Note: Descriptions are shown in the official language in which they were submitted.
- 213~97~ ~
W o 93t23sl6 PCT/VS93/04192
GRANULAR DETERGENT COMPOSITIONS WITH LIPASE
!
FIELD_OF THE INYENTION
This invention relates to a granular detergent composition
containing lipase produced by a lipase producing strain from the
fungi Humicola sp. on Thermomyces sp., or the bacteria Pseudomonas
Dseudoalcaliqenes or Pseudomonas fluorescens. A method of
cleaning fabrics using such a composition is also included.
BACKGROUND Ofl HE INVENTION
- The inclusion of lipase in detergent compositions for
improved cleaning performance is known. Examples are European
Patent ~pplication 0368 589, published May 16, 1990; U.S. Patents
4,707,291, Thom et al, issued November 18, 1987, 4,769,173,
Cornelissen et al issued Septembcr 6, 1988, 4,861,509, Cornelissen
et al, issued August 29, 1989, 5,069,809, Lagerwaard et al, issued
December 3,1991; and Japanese Publication 01161-096, published
December 17, 1987.
Unfortunately, although cleaning benefits from using granular
laundry detergent compositions on stained or soiled laundry are
clear after multiple laundry cycles, it has heretofore been
difficult to see those benefits (particularly on grease and oil
stains such as bacon grease and spag~etti sauce) after only one
cycle in the washing machine and clothes drier. In fact, washing
in granular detergents containing lipase at the conventional
higher levels (in commercial products) often brings about a first
cycle cleaning loss although there is a multi-cycle cleaning
benefit. It has -been found that, for the lipases shown below,
keeping the amount of lipase low (i.e. at the level shown below),
and including certain anionic or nonionic surfactants in a
specified ~eight ratio in the granular deter~ent composition, will
5 result in improvement in the removal of triglyceride-based stains
or soils, such as greasy food stains and body soils, from fabrics
even after the first laundry cycle.
~13 ~
W o 93/235l6 ' PCT/~S93/04192
--2--
SUMMARY OF THE TNVENTION
The present invention relates to a granular detergent
composition comprising, by weight: ¦ (a) from about 0.00025 to about 0.015, preferably about
0.0025 to about 0.010, grams of actiYe enzyme per 100 grams of
composition, of lipase produced by a lipase producing strain of
Humicola sp. or Thermomyces sp. or Pseudomonas Dseudoalcaliqenes
or Pseudomonas fluorescens.;
(b) from about 0.5 to about 10% of alkyl alkoxy sulfate
and/or polyhydroxy fatty acid a~ide; and
(c) from about 2 to about 30% of additional anionic or
nonionic surfactant;
wherein (a)/(b) is between about 0.~9 and about 0.28.
~.
DETAILED DESCRIPTION OF THE INVENTION
The granular detergent compositions herein comprise lipase,
alkyl alkoxy sulfate or polyhydroxy fatty acid amide and
additional anionic or nonionic surfactant. The weight ratio of
lipase to alkyl alkoxy sulfate or polyhydroxy fatty acid amide (or -mixtures of the two) is between about O.O9 (9%~ and about 0.28
(28X). Preferably, the amount of lipase divided by the amount of
alkyl alkoxy sulfate or polyhydroxy fatty acid amide is between
about 0.10 and about 0~20. The present compositions preferably r~ ,.
additionally comprise detergency builder, second enzymes, and
other conventional detergent ingredients.
The present granular detergent compositions remove
triglyceride-based soils (eg spaghetti sauce and bacon grease) I `-
after the first laundry cycle ~ie the first time the fabric is !washed after it is soiled) better than granular compositions with
higher levels of lipase do. Without meaning to be bound by theory~
it is believed that this is because the present formulas allow the
hydrolytic products remaining after breakdown of the
triglyceride-based soil by the lipase in the wash to be removed
more efficiently than do formulas outside this inYention. The
present optimized weight ratio of lipase:alkyl alkoxy sulfate or
polyhydroxy fatty acid amide in combination with the low lipase
213~978
W O 93/23516 PCT/US93/04192
levels employed herein are believed to bring about this first
cycle benefit.
A. LiDase
An essential ingredient of the present granular detergent
composition is from about 0.00025 to about 0.015, preferably about
0.002~ to about 0.010, grams of active enzyme per 100 grams of
composition, of lipase produced by a lipase producing strain of
Humicola sp. or Thermomvces sp. or Pseudomonas Dseudoalcaliqenes
or Pseudomonas fluorescens.
Lipase from chemically or genetically modified mutants of
these strains are also included herein. Mixtures of lipase from
various strains are included herein, though not preferred.
A preferred lipase is derived from Pseudomonas
~ Dseudoalcaliaenes, which is described in U.S. Patent 4,9~3,287,
Farin et al, issued June 12, 1990, incorporated herein by
reference.
The most preferred lipase herein is obtained by cloning the
gene from Humicola lanuqinosa and expressing the gene in
AsDerqillus orYzae as described in European Patent Application 0
2S8 068, incorporated herein by reference, which is commercially
available from Novo Industri A~S, Bagsvaerd, Denmark~ under the
trade name Lipolase~. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989,
incorporated herein by reference. Preferably, from about 0.001 to
about 0.6, preferably about 0.1 to about 0.4, wt.% of Lipolase~
(100,000 LU/g) is employed in the present composition.
Lipases herein are preferably compatible with anionic (and
nonionic) surfactants and have high activity at alkaline pH. They
are preferably compatible with and stable in the present
compositions and improve cleaning when they are included in the
present compositians.
Suitable lipases include those which show a positive
immunological cross-reaction with the antibody of the lipase
produced by Pseudomonas fluorescens. This lipace is described in
Japanese Patent Application 53-20487, laid open February 24, 1978,
which is incorporated herein by reference. It is available under
the trade name Lipase P Amano. A method for testing immunological
W O 93/~3sl6 2-~ 3 `I 9 7 8 PCT/U593/04192
cross-reaction with Amano P antibody is described in U.S. Patent
4,707,291, Thom et al, issued November 17, 1987, incorporated
herein by reference.
A lipase unit (LU) is defined as the amount of lipase which
produces 1 umol of titratable butyric acid per minute in a pH
stat, where pH is 7.0, temperature is 30-C, and substrate is an
emulsion of tributyrin and gum arab k in the presence of Ca++ and
NaCl in phusphate buffer.
B. Surfactant
lo The granular detergent compositions herein also comprise from
about 0.5 to about 10 wt~Yo~ preferably from about 0.5 to about 5
wt.%, most preferab1y from about 1 to about 2 wt. %, of alkyl
alkoxy sulfate, preferably alkyl sulfate which has been
~ ethoxylated with from about 0.5 to about 10, preferably from about
0.5 to about 2, moles of ethylene oxide per mole of alkyl sulfate,
and/or polyhydroxy fatty acid amide. Mixtures of the two
surfactants are included herein. The compositions further
comprise from about 2 to about 30 wt.%, preferably from about 10
to about 20 wt.%, of additional anionic or nonionic surfactant.
1. Alkvl Alkoxv Sulfate
Alkyl alkoxylated sulfate surfactants are water soluble salts
or acids typically of the formula R0(A)mS03M wherein R is an
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C
alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
~; preferably C12-Cl~ alkyl or hydroxyalkyl, A is an ethoxy or
propoxy unit, m is greater than zero, typically between about 0.5
and about 6, more preferably between about 0.5 and about 3, and M
is H or a cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well
as alkyl propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium cations,
such as tetramethyl-ammonium, dimethyl piperydinium and cations
deriYed from alkanolamines, e.a. monoethanGlamine, diethanolamine,
and triethanolamine, and mixtures thereof. Exemplary surfactants
are C12-Clg alkyl polyethoxylate (1.0) sulfate, C12-Clg alkyl
- - WO 93/23516 2 1 3 ~ 9 7 PCI/US93/04192
polyethoxylate (2.25) sulfate, C12-Clg alkyl polyethoxylate (3.0)
sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M
is conveniently selected from sodium and potassium.
2. Polvh~droxy Fatty Acid Amide
Polyhydroxy fatty acid amide surfactant comprises compounds
of the structural formula:
O Rl
Il I
(I) R2 - C - N - z
o wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably Cl-C4 alkyl, more
preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e.,
methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight chain
- C7-Clg alkyl or alkenyl, more preferably straight chain Cg-C17
alkyl or alkenyl, most preferably straight chain Cll-Cl~ alkyl or
alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls
directly connected to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably
will be derived from a reducing sugar in a reductive amination
reac~ion; more preferably Z will be a glycityl. Suitable reducing
-sugars include glucose, fructose, maltose, lactose, galactose,
mannose, and xylose. Z preferably will be se7ected from the group l-
consisting of -CH2-(CHOH)n-CH20H, -CH~CH20H)-(CHOH)n l-CH20H,
~5 -CH2-(CHOH)2(CHOR')(CHOH)-CH20H, and alkoxylated derivatives
- thereof, where n is an integer from 3 to 5, inclusive, and R' is H
or a cyclic or aliphatic monosaccharide. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH~OH.
The polyhydroxy fatty acid amide preferred herein is glucose
am~de, preferably C12-l8 N-acetyl glucamide.
3. Additional Anionic Surfactant
Anionic surfactants useful for detersive purposes are
included in the compositions hereof. These can include salts
(including, for example, sodium, potassium, ammonium, and
3j substituted ammonium salts such as mono-, di- and triethanolamine
salts) of soap, Cg-C20 linear alkylbenzenesulphonates, C~-C22
primary or secondary alkanesulphonates, Cg-C24 olefinsulphonates,
W o 93/23S~6 2 1 3 ~ g 7 ~ PCT/US93/04192 , ~
--6--
sulphonated polycarboxylic acids prepared by sulphonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as
described in British Patent Specification No. 1,082,179, alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isothionates such as the
acyl isothionates, N-acyl taurates, fatty acid amides of methyl
tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfos~ccinate (especially saturated and unsaturated C12-C1g
o monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below),
- branched primary alkyl sulfates, alkyl polyethoxy carboxylates
such as those of the formula R0(CH2CH20)kCH2COO-M~ wherein R is a
Cg-C22 alkyl, k is an integer from 0 to 10, and M is a soluble
salt-for~ing cation, and fatty acids esterified with isothionic
acid and neutralized with sodium hydroxide. Resin acids and
hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tall oil. Further examples are given
in "Surface Active Agents and Detergents" (~ol. I and II by
Schwartz, Perry and Berch). A variety of such surfactants are
also generally disclosed in U.S. Patent 3,g29,678, issued December
30, 1975 to Laughlin, et al. at Column 23, line 58 through Column
29, line 23 (herein incorporated by reference).
Alkyl sulfate surfactants are a type of anionic surfactant
preferred for use herein. In addition to providing excellent
overall cleaning ability when used in combination with polyhydroxy
3~ fatty acid amides (see below), including good grease/oil cleaning
over a wide range of temperatures, wash concentrations, and wash
times, dissolution of alkyl sulfates can be obtained, as well as
improved formulability in liquid detergent formulations are water
soluble salts or acids of the formula ROS03M wherein R preterably
3j is a C1o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C1o-C20 alkyl component, more preferably a C12-C1g alkyl
or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
1~,
--- W O 93/2351~ 2 1 ~ 4 9 7 8 PCT/~S93t~41g2 )
--7--
cation (e.g., sodium, potassium, lithium), substituted or
unsubstitut2d ammonium cations such as methyl-, dimethyl-, and
trimethyl ammonium and quaternary ammonium cations, e.g.,
tetramethyl-ammonium and dimethyl piperdinium, and cations derived
from alkanolamines such as ethanolamine, diethanolamine,
triethanolamine, and mixtures thereof, and the like. Typically,
alkyl chains of C12 16 are preferred for lower wash temperatures
(e.~., below about 50-C) and C16 18 alkyl chains are preferred for
higher wash temperatures ~e.g., above about 50-C).
loPreferred for use herein are C12-C20 alkyl sulfate ("AS~),
and/or Cg-C~o linear alkylbenzene sulfonate (preferably sodium
salts). Preferred are from about 2 to about 10 wt.~o of the C12 20
AS and from about 10 to about 15 wt.% of the C3 20 LAS.
~ Preferably the nonionic surfactant is the condensation product of
15C1o-C20 alcohol and between about 2 and about 20 moles of ethylene
oxide per mole of alcohol ("E2 20 ethoxylated C1Q ~o alcohol").
4. Additional Nonionic Surfactant
Suitable nonionic detergent surfactants are generally
disclosed in U.S. Patent 3,929t678, Laughlin et al., issued
December 30, 1975, at column 13, line 14 through column 16, line
6, incorporated herein by reference. Exemplary, non-limiting
classes of useful nonionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
,5 condensates are preferred. These compounds include the
condensation products of alkyl phenols having an alkyl group
containing from about 6 to about 12 carbon atoms in either a
straight chain or branched chain configuration with the alkylene
oxide. These compounds are commonly referred to as alkyl phenol
alkoxylates, (e.g., alkyl phenol ethoxylates).
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of
the aliphatic alcohol can either be straight or branched, primary
or secondary, and generally contains from about 8 to about 22
carbon atoms. This category of nonionic surfactant is referred to
generally as "alkyl ethoxylates." Preferred are C12-16,
W 0 93/23516 ` 2 1 3 ~ 9 7 8 P~T/US93/Q4192
--8--
preferably C12-13, ~liphatic alcohols ethoxylated with from about
3 to about 10 moles of ethylene oxide per mole of alcohol. :~
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide
; with propylene glycol. I
4. The condensation products of ethylene oxide with the
product resulting from the reaction of prspylene oxide and
ethylenediamine. :~
5. Semi-polar nonionic surfactants are a special category
lo of nonionic surfactants which include water-soluble amine oxides ~:
containing one alkyl moiety of from about 10 to about 18 carbon ` ~`
atoms and 2 moieties selected from the group consisting of alkyl
- groups and hydroxyalkyl groups containing from about 1 to about ~ -
~ carbon atoms; water-soluble phosphine oxides containing one alkyl ~-
moiety of from about 10 to about 18 carbon atoms and 2 moieties
selected fro~ the group consisting of alkyl groups and
hydroxyal~yl groups containing from about 1 to about 3 carbon
atoms; and water-soluble sulfoxides containing one alkyl moiety of
from about 10 to about 18 carbon atoms and a moiety selected from
qO the group consisting of alkyl and hydroxyalkyl moieties of from
about 1 to about 3 carbon atoms.
- 6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1386, ha~ing a hydrophobic group ;
containing from about 6 to about 30 carbon atoms, preferably from
.; about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group containing from about 1.3 to
about lC, preferably from about 1.3 to about 3, most preferably
from about 1.3 to about 2.7 saccharide units.
7. Fatty acid amide surfactants having the formula:
0
Il . .~
R6 C - N(R7)2 ..
wherein R6 is an alkyl group containing from about 7 to about 21
(preferably from about 9 to about 17) carbon atoms and each R7 is
selected from the group consisting of hydrogen, Cl-C4 alkyl, Cl-C4
- WO 93/23516 2 1 3 ~ 9 7 8 P~/US93tO4192
_g_ . .
hydroxyalkyl, and -(C2H40~XH where x varies from about 1 to about
3.
C. DeterQencv_Builder
From 1 to about 80, preferably about 20 to about 70, weight %
; of detergency builder can optionally be, and preferably is,
included herein. Inorganic as well as organic builders can be
used.
Inorganic detergency builders include, but are not limited
to, the alkali metal, ammonium and alkanolammonium salts of
pclyphosphates (e%emplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicar~onates), sulphates, and alu~inosili-
~ cates. Borate builders, as well as builders containing
borate-forming materials that can produce borate under detergent
storage or wash conditions (hereinafter, collectively "borate
builders"), can also be used. Preferably, non-borate builders are
used in the compositions of the invention intended for use at wash
conditions less than about 50 C, especially less than about 40'C.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na20 ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium silicates
described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck, incorporated herein by reference. However, other silicates
,5 may also be useful such as for example magnesium silicate, which
can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and
sesquicarbonate and mixtures thereof with ultra-fine calcium
carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973, the disclosure of which is
incorporated herein by reference.
- Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also
::
wo g3J23516 2 1 3 4 9 i 8 Pcr/usg3/o4lg2 ~- ~
--10--
be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those having the
empirical formula:
MZ(zAlo2-ysio2)
wherein M is sodium, potassium, ammonium or substituted ammonium,
z is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous
aluminosilicate. Preferred aluminosilicates are zeolite builders
which have the formula:
Naz[(A102)z (sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z
to y is in the range from 1. a to about 0.5, and x is an integer
~ from about 15 to about 264.
Useful aluminosilicate ion exchange materials are
commercially aYailable. These aluminosilicates can be crystalline
or amorphous in structure and can be naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al., issued October 12, 1976, incorporated
herein by reference. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), and Zeolite X.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta phosphate in which the
degree of polymerization ranges from about 6 to about 21, and
salts of phytic acid.
Examples of phosphonate builder salts are the water-soluble
salts of ethane l-hydro~y-l, l-diphosphonate particularly the
sodium and potassium salts, the water-soluble salts of methylene
diphosphonic acid e.g. the trisodium and tripotassium salts and
the water-soluble salts of substituted methylene diphosphonic
acids, such as the trisodium and tripotassium ethylidene,
isopyropylidene benzylmethylidene and halo methylidene
phosphonates. Phosphonate builder salts of the aforementioned
w 0 93/~3516 213~978 Pcr/US93/04192
types are disclosed in U.S. Patents 3,159,581 and 3,213,030 issued
December 1, 1964 and October 19, 1965, to Diehl; U.S. Patent
3~422,021 issued January 14, 1969, to Roy; and U.S. Patents
3,400,148 and 3,422,137 issued September 3, 1968, and January 14,
1969 to Quimby.
Organic detergent builders preferred for the purposes of the
present invention include a wide ~ariety of polycarboxylate
compounds. As used herein, "polycarboxylate" refers to compounds
having a plurality of earboxylate groups, preferably at least 3
carboxylates.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such
~ as sodiumt potassium, and lithium, or alkanolammonium salts are
preferred. -
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates.
A number of ether polycarboxylates have been discloscd for` use as
detergent builders. Examples of useful ether polycarboxylates
include oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent
3,635,830, issued January 18, 1972, both of which are incorporated
herein by reference.
~; A specific type of ether polycarboxylates useful as builders
in the present invention also include those having the general
formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)
wherein A is H or OH; B is H or -~-CH(COOX)-CH2(COOX); and X is H
or a salt-forming cation. For example, if in the above general
formula A and B are both H, then the compound is oxydissuccinic
acid and its water-soluble salts. If A is OH and B is H, then the
compound is tartrate monosuccinic acid (TMS) and its water-soluble
salts. If A is H and B is -O-CH(COOX)-CH2(COOX), then the
3, compound is tartrate disuccinic acid (TDS) and its water-soluble
salts. Mixtures of these builders are especially preferred for
use herein. Particularly preferred are mixtures of TMS and TD5 in
W 0 93/23S16 2 1 3 4 9 7 8 PCT/US~3/04192
-12-
a weight ratio of TMS to TDS of from about 97:3 to about 20:80.
These builders are disclosed in U.S. Patent 4,663,071, issued to
Bush et al., on May 5, 1987.
Suitable ether polycarboxylates also include cyclic
compounds, particularly alicyclic compounds, such as those
described in U.S. Patents 3,923,679; 3,835~163; 4,158,635;
4,120,874 and 4,102,903, all of which are incorporated herein by
reference.
Other useful detergency builders include the ether
lo hydroxypolycarboxylates represented by the structure:
HO-~C(R)(COOM)-C(R)(COOM)-O~n-H
wherein M is hydrogen or a cation wherein the resultant salt is
water-soluble, preferably an alkali metal, ammonium or substituted
~ ammonium cation, n is from about 2 to about 15 (preferably n is
from about 2 to about 10, more preferably n averages from about 2
to about 4) and each R is the same or different and selected from
hydrogen, Cl 4 alkyl or Cl 4 substituted alkyl (preferably R is
hydrogen).
Still other ether polycarboxylates include copolymers of
maleic anhydride with ethylene or vinyl methyl ether, 1, 3,
5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of
polyacetic acids. Examples include the sodium, potassium,
lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid~ and
soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders which can
also be used in granular compositions.
Other carboxylate builders include the carboxylated
carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued
March 28, 1973, incorporated herein by reference.
W 0 93/23~16 1 2i3-1978 PCT/~593/04192
-13-
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
January 28, 1986, incorporated herein by reference. Useful
succinic acid builders include the Cs-C20 alkyl succinic acids and
salts thereof. A particularly preferred compound of this type is
dodecenylsuccinic acid. Alkyl succinic acids typically are of the
general formula R-CH(COOH)CH2~COOH) i.e., derivatives of succinic
acid, wherein R is hydrocarbon, e.g., Clo-c2o alkyl or alkenyl,
preferably C12-C16 or wherein R may be substituted with hydroxyl,
sulfo, sulfoxy or sulfone substituents, all as described in the
above-mentioned patents.
The su cinate builders are preferably used in the form of
- their water-soluble salts, including the sodium, potassium,
ammonium and alkanolammonium salts.
Specific examples of succinate builders include: laurylsuc-
cinate, myristylsuccinate, palmitylsuccinate, 2-dodeoenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuc-
cinates are the preferred builders of this group, and are
described in European Patent Application 86200690.5/0,200,263,
published November 5, 1986.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-
hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
~S soluble polyacrylates (these polyacrylates having molecular
weights to above about 2,000 can also be effecitvly utilized as
dispersants), and the copolymers of maleic anhydride with vinyl
methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal car-
boxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al.,
issued March i3, 1979, incorporated herein by reference. These
polyacetal carboxylates can be preDared by bringing together,
under polymerization conditions, an ester of glyoxylic acid and a
polymerization initiator. The resulting polyacetal carboxylate
ester is then attached to chemically stable end groups to
stabilize the polyacetal ~arboxylate against rapid
W O 93/23516 2 i 3 4 9 7 8 PCT/US93/04192 ~ `
-14-
depolymerization in alkaline solution, converted to the
corresponding salt, and added to a surfactant.
Polycarboxylate builders are also disclosed in U.S. Patent
3,308,067, Diehl, issued March 7, 1967, incorporated herein by
; reference. Such materials include the water-soluble salts of
homo- and copolymers of aliphatic carboxylic acids such as maleic
acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,
citraconic acid and methylenemalonic acid.
Other organic builders known in the art can also be used.
For example, monocarboxylic acids, and soluble salts thereof,
having long chain hydrocarbyls can be utilized. These would
include materials generally referred to as "soaps." Chain lengths
of C1o-C20 are typically utilized. The hydrocarbyls can be
~ saturated or unsaturated.
Preferably the detergency builder herein is selected from the
group consisting of the salts, preferably the sodium salt, of
- carbonate, silicate, sulfate, phosphate, aluminosilicate, and
citric acid and mixtures thereof.
D. Second EnzYme
Optional, and preferred, ingredients include second enzymes,
which include protease (most preferred), amylase, peroxidase,
cellulase, and mixtures thereof. By "second enzyme" is meant
enzymes in addition to lipase which are also added to the
composition. Setond enzymes from chemically or genetically
~; modified mutants, and from bacterial or fungal origin, are
included herein.
The amount of second enzyme used in the composition varies
according to the type of enzyme and the use intended. In general,
from about 0.0001 to about 1.0, more preferably about 0.001 to
about 0.5, weight % on an active basis of these second enzymes are
preferably use`d. Mixtures of enzymes from the same class (e.g.
protease) or two or more classes (e.g. cellulase and protease) may
be used.
Any cellulase suitable for use in a detergent composition can
;5 be used in these compositions. From about 0.0001 to 1.0,
preferably 0.001 to 0.5, weight % on an active enzyme basis of
cellulase can be used.
- W O 93/23516 2 1 3 i 9 7 8 PCT/US93/04192
~5
Suitable ce ulases are ~isclosed in U.S. Patent 4,435,307,
8arbesgaard et a ! issued March 6, 1984, incorporated herein by
reference, which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in
G~-A-2.075.028, G8-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a
strain of ~Y~C~9~ insolens (Humicola q~isea var. thermoidea),
particularly the Humicola strain DSM 1800, and cellulases produced
by a fungus of Bacillus N or a cellulase 212-producing fungus
10belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
Any amylase suitable for use in a detergent composition can
be used in these compositions. Amylases include, for example,
~ ~-amylases obtained from a special strain of B.licheniforms,
described in more detail in British Patent Specification No.
1,296,839. Amylolytic proteins include, for example, RapidaseTM,
MaxamylTM and TermamylTM.
From about 0.0001% to 1.0, preferably 0.0005 to 0.~, weight %
on an active en~yme basis of amylase can be used.
20Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "solution bleaching," i.e. to
prevent transfer of dyes or pigments removed from substrates
during wash operations to other substrates in the wash solution.
~5Peroxidase enzymes are known in the art, and include, for example,
horseradish peroxidase, ligninase, and haloperoxidase such as
chloro-and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example. in PCT International
Application WO 89/099813, published October 19, 1989, by 0. Kirk,
30assigned to Novo Industries A/S, incorporated herein by reference.
From about 0.0001 to about 1.0, preferably about 0.0005 to
about 0.5, most preferably about 0.002 to about 0.1, weight % on
an active basis of detergent-compatible protease is preferred for
use herein. Mixtures of protease enzymes are also included. The
3;protease can be of animal, vegetable or microorganism (preferred)
origin. More preferred is serine protease enzyme of bacterial
origin. Purified or nonpurified forms of this enzyme may be used.
W O 93t23~16 PCT/US93/04192
-16-
Proteases produced by chemically or genetically modified mutants
are included by definition, as are close structural enzyme
variants. Particularly preferred is bacterial serine protease
enzyme obtained from Bacillus subtilis and/or Bacillus
lichen ~ormis.
Suitable proteases include Alcalase0, Esperase~, Savinase0
(preferred); Maxatase~, Maxacal~ (preferred), and Maxapem 150
(protein engineered Maxacal~); and subtilisin BPN and BPN'
(preferred); which are commercially available. Preferred
proteases are also modified bacterial serine proteases, such as
those described in European Patent Application Serial Number 87
303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98),
and which is called herein "Protease B", and in European Patent
~ Application 199,404, Venegas, published October 29, 19~6, which
refers to a modified bacterial serine proteolytic enzyme which is
called "Protaase A" herein. Preferred proteolytic en~ymes, then,
are selected from the group consisting of Savinase~, Maxacal~,
BPN', Protease A, Protease B, and mixtures thereof. Protease B is
most preferred.
E. Other Inqredients
Other ingredients suitable for use in the present
compositions, such as water, perfume, brightener, conditioners
such as fumed silica, polyethylene glycol, dyes and colorants, and
peroxyacids, can be included. Preferred ingredients are from
_5 about 0.5 to about 5 wt.% of polyethylene glycol (preferably with
molecular weight between 5,000 and 10,000, most preferably 8,000),
- from about 0.01 to about 0.7 wt.% of fluorescent whitening and/or
brightening agents, and from about 0.01 to about 1.0 wt.Z of
perfume.
Bleaching agents, including preformed peroxyacids, activated
perborate, and activated percarbonate may also be present in the
granular compositions, though they are not preferred. Suggested
levels are from about 0.5 to about 5 wtYo of peroxyacid, from 5 to
about 25 wt.% of percarbonate or perborate and from about 0.1 to
about 10 wt% of activator. A preferred activator for use with
lipase is tetra acetyl ethylene diamine. Preferred are formulas
~ W O 93/23516 2 1 3 ~ 9 7 8 PCT/US93/04192
~ 17-
without bleaching agent except for from about 0.5 to about 1.0
wt.~. af sodium perborate.
The granular detergent composition is added to the wash?
usually at levels of 1/4 to 1 cup.
This invention further provides a method for cleaning fabrics
in the wash by contacting the fabrics with effective amounts of a
granular detergent composition comprising:
(a) from about 0.0000025 to about 0.006 grams of active
enzyme per gram of composition, of lipase produced by a lipase
producing strain of Humicola sp. or Thermomvces sp. or Pseudomonas
Dseudoalcaligenes or Pseudomonas fluorescens;
(b) from about 0.5 to about 10 wt.% of alkyl alkoxy sulfate
or polyhydroxy fatty acid amide; and
~ (c) from about 2 to about 30 wt.% of additional anionic or
nonionic surfactant;
wherein (a)/(b) is between about 0.09 and about 0.28.
Agitation is preferably provided in the washing machine for
good cleaning. Washing is preferably followed by drying the wet
fabric in a conventional clothes dryer. An effective amount of
the granular detergent composition is preferably from about 500 to
about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
The following examples illustrate the compositions of the
present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention.
All parts, percentages and ratios used herein are by weight
unless otherwise specified.
i
EXAMP~E I
The following wash tests were done to observe the effects on
cleaning when a lower amount of lipase is used, and a more robust
detergent is evaluated with and without lipase.
~`
METHOD
Both polycotton and cotton fabrics were stained with greasy
foods using either a bacon grease composite (4 drops) or a
spaghetti sauce composite (brushed on). These stains were washed
in duplicate in three washing machines for each product evaluated
W o 93/23~16 2 1 3 4 9 7 8 PCT/US93/04192
~ i -18-
(see Detergents A and B below); thus, comparisons were based on
six different stained swatches for each bacon grease or spaghetti
stain. After a 12 minute wash cycle and a 35 minute dry cycle,
the stains were "graded", or compared for overall stain removal by
three graders (blind test), with results listed below.
CONCLUSION ' '~
The Detergent A samples do not contain alkyl alkoxy sulfate
or polyhydroxy fatty acid amide. The Detergent A samples do
contain lipase at three levels: 0; 0.012 grams of aotive enzyme
per lOO grams of composition (500 LU/l; 0.48 wt.%); and 0.036
g/lOOg ~1500 LU/l; 1.44 wt.%). As shown in Table A, Detergent A
with lipase (both samples) performed worse than Detergent A
~ without lipase after the ~irst wash cycle.
Table B concerns 'Detergent B. Surprisingly, Detergent B ,~
containing polyhydroxy fatty acid amide (N-acetyl fatty acid
glucamide)' and 0.0129/1009 lipase (5QO LU/l) performs
significantly better than both Detergent B with three times as
much lipase (0.036 9/1009; 1500 LU/1), and Detergent B without `~lipase (Table B). Detergent B with 0.0l2g/lOOg lipase is within
the present invention. The other two Detergent B samples are not.
RESULTS
Table A
Det. A; Det. A;
~et. A 500 LU/l 1500 LU/l
Stain alone liDase liDase
bacon grease/polycotton 0.0 -0.68 -1.34*
bacon grease/cotton 0.0 -0.03 -0.76
spaghetti/polycotton 0.0 -1.05 -1.53*
spaghetti/cotton 0.0 -l.16* -1.07*
c~
Scale used: O = stain after detergent treatment; +1 to +4 shows
degrees of improved removal over detergent alone; -1 to -4 shows
degrees of decreased removal over detergent alone.
* = significant difference, at 95% Confidence Interval (LSD).
213~978
WO 93/23516 PC~/US93/041g2
.
--19--
Note:500 LU/l is 0.0129/1009 or 0.4~ wt.% and 1500 LU/l is
0.036g/100g or 1.44 wt.% in the composition.
Table B
Det. B; Det. B;
; Det. B 500 LU/l 1500 LU/l
Stai n al one 1 i pase 1 i Dase
bacon grease/polycotton 0.0 0.12 0.18
bacon grease/catton 0.0 1.34* 0.18*
spaghetti/polycotton 0.0 1.24* 0.30
spaghettijcotton 0.0 1.27* 0.33
Scale used: same as in Table A
* = significant difference, at 95% Confidence Interval (LSD).
- Detergent A ~without alkyl alkoxy
sul~ate or Polyh~drox~fattY acid amide)
Comwnent Weiqht %
Sodium 12.3 linear alkyl benzene sulfonate 18.41
Sodium C14-15 alkyl sulfate 5.95
Sodium carbonate 21.33
Sndi um al uminosilicate 26.30
Silicate solids (2.0r) 2.29
Polyethylene glycol (MW 8QOO) 1.74
C12 13 Alcohol polyethoxylate (E6.5) 0.50
Brightener 0.30
~; Perfume 0.10
Water 10.06
Citric acid 3.50
Admix:
Sodium carbonate 8.39
Sodium perborate 0.35
Perfume 0.26
Savinase~ protease 0.52
Deterqent B (with polYhvdroxY fattY acid amide)
ComDonent Weiqht %
Sodium 12.3 linear alkyl benzene sulfonate 22.39
w o 93/23516 2 1 ~ 4 9 7 8 PCT/US93/04192 i~
-20-
Sodium C14-15 alkyl sulfate 9.59
- Sodium carbonate 26.69
Polyethylene glycol (MW 8000) 2.04
N-acetyl fatty acid glucamide 1.94
Brightener 0.30
Perfume 0-10
Water 10.06
Citric acid 11.29
Layered silicate 6.48
Admix: .
Sodium carbonate 8.39
Sodium perborate 0.35
- Perfume 0.26
SaYinase~ protease 0.21
EXAMPLE II
The effectiYeness of lipolytic enzyme in a detergent :
composition of the type described, and the comparative
effectiveness of lipolytic enzyme in a comparative detergent
formulation, are estimated as follows:
(a) Triolein-soiled polyester materials are washed in a
miniwasher under uniform conditions using two detergent
formulations as given below. .;~,
(b) Gravimetric analysis of the residue remaining on the fabric
is carried out to show an index quantity of oil remaining per
standard test cloth. Additionally, gas chromatographic
readings of the thereafter extracted residues were carried
out to show the relative efficiency of the lipolytic enzyme
under each condition.
The detergent formulas are as follows: l(a) (b)
% %
Sodium linear alkylbenzene sulfonate/
sodium alkyl sulfate (70~30) 19 21
C12 13 Alcohol polyethoxylate (6.5) 0 3
Alkylethoxy (E1) sulfate 0
Glucose amide 0 3
w o 93/13516 213~8 PCT/US93/04192
-21-
Sodium carbonate 23 71
Citric acid 3 3
Savinase~ protease 1 1
Lipase (Lipolase0) is used in each case in an equal amount.
Wash temperature is 40-C. ~,
After washing with formulation (a) the test shows the
presence of 0.189 oil and 48% triglyceride remaining in the
extracted material. After washing with formulation (b) the test
o shows the presence of 0.119 oil and 50X triglyceride remaining.
It is apparent that formulation (b) enables the removal of
more free fatty acids (FFA) from the material (0.79 more removed)
while the lipolytic enzyme functions to release the same
~ percentage of FFA from both treatments (48% vs. SO~O).
Conclusion: Improved surfactant formulation (e.g. Detergent
b with glucose amide and alkylethoxy sulfate; within the present
invention) allows hydrolytic products of lipase to be removed more
efficiently than the weaker surfactant formulation (e.g. Detergent
a, which is outside the present invention).
EXAMPLE III
A composition of the present invention is as follows:
ComDonent Weiqht %
Sodium 12.3 linear alkyl benzene sulfonate 14.31
Sodium C14-15 alkyl sulfate 4.09
Phosphate solids 43.85
Sodium carbonate 0.32
Sodium silicate (2.0r) 6.47
Polyethylene glycol (MW 8000) 0.80
Alkyl ethoxy (El) sulfate 2.00
C12 15 Alcohol polyethoxylate (E9) 0.50 ,
Brightener 0.28 ~,
Perfume 0.10
Water 6.13
Admix:
- Sodium carbonate 8.39
WO 93J23516 ~ 1 3 4 9 7 8 PCI /US93/04192
--22--
Sodium perborate 0.35
Perfume 0.21
Lipolase~ 0.29
Protease B 0.52 ' :
Silicone flake 0.20 t
.. ~.
EXAMPLE IV
A composition of the present invention is as follows:
ComDonent Wei~ht %
Sodium 12.3 linear alkyl benzene sulfonate 13.16 ~:
Sodium C14 15 alkyl sulfate 3.70
Sodium carbonate 9.46
Sodium aluminosilicate 26.30
~ Silicate solids 2.29
Sodium polyacrylate 3.39
Sodium sulfate 10.36
Alkyl ethoxy (E1) sulfate 1.94
C12 15 Alcohol polyethoxylate (E9) 0.50
Brightener 0.30
Water - 9.81
Admix:
Sodium carbonate 14.70
Sodium perborate 1.~0
Perfume 0.35
Lipolase~ 0.29
Protease B 0.26
Fumed silica 0.45
EXAMPLF V
A compasition of the present invention is as follows:
ComDonent Weiqht %
Sodium C14 15 alkyl sulfate 6.36
C16 18 N-acetyl glucamide 3.82
Alkylethoxy (E2.25) sulfate 1.27
C12 13 Alcohol polyethoxylate (6.5) 3.44
Sodium aluminosilicate 14.00
W O 93/23516 2 1 3 ~ 9 7 ~ ~ i PCTIUS93/04192
-23-
Citric acid 3.82
Layered silicate 14.00
Tetra acetyl ethylene diamine ` 6.36
Sodium percarbonate 20.36
Diethylene triamine pentamethyl phosphonic acid 0.48
Magnesium sulfate 0.51
Savinase0 protease 1.78
Lipase * 0.46
Cellulase 0.32
Sodium carbonate 7.64
50il release polymer 0.64
Acrylic acid/maleic acid co-polymer 3.82
Brightener 0.31
~ Zinc pthalocyanine sulfonate 0.29
Perfume 0.41
Suds suppressor 2.04
Water and miscellaneous Balance
* from Pseudomonas Dseudoalcaliqenes (100,000 LU/g)
Lipolase~ from Humicola lanuqinosa can be substituted herein.
~5
30 ~ x :;
