U.S. patent application number 10/386840 was filed with the patent office on 2003-10-30 for fabric care method.
Invention is credited to Bachmann, Frank, Dannacher, Josef, Freiermuth, Beat, Makowka, Cornelia, Richter, Grit, Schlingloff, Gunther, Studer, Martin, Weingartner, Peter.
Application Number | 20030203828 10/386840 |
Document ID | / |
Family ID | 26312203 |
Filed Date | 2003-10-30 |
United States Patent
Application |
20030203828 |
Kind Code |
A1 |
Bachmann, Frank ; et
al. |
October 30, 2003 |
Fabric care method
Abstract
The present invention provides a process for inhibiting the
re-absorption of migrating dyes in the wash liquor, comprising
introducing into a wash liquor containing a peroxide-containing
detergent, from 0.5 to 150, preferably from 1.5 to 75, especially
from 7.5 to 40 mg, per litre of wash liquor, of one or more
compounds having the formula: 1 in which n is 1, 2 or 3; A is an
anion; Y is --(CH.sub.2).sub.m in which m is an integer ranging
from 1 to 8; --(CH.sub.2).sub.p--CH(R.sub.1)-- in which p is an
integer ranging from 1 to 7 and R.sub.1 is linear or branched
C.sub.1-C.sub.4-alkyl, preferably methyl; --CX.dbd.CX-- in which X
is cyano, linear or branched C.sub.1-C.sub.8-alkyl or di(linear or
branched C.sub.1-C.sub.8-alkyl)-ami- no;
--(CH.sub.2).sub.qNR.sub.1--(CH.sub.2).sub.q in which R.sub.1 has
its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene residue having the formula: 2 and R is cyano;
halogen; hydroxy; OR.sub.1 in which R.sub.1 has its previous
significance; CO.sub.2R.sub.2 in which R.sub.2 is hydrogen or
linear or branched C.sub.1-C.sub.4-alkyl; nitro; linear or branched
C.sub.1-C.sub.8-alkyl; di-(C.sub.1-C.sub.12alkyl)amino;
NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4 are the same or
different and each is linear or branched C.sub.1-C.sub.12-alkyl; or
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance.
Inventors: |
Bachmann, Frank; (Freiburg,
DE) ; Dannacher, Josef; (Basel, CH) ; Studer,
Martin; (Basel, CH) ; Freiermuth, Beat;
(Buschwiller, FR) ; Makowka, Cornelia;
(Laufenburg, DE) ; Weingartner, Peter; (Diegten,
CH) ; Richter, Grit; (Neuenburg, DE) ;
Schlingloff, Gunther; (Riehen, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
26312203 |
Appl. No.: |
10/386840 |
Filed: |
March 12, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10386840 |
Mar 12, 2003 |
|
|
|
10067001 |
Feb 4, 2002 |
|
|
|
6562775 |
|
|
|
|
10067001 |
Feb 4, 2002 |
|
|
|
09835176 |
Apr 13, 2001 |
|
|
|
6486110 |
|
|
|
|
09835176 |
Apr 13, 2001 |
|
|
|
09148938 |
Sep 4, 1998 |
|
|
|
Current U.S.
Class: |
510/303 |
Current CPC
Class: |
C07C 251/24 20130101;
C07F 13/005 20130101; C11D 3/0021 20130101; C11D 3/3932
20130101 |
Class at
Publication: |
510/303 |
International
Class: |
C11D 007/18; C11D
009/42 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 9, 1997 |
GB |
9719009.4 |
Aug 5, 1998 |
GB |
9816928.7 |
Claims
1. A process for inhibiting the re-absorption of migrating dyes in
the wash liquor, comprising introducing into a wash liquor
containing a peroxide-containing detergent, from 0.5 to 150 mg, per
litre of wash liquor, of one or more compounds having the formula:
21in which n is 1, 2 or 3; A is an anion; R.sub.1 is hydrogen or
C.sub.1-C.sub.4-alkyl, Y is linear or branched alkylene of the
formula --[C(R.sub.1).sub.2].sub.m in which m is an integer ranging
from 1 to 8 and each R.sub.1 independently from the others has its
previous significance; --CX.dbd.CX-- in which X is cyano, linear or
branched C.sub.1-C.sub.8-alkyl or di(linear or branched
C.sub.1-C.sub.8-alkyl-amino; --(CH.sub.2).sub.q--NR.sub.1--(CH.s-
ub.2).sub.q-- in which R.sub.1 has its previous significance and q
is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having
the formula: 22in which R.sub.7 is hydrogen, CH.sub.2OH or
CH.sub.2NH.sub.2 or SO.sub.3M, where M is hydrogen, an alkali metal
atom, ammonium or a cation formed from an amine, R and R' are each
independently from the other cyano; halogen; hydroxy; OR.sub.1 or
COOR.sub.1 in which R.sub.1 has its previous significance; nitro;
linear or branched partially or completely fluorinated
C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4
are the same or different and each is hydrogen or linear or
branched C.sub.1-C.sub.12-alkyl; --N.sup..sym.R.sub.1R.sub.3R.s-
ub.4 in which R.sub.1, R.sub.3 and R.sub.4 have their previous
significance or linear or branched C.sub.1-C.sub.8-alkylene-R.sub.2
in which R.sub.2 is OR.sub.1, COOR.sub.1 or NR.sub.3R.sub.4,
R.sub.5 and R.sub.6 are each independently from the other hydrogen;
linear or branched C.sub.1-C.sub.4-alkyl; unsubstituted aryl or
aryl which is substituted by cyano, halogen, OR.sub.1 or
COOR.sub.1, nitro, linear or branched C.sub.1-C.sub.8-alkyl,
NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4 are the same or
different and each is hydrogen or linear or branched
C.sub.1-C.sub.12-alkyl; --N.sup..sym.R.sub.1R.sub.3R.sub.4 in which
R.sub.1, R.sub.3 and R.sub.4 have their previous significance or
linear or branched C.sub.1-C.sub.8-alkylene-R.sub.2 in which
R.sub.2 is OR.sub.1, COOR.sub.1 or NR.sub.3R.sub.4, with the
proviso that each n is 1, if R and R' are both
C.sub.1-C.sub.4-alkyl.
2. A process according to claim 1 in which from 1.5 to 75 mg, per
litre of wash liquor, of one or more compounds having the formula
(1) or (2) is introduced into the wash liquor.
3. A process according to claim 2 in which from 7.5 to 40 mg, per
litre of wash liquor, of one or more compounds having the formula
(1) or (2) is introduced into the wash liquor.
4. A process according to claim 1 in which the anion A is halide,
perchlorate, sulphate, nitrate, hydroxide, BF.sub.4.sup.-,
PF.sub.6.sup.- or a carboxylate.
5. A process according to claim 4 in which the halide anion A is
chloride.
6. A process according to claim 4 in which the carboxylate anion A
is acetate, triflate or tosylate.
7. A process according to claim 1 in which Y is
--[C(R.sub.8).sub.2].sub.2 wherein R.sub.8 is hydrogen or methyl,
--CX.dbd.CX-- in which X is cyano,
--(CH.sub.2).sub.q--NR.sub.8--(CH.sub.2).sub.q-- in which R.sub.8
has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 23
8. A process according to claim 1 in which R and R' are
dimethylamino, diethylamino, hydroxy, methoxy, ethoxy, chloro or
nitro.
9. A process according to claim 1 in which when n is 1, the group R
or R' is in the 4-position of the respective benzene ring, with the
exceptions that when R or R' is nitro or CO.sub.2R.sub.2, the group
R or R' is in the 5-position of the respective benzene ring.
10. A process according to claim 1 in which when n is 2, the groups
R or R' are in the 4,6-positions of the respective benzene ring,
with the exceptions that when R or R' is nitro or CO.sub.2R.sub.2
the groups R or R' are in the 3,5-positions of the respective
benzene ring.
11. A process according to claim 1 in which R or R' is
di-(C.sub.1-C.sub.12alkyl)amino, preferably
di-(C.sub.1-C.sub.8alkyl)amin- o.
12. A process according to claim 11 in which the alkyl moiety in
the group di-(C.sub.1-C.sub.12alkyl)amino contains from 1 to 4
carbon atoms.
13. A process according to claim 12 in which the alkyl moiety in
the group di-(C.sub.1-C.sub.12alkyl)amino contains 1 or 2 carbon
atoms.
14. A process according to claim 1 in which the compound of formula
(1) is one or more of the compounds of formulae: 24
15. A detergent composition comprising: i) 5-90% of A) an anionic
surfactant and/or B) a nonionic surfactant; ii) 5-70% of C) a
builder; iii) 0.1-30% of D) a peroxide; and iv) 0.005-2% of E) a
compound of formula (1) or (2) as defined in claim 1, each by
weight, based on the total weight of the detergent.
16. A composition according to claim 15 comprising: i) 5-70% of A)
an anionic surfactant and/or B) a nonionic surfactant; ii) 5-50% of
C) a builder; iii) 1-12% of D) a peroxide; and iv) 0.02-1% of E) a
compound of formula (1) or (2) as defined in claim 1, each by
weight, based on the total weight of the detergent.
17. A composition according to claim 16 comprising: i) 5-70% of A)
an anionic surfactant and/or B) a nonionic surfactant; ii) 5-40% of
C) a builder; iii) 1-12% of D) a peroxide; and iv) 0.1-0.5% of E) a
compound of formula (1) or (2) as defined in claim 1, each by
weight, based on the total weight of the detergent.
18. A composition according to claim 15 comprising a combination of
two or more of the compounds of formula (1) or (2) as defined in
claim 1.
19. A composition according to claim 15 comprising 0.5-5% by weight
of a polymer useful in preventing the transfer of labile dyes
between fabrics during a washing cycle.
20. A composition according to claim 19 comprising 0.2-1.7% of the
polymer.
21. A composition according to claim 19 in which the polymer is a
polyvinylpyrrolidone optionally containing an anionic or cationic
substituent.
22. A composition according to claim 15 in which the detergent is
in powder or granulate form.
23. A composition according to claim 15 in which the detergent is
in liquid form and contains 0-5% water.
24. A composition according to claim 23 in which the detergent is
in liquid form and contains 0-1% water.
25. A composition according to claim 15, containing additionally
TAGU or TAED:
26. A process for the production of a detergent as claimed in claim
22 in which the components of the detergent are mixed in dry
form.
27. A process for the production of a detergent as claimed in claim
22 in which a base powder is produced by spray-drying an aqueous
slurry which contains all the components defined in claim 22, apart
from the components D) and E); and then adding the components D)
and E) by dry-blending them into the base powder.
28. A process for the production of a detergent as claimed in claim
22 in which the component E) is added to the slurry containing
components A), B) and C), which slurry is then spray-dried before
component D) is dry-blended into the mixture.
29 A process for the production of a detergent as claimed in claim
22 in which component B) is not present, or is only partly present
in a slurry containing components A) and C); the component E) is
incorporated into component B), which is then added to the
spray-dried base powder; and finally component D) is dry-blended
into the mixture.
30. Manganese complexes of formula (3) 25or of formula (2) 26in
which n is 1, 2 or 3; A is an anion; R and R' are each
independently from the other cyano; halogen; hydroxy; OR.sub.1 or
COOR.sub.1 in which R.sub.1 has its previous significance; nitro;
linear or branched partially or completely fluorinated
C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4
are the same or different and each is hydrogen or linear or
branched C.sub.1-C.sub.12-alkyl; --N.sup..sym.R.sub.1R.sub.3R.s-
ub.4 in which R.sub.1, R.sub.3 and R.sub.4 have their previous
significance or linear or branched C.sub.1-C.sub.8-alkylene-R.sub.2
in which R.sub.2 is OR.sub.1, COOR.sub.1 or NR.sub.3R.sub.4,
R.sub.1 is hydrogen or C.sub.1-C.sub.4-alkyl, Y.sub.1 is
--CX.dbd.CX-- in which X is cyano,
--(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which R.sub.1
has its previous significance and q is 1, 2, 3 or 4; linear or
branched alkylene of the formula --[C(R.sub.1).sub.2].sub.m in
which m is an integer ranging from 1 to 8 and each R.sub.1
independently from the other has its previous significance, with
the proviso that at least one R.sub.1 is C.sub.1-C.sub.4-alkyl; or
a 1,2-cyclohexylene or phenylene residue having the formula: 27in
which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2 or
SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium or a
cation formed from an amine, with the proviso that each n is 1 if R
and R' are both C.sub.1-C.sub.4-alkyl and Y.sub.1 is an
unsubstituted 1,2-cyclohexylene residue, Y is linear or branched
alkylene of the formula --[C(R.sub.1).sub.2].sub.m in which m is an
integer ranging from 1 to 8 and each R.sub.1 independently from the
other has its previous significance; --CX.dbd.CX-- in which X is
cyano, linear or branched C.sub.1-C.sub.8-alkyl or di(linear or
branched C.sub.1-C.sub.8-alkyl)-amino;
--(CH.sub.2).sub.q,NR.sub.1--(CH.sub.2).sub- .q--in which R.sub.1
has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 28in
which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2 or
SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium or a
cation formed from an amine, R.sub.5 and R.sub.6 are each
independently from the other hydrogen; linear or branched
C.sub.1-C.sub.4-alkyl; unsubstituted aryl or aryl which is
substituted by cyano, halogen, OR.sub.1 or COOR.sub.1, nitro,
linear or branched C.sub.1-C.sub.8-alkyl, NR.sub.3R.sub.4 in which
R.sub.3 and R.sub.4 are the same or different and each is hydrogen
or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.s- ub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4.
31. Compounds of the formula (4) 29or of formula (5) 30in which n
is 1, 2 or 3; R and R' are each independently from the other cyano;
halogen; hydroxy; OR.sub.1 or COOR.sub.1 in which R.sub.1 has its
previous significance; nitro; linear or branched partially or
completely fluorinated C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in
which R.sub.3 and R.sub.4 are the same or different and each is
hydrogen or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4, R.sub.1 is hydrogen or
C.sub.1-C.sub.4-alkyl, Y.sub.1 is --CX.dbd.CX-- in which X is
cyano, --(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which
R.sub.1 has its previous significance and q is 1, 2, 3 or 4; linear
or branched alkylene of the formula --[C(R.sub.1).sub.2].sub.m in
which m is an integer ranging from 1 to 8 and each R.sub.1
independently from the other has its previous significance, with
the proviso that at least one R.sub.1 is C.sub.1-C.sub.4-alkyl; or
a 1,2-cyclohexylene or phenylene residue having the formula: 31in
which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2 or
SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium or a
cation formed from an amine, with the proviso that each n is 1 if R
and R' are both C.sub.1-C.sub.4-alkyl and Y.sub.1 is an
unsubstituted 1,2-cyclohexylene residue, Y is linear or branched
alkylene of the formula --[C(R.sub.1).sub.2].sub.m in which m is an
integer ranging from 1 to 8 and each R.sub.1 independently from the
other has its previous significance; --CX.dbd.CX-- in which X is
cyano, linear or branched C.sub.1-C.sub.8-alkyl or di(linear or
branched C.sub.1-C.sub.8-alkyl)-amino;
--(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).su- b.q-- in which R.sub.1
has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 32in
which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2 or
SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium or a
cation formed from an amine, R.sub.5 and R.sub.6 are each
independently from the other hydrogen; linear or branched
C.sub.1-C.sub.4-alkyl; unsubstituted aryl or aryl which is
substituted by cyano, halogen, OR.sub.1 or COOR.sub.1, nitro,
linear or branched C.sub.1-C.sub.8-alkyl, NR.sub.3R.sub.4 in which
R.sub.3 and R.sub.4 are the same or different and each is hydrogen
or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.s- ub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4.
32. Compounds of the formula 333435
Description
[0001] The present invention relates to a process for inhibiting
the re-absorption of migrating dyes in the wash liquor.
[0002] It is well known that various metal compounds, e.g.
manganese complexes, are useful in detergents as catalysts for
oxidation with peroxygen compounds such as perborate or peroxides.
It is also known that certain other manganese complexes cause
enhanced bleaching effects on dirt or dyes in the wash bath.
Moreover, these manganese complexes do not exhaust at all on to
cotton, polyamide or polyester fibres so that the complexes cannot
lead to fibre discolouration problems.
[0003] One problem associated with the evaluation of a compound as
a candidate for use in a process for inhibiting the re-absorption
of migrating dyes in the wash liquor, is the lack of a sufficiently
reliable and comprehensive screening technique. Such a technique
has now been developed and used to quantify the dye transfer
inhibition performance of potential substances. This screening
procedure comprises a variety of tests which makes it possible to
determine the usefulness/damage balance of any candidates on a
quantitative basis. A product is characterised in terms of its
specific effectivity, scope of use, compatibility with the most
important system components, oxygen demand and its fibre- and
dyestuff degradation potential. Moreover, the precision of the data
is such that structure/effect relationships can be developed. The
application of the new evaluation technique to manganese complexes
has resulted in the identification of further manganese complexes
which exhibit excellent performance as dye transfer inhibitors,
which are of relatively low molecular weight and the effectiveness
of which is substantial even at low levels of addition.
[0004] Accordingly, the present invention provides a process for
inhibiting the re-absorption of migrating dyes in the wash liquor,
comprising introducing into a wash liquor containing a
peroxide-containing detergent, from 0.5 to 150, preferably from 1.5
to 75, especially from 7.5 to 40 mg, per litre of wash liquor, of
one or more compounds having the formula: 3
[0005] in which n is 1, 2 or 3;
[0006] A is an anion;
[0007] R.sub.1 is hydrogen or C.sub.1-C.sub.4-alkyl,
[0008] Y is linear or branched alkylene of the formula
--[C(R.sub.1).sub.2].sub.m in which m is an integer ranging from 1
to 8 and each R.sub.1 independently from the other has its previous
significance; --CX.dbd.CX-- in which X is cyano, linear or branched
C.sub.1-C.sub.8-alkyl or di(linear or branched
C.sub.1-C.sub.8-alkyl-amin- o;
[0009] --(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which
R.sub.1 has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 4
[0010] in which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2
or SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium
or a cation formed from an amine,
[0011] R and R' are each independently from the other cyano;
halogen; hydroxy; OR.sub.1 or COOR.sub.1 in which R.sub.1 has its
previous significance; nitro; linear or branched partially or
completely fluorinated C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in
which R.sub.3 and R.sub.4 are the same or different and each is
hydrogen or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4,
[0012] R.sub.5 and R.sub.6 are each independently from the other
hydrogen; linear or branched C.sub.1-C.sub.4-alkyl; unsubstituted
aryl or aryl which is substituted by cyano, halogen, OR.sub.1 or
COOR.sub.1, nitro, linear or branched C.sub.1-C.sub.8-alkyl,
NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4 are the same or
different and each is hydrogen or linear or branched
C.sub.1-C.sub.12-alkyl; --N.sup..sym.R.sub.1R.sub.3R.s- ub.4 in
which R.sub.1, R.sub.3 and R.sub.4 have their previous significance
or linear or branched C.sub.1-C.sub.8-alkylene-R.sub.2 in which
R.sub.2 is OR.sub.1, COOR.sub.1 or NR.sub.3R.sub.4,
[0013] with the proviso that each n is 1, if R and R' are both
C.sub.1-C.sub.4-alkyl.
[0014] When Y is a 1,2-cyclohexylene residue, this residue may be
in any of its cis/trans stereoisomeric forms.
[0015] Y is preferably --[C(R.sub.8).sub.2].sub.2 wherein R.sub.8
is hydrogen or methyl, --CX.dbd.CX-- in which X is cyano,
--(CH.sub.2).sub.q--NR.sub.8--(CH.sub.2).sub.q-- in which R.sub.8
has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 5
[0016] Preferred halogen atoms R or R' are chlorine, bromine and
fluorine atoms.
[0017] When n is 1, preferably the group R or R' respectively is in
the 4-position of the respective benzene ring, with the exceptions
that when R or R' is nitro or CO.sub.2R.sub.2, the group R or R' is
preferably in the 5-position of the respective benzene ring. When n
is 2, preferably the groups R or R' are in the 4,6-positions of the
respective benzene ring, with the exceptions that when R or R' is
nitro or CO.sub.2R.sub.2 the groups R or R' are preferably in the
3,5-positions of the respective benzene ring.
[0018] When R or R' is the group di-(C.sub.1-C.sub.12alkyl)amino,
the alkyl moiety may be a straight- or branched chain alkyl moiety,
and it preferably contains from 1 to 8, more preferably from 1 to 4
and, especially, 1 or 2 carbon atoms.
[0019] Preferred groups R and R' are dimethylamino, diethylamino,
hydroxy, methoxy, ethoxy, chloro or nitro.
[0020] Anions A include halide, especially chloride, perchlorate,
sulphate, nitrate, hydroxide, BF.sub.4.sup.-, PF.sub.6.sup.-,
carboxylate, especially acetate, triflate or tosylate.
[0021] Some of the compounds of formula (1) and the ligands from
which they are derived are known compounds. For example, in U.S.
Pat. No. 5,281,578 there is described the preparation of
N,N-bis(4-dimethylaminosa- licylidene)diiminoethylene; in EP-A-0
693 550 there is disclosed the production of the manganese complex
of N,N-bis(4-diethylaminosalicylidene- )diiminoethylene; and in
Bernado et. al., Inorg. Chem. 35 (2) 387 (1996), there is disclosed
the production of N,N-bis(4-diethylaminosalicylidene)d-
iiminocyclohexylene as well as the production of the manganese
complex N,N-bis(4-diethylaminosalicylidene)diiminocyclohexylene.
New compounds of formula (1) and new ligands from which they are
derived form further aspects of the present invention.
[0022] Moreover, the use, as dye transfer inhibitors, of those
compounds of formula (1) in which A is an anion and a) Y is
--CH.sub.2CH.sub.2-- each R is di-(C.sub.1-C.sub.2alkyl)amino; or
b) Y is cyclohexylene and each R is di-(C.sub.1-C.sub.2alkyl)amino
has been broadly indicated, but not specifically described, in
GB-A-2,296,015. On the other hand, the use, as dye transfer
inhibitors, of those compounds of formula (1) in which A is an
anion, Y is --CH.sub.2CH.sub.2-- and each R is hydroxy, is believed
to be completely new.
[0023] Of particular interest for use in in the method of the
present invention are those compounds of formulae: 6
[0024] The present invention also provides a detergent composition
comprising:
[0025] i) 5-90%,preferably 5-70% of A) an anionic surfactant and/or
B) a nonionic surfactant;
[0026] ii) 5-70%, preferably 5-50%, especially 5-40% of C) a
builder;
[0027] iii) 0.1-30%, preferably 1-12% of D) a peroxide; and
[0028] iv) 0.005-2%, preferably 0.02-1%, especially 0.1-0.5% of E)
a compound of formula (1) or (2) as defined above, each by weight,
based on the total weight of the detergent.
[0029] The detergent may be formulated as a solid; or as a
non-aqueous liquid detergent, containing not more than 5,
preferably 0-1 wt. % of water, and based on a suspension of a
builder in a non-ionic surfactant, as described, e.g., in
GB-A-2158454.
[0030] Preferably, the detergent is in powder or granulate
form.
[0031] Such powder or granulate forms may be produced by firstly
forming a base powder by spray-drying an aqueous slurry containing
all the said components, apart from the components D) and E); then
adding the components D) and E) by dry-blending them into the base
powder. In a further process, the component E) may be added to an
aqueous slurry containing components A), B) and C), followed by
spray-drying the slurry prior to dry-blending component D) into the
mixture. In a still further process, component B) is not present,
or is only partly present in an aqueous slurry containing
components A) and C); component E) is incorporated into component
B), which is then added to the spray-dried base powder; and finally
component D) is dry-blended into the mixture.
[0032] The anionic surfactant component A) may be, e.g., a
sulphate, sulphonate or carboxylate surfactant, or a mixture of
these.
[0033] Preferred sulphates are alkyl sulphates having 12-22 carbon
atoms in the alkyl radical, optionally in combination with alkyl
ethoxy sulphates having 10-20 carbon atoms in the alkyl
radical.
[0034] Preferred sulphonates include alkyl benzene sulphonates
having 9-15 carbon atoms in the alkyl radical.
[0035] In each case, the cation is preferably an alkali metal,
especially sodium.
[0036] Preferred carboxylates are alkali metal sarcosinates of
formula R--CO--N(R.sup.1)--CH.sub.2COOM.sup.1 in which R is alkyl
or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl
radical, R.sup.1 is hydrogen or C.sub.1-C.sub.4 alkyl and M.sup.1
is alkali metal.
[0037] The nonionic surfactant component B) may be, e.g., a
condensate of ethylene oxide with a C.sub.9-C.sub.15 primary
alcohol having 3-8 moles of ethylene oxide per mole.
[0038] The builder component C) may be an alkali metal phosphate,
especially a tripolyphosphate; a carbonate or bicarbonate,
especially the sodium salts thereof; a silicate; an
aluminosilicate; a polycarboxylate; a polycarboxylic add; an
organic phosphonate; or an aminoalkylene poly (alkylene
phosphonate); or a mixture of these.
[0039] Preferred silicates are crystalline layered sodium silicates
of the formula NaHSi.sub.mO.sub.2m+1.pH.sub.2O or
Na.sub.2Si.sub.mO.sub.2m+1.pH.- sub.2O in which m is a number from
1.9 to 4 and p is 0 to 20.
[0040] Preferred aluminosilicates are the commercially-available
synthetic materials designated as Zeolites A, B, X, and HS, or
mixtures of these. Zeolite A is preferred.
[0041] Preferred polycarboxylates include hydroxypolycarboxylates,
in particular citrates, polyacrylates and their copolymers with
maleic anhydride.
[0042] Preferred polycarboxylic acids include nitrilotriacetic acid
and ethylene diamine tetra-acetic acid, ethylenediaminedisuccinate
in racemic form as well as the enantiomeric S,S-form
[0043] Preferred organic phosphonates or aminoalkylene poly
(alkylene phosphonates) are alkali metal ethane 1-hydroxy
diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine
tetra methylene phosphonates and diethylene triamine penta
methylene phosphonates.
[0044] The peroxide component D) may be any organic or inorganic
peroxide compound, described in the literature or available on the
market, which bleaches textiles at conventional washing
temperatures, e.g. temperatures in the range of from 30.degree. C.
to 90.degree. C. In particular, the organic peroxides are, for
example, monoperoxides or polyperoxides having alkyl chains of at
least 3, preferably 6 to 20, carbon atoms; in particular
diperoxydicarboxylates having 6 to 12 C atoms, such as
diperoxyperazelates, diperoxypersebacates, diperoxyphthalates
and/or diperoxydodecanedioates, especially their corresponding free
acids, are of interest. It is preferred, however, to employ very
active inorganic peroxides, such as persulphate, perborate and/or
percarbonate. It is, of course, also possible to employ mixtures of
organic and/or inorganic peroxides. Peroxides can have different
crystalline forms and/or different degrees of hydration. They may
be used in admixture with other organic or inorganic salts, thereby
improving their stability to storage.
[0045] The addition of the peroxides to the detergent is effected,
in particular, by mixing the components, for example by means of
screw-metering systems and/or fluidized bed mixers.
[0046] The detergents may contain, in addition to the combination
according to the invention, one or more of fluorescent whitening
agents, such as a bis-triazinylamino-stilbene-disulphonic acid, a
bis-triazolyl-stilbene-disulphonic add, a bis-styryl-biphenyl, a
bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a
bis-benzimidazolyl derivative, a coumarine derivative or a
pyrazoline derivative; soil suspending agents, for example sodium
carboxymethylcellulose; salts for adjusting the pH, for example
alkali or alkaline earth metal silicates; foam regulators, for
example soap; salts for adjusting the spray drying and granulating
properties, for example sodium sulphate; perfumes; and also, if
appropriate, antistatic and softening agents; such as smectite
clays; enzymes, such as amylases; photobleaching agents; pigments;
and/or shading agents. These constituents should, of course, be
stable to the bleaching system employed.
[0047] A particularly preferred detergent co-additive is a polymer
known to be useful in preventing the transfer of labile dyes
between fabrics during the washing cycle. Preferred examples of
such polymers are polyvinyl pyrrolidones, optionally modified by
the inclusion of an anionic or cationic substituent, especially
those having a molecular weight in the range from 5000 to 60,000,
in particular from 10,00 to 50,000. Preferably, such polymer is
used in an amount ranging from 0.05 to 5%, preferably 0.2-1.7% by
weight, based on the weight of the detergent.
[0048] The detergents may additionally contain so-called
perborate-activators, e.g. TAGU or, preferably TAED. This is
preferably used in an amount of 0,05 through 5% by weight,
especially 0,2 through 1,7% by weight, relative to the total weight
of the detergent.
[0049] The manganese complexes of formula (2) are new compounds and
some of the manganese complexes of formula (1) are new too.
[0050] The invention consequently also relates to manganese
complexes of formula (3) 7
[0051] or of formula (2) 8
[0052] in which n is 1, 2 or 3;
[0053] A is an anion;
[0054] R and R' are each independently from the other cyano;
halogen; hydroxy; OR.sub.1 or COOR.sub.1 in which R.sub.1 has its
previous significance; nitro; linear or branched partially or
completely fluorinated C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in
which R.sub.3 and R.sub.4 are the same or different and each is
hydrogen or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4,
[0055] R.sub.1 is hydrogen or C.sub.1-C.sub.4-alkyl,
[0056] Y.sub.1 is --CX.dbd.CX-- in which X is cyano,
--(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which R.sub.1
has its previous significance and q is 1, 2, 3 or 4; linear or
branched alkylene of the formula --[C(R.sub.1).sub.2].sub.m in
which m is an integer ranging from 1 to 8 and each R.sub.1
independently from the other has its previous significance, with
the proviso that at least one R.sub.1 is C.sub.1-C.sub.4-alkyl; or
a 1,2-cyclohexylene or phenylene residue having the formula: 9
[0057] in which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2
or SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium
or a cation formed from an amine, with the proviso that each n is 1
if R and R' are both C.sub.1-C.sub.4-alkyl and Y.sub.1 is an
unsubstituted 1,2-cyclohexylene residue, Y is linear or branched
alkylene of the formula --[C(R.sub.1).sub.2].sub.m in which m is an
integer ranging from 1 to 8 and each RI independently from the
other has its previous significance; --CX.dbd.CX-- in which X is
cyano, linear or branched C.sub.1-C.sub.8-alkyl or di(linear or
branched C.sub.1-C.sub.8-alkyl)-ami- no;
[0058] --(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which
R.sub.1 has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 10
[0059] in which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2
or SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium
or a cation formed from an amine,
[0060] R.sub.5 and R.sub.6 are each independently from the other
hydrogen; linear or branched C.sub.1-C.sub.4-alkyl; unsubstituted
aryl or aryl which is substituted by cyano, halogen, OR.sub.1 or
COOR.sub.1, nitro, linear or branched C.sub.1-C.sub.8-alkyl,
NR.sub.3R.sub.4 in which R.sub.3 and R.sub.4 are the same or
different and each is hydrogen or linear or branched
C.sub.1-C.sub.12-alkyl; --N.sup..sym.R.sub.1R.sub.3R.s- ub.4 in
which R.sub.1, R.sub.3 and R.sub.4 have their previous significance
or linear or branched C.sub.1-C.sub.8-alkylene-R.sub.2 in which
R.sub.2 is OR.sub.1, COOR.sub.1 or NR.sub.3R.sub.4.
[0061] The ligands of formulae (4) or (5) which are contained in
the manganese complexes are new themselves and these ligands are
also part of the instant invention. The invention consequently also
relates to compounds of the formula (4) 11
[0062] or of formula (5) 12
[0063] in which n is 1, 2 or 3;
[0064] R and R' are each independently from the other cyano;
halogen; hydroxy; OR.sub.1 or COOR.sub.1 in which R.sub.1 has its
previous significance; nitro; linear or branched partially or
completely fluorinated C.sub.1-C.sub.8-alkyl; NR.sub.3R.sub.4 in
which R.sub.3 and R.sub.4 are the same or different and each is
hydrogen or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R,
[0065] R.sub.1 is hydrogen or C.sub.1-C.sub.4-alkyl,
[0066] Y.sub.1 is --CX.dbd.CX-- in which X is cyano,
--(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which R.sub.1
has its previous significance and q is 1, 2, 3 or 4; linear or
branched alkylene of the formula --[C(R.sub.1).sub.2].sub.m in
which m is an integer ranging from 1 to 8 and each R.sub.1
independently from the other has its previous significance, with
the proviso that at least one R.sub.1 is C.sub.1-C.sub.4-alkyl; or
a 1,2-cyclohexylene or phenylene residue having the formula: 13
[0067] in which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2
or SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium
or a cation formed from an amine, with the proviso that each n is 1
if R and R' are both C.sub.1-C.sub.4-alkyl and Y.sub.1 is an
unsubstituted 1,2-cylohexylene residue, Y is linear or branched
alkylene of the formula --[C(R.sub.1).sub.2].sub.m in which m is an
integer ranging from 1 to 8 and each R.sub.1 independently from the
other has its previous significance; --CX.dbd.CX-- in which X is
cyano, linear or branched C.sub.1-C.sub.8-alkyl or di(linear or
branched C.sub.1-C.sub.8-alkyl)-ami- no;
[0068] --(CH.sub.2).sub.q--NR.sub.1--(CH.sub.2).sub.q-- in which
R.sub.1 has its previous significance and q is 1, 2, 3 or 4; or a
1,2-cyclohexylene or phenylene residue having the formula: 14
[0069] in which R.sub.7 is hydrogen, CH.sub.2OH or CH.sub.2NH.sub.2
or SO.sub.3M, where M is hydrogen, an alkali metal atom, ammonium
or a cation formed from an amine,
[0070] R.sub.5 and R.sub.6 are each independently from the other
hydrogen; linear or branched C.sub.1-C.sub.4-alkyl; unsubstituted
aryl or aryl which is substituted by cyano, halogen, OR, or
COOR.sub.1, nitro, linear or branched C.sub.1-C.sub.8-alkyl,
NR.sub.3R in which R.sub.3 and R.sub.4 are the same or different
and each is hydrogen or linear or branched C.sub.1-C.sub.12-alkyl;
--N.sup..sym.R.sub.1R.sub.3R.sub.4 in which R.sub.1, R.sub.3 and
R.sub.4 have their previous significance or linear or branched
C.sub.1-C.sub.8-alkylene-R.sub.2 in which R.sub.2 is OR.sub.1,
COOR.sub.1 or NR.sub.3R.sub.4.
[0071] Preferred compounds of formula (4) are the following:
151617
[0072] Preferred compounds of formula (5) are 18
[0073] The following Examples serve to illustrate the invention;
parts and percentages are by weight, unless otherwise stated.
[0074] Preparation of the New Ligands:
[0075] Ligand 2a:
[0076] a) Preparation of the Corresponding Aldehyde
[0077] Firstly, the starting compound
N,N-dibutyl-4-amino-2-hydroxy-benzal- dehyde had to be prepared by
Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer
reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of
phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl
formamide with stirring for 15 minutes at room temperature.
Stirring was continued for 30 more minutes before this Vilsmeyer
reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol,
prepared by alkylation of 3-aminophenol after the procedure
described in EP 0356173 was dissolved in 13 ml N,N-dimethyl
formamide. This solution was added dropwise at room temperature to
the Vilsmeyer reagent described above. The solution was stirred for
3 h, heated to 50.degree. C. for 10 minutes. The solution was
cooled to room temperature and stirred for another 2 h. Then, the
reaction mixture was poured onto 70 g ice and stirred for 1 h. The
aequous layer was extracted three times with 100 ml chloroform. The
combined organic layers were evaporated in vacuo. The raw product
was purified by column chromatography (450 g silicagel, eluent
hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%)
N,N-Dibutyl4-amino-2-hydroxy-benzaldehyde was obtained as an orange
oily compound.
[0078] b) Preparation of the Ligand 2a
[0079] To a solution of 1 g (0.004 mol) 4
N,N-dibutyl-4-amino-2-hydroxy-be- nzaldehyde in 2 ml ethanol at
55.degree. C. were added dropwise 0.13 ml (0.00191 mol) of ethylene
diamine. The resulting clear solution was kept under stirring for 4
h between 60-65.degree. C. The solution was cooled and the
precipitate formed was filtered and dried to give 540 mg (54%) of a
slightly brownish solid.
[0080] .sup.13C NMR (CDCl.sub.3): .delta.=14.0 (aliph. CH.sub.3),
20.2, 29.5, 50.8, 58.2 (aliph. CH.sub.2), 98.2, 103.1, 132.9 (tert.
Aryl-C), 108.2, 151.9, 165.7 (quart Aryl-C), 164.3 (C.dbd.N).
[0081] Calc. C 73.52H 9.65 N 10.72
[0082] Found C 73.14H 9.34 N 10.55
[0083] Ligand 2b
[0084] Preparation of the Corresponding Aldehyde:
[0085] A solution of 13 g (0.04255 mol) of
N,N-heptyl-3-amino-phenol, prepared after the procedure described
in EP 0356173, in 30 ml chloroform was treated with 6.7 g (0.04255
mol) of phosphorus oxychloride and 12.4 g (0.169 mol) of
N,N-dimethyl formamide and worked-up as described for compound 2a.
Purification was accomplished by column chromatography a mixture of
chlorobenzene/ethyl acetate/ethanol (90:5:5, vol. ratio). 1.78 g
(13%) of N,N-heptyl-4-amino-2-hydroxy-benzaldehyde was obtained as
a green oily compound. A solution of 0.8 g (0.0024 mol).
N,N-heptyl-4-amino-2-hydroxy-benzaldehyde in 1 ml ethanol was
treated and worked-up as described for compound 2a. 720 mg (91%) of
the ligand was obtained as a brown oil which slowly crystallized
when stored at 5 C for three days.
[0086] .sup.13C NMR (CDCl.sub.3): .delta.=14.1 aliph. CH.sub.3),
22.6, 27.1, 27.5, 29.2, 31.9, 51.0, 57.7 (aliph. CH.sub.2), 98.3,
103.2, 133.0 (tert. Aryl-C), 108.2, 152.1, 166.5 (quart Aryl-C),
164.2 (C.dbd.N).
[0087] Calc. C 76.47H 10.79 N 8.11
[0088] Found C 76.18H 10.60 N 7.95
[0089] Ligand 2 c
[0090] To a stirred solution of 2 g (0.0121 mol) of
5-dimethylamino-2-hydroxy-benzaldehyde [prepared after Bull. Chem.
Soc. Jpn. 51 (1978) 2433] in 6 ml ethanol at 50.degree. C. was
added dropwise 0.35 g (0.0058 mol) of ethylene diamine. An orange
suspension was formed which was stirred at 60.degree. C. for 4 h.
The suspension was cooled to room temperature, filtered and dried
in vacuo at 30.degree. C. The pure ligand was obtained as a yellow
solid (1.77 g, 87%).
[0091] .sup.13C NMR (CDCl.sub.3): .delta.=45.0 (aliph. NCH.sub.3),
60.0 (aliph. CH.sub.2), 116.2, 117.2, 119.6 (tert. Aryl-C), 118.4,
144.2, 153.3 (quart Aryl-C), 166.8 (C.dbd.N).
[0092] Calc. C 67.77H 7.39 N 15.81
[0093] Found C 67.56H 7.35 N 15.25
[0094] Ligand 2 d
[0095] To a solution of 2.5 g (0.015 mol)
N,N-dimethyl-4-amino-2-hydroxy-b- enzaldehyde in 7 ml ethanol was
added within 2 minutes a solution of 0.82 g (0.00721 mol) of
diamino maleic acid dinitrile in 14 ml methanol. The reaction
mixture was heated for 5 h at 65.degree. C. A brown suspension was
obtained which was cooled, filtered and dried to give a brown solid
(2.03 g, 70%).
[0096] .sup.13C NMR (CDCl.sub.3): .delta.=40.0 (aliph. NCH.sub.3),
110.4, 115.1 (aliph. quart. C), 98.2, 105.8, 133.0 (tert. Aryl-C),
110.4, 115.1, 161.2 (quart Aryl-C), 156.2 (C.dbd.N).
[0097] Ligand 2 e
[0098] A solution of 5.0 g (0.0259 mol)
4-diethylamino-2-hydroxy-benzaldeh- yde in 12 ml ethanol was
treated with 1.66 g (0.0123 mol) of bis-(3-aminopropyl)amine and
worked-up as described for ligand 2a. The raw product was dried in
high vacuo to give 5.7 g (98%) of a red oil.
[0099] .sup.13C NMR (CDCl.sub.3): .delta.=12.8 (aliph. CH.sub.3),
31.1, 44.5, 47.2, 53.6 (aliph. CH.sub.2), 98.7, 103.1, 133.2 (tert.
Aryl-C), 108.2, 152.2, 169.0 (quart Aryl-C), 162.5 (C.dbd.N).
[0100] Calc. C 68.77H 9.00 N 14.32.
[0101] Found C 67.09H 8.66 N 13.38 (Substance contains 1.51%
water)
[0102] Ligand 2 f
[0103] A solution of 0.81 g (0.00517 mol)
4-chloro-2-hydroxy-benzaldehyde prepared after Beilstein (E IV,
vol.8, 223) in 2.5 ml ethanol was treated with 0.29 g (0.00246 mol)
trans-1,2-diaminohexane and worked-up as described for ligand 2a.
The ligand was obtained as a yellow oil (0.96 g, 100%) which upon
standing slowly crystallized.
[0104] .sup.13C NMR (CDCl.sub.3): .delta.=24.1, 32.9 (CH.sub.2),
54.6, 72.4 (CH), 117.0, 138.1, 162.0 (quart Aryl-C), 117.2,118.9
(tert. Aryl-C), 164.0(C.dbd.N).
[0105] Calc. C 61.39H 5.15 N 7.16 Cl 18.12
[0106] Found C 61.50H 5.34 N 7.70 Cl 17.26
[0107] Ligand 2g
[0108] To a stirred solution of 2 g (0.013 mol)
2-hydroxy-4-methoxy-benzal- dehyde in 10 ml ethanol at room
temperature were added at once 579 mg (0.0065 mol)
1,2-diethylamino-2-methylpropane. The solution was heated at
60.degree. C. for 3 h and cooled to room temperature. The clear
solution was evaporated and dried in high vacuo to give the ligand
as a red-brown oil (2.58 g, 100%).
[0109] .sup.13C NMR (CDCl.sub.3):
.delta.=25.3((CH.sub.3).sub.2C--), 55.3 (OCH.sub.3), 59.2 (aliph,
quart. C), 69.2 (NCH.sub.2), 101.2, 101.4 (tert. Aryl-C), 106.3,
106.4 (tert. Aryl-C), 112.2, 112.3 (quart Aryl-C), 132.9, 133.1
(tert. Aryl-C), 160.3, 165.6 (C.dbd.N), 163.7, 163.9 (quart.
Aryl-C), 165.0, 166.7 (quart. Aryl-C).
[0110] Calc. C 67.39H 6.79 N 7.86
[0111] Found C 67.51H 6.91 N 7.69
[0112] Ligand 2h
[0113] 2 g (0.0103 mol) 4-diethylamino-2-hydroxy-benzaldehyde and
456 mg (0.00517 mol) 1,2-diethylamino-2-methylpropane were treated
and worked-up as described for ligand 2g. The ligand was obtained
as a red-brown solid (1.9 g, 84%).
[0114] .sup.13C NMR (CDCl.sub.3): .delta.=12.7 (CH.sub.3CH.sub.2N),
25.4 ((CH.sub.3).sub.2C--), 44.4 (NCH.sub.2CH.sub.3), 58.4 (quart.
C), 68.6 (NCH.sub.2), 98.1, 98.6 (tert. Aryl-C), 103.0, 103.1
(tert. Aryl-C), 108.3, 108.4 (quart Aryl-C), 133.1, 133.4 (tert.
Aryl-C), 151.6, 151.9 (quart. Aryl-C), 158.9, 164.5 (C.dbd.N),
166.0, 168.4 (quart. Aryl-C).
[0115] Calc. C 71.91H 8.74 N 12.72
[0116] Found C 70.88H 8.65 N 12.35
[0117] Ligand 2i
[0118] 1.21 g (0.006 mol) 4-diethylamino-2-hydroxy-benzaldehyde was
dissolved under stirring in 2 ml ethanol at 50.degree. C. At this
temperature, a solution of 2,3-diamino-2,3-dimethyl-butane
(prepared after Beilstein E IV, vol. 4, 1354) in 2 ml ethanol was
added within 30 minutes. The reaction mixture was heated to 70 C
for 3 h and stirred at room temperature for another 8 h. The
resulting suspension was filtered and the precipitate was washed
with cold ethanol and dried in high vacuo to give a brown solid
(890 mg, 66%).
[0119] .sup.13 C NMR (CDCl.sub.3): .delta.=12.8, 23.0 (CH.sub.3),
44.5 (CH.sub.2), 63.3 (quart. alipht. C), 98.6, 103.0, 133.5 (tert.
Aryl-C), 108.2, 152.1, 169.1 (quart. Aryl-C), 158.9 (C.dbd.N).
[0120] Calc. C 72.07H 9.07 N 12.01
[0121] Found C 71.78H 9.03 N 11.88
[0122] Ligand 2j
[0123] To a solution of 974 mg (0.0045 mol)
2,3,6,7-tetrahydro-8-hydroxy-1-
H,5H-benzo[ij]quinolizine-9-carboxaldehyde in 30 ml methanol was
added a solution of 148 mg (0.0025 mol) ethylene diamine. The
reaction mixture was heated under reflux for 1 h. The formed
precipitate was filtered and crystallized in 100 ml of methanol to
yield 590 mg (29%) of yellow crystals.
[0124] .sup.13C NMR (CDCl.sub.3): .delta.=20.4, 21.3, 22.2, 27.2,
49.8, 50.1, 58.2 (CH.sub.2,), 106.8, 107,9, 112,2,
129.0,146.4,164.3 (C.dbd.N).
[0125] Calc. C 73.33H 7.47 N 12.22
[0126] Found C 73.37H 7.54 N 12.22
[0127] Ligand 2k
[0128] A solution of 1.95 g (0.00714 mol)
8-hydroxy-1,1,7,7-tetramethyljul- olidine-9-carboxaldehyde in 60 ml
methanol was reacted with 236 mg (0.0393 mmol) ethylene diamine as
described for ligand 2j. The precipitate was filtered and washed
with methanol to give 1.52 g (75%).
[0129] .sup.13C NMR (CDCl.sub.3): .delta.=28.5 (prim. C), 31.2
(prim. C), 31.7, 32.2, 36.6, 40.1, 47.0, 47.4, 58.9, 108.7, 114.8,
121.6, 127.5), 145.7, 161.2, 165.4 (C.dbd.N).
[0130] Ligand 2l
[0131] A solution of 5.0 g (0.0355 mol) 2,4-dihydroxy-benzaldehyde
in 17 ml ethanol was treated with 1.97 g (0.0169 mol) of
trans-1,2-diaminocylohexane and heated at 65.degree. C. for 5 h. A
yellow suspension was formed which was cooled to 2.degree. C. The
precipitate was filtered, washed with ethanol and dried to give 5.9
g (99%) of a yellow solid.
[0132] .sup.13C NMR (DMSO-d.sub.6): .delta.=24.9, 33.6 (CH.sub.2),
71.3 (CH), 103.3,107.8,134.1 (tert. Aryl-C), 112.0,162.6 (quart.
Aryl-C), 164.9 (C.dbd.N)
[0133] Ligand 2m
[0134] A solution of 5 g (0.025 mol)
4-diethylamino-2-hydroxy-benzaldehyde in 12 ml ethanol was treated
with 0.92 g (0.0123 mol) of 1,2-diaminopropane and heated at
65.degree. C. for 5 h. The solution was cooled and stirred for 8 h.
The solution was concentrated to give 4.68 g (90%) of a brown
solid.
[0135] .sup.13C NMR (CDCl.sub.3): .delta.=12.7, 20.3 (CH.sub.3),
44.5, 63.8 (CH.sub.2), 98.2, 103.1, 133.1 (tert. Aryl-C), 108.3,
151.5, 165.5 (quart. Aryl-C), 162.5 (C.dbd.N)
[0136] The following ligands are known compounds. 1920
[0137] These ligands were prepared according to known literature
procedures:
[0138] All described ligands were transformed into its manganese
complexes. The syntheses of these complexes were performed
according to the literature as described by E. N. Jacobsen et al.
J. Org. Chem., 59 (1994) 1939 or in Patent GB-A-2,296,015. As an
example for the standard procedure, the synthesis of the manganese
complex 1b is described: To a stirred solution of 667 mg of ligand
3f dissolved in 10 ml of ethanol was added 465 mg
manganese-II-acetate-tetrahydrate. The reaction solution was heated
at 65-70.degree. C. for 4 h. Afterwards, the solution was
evaporated and the residue was dissolved in 40 ml of water. The
solution were treated with 3.7 g of sodium chloride. The resulting
precipitate was filtered and dried in vacuo. The manganese complex
was obtained as red-brown powder (820 mg, 86%).
EXAMPLE 1
[0139] Each of the test compounds is then evaluated to determine
its activity as a dye transfer inhibitor according to the following
method.
[0140] 7.5 g of white cotton are washed in 80 ml of wash liquor.
The wash liquor contains 8.6 mmol/l H.sub.2O.sub.2, a solution of a
test dyestuff and 7.5 g/l of the standard detergent ECE
phosphate-free (456 IEC) EMPA, Switzerland:
1 9.74% Sodium linear alkylbenzenesulfonate (Mailon A375); 5.19%
Ethoxylated C.sub.12-C.sub.18 fatty alcohol (7 moles EO); 3.64%
Sodium soap; 6.49% Silicon foam inhibitor 32.47% Sodium aluminium
silicate Zeolite 4A; 11.82% Sodium carbonate; 5.19% Sodium salt of
acrylic acid/maleic acid copolymer (Sokolan CP 5) 3.38% Sodium
silicate (SiO.sub.2:Na.sub.2O = 3.3:1); 1.30%
Carboxymethylcellulose; 0.26% EDTA; 7.40% Sodium sulfate; 12.21%
Water; 0.65% Proteolytic enzyme prills; 0.26% Fluorescent whitening
agent 20.0% Sodium percarbonate; and 3.0% TAED.
[0141] The washing is conducted in beakers in a LINITEST apparatus
at 40.degree. C. over 30 minutes. The test dye transfer inhibitor
is added at a level of 50 .mu.mol/l. The commercially available
test dye used is either Cuprophenyl Brown 2GL (Dye 1) used at a
level of 10 mg/l of the 250% formulation, or Reactive Blue 238 (Dye
2) used at a level of 6 mg/l of the 100% formulation. The
reflection spectra of the respective test samples are measured with
a SPECTRAFLASH 2000 instrument and are transformed into brightness
values according to the CIE standard procedure.
[0142] The percentage DTI (dye transfer inhibition) effectivity (a)
is then calculated in accordance with the following equation:
a={[Y(E)-Y(A)]/[Y(W)-Y(A)]}.times.100
[0143] in which Y(W), Y(A) and Y(E), respectively, are the
CIE-brightness values of the white material before treatment, of
the fabric as obtained when washed without a dye transfer inhibitor
and of the fabric as obtained when washed with a dye transfer
inhibitor. A zero percent value for the a-value denotes a
completely ineffective dye transfer inhibitor, that is a compound,
the addition of which to a wash liquor allows full dye transfer on
to the white material. By contrast, a 100 percent value for a
denotes a perfect dye transfer inhibitor, that is a compound, the
addition of which to a wash liquor allows no dye transfer on to the
white material.
[0144] The results obtained are set out in the following Table
1.
2 TABLE 1 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye
2 inhibitor 1(A) 90 98 inhibitor 1(B) 82 87 inhibitor 1(C) 80 85
inhibitor 1(D) 84 86 Manganese complexes of ligand 2a 71 2b 78 2c
70 2d 73 2e 68 2f 84 2g 80 2h 87 2i 69 2j 90 2k 77 2l 85 2m 85
[0145]
3TABLE 1B DTI-effiency of manganese complexes derived from known
ligands Test dye transfer inhibitor DTI effectivity (a) 3a 92 3b 74
3c 76 3d 61 3e 78 3f (Ligand for Mn complex 1b) cf. table 1 3g
(Ligand for Mn complex 1c) " 3h (Ligand for Mn complex 1a) " 3i
(Ligand for Mn complex 1d) " 3j 97
[0146] The results in Table 1 clearly demonstrate that claimed
manganese complexes exhibit excellent performance as dye transfer
inhibitors.
EXAMPLE 2
[0147] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that the amounts
used of these inhibitors are varied over a wide range.
[0148] The results obtained are set out in the following Table
2.
4TABLE 2 Test dye transfer DTI effectivity (a) inhibitor
Concentration .mu.mol/l Dye 1 Dye 2 inhibitor 1(A) 5 59 64 10 69 85
20 83 95 30 90 103 50 90 98 70 98 105 inhibitor 1(B) 5 50 43 10 61
76 20 76 78 30 77 78 50 82 87 70 82 88
[0149] The results in Table 2 show that manganese complexes of
formula (1) exhibit excellent performance as dye transfer
inhibitors even at very low levels of addition.
EXAMPLE 3
[0150] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that their
effectiveness in controlling transfer of a wide range of dyes, at
various levels of dye addition, is examined.
[0151] The results obtained are set out in the following Table
3.
5TABLE 3 DTI effectivity (a) Test dye Concentration .mu.mol/l
inhibitor 1(A) inhibitor 1(B) Cuprophenyl Brown 2GL 250% 10 90 82
Reactive Blue 238 100% 6 98 87 Reactive Black 5 133% 12 80 65
Direct Black 22 400% 6 76 73 Reactive Blue 19 Special 100% 20 97 88
Acid Blue 113 180% 6 96 90 Disperse Violet 1 100% 6 90 72
[0152] The results in Table 3 show that manganese complexes of
formula (1) exhibit excellent performance as dye transfer
inhibitors against migration of a a wide range of dyes, at various
levels of dye addition.
EXAMPLE 4
[0153] The procedure in Example 1 is repeated for a washing
temperature of 20.degree. C.
[0154] The results obtained are set out in the following Table
4.
6 TABLE 4 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye
2 inhibitor 1(A) 82 86 inhibitor 1(B) 79 73 inhibitor 1(C) 70 86
inhibitor 1(D) 80 80
[0155] The results in Table 4 show that manganese complexes of
formula (1) exhibit excellent performance as dye transfer
inhibitors even at washing temperatures as low as 20.degree. C.
EXAMPLE 5
[0156] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that the detergent
composition used is modified by the addition of 4% by weight of
TAED, as bleach activator.
[0157] The results obtained are set out in the following Table
5.
7 TABLE 5 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye
2 inhibitor 1(A) 99 100 inhibitor 1(B) 96 97
[0158] The results in Table 5 show that manganese complexes of
formula (1) exhibit excellent performance as dye transfer
inhibitors and that their effectiveness is not impaired by their
co-use with activated bleach systems.
[0159] Moreover, the compatibility between manganese complexes of
formula (1) and activated bleach systems has recriprocal benefits.
In particular, under the conditions described in Example 1, the
bleach-promoting action of TAED is maintained, even in the presence
of 20 .mu.M of a manganese complex of formula (1). Thus, the
brightness increase (.DELTA.Y) obtained with tea-stained cotton
test material is 24 when no dye transfer inhibitor is present
(control test); 23 using inhibitor 1(A); and 24 using inhibitor
1(B).
EXAMPLE 6
[0160] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that the detergent
composition used is modified by the addition of 100 .mu.M of
DEQUEST 2041 [ethylenediamine-tetra-(methylenephosphonic acid)], as
sequestering agent.
[0161] The results obtained are set out in the following Table
6.
8TABLE 6 Test dye transfer DTI effectivity (a) inhibitor Dye 1 Dye
2 inhibitor 1(A) 20 .mu.mol/l 50 .mu.mol/l 20 .mu.mol/l 50
.mu.mol/l without DEQUEST 83 90 95 98 with DEQUEST 89 93 95 98
inhibitor 1(B) 20 .mu.moL/l 50 .mu.mol/l 20 .mu.mol/l 50 .mu.mol/l
without DEQUEST 76 82 78 87 with DEQUEST 82 87 79 83
[0162] The results in Table 6 show that manganese complexes of
formula (1) exhibit excellent performance as dye transfer
inhibitors and that their effectiveness is not impaired by their
co-use with a sequestering agent. Sequestering agents are usually
present in detergent formulations and their presence can often lead
to the observation of higher a-values. This is because heavy metal
ions are masked, and therefore the reservoir of peroxidic oxygen is
not depleted by useless degradation processes.
EXAMPLE 7
[0163] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that the amounts
used of H.sub.2O.sub.2 in the detergent are varied.
[0164] The results obtained are set out in the following Table
7.
9 DTI effectivity (a) inhibitor 1(A) inhibitor 1(B) H.sub.2O.sub.2
Concentration .mu.mol/l Dye 1 Dye 2 Dye 1 Dye 2 2.1 84 85 65 60 4.3
86 88 83 79 8.6 89 89 85 82
[0165] The results in Table 7 show that, even when the conventional
amount of H.sub.2O.sub.2 present in the detergent formulation is
reduced by a factor of 4, the effectiveness of manganese complexes
of formula (1) as dye transfer inhibitors is retained.
EXAMPLE 8
[0166] The procedure in Example 1 is repeated with the exceptions
that only inhibitors 1(A) and 1(B) are used and that a series of
dyed cotton fabrics is used which are known to very sensitive to
aggressive bleaching systems. For the purpose of comparison, an
analogous test using TAED instead of inhibitor 1(A) or 1(B) is
conducted. The washing treatment is carried out five times with
each respective detergent composition and, after completion of the
fifth respective wash, the percentage loss of dye is
determined.
[0167] The results are set out in the following Table 8.
10 TABLE 8 % Dyestuff Loss Test Dye inhibitor 1(A) inhibitor 1(B)
TAED Reactive Brown 017 16 17 15 Vat Brown 001 0 4 2 Reactive Red
123 16 10 13 Direct Blue 085 18 14 14
[0168] The results in Table 8 show that the dyestuff loss observed
when using a detergent containing a manganese complex of formula
(1) as dye transfer inhibitor, is of the same order as that
experienced when a detergent containing a TAED-activated bleach
system is used. The latter detergent composition represents the
state of the art for oxygen bleaches, and its dye damage/usefulness
balance is accepted in the industry.
[0169] Using the same test conditions, after completion of the
fifth respective wash, the percentage relative reduction of DP
(average degree of polymerisation) is determined, in order to
assess the damage to the fibre.
[0170] The results are set out in the following Table 9.
11 TABLE 9 % Relative DP-Reduction Test Dye inhibitor 1(A)
inhibitor 1(B) TAED Reactive Brown 017 4 12 5 Vat Brownool 18 20 19
Reactive Red 123 26 19 7 Direct Blue 085 0 1 2
[0171] The results in Table 9 show that the fibre damage on dyed
cotton material observed when using a detergent containing a
manganese complex of formula (1) as dye transfer inhibitor, is of
the same order as that experienced when a detergent containing a
TAED-activated bleach system is used.
* * * * *