Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – With oxygen or halogen containing chemical bleach or oxidant...
Reexamination Certificate
2002-01-24
2004-12-07
Del Cotto, Gregory R. (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
With oxygen or halogen containing chemical bleach or oxidant...
C510S309000, C510S311000, C510S499000, C502S200000, C502S324000
Reexamination Certificate
active
06828293
ABSTRACT:
The present invention relates to water-soluble granules of salen-type manganese complexes, to a process for the preparation thereof and to the use thereof as dye-transfer inhibitors in washing agent preparations.
A number of salen-type manganese complexes are already known to be suitable catalysts for oxidations with peroxy compounds, especially within the context of washing procedures. The use of certain manganese complexes as catalysts for preventing the redeposition of migrating dyes in peroxide-containing washing liquors is described in EP 902 083, but the action of those manganese complexes as dye-transfer inhibitors is not optimum under all washing conditions. A further problem is that the peroxy compound and/or the catalyst in the washing agent formulation decompose(s) during prolonged storage in a moist atmosphere.
Surprisingly, it has now been found that granules comprising a salen-type manganese complex and at least 10% by weight of an anionic or non-ionic dissolution restrainer provide better inhibition of the redeposition of migrating dyes in washing liquors than is provided by the pure manganese complexes when the total amount of manganese complex entering into the washing liquor is the same in both cases. A further advantage of the granules is that the storage stability of peroxide-containing washing agent formulations comprising such granules is improved. In addition, these granules inhibit undesired colouration of the washing agent as a result of the gradual dissolution of the manganese complexes in one or more of the washing agent components.
The present invention accordingly relates to water-soluble granules of salen-type manganese complexes, comprising
a) from 1 to 89% by weight, preferably from 1 to 30% by weight, of a water-soluble salen-type manganese complex,
b) from 10 to 95% by weight of a dissolution restrainer,
c) from 0 to 20% by weight of a further additive and
d) from 1 to 15% by weight of water, based on the total weight of the granules.
As manganese complexes for the granules according to the invention there come into consideration compounds that contain, complexed with manganese, from 1 to 3 saldimine groups, that is to say, groups obtainable by condensing unsubstituted or substituted salicylaldehydes with amines.
Especially suitable are compounds of formula
wherein
A is an anion;
m, n and p are each independently of the others 0, 1, 2 or 3,
R
4
is hydrogen or linear or branched C
1
-C
4
alkyl,
Y is a linear or branched alkylene radical of formula —[C(R
4
)
2
]
r
—, wherein r is an integer from 1 to 8 and the R
4
radicals are each independently of the others as defined above; —CX═CX—, wherein X is cyano, linear or branched C
1
-C
8
alkyl or di(linear or branched C
1
-C
8
alkyl)amino; —(CH
2
)
q
—NR
4
—(CH
2
)
q
—, wherein R
4
is as defined above and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula:
wherein R
9
is hydrogen, SO
3
H, CH
2
OH or CH
2
NH
2
,
R, R
1
and R
1
′ are each independently of the others cyano; halogen; OR
4
or COOR
4
wherein R
4
is as defined above; nitro; linear or branched C
1
-C
8
alkyl; linear or branched partially fluorinated or perfluorinated C
1
-C
8
alkyl; or NHRR
6
, NR
5
R
6
or N
⊕
R
5
R
6
R
7
wherein R
5
, R
6
and R
7
are the same or different and are each hydrogen or linear or branched C
1
-C
12
alkyl or wherein R
5
and R
6
together with the nitrogen atom to which they are bonded form a 5-, 6- or 7-membered ring, which may contain further hetero atoms, or are linear or branched C
1
-C
8
alkyl-R
6
wherein R
6
is a radical OR
4
, COOR
4
or NR
5
R
6
as defined above or is NH
2
or N
⊕
R
5
R
6
R
7
wherein R
5
, R
6
and R
7
are as defined above,
R
2
and R
3
are each independently of the other hydrogen, linear or branched C
1
-C
4
alkyl, unsubstituted aryl or aryl that is substituted by cyano, by halogen, by OR
4
or COOR
4
wherein R
4
is hydrogen or linear or branched C
1
-C
4
alkyl, by nitro, by linear or branched C
1
-C
8
alkyl, by NHR
5
or NR
5
R
6
, wherein R
5
and R
5
are the same or different and are each linear or branched C
1
-C
12
alkyl or wherein R
5
and R
5
together with the nitrogen atom to which they are bonded form a 5-, 6- or 7-membered ring, which may contain further hetero atoms, by linear or branched C
1
-C
8
alkyl-R
7
wherein R
7
is an OR
4
, COOR
4
or NR
5
R
6
radical as defined above or is NH
2
, or by N
⊕
R
5
R
6
R
7
wherein R
5
, R
6
and R
7
are as defined above.
When, in the compounds of formulae (1) and (3), R, R
1
, R
1
′ and/or R
8
are N
⊕
R
5
R
6
R
7
or R
2
and/or R
3
are N
⊕
R
5
R
6
R
7
substituted aryl wherein R
5
, R
6
and R
7
are as defined above, the following anions are suitable for balancing the positive charge on the N
⊕
R
5
R
6
R
7
group: halide, for example chloride, perchlorate, sulfate, nitrate, hydroxide, BF
4
−
, PF
6
−
, carboxylate, acetate, tosylate and triflate. Of those anions, bromide and chloride are preferred.
In compounds of formulae (1) and (3) in which n, m or p is 2 or 3, the radicals R, R
1
and R
1
′ have the same or different meanings.
When Y is a 1,2-cyclohexylene radical, it may be present in any of its stereoisomeric cisitrans forms.
Preferably, Y is a radical of formula —(CH
2
)
r
— wherein r is an integer from 1 to 4, especially 2, or is a radical of formula —C(R
4
)
2
—(CH
2
)P—C(R
4
)
2
— wherein p is a number from 0 to 3, especially 0, and each R
4
, independently of the others, is hydrogen or C
1
-C
4
alkyl, especially hydrogen or methyl, or is a 1,2-cyclohexylene radical or a 1,2-phenylene radical of formula:
Halogen is preferably chlorine, bromine or fluorine, chlorine being especially preferred.
When n, m or p is 1, the groups R, R
1
and R
1
′ are preferably in the 4-position of the respective benzene ring except when R, R
1
or R
1
′ is nitro or COOR
4
, in which case that group is preferably in the 5-position. When R, R
1
or R
1
′ is a N
⊕
R
5
R
6
R
7
group, that group is preferably in the 4- or 5-position.
When n, m or p is 2, the two R, R
1
or R
1
′ groups are preferably in the 4,6-position of the respective benzene ring except when they are nitro or COOR
5
, in which case the two groups are preferably in the 3,5-position.
When R, R
1
or R
1
′ is di(C
1
-C
12
alkyl)amino, the alkyl group may be straight-chain or branched.
Preferably, it contains from 1 to 8, especially from 1 to 3, carbon atoms.
Preferably, the radicals R, R
1
and R
1
′ are hydrogen, OR
4
, N(R
4
)
2
or N
⊕
(R
4
)
3
, wherein the R
4
groups in N(R
4
)
2
or N
⊕
(R
4
)
3
may be different and are hydrogen or C
1
-C
4
alkyl, especially methyl, ethyl or isopropyl.
The radicals R
2
and R
3
are especially hydrogen, methyl, ethyl or unsubstituted phenyl.
Aryl is, for example, naphthyl or, especially, phenyl.
When R
5
and R
6
together with the nitrogen atom to which they are bonded form a 5-, 6- or 7-membered ring, the ring is especially a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted, for example by alkyl, at the nitrogen atom that is not bonded to the phenyl or alkyl radical.
Suitable anions A include, for example, halide, such as chloride or bromide, perchlorate, sulfate, nitrate, hydroxide, BF
4
−
, PF
6
−
, carboxylate, acetate, tosylate and triflate. Of those anions, chloride, bromide and acetate are preferred.
The compounds of formulae (1), (2) and (3) are known or can be prepared in a manner known per se. The manganese complexes are prepared from the corresponding ligands and a manganese compound. Such preparation procedures are described, for example, in U.S. Pat. Nos. 5,281,578 and 4,066,459 and by Bernardo et al., Inorg. Chem. 45 (1996) 387.
Preferred formulations of the granules comprise from 1 to 90% by weight, especially from 1 to 30% by weight, of salen-type manganese complex of formula (1), (2) or (3), based on the total weight of the granules.
Instead of a single, homogeneous manganese complex of formula (
Bachmann Frank
Hazenkamp Menno
Kuratli Rolf
Kvita Petr
Makowka Cornelia
Ciba Specialty Chemicals Corporation
Del Cotto Gregory R.
Mansfield Kevin T.
LandOfFree
Water-soluble granules of salen-type manganese complexes does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Water-soluble granules of salen-type manganese complexes, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Water-soluble granules of salen-type manganese complexes will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3328295