in aqueous solution at a pH of 0 to 9. The condensation is preferably carried out using 0.4 to 1.5 mol, especially 0.4 to 1.0 mol, of component B) per mole of the sulphonated aromatic A) or per mole of a mixture of sulphonated aromatics of component A) and unsulph

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