Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...
Reexamination Certificate
1999-12-08
2001-06-26
Green, Anthony (Department: 1755)
Compositions: coating or plastic
Materials or ingredients
Pigment, filler, or aggregate compositions, e.g., stone,...
C008S661000, C106S031460, C106S411000, C106S412000, C106S413000, C540S122000, C540S139000, C540S140000
Reexamination Certificate
active
06251177
ABSTRACT:
The invention relates to solid preparations of phthalocyanine dyes, to a process for their preparation, and to their use for the dyeing of cellulosic materials.
Liquid preparations of copper phthalocyanine dyes are known, for example, from EP-A 596,383 (counterpart of U.S. Pat. No. 5,489,330) and JP-297 468 and are used for the dyeing of cellulosic materials, in particular of paper. Such liquid preparations, which generally have a dye content of from 5 to 25% by weight, are subject to high requirements as, regards storage stability. In this connection, they must not exhibit dye precipitation over a long period since, on the one hand, this changes the set dye content and, on the other hand, can block the metering equipment.
We have now found solid preparations of metal-containing or metal-free phthalocyanine dyes which
a) have an average particle size of greater than 100 &mgr;m, and
b) have a pH of greater than or equal to 10 when dissolved in 10 times the amount of water.
Solid preparations, which preferably have an average particle size like that of the preparations according to the invention, are generally referred to as granules. The preparations according to the invention preferably have an average particle size of from 100 to 800 &mgr;m, in particular from 100 to 400 &mgr;m. The pH of the aqueous solution which is automatically established
when the solid preparation is dissolved in 10 times the amount of water is preferably from 10 to 13, in particular from 11.0 to 12.5.
The preparation according to the invention preferably comprises metal-containing phthalocyanines, in particular Cu or Ni phthalocyanines. They particularly preferably comprise Cu phthalocyanines containing sulphonamide groups.
The metal-containing or metal-free phthalocyanines, in particular Cu phthalocyanines, carry, in a preferred embodiment, sulphonamide groups and sulphonic acid groups, where, in particular, from 0.5 to 3, in particular from 0.5 to 2, sulphonic acid groups are present per phthalocyanine molecule. Also preferred are phthalocyanines, in particular Cu phthalocyanines, which have an aliphatic sulphonamide as sulphonamide.
Particular preference is given to Cu phthalocyanines which, in the form of the free acid, carry
y SO
3
H groups and
x identical or different radicals of the formula —SO
2
NHB, where, if the radicals SO
2
NHB are different, their sum per molecule is x,
in which
B is an optionally substituted aliphatic or cycloaliphatic radical, and
x is from 1 to 3.5, and
y is from 0.5 to 3.0
and the sum x+y is from 2.5 to 4.
Preferably,
x is from 2 to 3.5, and
y is from 0.5 to 2.0
and the sum x+y is from 2.5 to 4, preferably from 3 to 4.
In a preferred embodiment, the solid preparation comprises copper phthalocyanines which, in the form of the free acid, correspond to the formula (I)
in which
CuPc is a copper phthalocyanine radical,
A is an optionally substituted straight-chain or branched C
2
-C
6
-alkylene,
R
1
and R
2
independently are hydrogen, or in each case are optionally substituted straight-chain or branched C
1
-C
6
-alkyl, in particular optionally substituted C
1
-C
6
-hydroxyalkyl, and are unsubstituted C
1
-C
6
-alkyl, or R
1
and R
2
together with the N atom to which they are bonded form a heterocyclic 5- or 6-membered ring which optionally contains other heteroatoms, in particular S, N and O,
x is from 1 to 3.5, in particular from 2 to 3.5,
y is from 0.5 to 3, in particular from 0.5 to 2
and the sum x+y is from 2.5 to 4, preferably from 3 to 4.
Possible substituents for straight-chain or branched C
2
-C
6
-alkylene in the definition of A are, for example, OH and/or C
1
-C
6
-alkoxy.
Possible substituents for straight-chain or branched C
1
-C
6
-alkyl in the definition of RI and R
2
which may be mentioned are, for example: OH, C
1
-C
6
-alkoxy, sulpho, amino, C
1
-C
6
-alkylamino and/or C
1
-C
6
-dialkylamino, where the alkyl radicals of the amino substituents are optionally substituted, preferably by OH, COOH and SO
3
H.
Preference is given to preparations which comprise copper phthalocyanine compounds of the formula (1), in which
A is ethylene or propylene,
R
1
and R
2
independently of one another are hydrogen or straight-chain or branched C
1
-C
4
-alkyl optionally substituted by OH, CO
2
H or SO
3
H, in particular unsubstituted C
1
-C
3
-alkyl, preferably CH
3
.
Particular preference is given to preparations comprising at least one compound of the formulae (IIa) to (IId)
in which
CuPc, x and y have the broadest meanings given for the abovementioned formulae.
The solid preparations according to the invention preferably comprise
from 60 to 98% by weight, in particular from 60 to 90% by weight, preferably from 70 to 85% by weight, of metal-containing or metal-free phthalocyanine dyes, in particular copper phthalocyanine dyes,
from 2 to 12% by weight, in particular from 5 to 10% by weight, of residual moisture,
from 0 to 25% by weight, in particular from 10 to 20% by weight, of inorganic salts,
from 0 to 4% by weight, in particular from 0 to 1% by weight, of further additives,
in each case based on the preparation, the sum of said additives giving 100%.
The preparations according to the invention are particularly low in dust and free-flowing and are characterized by very good storage stability. Furthermore, upon stirring into water, they exhibit a high dissolution rate and dissolve completely.
The invention further relates to a process for the preparation of the solid preparations according to the invention, which is characterized in that an aqueous solution or suspension of a metal-containing or metal-free phthalocyanine dye is adjusted to a pH such that, after dissolution of the dried phthalocyanine preparation in 10 times the amount of water, the pH is greater than or equal to 10, and this solution or suspension, optionally after the addition of further additives, is dried.
The aqueous solution or suspension to be dried preferably comprises from 10 to 50% by weight of metal-containing or metal-free phthalocyanine, and optionally inorganic salts, in particular neutral salts, such as, for example, sodium chloride and/or sodium sulphate. Suitable further additives are, for example, surfactants, wetting agents, dedusting agents etc. Preferred further additives are surfactants. The bases which may still be present are also included under further additives.
Preferably, the reaction solution or suspension is used directly as solution or suspension to be dried.
Particularly preferably, the alkaline solutions which are produced in the preparation of the phthalocyanine dyes are dried directly without flirther additives.
It can also be advantageous to purify, in particular to demineralize, the aqueous solution or suspension to be dried using membrane techniques prior to drying.
The drying to form the solid preparation according to the invention can be carried out in a variety of ways. Preference is given to spray drying, suitable spraying elements being, inter alia, either rotating discs or else single- or two-component nozzles. Preference is given in this connection to the single-component nozzle, in particular the swirling chamber nozzle, which is preferably operated at a feed pressure of from 20 to 80 bar.
The inlet and outlet temperatures for the spray drying are dependent on the desired residual moisture, on the safety measures and economical factors. The inlet temperature is preferably from 150 to 180° C., and the outlet temperature is from 40 to 80° C.
The base used to adjust the pH is preferably alkali metal hydroxide, in particular NaOH and/or LiOH.
The invention further relates to the use of the preparations according to the invention for the dyeing and printing of cellulosic materials, in particular paper and pulp after dissolution in water and optional adjustment of the pH to from 11 to 13, and for the preparation of printing inks, in particular those for inkjet printing, after dissolution of the preparations in an aqueous solvent. For the preparation of inkjet inks it is preferable that the preparation according to the invention has been deminer
Bayer Aktiengesellschaft
Gil Joseph C.
Green Anthony
Henderson Richard E. L.
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