Liquid laundry detergent compositions containing proteolytic...

Details Liquid laundry detergent compositions containing proteolytic... Liquid laundry detergent compositions containing proteolytic...

1999-03-24

2001-01-30

Fries, Kery (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

Enzyme component of specific activity or source

C510S393000, C510S530000, C510S320000, C510S321000, C510S334000, C510S499000

Reexamination Certificate

active

06180586

ABSTRACT:

TECHNICAL FIELD
This invention relates to liquid laundry detergent compositions containing protease enzymes. More specifically, this invention pertains to liquid laundry detergent compositions containing a detersive surfactant, a proteolytic enzyme, and a protease inhibitor selected from the group consisting of proteins, peptides and peptide derivatives, such as peptide aldehydes and peptide trifluromethyl ketones.
BACKGROUND OF THE INVENTION
Protease-containing liquid aqueous detergents are well-known, especially in the context of laundry washing. A commonly encountered problem in such protease-containing liquid aqueous detergents is the degradation phenomenon by the proteolytic enzyme of second enzymes in the composition, such as amylase, lipase, and cellulase, or on the protease itself. As a result, the stability of the second enzyme or the protease itself in the detergent composition is affected and the detergent composition consequently performs less well.
In response to this problem, it has been proposed to use various protease inhibitors or stabilizers. For instance, various references have proposed the use of the following compounds to aid in the stabilization of enzymes: proteins, benzamidine hydrochloride, lower aliphatic alcohols or carboxylic acids, mixtures of a polyol and a boron compound, aromatic borate esters, and calcium, particularly calcium formate. Recently, it was discovered that certain peptide aldehydes and peptide trifluromethyl ketones act to stabilize protease enzyme.
Although these compounds have been used to varying success in liquid detergents, there is still a need for stable protease-containing liquid laundry detergent compositions.
BACKGROUND ART
It has been proposed to use various protease inhibitors or stabilizers. For instance, U.S. Pat. No. 4,566,985 proposes to use benzamidine hydrochloride; EP 376 705 proposes to use lower aliphatic alcohols or carboxylic acids; EP 381 262 proposes to use a mixture of a polyol and a boron compound; and EP91870072.5 proposes to use aromatic borate esters. See also U.S. Pat. No. 5,030,378 issued Jul. 9, 1991. Also see U.S. Pat. No. 4,261,868; U.S. Pat. No. 4,404,115; U.S. Pat. No. 4,318,818; and EP130,756.
The use of peptide derivatives for the inhibition of proteins appears to have been disclosed in therapeutic applications. EP 293 881 discloses the use of peptide boronic acids as inhibitors of trypsin-like serine proteases. EP 185 390 and U.S. Pat. No. 4,399,065 disclose the use of certain peptide aldehydes derivatives for the inhibition of blood coagulation. J 90029670 discloses the use of optically active alpha amino aldehydes for the inhibition of enzymes in general. See also “Inhibition of Thrombin and Trypsin by Tripeptide Aldehydes”,
Int. J. Peptide Protein Res
., Vol 12 (1978), pp. 217-221; Gaal, Bacsy & Rappay, and “Tripeptide Aldehyde Protease Inhibitors May Depress in Vitro Prolactin and Growth Hormone Release”
Endocrinology
, Vol. 116, No. 4 (1985), pp. 1426-1432; Rappay, Makara, Bajusz & Nagy. Certain peptide aldehydes have also been disclosed in EP-A-473 502 for inhibiting protease-mediated skin irritation.
In particular see EP185,390, WO94/04651, published Mar. 3, 1994, WO94104652, published Mar. 3, 1994, EP 583,536, published Feb. 23, 1994, EP 583,535, published Feb. 3, 1994, EP 583,534, published Feb. 23, 1994, WO 93/13125, published Jul. 8, 1993, U.S. Pat. No. 4,529,525, U.S. Pat. No. 4,537,706, U.S. Pat. No. 4,537,707, and U.S. Pat. No. 5,527,487.
SUMMARY OF THE INVENTION
The invention herein is a liquid laundry detergent composition comprising:
a) an effective amount of a detersive surfactant;
b) an active proteolytic enzyme; and
c) a protease inhibitor selected from the group consisting of proteins, peptides and peptide derivatives, preferably a protease inhibitor which is a peptide derivative having the formula:
Z—B—NH—CH(R)—C(O)—X
wherein B is a peptide chain comprising from 1 to 5 amino acid moieties; X is hydrogen or CF
3
; Z is an N-capping moiety selected from the group consisting of phosphoramidate [(R″O)
2
(O)P—], sulfenamide [(SR″)
2
-], sulfonamide [(R″(O)
2
S—], sulfonic acid [SO
3
H], phosphinamide [(R″)
2
(O)P—], sulfamoyl derivative [R″O(O)
2
S—], thiourea [(R″)
2
N(O)C—], thiocarbamate [R″O(S)C—], phosphonate [R″P(O)OH], amidophosphate [R″O(OH)(O)P—], carbamate (R″O(O)C—), and urea (R″NH(O)C—), wherein each R″ is independently selected from the group consisting of straight or branched C
1
-C
6
unsubstituted alkyl, phenyl, C
7
-C
9
alkylaryl, and cycloalkyl moieties, wherein the cycloalkyl ring may span C
4
-C
8
and may contain one or more heteroatoms selected from the group consisting of O,N,and S (preferred R″ is selected from the group consisting of methyl, ethyl, and benzyl); and R is selected from the group consisting of straight or branched C
1
-C
6
unsubstituted alkyl, phenyl, and C
7
-C
9
alkylaryl moieties;
wherein the protease activity in the laundry detergent composition is less than 1% of the activity without the protease inhibitor, and the ratio of the percent of free protease in the wash to the percent of free protease in the laundry detergent composition is greater than about 100, preferably greater than about 200, and more preferably greater than about 400.
Preferably, the liquid laundry detergent compositions herein comprise, by weight of composition:
a) from about 1 to about 95%, preferably from about 8% to about 70%, of said detersive surfactant;
b) from about 0.0001% to about 5%, preferably from about 0.0003% to about 0.1%, of an active proteolytic enzyme;
c) from about 0.00001% to about 5%, preferably from about 0.0001% to about 1%, more preferably from about 0.0006% to about 0.5%, of the described protease inhibitor;
d) optionally, from about 0.01% to about 1%, preferably from about 0.05% to about 0.5%, of calcium ion; and
e) optionally, from about 0.25% to about 10%, preferably from about 0.5% to about 5%, of boric acid or a compound capable of forming boric acid, preferably with a diol;
wherein the protease activity in the laundry detergent composition is less than 1% of the activity without the protease inhibitor, and the ratio of the percent of free protease in the wash to the percent of free protease in the laundry detergent composition is greater than about 100, preferably greater than about 200, and more preferably greater than about 400.
The preferred compositions here also preferably comprise protease inhibitor and protease in a molar ratio of inhibitor to protease greater than 1:1, preferably greater than about 1.1:1, and more preferably greater than about 1.2:1. Preferred for inhibitors which are proteins are ratios (inhibitor:protease) within the range of from about 1:1 to about 3:1, more preferably from about 1.1:1 to about 2:1. Preferred for inhibitors which are peptide variants are ratios (inhibitor:protease) within the range of from about 1:1 to about 20:1, more preferably from about 2:1 to about 10:1.
In addition, the present invention liquid laundry detergent composition comprise:
a) an effective amount of a detersive surfactant;
b) an active proteolytic enzyme; and
c) a protease inhibitor selected from the group consisting of proteins, peptides and peptide derivatives, preferably a protease inhibitor which is a peptide derivative having the formula:
Z—B—NH—CH(R)—C(O)—X
wherein B is a peptide chain comprising from 1 to 5 amino acid moieties; X is hydrogen or CF
3
; Z is an N-capping moiety selected from the group consisting of phosphoramidate [(R″O)
2
(O)P—], sulfenamide [(SR″)
2
-], sulfonamide [(R″(O)
2
S—], sulfonic acid [SO
3
H], phosphinamide [(R″)
2
(O)P—], sulfamoyl derivative [R″O(O)
2
S—], thiourea [(R″)
2
N(O)C—], thiocarbamate [R″O(S)C—], phosphonate [R″P(O)OH], amidophosphate [R″O(OH)(O)P—&

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