U.S. patent number RE39,557 [Application Number 10/835,583] was granted by the patent office on 2007-04-10 for laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewith.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Eugene Paul Gosselink, Jennifer Leupin Moe (formerly, Jennifer Ann Leupin.
United States Patent |
RE39,557 |
|
April 10, 2007 |
Laundry detergent compositions with cellulosic based polymers to
provide appearance and integrity benefits to fabrics laundered
therewith
Abstract
Compositions and methods which utilize certain cellulosic based
polymer or oligomeric materials as fabric treatment agents that can
impart fabric appearance and integrity benefits to fabrics and
textiles laundered in washing solutions which contain such
materials. Specifically, the cellulosic based polymers or oligomers
are of the general formula: ##STR00001## Wherein each R is selected
from the group consisting of R.sub.2, R.sub.C, and ##STR00002##
each R.sub.2 is independently selected from the group consisting of
H and C.sub.1-C.sub.4 alkyl; each R.sub.C is ##STR00003## each Z is
independently selected from the group consisting of M, R.sub.2,
R.sub.C, and R.sub.H; and each R.sub.H is independently selected
from the group consisting of C.sub.5-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, substituted alkyl, hydroxyalkyl,
C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl, C.sub.7-C.sub.20
alkylaryloxy-2-hydroxyalkyl, (R.sub.4).sub.2N-alkyl,
(R.sub.4).sub.2N-2-hydroxyalkyl, (R.sub.4).sub.3N-alkyl,
(R.sub.4).sub.3N-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl, ##STR00004## The Degree of Substitution for
group R.sub.H in these cellulosic based polymers or oligomers is
between about 0.001 and 0.1, and the Degree of Substitution for
group R.sub.C wherein Z is H or M in these cellulosic based
polymers or oligomers is between about 0.2 and 2.0.
Inventors: |
Moe (formerly, Jennifer Ann Leupin;
Jennifer Leupin (West Chester, OH), Gosselink; Eugene
Paul (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
22019558 |
Appl.
No.: |
10/835,583 |
Filed: |
September 15, 1998 |
PCT
Filed: |
September 15, 1998 |
PCT No.: |
PCT/US98/19142 |
371(c)(1),(2),(4) Date: |
December 11, 1998 |
PCT
Pub. No.: |
WO99/14295 |
PCT
Pub. Date: |
March 25, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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60058892 |
Sep 15, 1997 |
|
|
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Reissue of: |
09202387 |
Dec 11, 1998 |
06384011 |
May 7, 2002 |
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Current U.S.
Class: |
510/473; 8/137;
510/470; 510/461 |
Current CPC
Class: |
C08B
15/06 (20130101); C11D 3/3723 (20130101); C08B
11/20 (20130101); C08B 15/00 (20130101); C08G
73/0616 (20130101); C11D 3/3776 (20130101); C11D
3/227 (20130101); C08G 73/02 (20130101); C11D
3/225 (20130101); C08B 11/193 (20130101); C11D
3/0015 (20130101); C08G 73/022 (20130101); C08G
73/0273 (20130101); C08B 11/12 (20130101) |
Current International
Class: |
C11D
3/22 (20060101); B08B 3/04 (20060101); C11D
3/37 (20060101) |
Field of
Search: |
;510/461,470,473
;8/137 |
References Cited
[Referenced By]
U.S. Patent Documents
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4000093 |
December 1976 |
Nicol et al. |
4011169 |
March 1977 |
Diehl et al. |
4174305 |
November 1979 |
Burns et al. |
4220548 |
September 1980 |
Hashimoto et al. |
4786494 |
November 1988 |
Hirota et al. |
4976885 |
December 1990 |
Wisotzki et al. |
5049302 |
September 1991 |
Holland et al. |
5211883 |
May 1993 |
Yamashina et al. |
5385585 |
January 1995 |
Kiesewetter et al. |
5466461 |
November 1995 |
della Valle et al. |
5658870 |
August 1997 |
Leu |
5837666 |
November 1998 |
Murata et al. |
5925181 |
July 1999 |
Cook et al. |
6579840 |
June 2003 |
Heltovics |
6803355 |
October 2004 |
Panandiker et al. |
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Foreign Patent Documents
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0 100 125 |
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Jul 1983 |
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EP |
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0 615 979 |
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May 1989 |
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EP |
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0 374 633 |
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Dec 1989 |
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EP |
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0 702 697 |
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Mar 1994 |
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EP |
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2 219 587 |
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Dec 1989 |
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GB |
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WO 94/24169 |
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Oct 1994 |
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WO |
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WO 97/31950 |
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Sep 1997 |
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WO |
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WO 98/29528 |
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Jul 1998 |
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WO |
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Primary Examiner: Mruk; Brian P.
Attorney, Agent or Firm: Corstanje; Brahm J. Charles; Mark
A. Zerby; Kim W.
Parent Case Text
CROSS REFERENCE
Under 35 U.S.C .sctn.119(e), this application claims the benefit of
U.S. Provisional Application No. 60/058,892, filed on Sep. 15,
1997.
Claims
What is claimed is:
1. A detergent composition comprising: a) from about 1% to about
80% by weight of surfactants selected from the group consisting of
nonionic, anionic, cationic, amphoteric, zwitterionic surfactants,
or mixtures thereof; and b) from about 0.1% to about 5.0% by weight
of a mixture of cellulosic based polymers or oligomers of the
general formula: ##STR00018## wherein each R is selected from the
group consisting of R.sub.C, and H; wherein: each R.sub.C is
##STR00019## wherein each Z is independently selected from the
group consisting of M, R.sub.2,R.sub.C, and R.sub.H; each R.sub.2
is independently selected from the group consisting of H and
C.sub.1-C.sub.4 alkyl; each R.sub.H is independently selected from
the group consisting of C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7
cycloalkyl, C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl,
substituted alkyl, hydroxyalkyl, C.sub.1-C.sub.20
alkoxy-2-hydroxyalkyl, C.sub.7-C.sub.20
alkylaryloxy-2-hydroxyalkyl, (R.sub.4).sub.2N-alkyl,
(R.sub.4).sub.2N-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl, ##STR00020## each R.sub.4is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl; each R.sub.5 is
independently selected from the group consisting of H,
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, (R.sub.4).sub.2N-alkyl, and
(R.sub.4).sub.3N-alkyl; wherein: M is a suitable cation selected
from the group consisting of Na, K, 1/2 Ca, and 1/2 Mg; each y is
from about 1 to about 5; and provided that: the Degree of
Substitution for group R.sub.H is between about 0.001 and 0. 1; the
Degree of Substitution for group R.sub.C wherein Z is H or M is
between about 0.2 and 2.0; if any R.sub.H bears a positive charge,
it is balanced by a suitable anion; and two R.sub.4's on the same
nitrogen can together form a ring structure selected from the group
consisting of piperidine and morpholine.
2. The detergent composition of claim 1, wherein each R.sub.H is
independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, (R.sub.4).sub.2N-hydroxyalkyl, and
C.sub.6-C.sub.12 aryloxy-2-hydroxyalkyl.
3. The detergent composition of claim 1, wherein each R.sub.H is
independently selected from the group consisting of
##STR00021##
4. The detergent composition of claim 1, wherein the cellulosic
based polymer or oligomer has an average molecular weight of from
about 5,000 to about 2,000,000.
5. The detergent composition of claim 1, wherein the cellulosic
based polymer or oligomer has an average molecular weight of from
about 10,000 to about 1,000,000.
6. A laundry additive composition comprising: a) from about 1% to
about 80% by weight of water; and b) from about 0.1% to about 80.0%
by weight of cellulosic based polymers or oligomers of the general
formula: ##STR00022## wherein each R is selected from the group
consisting of R.sub.C, .Iadd.R.sub.H, .Iaddend.and H; wherein: each
R.sub.C, is ##STR00023## wherein each Z is independently selected
from the group consisting of M, R.sub.2, R.sub.C, and R.sub.H; each
R.sub.2 is independently selected from the group consisting of H
and C.sub.1-C.sub.4 alkyl; each R.sub.H is independently selected
from the group consisting of C.sub.5-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, substituted alkyl, hydroxyalkyl,
C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl, C.sub.7-C.sub.20
alkylaryloxy-2-hydroxyalkyl, (R.sub.4).sub.2N-alkyl,
(R.sub.4).sub.2N-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl, ##STR00024## each R.sub.4 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl; each R.sub.5 is
independently selected from the group consisting of H,
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, (R.sub.4).sub.2N-alkyl, and
(R.sub.4).sub.3N-alkyl; wherein: M is a suitable cation selected
from the group consisting of Na, K, 1/2 Ca, and 1/2 Mg; each y is
from about 1 to about 5; and provided that: the Degree of
Substitution for group R.sub.H is between about 0.001 and 0.1; the
Degree of Substitution for group R.sub.C wherein Z is H or M is
between about 0.2 and 2.0; if any R.sub.H bears a positive charge,
it is balanced by a suitable anion; and two R.sub.4's on the same
nitrogen can together form a ring structure selected from the group
consisting of piperidine and morpholine.
7. The laundry additive composition of claim 6, wherein each
R.sub.H is independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, (R.sub.4).sub.2N-2-hydroxyalkyl, and
C.sub.6-C.sub.12 aryloxy-2-hydroxyalkyl.
8. The laundry additive composition of claim 6, wherein each
R.sub.H is independently selected from the group consisting of
##STR00025##
9. The detergent additive composition of claim 6, wherein the
cellulosic based polymer or oligomer has an average molecular
weight of from about 5,000 to about 2,000,000.
10. The detergent additive composition of claim 1, wherein the
cellulosic based polymer or oligomer has an average molecular
weight of from about 10,000 to about 1,000,000.
.Iadd.11. The detergent composition of claim 1 wherein the
cellulosic based polymers or oligomers is:
--(C(O)--CH(C.sub.16H.sub.33)--C(O)CH.sub.2(C.sub.16H.sub.33) ester
of carboxymethylcellulose..Iaddend.
.Iadd.12. A laundry additive composition of claim 6, wherein the
cellulosic based polymers or oligomers is:
--(C(O)--CH(C.sub.16H.sub.33)--C(O)CH.sub.2(C.sub.16H.sub.33) ester
of carboxymethylcellulose..Iaddend.
.Iadd.13. A method for laundering fabrics comprising contacting the
fabrics with an aqueous washing solution comprising a detergent
composition, wherein the detergent composition comprises: a) from
about 1% to about 80% by weight of surfactants selected from the
group consisting of nonionic, anionic, cationic, amphoteric,
zwitterionic surfactants, or mixtures thereof; and b) from about
0.1% to about 5.0% by weight of a mixture of cellulosic based
polymers or oligomers of the general formula: ##STR00026## wherein
each R is selected from the group consisting of R.sub.C, and
R.sub.H, and H; wherein: each R.sub.C is ##STR00027## wherein each
Z is independently selected from the group consisting of M,
R.sub.2, R.sub.C, and R.sub.H; each R.sub.2 is independently
selected from the group consisting of H and C.sub.1-C.sub.4 alkyl;
each R.sub.H is independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydoxyalkyl, ##STR00028## each R4 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl; each R5 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, substituted alkyl, hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, and (R.sub.4).sub.3N-alkyl; wherein: M is a
suitable cation selected from the group consisting of Na, K, 1/2
Ca, and 1/2 Mg; each y is from about 1 to about 5; and provided
that: the Degree of Substitution for group R.sub.H is between about
0.001 and 0.1; the Degree of Substitution for group R.sub.C wherein
Z is H or M is between about 0.2 and 2.0; if any R.sub.H bears a
positive charge, it is balanced by a suitable anion; and two
R.sub.4's on the same nitrogen can together form a ring structure
selected from the group consisting of piperidine and
morpholine..Iaddend.
.Iadd.14. The method of claim 13, wherein each R.sub.H is
independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl, and C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl..Iaddend.
.Iadd.15. The method of claim 13, wherein each R.sub.H is
independently selected from the group consisting of ##STR00029##
.Iaddend.
.Iadd.16. The method of claim 13, wherein the cellulosic based
polymer or oligomer has an average molecular weight of from about
5,000 to about 2,000,000..Iaddend.
.Iadd.17. The method of claim 13, wherein the cellulosic based
polymer or oligomer has an average molecular weight of from about
10,000 to about 1,000,000..Iaddend.
.Iadd.18. The method of claim 13, wherein the cellulosic based
polymers or oligomers is:
--(C(O)--CH(C.sub.16H.sub.33)--C(O)CH.sub.2(C.sub.16H.sub.33) ester
of carboxymethylcellulose..Iaddend.
.Iadd.19. A method for laundering fabrics comprising contacting the
fabrics with an aqueous washing solution comprising a laundry
additive composition comprising: a) from about 1% to about 80% by
weight of water; and b) from about 0.1% to about 5.0% by weight of
cellulosic based polymers or oligomers of the general formula:
##STR00030## wherein each R is selected from the group consisting
of R.sub.C, R.sub.H, and H; wherein: each R.sub.C is ##STR00031##
wherein each Z is independently selected from the group consisting
of M, R.sub.2, R.sub.C, and R.sub.H; each R.sub.2 is independently
selected from the group consisting of H and C.sub.1-C.sub.4 alkyl;
each R.sub.H is independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydoxyalkyl, ##STR00032## each R4 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl; each R5 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, substituted alkyl, hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, and (R.sub.4).sub.3N-alkyl; wherein: M is a
suitable cation selected from the group consisting of Na, K, 1/2
Ca, and 1/2 Mg; each y is from about 1 to about 5; and provided
that: the Degree of Substitution for group R.sub.H is between about
0.001 and 0.1; the Degree of Substitution for group R.sub.C wherein
Z is H or M is between about 0.2 and 2.0; if any R.sub.H bears a
positive charge, it is balanced by a suitable anion; and two
R.sub.4's on the same nitrogen can together form a ring structure
selected from the group consisting of piperidine and
morpholine..Iaddend.
.Iadd.20. The method of claim 19, wherein each R.sub.H is
independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl, and C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl..Iaddend.
.Iadd.21. The method of claim 19, wherein each R.sub.H is
independently selected from the group consisting of ##STR00033##
.Iaddend.
.Iadd.22. The method of claim 19, wherein the cellulosic based
polymer or oligomer has an average molecular weight of from about
5,000 to about 2,000,000..Iaddend.
.Iadd.23. The method of claim 19, wherein the cellulosic based
polymer or oligomer has an average molecular weight of from about
10,000 to about 1,000,000..Iaddend.
.Iadd.24. The method of claim 19, wherein the cellulosic based
polymers or oligomers is:
--(C(O)--CH(C.sub.16H.sub.33)--C(O)CH.sub.2(C.sub.16H.sub.33) ester
of carboxymethylcellulose..Iaddend.
Description
TECHNICAL FIELD
The present invention relates to compositions, in either liquid or
granular form, for use in laundry applications, wherein the
compositions comprise certain cellulosic based polymer or oligomer
materials which impart appearance and integrity benefits to fabrics
and textiles laundered in washing solutions formed from such
compositions.
BACKGROUND OF THE INVENTION
It is, of course, well known that alternating cycles of using and
laundering fabrics and textiles, such as articles of worn clothing
and apparel, will inevitably adversely affect the appearance and
integrity of the fabric and textile items so used and laundered.
Fabrics and textiles simply wear out over time and with use.
Laundering of fabrics and textiles is necessary to remove soils and
stains which accumulate therein and thereon during ordinary use.
However, the laundering operation itself, over many cycles, can
accentuate and contribute to the deterioration of the integrity and
the appearance of such fabrics and textiles.
Deterioration of fabric integrity and appearance can manifest
itself in several ways. Short fibers are dislodged from woven and
knit fabric/textile structures by the mechanical action of
laundering. These dislodges fibers may form lint, fuzz or "pills"
which are visible on the surface of fabrics and diminish the
appearance of newness of the fabric. Further, repeated laundering
of fabrics and textiles, especially with bleach-containing laundry
products, can remove dye from fabrics and textiles and impart a
faded, worn out appearance as a result of diminished color
intensity, and in many cases, as a result of changes in hues or
shades of color.
Given the foregoing, there is clearly an ongoing need to identify
materials which could be added to laundry detergent products that
would associate themselves with the fibers of the fabrics and
textiles laundered using such detergent products and thereby reduce
or minimize the tendency of the laundered fabric/textiles to
deteriorate in appearance. Any such detergent product additive
material should, of course, be able to benefit fabric appearance
and integrity without unduly interfering with the ability of the
laundry detergent to perform its fabric cleaning function. The
present invention is directed to the use of cellulosic based
polymer or oligomer materials in laundry applications which perform
in this desired manner.
SUMMARY OF THE INVENTION
Cellulosic based polymer or oligomer materials which are suitable
for use in laundry operations and provide the desired fabric
appearance and integrity benefits can be characterized by the
following general formula: ##STR00005## wherein each R is selected
from the group consisting of R.sub.2, R.sub.C, and ##STR00006##
wherein: each R.sub.2 is independently selected from the group
consisting of H and C.sub.1-C.sub.4 alkyl; each R.sub.C is
##STR00007## wherein each Z is independently selected from the
group consisting of M, R.sub.2, R.sub.C, and R.sub.H; each R.sub.H
is independently selected from the group consisting of
C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, C.sub.1-C.sub.20 alkoxy-2-hydroxyalkyl,
C.sub.7-C.sub.20 alkylaryloxy-2-hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, (R.sub.4).sub.2N-2-hydroxyalkyl,
(R.sub.4).sub.3N-alkyl, (R.sub.4).sub.3N-2-hydroxyalkyl,
C.sub.6-C.sub.12 aryloxy-2-hydroxyalkyl, ##STR00008## each R.sub.4
is independently selected from the group consisting of H,
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, aminoalkyl,
alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl,
morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each
R.sub.5 is independently selected from the group consisting of H,
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.7 cycloalkyl,
C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl, substituted
alkyl, hydroxyalkyl, (R.sub.4).sub.2N-alkyl, and (R.sub.4).sub.3
N-alkyl; wherein: M is a suitable cation selected from the group
consisting of Na, K, 1/2 Ca, and 1/2 Mg; each x is from 0 to about
5; each y is from about 1 to about 5, and provided that: The Degree
of Substitution for group R.sub.H is between about 0.001 and 0.1,
more preferably between about 0.005 and 0.05, and most preferably
between about 0.01 and 0.05; the Degree of Substitution for group
R.sub.C wherein Z is H or M is between about 0.2 and 2.0, more
preferably between about 0.3 and. 1.0, and most preferably between
about 0.4 and 0.7; if any R.sub.H bears a positive charge, it is
balanced by a suitable anion; and two R.sub.4's on the same
nitrogen can together form a ring structure selected from the group
consisting of piperidine and morpholine.
The cellulosic based polymer or oligomer materials defined above
can be used as a washing solution additive in either granular or
liquid form. Alternatively, they can be admixed to granular
detergents, dissolved in liquid detergent compositions or added to
a fabric softening composition. The forgoing description of uses
for the cellulosic based fabric treatment materials defined herein
are intended to be exemplary and other uses will be apparent to
those skilled in the art and are intended to be within the scope of
the present invention.
The laundry detergent compositions herein comprise from about 1% to
80% by weight of a detersive surfactant, from about 0.1% to 80% by
weight of an organic or inorganic detergency builder and from about
0.1% to 5% by weight of the cellulosic based fabric treatment
materials of the present invention. The detersive surfactant and
detergency builder materials can be any of those useful in
conventional laundry detergent products.
Aqueous solutions of the cellulosic based polymer or oligomer
materials of the subject invention comprise from about 0.1% to 80%
by weight of the cellulosic based fabric treatment materials
dissolved in water and other ingredients such as stabilizers and pH
adjusters.
In its method aspect, the present invention relates to the
laundering or treating of fabrics and textiles in aqueous washing
or treating solutions formed from effective amounts of the
detergent compositions described herein, or formed from the
individual components of such compositions. Laundering of fabrics
and textiles in such washing solutions, followed by rinsing and
drying, imparts fabric appearance benefits to the fabric and
textile articles so treated. Such benefits can include improved
overall appearance, pill/fuzz reduction, antifading, improved
abrasion resistance, and/or enhanced softness.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in wash solutions
which comprise the cellulosic based polymer or oligomer materials
of the present invention fabric appearance and integrity are
enhanced. The cellulosic based fabric treatment materials can be
added to wash solutions by incorporating them into a detergent
composition, a fabric softener or by adding them separately to the
washing solution. The cellulosic based fabric treatment materials
are described herein primarily as liquid or granular detergent
additives but the present invention is not meant to be so limited.
The cellulosic based fabric treatment materials, detergent
composition components, optional ingredients for such compositions
and methods of using such compositions, are described in detail
below. All percentages are by weight unless other specified.
A) Cellulosic Based Polymer or Oligomer Materials
The essential component of the compositions of the present
invention comprises one or more cellulosic based polymer or
oligomer. Such materials have been found to impart a number of
appearance benefits to fabrics and textiles laundered in aqueous
washing solutions formed from detergent compositions which contain
such cellulosic based fabric treatment materials. Such fabric
appearance benefits can include, for example, improved overall
appearance of the laundered fabrics, reduction of the formation of
pills and fuzz, protection against color fading, improved abrasion
resistance, etc. The cellulosic based fabric treatment materials
used in the compositions and methods herein can provide such fabric
appearance benefits with acceptably little or no loss in cleaning
performance provided by the laundry detergent compositions into
which such materials are incorporated.
As will be apparent to those skilled in the art, an oligomer is a
molecule consisting of only a few monomer units while polymers
comprise considerably more monomer units. For the present
invention, oligomers are defined as molecules having an average
molecular weight below about 1,000 and polymers are molecules
having an average molecular weight of greater than about 1,000. One
suitable type of cellulosic based polymer or oligomer fabric
treatment material for use herein has an average molecular weight
of from about 5,000 to about 2,000,000, preferably from about
50,000 to about 1,000,000.
The cellulosic based fabric treatment component of the detergent
compositions herein will generally comprise from about 0.1% to
about 5% by the weight of the detergent composition. More
preferably, such cellulosic based fabric treatment materials will
comprise from about 0.5% to about 4% by weight of the detergent
compositions, most preferably from about 0.75% to about 3%.
However, as discussed above, when used as a washing solution
additive, i.e. when the cellulosic based fabric treatment component
is not incorporated into a detergent composition, the concentration
of the cellulosic based component can comprise from about 0.1% to
about 80% by weight of the additive material.
One suitable group of cellulosic based polymer or oligomer
materials for use herein is characterized by the following formula:
##STR00009## wherein each R is selected from the group consisting
of R.sub.2, R.sub.C, and ##STR00010## wherein: each R.sub.2 is
independently selected from the group consisting of H and
C.sub.1-C.sub.4 alkyl; each R.sub.C is ##STR00011## wherein each Z
is independently selected from the group consisting of M, R.sub.2,
R.sub.C, and R.sub.H; each R.sub.H is independently selected from
the group consisting of C.sub.5-C.sub.20 alkyl, C.sub.5-C.sub.7
cycloalkyl, C.sub.7-C.sub.20 alkylaryl, C.sub.7-C.sub.20 arylalkyl,
substituted alkyl, hydroxyalkyl, C.sub.1-C.sub.20
alkoxy-2-hydroxyalkyl, C.sub.7-C.sub.20
alkylaryloxy-2-hydroxyalkyl, (R.sub.4).sub.2N-alkyl,
(R.sub.4).sub.2N-2-hydroxyalkyl, (R.sub.4).sub.3N-alkyl,
(R.sub.4).sub.3N-2-hydroxyalkyl, C.sub.6-C.sub.12
aryloxy-2-hydroxyalkyl, ##STR00012## each R.sub.4 is independently
selected from the group consisting of H, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl,
cycloalkylaminoalkyl and hydroxyalkyl; each R.sub.5 is
independently selected from the group consisting of H, C.sub.1 -C20
alkyl, C.sub.5-C.sub.7 cycloalkyl, C.sub.7-C.sub.20 alkylaryl,
C.sub.7-C.sub.20 arylalkyl, substituted alkyl, hydroxyalkyl,
(R.sub.4).sub.2N-alkyl, and (R.sub.4).sub.3N-alkyl; wherein: M is a
suitable cation selected from the group consisting of Na, K, 1/2
Ca, and 1/2 Mg; each x is from 0 to about 5; each y is from about 1
to about 5, and provided that: The Degree of Substitution for group
R.sub.H is between about 0.001 and 0.1, more preferably between
about 0.005 and 0.05, and most preferably between about 0.01 and
0.05; the Degree of Substitution for group R.sub.C wherein Z is H
or M is between about 0.2 and 2.0, more preferably between about
0.3 and 1.0, and most preferably between about 0.4 and 0.7; if any
R.sub.H bears a positive charge, it is balanced by a suitable
anion; and two R.sub.4's on the same nitrogen can together form a
ring structure selected from the group consisting of piperidine and
morpholine.
The "Degree of Substitution" for group R.sub.H, which is sometimes
abbreviated herein "DS.sub.RH", means the number of moles of group
R.sub.H components that are substituted per anhydrous glucose unit,
wherein an anhydrous glucose unit is a six membered ring as shown
in the repeating unit of the general structure above.
The "Degree of Substitution" for group R.sub.C, which is sometimes
abbreviated herein "DS.sub.RC", means the number of moles of group
R.sub.C components, wherein Z is H or M, that are substituted per
anhydrous glucose unit, wherein an anhydrous glucose unit is a six
membered ring as shown in the repeating unit of the general
structure above. The requirement that Z be H or M is necessary to
insure that there are a sufficient number of carboxy methyl groups
such that the resulting polymer is soluble. It is understood that
in addition to the required number of R.sub.C components wherein Z
is H or M, there can be, and most preferably are, additional
R.sub.C components wherein Z is a group other than H or M.
The production of materials according to the present invention is
further defined in the Examples below.
B) Detersive Surfactant
The detergent compositions herein comprise from about 1% to 80% by
weight of a detersive surfactant. Preferably such compositions
comprise from about 5% to 50% by weight of surfactant. Detersive
surfactants utilized can be of the anionic, nonionic, zwitterionic,
ampholytic or cationic type or can comprise compatible mixtures of
these types. Detergent surfactants useful herein are described in
U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, U.S. Pat. No.
3,919,678, Laughlin et al., issued Dec. 30, 1975, U.S. Pat. No.
4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No.
4,239,659, Murphy, issued Dec. 16, 1980. All of these patents are
incorporated herein by reference. Of all the surfactants, anionics
and nonionics are preferred.
Useful anionic surfactants can themselves be of several different
types. For example, water-soluble salts of the higher fatty acids,
i.e., "soaps", are useful anionic surfactants in the compositions
herein. This includes alkali metal soaps such as the sodium,
potassium, ammonium, and alkylammonium salts of higher fatty acids
containing from about 8 to about 24 carbon atoms, and preferably
from about 12 to about 18 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutralization of free
fatty acids. Particularly useful are the sodium and potassium salts
of the mixtures of fatty acids derived from coconut oil and tallow,
i.e., sodium or potassium tallow and coconut soap.
Additional non-soap anionic surfactants which are suitable for use
herein include the water-soluble salts, preferably the alkali
metal, and ammonium salts, of organic sulfuric reaction products
having in their molecular structure an alkyl group containing from
about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric
acid ester group. (Included in the term "alkyl" is the alkyl
portion of acyl groups.) Examples of this group of synthetic
surfactants are a) the sodium, potassium and ammonium alkyl
sulfates, especially those obtained by sulfating the higher
alcohols (C.sub.8-C.sub.18 carbon atoms) such as those produced by
reducing the glycerides of tallow or coconut oil; b) the sodium,
potassium and ammonium alkyl polyethoxylate sulfate, particularly
those in which the alkyl group contains from 10 to 22, preferably
from 12 to 18 carbon atoms, and wherein the polyethoxylate chain
contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and
c) the sodium and potassium alkylbenzene sulfonates in which the
alkyl group contains from about 9 to about 15 carbon atoms, in
straight chain or branched chain configuration, e.g., those of the
type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkylbenzene
sulfonates in which the average number of carbon atoms in the alkyl
group is from about 11 to 13, abbreviated as C.sub.11-13 LAS.
Preferred nonionic surfactants are those of the formula
R.sub.1(OC.sub.2H.sub.4).sub.nOH, wherein R.sub.1 is a
C.sub.10-C.sub.16 alkyl group or a C.sub.8-C.sub.12 alkyl phenyl
group, and n is from 3 to about 80. Particularly preferred are
condensation products of C.sub.12-C.sub.15 alcohols with from about
5 to about 20 moles of ethylene oxide per mole of alcohol, e.g.,
C.sub.12-C.sub.13 alcohol condensed with about 6.5 moles of
ethylene oxide per mole of alcohol.
Additional suitable nonionic surfactants include polyhydroxy fatty
acid amides of the formula: ##STR00013## wherein R is a C.sub.9-17
alkyl or alkenyl, R.sub.1 is a methyl group and Z is glycityl
derived from a reduced sugar or alkoxylated derivative thereof.
Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl
N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty
acid amides are known and can be found in Wilson, U.S. Pat. No.
2,965,576 and Schwartz, U.S. Pat. No. 2,703,798, the disclosures of
which are incorporated herein by reference.
Preferred surfactants for use in the detergent compositions
described herein are amine based surfactants of the general
formula: ##STR00014## wherein R.sub.1 is a C.sub.6-C.sub.12 alkyl
group, n is from about 2 to about 4, X is a bridging group which is
selected from NH, CONH, COO, or O or X can be absent; and R.sub.3
and R.sub.4 are individually selected from H, C.sub.1-C.sub.4
alkyl, or (CH.sub.2--CH.sub.2--O(R.sub.5)) wherein R.sub.5 is H or
methyl. Especially preferred amines based surfactants include the
following: ##STR00015## wherein R.sub.1 is a C.sub.6-C.sub.12 alkyl
group and R.sub.5 is H or CH.sub.3. Particularly preferred amines
for use in the surfactants defined above include those selected
from the group consisting of octyl amine, hexyl amine, decyl amin,
dodecyl amine, C.sub.8-C.sub.12 bis(hydroxyethyl)amine,
C.sub.8-C.sub.12 bis (hydroxyisopropyl)amine, C.sub.8-C.sub.12
amido-propyl dimethyl amine, or mixtures thereof.
In a highly preferred embodiment, the amine based surfactant is
described by the formula:
R.sub.1--C(O)--NH--(CH.sub.2).sub.3--N(CH.sub.3).sub.2 wherein
R.sub.1 is C.sub.8-C.sub.12 alkyl.
C) Detergent Builder
The detergent compositions herein may also comprise from about 0.1%
to 80% by weight of a detergent builder. Preferably such
compositions in liquid form will comprise from about 1% to 10% by
weight of the builder component. Preferably such compositions in
granular form will comprise from about 1% to 50% by weight of the
builder component. Detergent builders are well known in the art and
can comprise, for example, phosphate salts as well as various
organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include
the various alkali metal, ammonium and substituted ammonium
polyacetates, carboxylates, polycarboxylates and polyhydroxy
sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium, potassium, lithium, ammonium and substituted
ammonium salts of ethylene diamine tetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and citric acid. Other suitable
polycarboxylates for use herein are the polyacetal carboxylates
described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to
Crutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27,
1979 to Crutchfield et al., both of which are incorporated herein
by reference. Particularly preferred polycarboxylate builders are
the oxydisuccinates and the ether carboxylate builder compositions
comprising a combination of tartrate monosuccinate and tartrate
disuccinate described in U.S. Pat. No. 4,663,071, Bush et al.,
issued May 5, 1987, the disclosure of which is incorporated herein
by reference.
Examples of suitable nonphosphorus, inorganic builders include the
silicates, aluminosilicates, borates and carbonates. Particularly
preferred are sodium and potassium carbonate, bicarbonate,
sesquicarbonate, tetraborate decahydrate, and silicates having a
weight ratio of SiO.sub.2 to alkali metal oxide of from about 0.5
to about 4.0, preferably from about 1.0 to about 2.4. Also
preferred are aluminosilicates including zeolites. Such materials
and their use as detergent builders are more fully discussed in;
Corkill et al., U.S. Pat. No. 4,605,509, the disclosure of which is
incorporated herein by reference. Also discussed in U.S. Pat. No.
4,605,509 are crystalline layered silicates which are suitable for
use in the detergent compositions of this invention.
D) Optical Detergent Ingredients
In addition to the surfactants, builders and cellulosic based
polymer or oligomer materials hereinbefore described, the detergent
compositions of the present invention can also include any number
of additional optional ingredients. These include conventional
detergent composition components such as enzymes and enzyme
stabilizing agents, suds boosters or suds suppressers, anti-tarnish
and anticorrosion agents, soil suspending agents, soil release
agents, germicides, pH adjusting agents, non-builder alkalinity
sources, chelating agents, organic and inorganic fillers, solvents,
hydrotropes, optical brighteners, dyes and perfumes.
pH adjusting agents may be necessary in certain applications where
the pH of the wash solution is greater than about 10.0 because the
fabric integrity benefits of the defined compositions begin to
diminish at a higher pH. Hence, if the wash solution is greater
than about 10.0 after the addition of the cellulosic based polymer
or oligomer materials of the present invention a pH adjuster should
be used to reduce the pH of the washing solution to below about
10.0, preferably to a pH of below about 9.5 and most preferably
below about 7.5. Suitable pH adjusters will be known to those
skilled in the art.
A preferred optional ingredient for incorporation into the
detergent compositions herein comprises a bleaching agent, e.g., a
peroxygen bleach. Such peroxygen bleaching agents may be organic or
inorganic in nature. Inorganic peroxygen bleaching agents are
frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic
acid bleaching agents and salts thereof. Suitable examples of this
class of agents include magnesium monoperoxyphthalate hexahydrate,
the magnesium salt of metachloro perbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic
acid. Such bleaching agents are disclosed in U.S. Pat. No.
4,483,781, Hartman, Issued Nov. 20, 1984; European Patent
Application EP-A-133,354, Banks et al., Published Feb. 20, 1985;
and U.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983.
Highly preferred bleaching agents also include
6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S.
Pat. No. 4,634,551, Issued Jan. 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used, generally in
particulate form, in the detergent compositions herein. Inorganic
bleaching agents are in fact preferred. Such inorganic peroxygen
compounds include alkali metal perborate and percarbonate
materials. For example, sodium perborate (e.g. mono- or
tetra-hydrate) can be used. Suitable inorganic bleaching agents can
also include sodium or potassium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate
bleach (e.g., OXONE, manufactured commercially by DuPont) can also
be used. Frequently inorganic peroxygen bleaches will be coated
with silicate, borate, sulfate or water-soluble surfactants. For
example, coated percarbonate particles are available from various
commercial sources such as FMC, Solvay Interox, Tokai Denka and
Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the
percarbonates, etc., are preferably combined with bleach
activators, which lead to the in situ production in aqueous
solution (i.e., during use of the compositions herein for fabric
laundering/bleaching) of the peroxy acid corresponding to the
bleach activator. Various non-limiting examples of activators are
disclosed in U.S. Pat. No. 4,915,854, Issued Apr. 10, 1990 to Mao
et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1, 1983 to Chung et
al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl
ethylene diamine (TAED) activators are typical and preferred.
Mixtures thereof can also be used. See also the hereinbefore
referenced U.S. Pat. No. 4,634,551 for other typical bleaches and
activators useful herein.
Other useful amido-derived bleach activators are those of the
formulae: R.sup.1N(R.sup.5)C(O)R.sup.2C(O)L or
R.sup.1C(O)N(R.sup.5)R.sup.2C(O)L wherein R.sup.1 is an alkyl group
containing from about 6 to about 12 carbon atoms, R.sup.2 is an
alkylene containing from 1 to about 6 carbon atoms, R.sup.5 is H or
alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon
atoms, and L is any suitable leaving group. A leaving group is any
group that is displaced from the bleach activator as a consequence
of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenol
sulfonate.
Preferred examples of bleach activators of the above formulae
include (6-octanamido-caproyl) oxybenzenesulfonate,
(6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl)
oxybenzenesulfonate and mixtures thereof as described in the
hereinbefore referenced U.S. Pat. No. 4,634,551.
Another class of useful bleach activators comprises the benzoxazin
type activators disclosed by Hodge et al. in U.S. Pat. No. 4,966,
723, Issued Oct. 30, 1990, incorporated herein by reference. A
highly preferred activator of the benzoxazin-type is:
##STR00016##
Still another class of useful bleach activators includes the acyl
lactam activators, especially acyl caprolactams and acyl
valerolactams of the formulae: ##STR00017## wherein R.sup.6 is H or
an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to
about 12 carbon atoms. Highly preferred lactarn activators include
benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethy hexanoyl
caprolactam, nonanoyl caprolactar, decanoyl caprolactan, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, nonanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactar,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Pat. No. 4,545,784, Issued to Sanderson, Oct. 8, 1985,
incorporated herein by reference, which discloses acyl
caprolactams, including benzoyl caprolactam, adsorbed into sodium
perborate.
If utilized, peroxygen bleaching agent will generally comprise from
about 2% to 30% by weight of the detergent compositions herein.
More preferably, peroxygen bleaching agent will comprise from about
2% to 20% by weight of the compositions. Most preferably, peroxygen
bleaching agent will be present to the extent of from about 3% to
15% by weight of the compositions herein. If utilized, bleach
activators can comprise from about 2% to 10% by weight of the
detergent compositions herein. Frequently, activators are employed
such that the molar ratio of bleaching agent to activator ranges
from about 1:1 to 10:1, more preferably from about 15:1 to 5:1.
Another highly preferred optional ingredient in the detergent
compositions herein is a detersive enzyme component. While it is
known that some enzymes will degrade the peptide bonds of
cellulosics, the cellulosic based polymer or oligomer materials
defined herein do not exhibit such degradation in the presence of
enzymes. Hence, enzymes can be added to detergent compositions
which comprise the cellulosic based fabric treatment materials of
the present invention with substantially no degradation.
Enzymes can be included in the present detergent compositions for a
variety of purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains from substrates,
for the prevention of refugee dye transfer in fabric laundering,
and for fabric restoration. Suitable enzymes include proteases,
amylases, lipases, cellulases, peroxidases, and mixtures thereof of
any suitable origin, such as vegetable, animal, bacterial, fungal
and yeast origin. Preferred selections are influenced by factors
such as pH-activity and/or stability, optimal thermostability, and
stability to active detergents, builders and the like. In this
respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a
cleaning, stain removing or otherwise beneficial effect in a
laundry detergent composition. Preferred enzymes for laundry
purposes include, but are not limited to, proteases, cellulases,
lipases, amylases and peroxidases.
Enzymes are normally incorporated into detergent compositions at
levels sufficient to provide a "cleaning-effective amount". The
term "cleaning-effective amount" refers to any amount capable of
producing a cleaning, stain removal, soil removal, whitening,
deodorizing, or freshness improving effect on substrates such as
fabrics. In practical terms for current commercial preparations,
typical amounts are up to about 5 mg by weight, more typically 0.01
mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated otherwise, the compositions herein will typically comprise
from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005
to 0.1 Anson units (AU) of activity per gram of composition. Higher
active levels may be desirable in highly concentrated detergent
formulations.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B.
licheniformis. One suitable protease is obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold as ESPERASE.RTM. by Novo Industries A/S of
Denmark, hereinafter "Novo". The preparation of this enzyme and
analogous enzymes is described in GB 1,243,784 to Novo. Other
suitable proteases include ALCALASE.RTM. and SAVINASE.RTM. from
Novo and MAXATASE.RTM. from Interaational Bio-Synthetics Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 A,
Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,
1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease
from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other
enzymes, and a reversible protease inhibitor are described in WO
9203529 A to Novo. Other preferred proteases include those of WO
9510591 A to Procter & Gamble. When desired, a protease having
decreased adsorption and increased hydrolysis is available as
described in WO 9507791 to Procter & Gamble. A recombinant
trypsin-like protease for detergents suitable herein is described
in WO 9425583 to Novo.
Cellulases usable herein include both bacterial and funga types,
preferably having a pH optimum between 5 and 10. U.S. Pat. No.
4,435,307, Barbesgoard et al., Mar. 6, 1984, discloses suitable
fungal cellulases from Humicola insolens or Humicola strain DSM1800
or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a
marine mollusk, Dolabella Auricula Solander. Suitable cellulases
are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and
DE-OS-2.247.832. CAREZYME.RTM. and CELLUZYME.RTM. (Novo) are
especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced
by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also, the
lipase in Japanese Patent Application 53,20487, laid open Feb. 24,
1978. This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P."
Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE.RTM.
enzyme derived from Humicola lanuginosa and commercially available
from Novo, see also EP 341,947, is a preferred lipase for use
herein.
The enzyme-containing compositions herein may optionally also
comprise from about 0.001% to about 10%, preferably from about
0.005% to about 8%, most preferably from about 0.01% to about 6%,
by weight of an enzyme stabilizing system. The enzyme stabilizing
system can be any stabilizing system which is compatible with the
detersive enzyme. Such a system may be inherently provided by other
formulation actives, or be added separately, e.g., by the
formulator or by a manufacturer of detergent-ready enzymes. Such
stabilizing systems can, for example, comprise calcium ion, boric
acid, propylene glycol, short chain carboxylic acids, boronic
acids, and mixtures thereof, and are designed to address different
stabilization problems depending on the type and physical form of
the detergent composition.
E) Detergent Composition Preparation
The detergent compositions according to the present invention can
be in liquid, paste or granular form. Such compositions can be
prepared by combining the essential and optional components in the
requisite concentrations in any suitable order and by any
conventional means.
Granular compositions, for example, are generally made by combining
base granule ingredients, e.g., surfactants, builders, water, etc.,
as a slurry, and spray drying the resulting slurry to a low level
of residual moisture (5-12%). The remaining dry ingredients, e.g.,
granules of the essential cellulosic based fabric treatment
materials, can be admixed in granular powder form with the spray
dried granules in a rotary mixing drum. The liquid ingredients,
e.g., solutions of the essential cellulosic based fabric treatment
materials, enzymes, binders and perfumes, can be sprayed onto the
resulting granules to form the finished detergent composition.
Granular compositions according to the present invention can also
be in "compact form", i.e. they may have a relatively higher
density than conventional granular detergents, i.e. from 550 to 950
g/l. In such case, the granular detergent compositions according to
the present invention will contain a lower amount of "inorganic
filler salt", compared to conventional granular detergents; typical
filler salts are alkaline earth metal salts of sulphates and
chlorides, typically sodium sulphate; "compact" detergents
typically comprise not more than 10% filler salt.
Liquid detergent compositions can be prepared by admixing the
essential and optional ingredients thereof in any desired order to
provide compositions containing components in the requisite
concentrations. Liquid compositions according to the present
invention can also be in "compact form", in such case, the liquid
compositions according to the present invention will contain a
lower amount of water, compared to conventional liquid detergents.
Addition of the cellulosic based polymer or oligomer materials to
liquid detergent or other aqueous compositions of this invention
may be accomplished by simply mixing into the liquid solutions the
desired cellulosic based fabric treatment materials.
F) Fabric Laundering Method
The present invention also provides a method for laundering fabrics
in a manner which imparts fabric appearance benefits provided by
the cellulosic based polymer or oligomer materials used herein.
Such a method employs contacting these fabrics with an aqueous
washing solution formed from an effective amount of the detergent
compositions hereinbefore described or formed from the individual
components of such compositions. Contacting of fabrics with washing
solution will generally occur under conditions of agitation
although the compositions of the present invention may also be used
to form aqueous unagitated soaking solutions for fabric cleaning
and treatment. As discussed above, it is preferred that the washing
solution have a pH of less than about 10.0, preferably it has a pH
of about 9.5 and most preferably it has a pH of about 7.5.
Agitation is preferably provided in a washing machine for good
cleaning. Washing is preferably followed by drying the wet fabric
in a conventional clothes dryer. An effective amount of a high
density liquid or granular detergent composition in the aqueous
wash solution in the washing machine is preferably from about 500
to, about 7000 ppm, more preferably from about 1000 to about 3000
ppm.
G) Fabric Conditioning
The cellulosic based polymer or oligomer materials hereinbefore
described as components of the laundry detergent compositions
herein may also be used to treat and condition fabrics and textiles
in the absence of the surfactant and builder components of the
detergent composition embodiments of this invention. Thus, for
example, a fabric conditioning composition comprising only the
cellulosic based fabric treatment materials themselves, or
comprising an aqueous solution of the cellulosic based fabric
treatment materials, may be added during the rinse cycle of a
conventional home laundering operation in order to impart the
desired fabric appearance and integrity benefits hereinbefore
described.
EXAMPLES
The following examples illustrate the compositions and methods of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention.
Example I
Granular Detergent Test Composition Preparation
Several heavy duty granular detergents compositions are prepared
containing various modified cellulosic polymers. These granular
detergent compositions all have the following basic formula:
TABLE-US-00001 TABLE A Component Wt. % C.sub.13 Linear alkyl
benzene sulfonate 9.31 C.sub.14-15 alkyl ether (0.35 EO) sulfate
12.74 Zeolite Builder 27.79 Sodium Carbonate 27.31 PEG 4000 1.60
Dispersant 2.26 C.sub.12-13 Alcohol Ethoxylate (9 EO) 1.5 Sodium
Perborate 1.03 Soil Release Polymer 0.41 Enzymes 0.59 Modified
Cellolosic Polymer (Except "Control") 3.0 Perfume, Brightener, Suds
Suppressor, Other Balance Minors, Moisture, Sulfate 100%
Example II
Liquid Detergent Test Composition Preparation
Several heavy duty liquid detergent compositions are prepared
containing various modified cellulosic polymers. These liquid
detergent compositions all have the following basic formula:
TABLE-US-00002 TABLE B Component Wt. % C.sub.12-15 alkyl ether
(2.5) sulfate 38 C.sub.12 glucose amide 6.86 Citric Acid 4.75
C.sub.12-14 Fatty Acid 2.00 Enzymes 1.02 MEA 1.0 Propanediol 0.36
Borax 6.58 Dispersant 1.48 Na Toluene Sulfonate 6.25 Modified
Cellolosic Polymer (Except "Control") 3.0 Dye, Perfume,
Brighteners, Preservatives, Suds Balance Suppressor, Other Minors,
Water 100%
Example III
Synthesis of Modified CMC Materials
The carboxylation of cellulose to produce CMC is a procedure that
is well known to those skilled in the art. To produce the modified
CMC materials of this invention, one adds during the CMC making
process the material, or materials, to be substituted. An example
of such as procedure is given below. This same procedure can be
utilized with the other substituent materials described herein by
replacing the hexylchloride with the substituent material, or
materials, of interest, for example, cetylchloride. The amount of
material that should be added to the CMC making process to achieve
the desired degree of substitution will be easily calculated by
those skilled in the art in light of the following Examples.
Synthesis of Hexylether of CMC
This example illustrates the preparation of a carboxymethyl
hydrophobically modified carboxymethyl cellulose and is
representative of preparation of all of the cellulose ether
derivatives of this invention.
Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and
ethanol (150 g) are charged into a 500 ml glass reactor. The
resulting alkali cellulose is stirred 45 minutes at 25.degree. C.
Then monochloroacetic acid (15 g) and hexylchoride (1 g) are added
and the temperature raised over time to 95.degree. C. and held at
95.degree. C. for 150 minutes. The reaction is cooled to 70.degree.
C., and then cooled to 25.degree. C. Neutralization is accomplished
by the addition of a sufficient amount of nitric acid/acetic acid
to achieve a slurry pH of between 8 and 9. The slurry is filtered
to obtain a hexylether of CMC.
Example IV
Cellulosic Polymers Used in Test Detergent Compositions
The representative modified cellulosic polymers used in the liquid
and granular detergent compositions described in Examples I and II
are characterized in Table C. The General Polymer Parameters are
common to all of the polymers, while the specific chemical
structure of the materials tested are listed under the Specific
Polymer Parameters.
TABLE-US-00003 TABLE C General Polymer Parameters Molecular
Parameters Description Polymer Backbone Carboxymethylcellulose
Degree of Carboxymethylation DS.sub.EC = 0.3-2.0; preferred
DS.sub.EC = 0.5-0.70. Distribution of Carboxymethyls Even and
random distribution of carboxylmethyls along the backbone Molecular
Weight Mw: 5,000-2,000000. Preferred: medium (approx 250,000 g/mol)
Type of Modification Ether modification (in addition to
carboxyethylation). Mixed cellulose ether Level of Modification
DS.sub.SM = about 0.001 to about 0.1
TABLE-US-00004 TABLE D Specific Polymer Parameters Type of Modifi-
ID Polymer cation*** Types of Chemistry *A Hexyl CMC Hexyl ether
Chlorohexane added to CMC *B Decyl CMC Decyl ether Chlorodecane
added to CMC **C C12-C13 C12-C13 C12-C13 alkyl gly- alkoxy-2
alkoxy-2 cidyl ether added to 2 hydrxoy- hydroxy- MC making propyl
CMC propyl ether process *D Hexadecyl CMC Hexadecyl
Chlorohexadecane ether added to CMC making process *E Chloride salt
of 3- chloride salt of 2,3-epoxypropyltri- trimethyl ammonio-2-
3-trimethyl- methyl ammonium hydroxypropyl ether ammonio-2-
chloride added to of CMC hydroxypropyl the CMC making ether process
*F [--(C(O)--CH(C16H33)]-- Cetyl Ketene Dimer C(O)CH2(C16H33)]
added to CMC ester of CMC or 1,3- making process. dioxo-2-
hexadecyloctadecyl ester of CMC CMC = Carboxymethylcellulose
*Manufactured by Metsa Specialty Chemicals **Manufactured by Akzo
***DS.sub.SM for these materials was in the range of from about
0.001 to about 0.1
Example V
Overall Appearance
In an Overall Appearance test, fabrics are washed using various
test compositions containing either no cellulosic polymers
(control) or one of the polmers defined in Tables C and D above.
The fabrics are washed and after ten cycles are then comparatively
graded by three judges who evaluate the overall appearance of the
washed fabrics. It is the decision of the judge as to what is to be
evaluated unless specific direction is given to evaluate one
attribute such as color, pilling, fuzz, etc. All tests are
conducted under the same conditions which are carefully monitored.
Examples of controlled conditions include: wash time, wash water
temperature and hardness; washer agitation; rinse time, rinse water
temperature and hardness, dryer time and temperature; wash load
fiber content and weight.
In the Overall Appearance test, the visual preference of the judge
is expressed using the Scheff scale.
That is: 0=No difference 1=I think this one is better (unsure). 2=I
know this one is a little better. 3=I know this one is a lot
better. 4=I know this one is a whole lot better. For the Overall
Appearance test, laundering conditions are as follows: Washer Type:
Kenmore (17 gallons) Wash Time: 12 min Wash Temperature: 90.degree.
F. (32.2.degree. C.) Wash Water Hardness: 6 grains per gallon
Washer Agitation: normal Rinse Time: 2 min Rinse Temperature:
60.degree. F. (15.6.degree. C.) Rinse Water Hardness: 6 grains per
gallon Wash Load Fabric Content: various colored and white garments
and fabrics Wash Load Weight: 5.5 lbs (2.5 kg) The average overall
appearance test results are shown in Table E.
TABLE-US-00005 TABLE E Overall Appearance Test Results Granular
Overall Test Appear- Composi- ance tion ID Polymer Tested Grade
Control None 0 A Hexyl ether of Carboxymethylcellulose 1.8 B Decyl
ether of Carboxymethylcellulose 1.8 C C12-C13 alkoxy-2
hydroxypropyl ether of 1.8 Carboxymethylcellulose D Hexadecyl ether
of Carboxymethylcellulose 2.0 E Chloride salt of
3-trimethylammonio-2- 1.0 hydroxypropyl ether of Carboxymethyl-
cellulose F [--(C(O)--CH(C16H33)--C(O)CH2(C16H33)] 1.5 ester of
Carboxymethylcellulose
Example VI
Pill Reduction
In a Pill Reduction test, fabrics are washed using the various test
compositions containing one of the cellulosic polymers defined in
Example IV and compared to control fabrics washed in the same
detergent compositions containing no cellulosic polymers. The wash
conditions are held constant and are the same as in Example V
above. The fabrics so washed are then graded for Pill Reduction
using a computer-assisted pilling image analysis system which
employs image analysis to measure the number of pills on tested
garments and fabrics. Pill reduction is calculated as: Pill
reduction(%)={[# pills (control)-# pills (polymers)]/# pills
(control)}.times.100% The average % Pill Reduction test results are
shown in Table F.
TABLE-US-00006 TABLE F Pill Reduction Test Results-Granules
Granular Pill/ Test Fuzz Composi- Reduction tion ID Polymer Tested
Grade Control None 0 A Hexyl ether of Carboxymethylcellulose 38% D
Hexadecyl ether of Carboxymethylcellulose 31% E Chloride salt of
3-trimethylammonio-2- 27% hydroxypropyl ether of
Carboxymethylcellulose F [--(C(O)--CH(C16H33)--C(O)CH2(C16H33)] 25%
ester of Carboxymethylcellulose
* * * * *