Process for the simultaneous tanning and dyeing of collagen containing fibrous material
A process for the simultaneous tanning and dyeing of collagen containing fibrous material, wherein the said material is treated with a liquor containing at least one reactive dyestuff selected from the group of formula (1) and (2) wherein A 1 , A 2 and A 3 are each independently of the others the radical of a monoazo, polyazo, metal-complexed azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore having at least one sulfo group, B is an organic bridge member, Q 1 , Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, G 1 and G 2 are halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, (Z 1 ) 2-3 is 2 to 3 identical or different fiber reactive radicals, Z 2 and Z 3 are each independently of the other identical or different fiber reactive radicals, and b is the number 0 or 1, by combining two steps of leather production, tanning and dyeing, into a single step, thus, preserving resources and reducing the environmental impact.
1. A process for the simultaneous tanning and dyeing of collagen containing fibrous material, the process comprising
treating a collagen containing fibrous material with an aqueous liquor comprising at least one reactive dyestuff, wherein the aqueous liquor has a pH less than a pH required to fix the at least one reactive dyestuff, and wherein treating comprises distributing the at least one reactive dyestuff throughout a thickness of the material; and
increasing the pH of the aqueous liquor to simultaneously tan the fibrous material by crosslinking the fibrous material and fix the dye to the fibrous material, wherein the at least one reactive dyestuff is selected from the group of formula (1) and (2)
wherein
A 1 , A 2 and A 3 are each independently of the others the radical of a monoazo, polyazo, metal-complexed azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore having at least one sulfo group,
B is an organic bridge member,
Q 1 , Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 -C 4 alkyl,
G 1 und G 2 are halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl,
(Z 1 ) 2-3 is 2 to 3 identical or different fiber reactive radicals,
Z 2 and Z 3 are each independently of the other identical or different fiber reactive radicals, and b is the number 0 or 1
wherein the process does not include chrome, vegetable and aldehyde tanning agents.
2. A process according to claim 1 , wherein
Z 1 , Z 2 and Z 3 are each independently of the others a radical of the formula
in which
Hal is chlorine or bromine;
X 1 is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;
T 1 independently has the meaning of X 1 , or is a substituent which is not fiber reactive, or is a fiber reactive radical of the formula
in which
R 1 , R 1a and R 1b independently of one another are each hydrogen or C 1 -C 4 alkyl,
R 2 is hydrogen, C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano or a radical
R 3 is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C 1 -C 4 alkoxycarbonyl,
C 1 -C 4 alkanoyloxy, carbamoyl or the group —SO 2 —Y,
alk and alk 1 independently of one another are linear or branched C 1 -C 6 alkylene, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen,
Q is a radical —O— or —NR 1 —, in which R 1 is as defined above,
W is a group —SO 2 —NR 2 —, —CONR 2 — or —NR 2 CO—, in which R 2 is as defined above,
Y is vinyl or a radical —CH 2 —CH 2 —U and U is a group which can be split off under alkaline conditions,
Y 1 is a group —CH(Hal)-CH 2 -Hal or —C(Hal)═CH 2 and Hal is chlorine or bromine and
l and m independently of one another are an integer from 1 to 6 and n is the number 0 or 1;
and
X 2 is halogen or C 1 -C 4 alkylsulfonyl;
X 3 is halogen or C 1 -C 4 alkyl; and
T 2 is hydrogen, cyano or halogen.
3. A process according to either claim 1 or claim 2 , wherein
Z 1 , Z 2 and Z 3 are each independently of the others a radical of the formula (3a), (3b) or (3f) according to claim 2 ,
in which
Y is vinyl, β-chloroethyl or β-sulfatoethyl,
R 1a is hydrogen,
I is the number 2 or 3,
X 1 is halogen,
T 1 is C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, hydroxyl, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or sulfo, morpholino, phenylamino or N—C 1 -C 4 alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or methoxy and in which the alkyl is unsubstituted or substituted by hydroxy, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups, or
T 1 is a fiber reactive radical of the formula
in which
Y is as defined above and
Y 1 is a group —CH(Br)—CH 2 —Br or —C(Br)═CH 2 .
4. A process according to claim 1 wherein
B is a C 2 -C 6 alkylene radical, which may be interrupted by 1, 2 or 3 —O— members and is unsubstituted or substituted by hydroxyl, or phenylene substituted by one or two sulfo groups, and
G 1 and G 2 are each independently of the other chlorine or fluorine.
5. A process according to claim 1 wherein A 1 A 2 and A 3 are each independently of the others a monoazo or polyazo chromophore.
6. A process according to claim 1 wherein
A 1 , A 2 and A 3 are each independently of the others a radical of the formula
wherein
(R 4 ) 0-3 denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl, halogen, amino, hydroxy, carboxy and sulfo,
(R 5 ) 0-2 denotes from 0 to 2 identical or different substituents from the group hydroxy, amino, N-mono-C 1 -C 4 alkylamino, N,N-di-C 1 -C 4 alkylamino, C 2 -C 4 alkanoylamino and benzoylamino, and q in formula (5) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
(R 5 ) 0-2 is as defined above, and
q in formula (6) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
(R 6 ) 0-3 and (R 7 ) 0-3 independently of the other denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo, and
q in formula (7) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
R 8 and R 10 are each independently of the other hydrogen, C 1 -C 4 alkyl or phenyl, R 9 hydrogen, cyano, carbamoyl or sulfomethyl, and
q in formula (8) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
(R 11 ) 0-3 is as defined for (R 4 ) 0-3 ,
(R 12 ) 0-3 denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, halogen, amino, carboxy and sulfo,
(R 13 ) 0-3 is as defined for (R 4 ) 0-3 , or R 13 is a radical —N═N-Ph, wherein Ph is phenyl that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or sulfo,
s is the number 0 or 1, and
q in formula (9) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
(R 11 ) 0-3 and (R 13 ) 0-3 independently of the other are as defined above,
(R 14 ) 0-2 denotes from 0 to 2 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, halogen, carboxy, sulfo, hydroxyl, amino, N-mono-C 1 -C 4 alkylamino, N,N-di-C 1 -C 4 alkylamino, C 2 -C 4 alkanoylamino and benzoylamino, and
q in formula (10) is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
the benzene nuclei do not contain any further substituents or are further substituted by
C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, halogen or by carboxy, and
q is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore;
wherein
Pc is the radical of a metal phthalocyanine,
W′ is —OH and/or —NR 16 R 16 ′ and R 16 and R 16 ′ are each independently of the other hydrogen or C 1 -C 4 alkyl that is unsubstituted or substituted by hydroxyl or by sulfo,
R 15 is hydrogen or C 1 -C 4 alkyl,
A is a phenylene radical that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or by sulfo, or is a C 2 -C 6 alkylene radical,
k is from 1 to 3, and
q is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore; or
wherein
A′ is a phenylene radical that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or by sulfo, or is a C 2 -C 6 alkylene radical,
r independently is the number 0, 1 or 2, and
v and v′ are each independently of the other the number 0 or 1.
7. A process according to claim 6 , wherein A 1 , A 2 and A 3 are each independently of the others a radical of formula (5), (6), (9) or (10).
8. A process according to claim 1 wherein the collagen containing fibrous material is treated with a liquor containing at least one reactive dyestuff of formula (1).
9. A process according to claim 8 , wherein the collagen containing fibrous material is treated with a liquor containing at least one reactive dyestuff of formula
A 1a -(Z 1 ) 2-3 (1a)
together with at least one reactive dyestuff of formula
A 1b -(Z 1 ) 2 (1b),
wherein
A 1a is a radical of formula
A 1b is a radical of the formula
wherein
(R 11 ) 0-3 denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl, halogen, amino, hydroxy, carboxy and sulfo,
(R 12 ) 0-3 denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, halogen, amino, carboxy and sulfo,
(R 13 ) 0-3 is as defined for (R 11 ) 0-3 , or R 13 is a radical —N═N-Ph, wherein Ph is phenyl that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or sulfo,
(R 14 ) 0-2 denotes from 0 to 2 identical or different substituents from the group C 1 -C 4 alkyl,
C 1 -C 4 alkoxy, halogen, carboxy, sulfo, hydroxyl, amino, N-mono-C 1 -C 4 alkylamino, N,N-di-C 1 C 4 alkylamino, C 2 -C 4 alkanoylamino and benzoylamino,
s is the number 0 or 1,
q is the number 2 or 3, that is q depicts 2 or 3 bonds attached to the chromophore, and
Z 1 independently denotes 2 or 3 identical or different fiber reactive radicals of formula
—SO 2 —Y (3a)
or
—NH—CO—(CH 2 ) l —SO 2 —Y (3b),
wherein
Y is vinyl, β-chloroethyl or β-sulfatoethyl, and
I is the number 2, 3 or 4.
10. A process according to claim 1 wherein the amount of the at least one reactive dyestuff is in the range of from 1.0% to 10% based on the pickle weight of the collagen containing fibrous material.
11. A process according to claim 1 wherein fixing further comprises increasing the temperature of the aqueous liquor to not more than 50° C.
12. A process according to claim 1 wherein fixing is conducted in the presence of at least one inorganic salt.
13. A process according to claim 1 wherein fixing is conducted in the presence of at least one salt of a carboxylic acid.
14. The leather or the leather imitation obtained by the process according to claim 1 .
15. The process according to claim 6 , wherein Pc is the radical of a copper or nickel phthalocyanine and r is independently 0 or 1.
16. The process according to claim 12 , wherein the inorganic salt is sodium sulphate (Glauber salt) or potassium sulphate.
17. The process according to claim 13 , wherein the carboxylic acid is sodium formate or tetrasodium ethylenediaminetetraacetic acid (EDTA).
18. The process according to claim 1 , wherein the aqueous liquor has a pH below 7.
19. The process according to claim 1 , wherein the aqueous liquor has a pH of 8.5 or less.
20. The process according to claim 1 , wherein the aqueous liquor has a pH below 7, and fixing comprises increasing the pH of the aqueous liquor to at least 10.