Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID LAUNDRY DETERGENTS
CONTAINING
SELECTED QUATERNARY AMMONI~M COMPOUNDS
Field of the Invention
-
The present invention relates to detergent compositions
containing surfactants selected from quaternary ammonium
surfactants.
More particularly, the invention is directed to detergent
compositions containing a nil-LAS surfactant system
comprising anionic surfactants selected from the group
consisting of alkyl alkoxylated sulfates and alkyl sulfates,
said composition further cont~in;ng specific quaternary
ammonium surfactants.
8ackground of the Invention
The present invention relates to liquid detergents
containing a surfactant system which is free of Linear alkyl
benzene sulfonate surfactants (LAS), said liquid detergent
having optimum greasy stain removal performance.
The recent trend towards partial or total replacement
of Linear alkyl benzene sulfonate surfactants (LAS) has
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urged the detergent formulators to rebalance their
formulations with different surfactants.
There is thus a standing desire for performance and
flexibility reasons to make available a surfactant system
capable of providing optimum detergency performance which is
equivalent to that of LAS-containing detergents.
The above objective has been met by a surfactant system
comprising anionic surfactants selected from the group
consisting of alkyl alkoxylated sulfates and alkyl sulfates,
said surfactant system further comprising a cosurfactant
selected from the group of quaternary ammonium surfactants.
It has been surprisingly found that detergent
compositions containing said surfactant system exhibit
detergency performance equivalent to that of LAS-containing
detergents.
~ In addition, it was found that the liquid detergent
compositions containing the selected quaternary ammonium
surfactants of the present invention, provide excellent
greasy stain removal performance without detriment to the
suds characteristics of the compositions. This finding
allows to reduce the level of suds suppressing agents,
thereby facilitating the formulation of concentrated liquid
detergents.
Quaternary ammonium surfactants are described in the
art. The properties of these surfactants are very strongly
influenced by the type of substituent. Chain length, degree
of saturation, branching or the presence and number of
hydroxylic or ethoxy groups mainly determine the properties
of the surfactant. Whereas typical textile-conditioning
actions are performed by cationic surfactants with two long
alkyl ch~'ns, cationic surfactants with only one long alkyl
chain have been reported to improve the detergency
performance in laundry detergents. EP-A-224 describes liquid
built laundry detergent compositions comprising a general
class of quaternary ammonium surfactants. Decyltrimethyl
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ammonium chloride is described. EP 8142 describes a liquid
builder-free heavy duty detergent comprising a quaternary
ammonium compound of a general formula.
Octyldihydroxyethylmethyl ammonium halides are described.
For optimum grease detergency performance, however,
these compositions of the prior art require high level of
cationic surfactant. These high levels of cationic
surfactants in turn, generate excessive foaming, thereby
raising problems of automatic washing machine compatibility.
If, on the other hand, the cationic surfactant is reduced at
a level at which foam regulation is no longer a problem, the
beneficial grease detergency characteristics of quaternary
compounds are ~; m i n ished~
In contrast, the surfactant system of the present
invention provides optimum grease and oil removal
performance, thereby not adversely affecting the suds
characteristic of the detergent compositions formulated
therewith.
In addition, it has been found that liquid detergent
compositions formulated with said surfactant system are
extremely useful when the liquid detergent compositions are
in direct contact with the fabrics such as during
pretreatment.
Summary of the Invention
The present invention relates to liquid detergent
compositions comprising a Nil-LAS surfactant system said
surfactant system comprising anionic surfactants selected
from the group of alkyl alkoxy sulfates and alkyl sulfates
and selected quaternary ammonium surfactants present in
specific weight ratio.
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The detergent compositions pre~erably comprise at least
5~, more preferably from 10~ to 65% and most preferably from
15% to 40% by weight of the surfactant system as described
hereinabove.
Detailed description of the Invention
The surfactant system of the detergent compositions
according to the present invention comprise anionic
surfactants selected from the group of alkylalkoxy sulfates
and alkyl sulfates.
Alkyl alkoxylated sulfates and/or alkyl sulfates
The alkyl alkoxylated sulfate surfactants hereof are
water soluble salts or acids of the formula RO(A)mS03M
wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl
group having a C1o-C24 alkyl component, preferably a C12-C1g
alkyl or hydroxyalkyl, more preferably C12-C1s 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 ethanol-, triethanol-, methyl-,
dimethyl, trimethyl-ammonium cations and quaternary ammonium
cations such as tetramethyl-ammonium and dimethyl
piperidinium cations and those derived from alkylamines such
as ethylamine, diethylamine, triethylamine, mixtures
thereof, and the like. Exemplary surfactants are C12-Cls
alkyl polyethoxylate (1.0) sulfate (C12-C1sE(l.O)M), C12-Cls
alkyl polyethoxylate (2.25) sulfate (C12-C1sE(2.25)M), C12-
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C1s alkyl polyethoxylate (3.0) sulfate (C12-C1sE(3.0)M), and
C12-C1s alkyl polyethoxylate (4.0) sulfate (C12-C1sE(4.0)M),
wherein M is conveniently selected from sodium and
potassium.
The alkyl sulfate surfactants hereof are water soluble
salts or acids of the formula ROSO3M wherein R preferably is
a C1o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C1o-C1g alkyl component, more preferably a C12-C1s
alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali metal cation (e.g. sodium, potassium, lithium), or
ammonium or substituted ammonium (e.g. methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium
cations such as tetramethyl-ammonium and dimethyl
piperidinium cations and quaternary ammonium cations derived
from alkylamines such as ethylamine, diethylamine,
~riethylamine, and mixtures thereof, and the like).
The quaternary ammonium compound
The quaternary ammonium surfactant according to the
present invention has the formula (I):
o ~ ~3 ~ X-
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or
alkylamidoalkyl of the formula (II) :
Formula II
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y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and
can be either a short chain alkyl (C1-C3) or alkoxylated
alkyl of the formula III,
whereby X~ is a counterion, preferably a halide, e.g.
chloride or methylsulfate.
R6
~Z
Formula III
R6 is C1-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as
defined in formula I whereby
Rl is Cg, C10 or mixtures thereof, x=o,
R3, R4 = CH3 and Rs = CH2CH2OH.
Preferred quaternary ammonium surfactants have the
general formula I, whereby the weight ratio of the
quaternary ammonium surfactant to the alkyl alkoxy sulfates
and alkyl sulfates is from 1:3 to 1:30, preferably from 1:3
to 1:15, most preferred from 1:5 to 1:10.
Detergent ingredients
In another embodiment of the present invention, a
liquid detergent composition is provided comprising the
surfactant system of the present invention mixed with
detergent ingredients. A wide range of surfactants can be
used in the detergent composition of the present invention.
The detergent compositions according to the present
invention comprise a surfactant system which is
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substantially free of linear alkylbenzene sulfonate
surfactant.
A typical listing of anionic, nonionic, ampholytic and
zwitterionic classes, and species of these surfactants, is
given in US Patent 3,664,961 issued to Norris on May 23,
1972.
Other suitable anionic surfactants that can be used are
alkyl ester sulfonate surfactants including linear esters of
Cg-C20 carboxylic acids (i.e., fatty acids) which are
sulfonated with gaseous SO3 according to "The Journal of the
American Oil Chemists Society", 52 (1975), pp. 323-329.
Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant,
especially for laundry applications, comprise alkyl ester
sulfonate surfactants of the structural formula:
R3 - CH(SO3M) -- C(O) - oR4
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as sodium,
potassium, and lithium, and substituted or unsubstituted
ammonium cations, such as monoethanolamine, diethanolamine,
and triethanolamine. Preferably, R3 is C1o-C16 alkyl, and R4
is methyl, ethyl or isopropyl. Especially preferred are the
methyl ester sulfonates wherein R3 is C1o-C16 alkyl.
Other anionic surfactants useful for detersive purposes
can also be included in the laundry detergent compositions
of the present invention. These can include salts
(including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and
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triethanolamine salts) of soap, Cg-C22 primary of secondary
alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as
described in British patent specification No. 1, 082,179, C8-
C24 alkylpolyglycolethersulfates (containing up to 10 moles
of ethylene oxide); alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl
phenol ethylene oxide ether sulfates, paraffin sulfonates,
alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated C12-C1 8 monoesters) and diesters
of sulfosuccinates (especially saturated and unsaturated C6-
C12 diesters), sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated
compounds being described below), and alkyl polyethoxy
carboxylates such as those of the formula RO(CH2CH20)k-
CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from
O to 10, and M is a soluble salt-forming cation. 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 described in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A
variety of such surfactants are also generally disclosed in
U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin,
et al. at Column 23, line 58 through Column 29, line 23
(herein incorporated by reference).
When included therein, the laundry detergent
compositions of the present invention typically comprise
from about 1% to about 40%, preferably from about 5% to
about 25% by weight of such anionic surfactants.
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One class of nonionic surfactants useful in the present
r invention are condensates of ethylene oxide with a
hydrophobic moiety to provide a surfactant having an average
hydrophilic-lipophilic balance ~HLB) in the range from 8 to
17, preferably from 9.5 to 14, more preferably from 12 to
14. The hydrophobic (lipophiliG) moiety may be aliphatic or
aromatic in nature and the length of the polyoxyethylene
group which is condensed with any particular hydrophobic
group can be readily adjusted to yield a water-soluble
compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are
the Cg-Cls primary alcohol ethoxylates containing 3-12 moles
of ethylene oxide per mole of alcohol, particularly the C12-
C1s primary alcohols containing 5-8 moles of ethylene oxide
Fer mole of alcohol,
Another class of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO (cnH2no)tzx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to
4, the compounds including less than 10% unreacted fatty
alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are
disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Very suitable as nonionic surfactants are poly hydroxy
fatty acid amide surfactants of the formula
R2 - C(O) - N(R1) ~ Z,
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wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is Cs_
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C~ s
alkyl or alkenyl chain such as coconut alkyl or mixtures
thereof, and Z is derived from a reducing sugar such as
glucose, fructose, maltose, lactose, in a reductive
amination reaction.
Highly preferred nonionics are amine oxide surfactants.
The compositions of the present invention may comprise amine
oxide in accordance with the general formula I:
R tEO) (PO) (BO) N(O)(CH2R')2.qH2O (I)
In general, it can be seen lthat the structure (I)
provides one long-chain moiety R (EO) (PO) (BO) and two
short chain moieties, CH2R'. R' is preferably selected from
hydrogen, methyl and -CH2OH. In general Rl is a primary or
branched hydrocarbyl moilety which can be saturated or
unsaturated, preferably, R is a primary alkyl moiety. When
x+y+z = 0, R is a hydrocarbyl moiety having chainlength of
flrom about 8 to about 18. When x+y+z is different from 0,
R may be somewhat longer, having a chainlength in the range
C12-C24. The general formula also encompasses amine oxides
wherein x+y+z = 0, R1 = Cg-Clg, R' = H and q = 0-2,
preferably 2. These amine oxides are illustrated by C12-14
alkyldimethyl amine oxide,hexadecyl dimethylamine oxide,
octadecylamine oxide and their hydrates, especially the
dihydrates as disclosed in U.S. Patents 5,075,501 and
5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein
x+y+z is different from zero, specifically x+y+z is from
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11
about 1 to about 10, R is a primary alkyl group containing
8 to about 24 carbons, preferably from about 12 to about 16
carbon atoms; in these embodiments y + z is preferably 0 and
x is preferably from about l to about 6, more preferably
from about 2 to about 4i EO represents ethyleneoxy; PO
represents propyleneoxy; and BO represents butyleneoxy. Such
amine oxides can be prepared by conventional synthetic
methods, e.g., by the reaction of alkylethoxysulfates with
dimethylamine followed by oxidation of the ethoxylated amine
with hydrogen peroxide.
Highly preferred amine oxides herein are solids at
ambient temperature, more preferably they have melting-
points in the range 30~C to 90~C. Amine oxides suitable for
use herein are made commercially by a number of suppliers,
including Akzo Chemie, Ethyl Corp., and Procter & Gamble.
See McCutcheon's compilation and Kirk-Othmer review article
for alternate amine oxide manufacturers. Preferred
commercially available amine oxides are the solid, dihydrate
ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from
Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine
oxide dihydrate, dodecyldimethylamine oxide dihydrate,
octadecyldimethylamine oxide dihydrate, hexadecyltris
(ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethyl-
amine oxide dihydrate.
Whereas in certain of the preferred embodiments R' = H,
there is some latitude with respect to having R' slightly
larger than H. Specifically, the invention further
encompasses embodiments wherein R' = CH20H, such as
hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-
hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine
oxide and oleylbis(2- hydroxyethyl)amine oxide,
dodecyldimethylamine oxide dihydrate.
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12
Suitable nonionic sur~actants include primary amines
according to the formula R1R2R3N wherein R1 and R2 are both
H, R3 is a C4-C1g, preferably C6-C12 alkyl chain, R3 alkyl
t-h~in.s may be straight or branched and may be interrupted
with up to 12 ethylene oxide moieties, most preferably
interrupted with up to 5 ethylene oxide moieties. Preferred
amines according to the formula herein above are n-alkyl
amines. Suitable amines for use herein may be selected from
1-hexylamine, 1-octylamine, laurylamine, palmitylamine,
stearylamine, oleylamine, coconutalkylamine, tallowalkyl-
amine.
Other suitable primary amines include amines according
to the formula R1R2R3N wherein R1 and R2 are both H ; R3 is
R4X(CH2)n, X is -O-,-C(O)NH- or -NH-, R4 is a C4-C18,
preferably C6-C12 alkyl chain and R4 may be branched or
straight, n is between 1 to 5. Preferred amines according to
the formula herein above 3-isopropoxypropylamine, 3-(2-
methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol,
Cg-C10 octyl oxy propylamine, 2-ethylhexyloxypropylamine,
lauryl amido propylamine and coco amido propylamine.
Suitable tertiary amines for use herein include amines
tertiary amines having the formula RlR2R3N wherein neither
R1 nor R2 is H, R1 and R2 are C1-C8 alkylchains or
Rls
- (CH2-CH O)xH
whereby n is between 2 to 4 and x is between 1 to 6;
R3 is either a C4-C1g, preferably C6-C12 alkyl chain, or R3
is R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-,R4 is a C4-
C1g, n is between 1 to 5, and Rs is H or C1-C2 alkyl.
R3, R4 are preferably C6-C12 alkyl ch~ins and may be
straight or branched ; R3 alkyl chains may be interrupted
with up to 12 ethylene oxide moieties, most preferably
interrupted with up to 5 ethylene oxide moieties.
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13
Suitable tertiary amines for use herein include
coconutalkyldimethylamine, dimethyloleylamine, hexa-
decyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2-
hydroxyethyl)amine, stearoylbis(2-hydroxyethyl)amine and
oleoylbis(2-hydroxyethyl)amine.
Of all of the foregoing amines the preferred materials
are the trialkyl amines marketed under the tradename ADOGEN,
the long chain alkyldimethyl amines marketed under the
tradename ARMEEN and the ethoxylated amines marketed under
the tradename ETHOMEEN. The most preferred amines for use in
the compositions herein are 1-hexylamine, 1-octylamine, 1-
decylamine, 1-dodecylamine. Especially desirable for odor
characteristics are n-dodecyl-dimethylamine (ARMEEN DM12D)
and bishydroxyethyl-coconutalkylamine (ETHOMEEN C/12, BEROL
307)and oleylamine 7 times ethoxylated(BEROL 28), lauryl
amido propylamine and coco amido propylamine.
Other suitable amines include tertiary amines having
the formula
Rl--C--NH--(CH2~--N--(R2)2
wherein R1 is C4-C10, preferably Cg-Clo alkyl; n is 2-4,
preferably n is 3; R2 is C1-C4 or
R3
I
(CH2-CH-O)xH, whereby x is 1-5, R3 is H or C1-C2 alkyl.
When included therein, the laundry detergent
compositions of the present invention typically comprise
nonionic surfactants in the weight ratio of anionic
surfactant to nonionic surfactant from 6:1 to 1:3,
preferably from 5:1 to 2:1.
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14
When included therein, the laundry detergent compositions
of the present invention typically comprise nonionic
surfactants in the weight ratio of anionic surfactant to
nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to
2:1.
The compositions according to the present invention may
further comprise a builder system. Any conventional builder
system is suitable for use herein including aluminosilicate
materials, silicates, polycarboxylates and fatty acids,
materials such as ethylenediamine tetra-acetate, metal ion
sequestrants such as aminopoly-phosphonates, particularly
ethylenediamine tetramethylene phosphonic acid and
diethylene triamine pentamethylene phosphonic acid. Though
~ess preferred for obvious environmental reasons, phosphate
builders can also be used herein.
Suitable polycarboxylates builders for use herein
include citric acid, preferably in the form of a water-
soluble salt, derivatives of succinic acid of the formula R-
CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl,
preferably C12-16, or wherein R can be substituted with
hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific
examples include lauryl succinate , myristyl succinate,
palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl
succinate. Succinate builders are preferably used in the
form of their water-soluble salts, including sodium,
potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and
mixtures of tartrate monosuccinic and tartrate disuccinic
acid such as described in US g,663,071.
Es,pecially for the liquid execution herein, suitable fatty
acid builders for use herein are saturated or unsaturated
C10-18 fatty acids, as well as the corresponding soaps.
Preferred saturated species have from 12 to 16 carbon atoms
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in the alkyl chain. The preferred unsaturated fatty acid is
oleic acid. Other preferred builder system for liquid
compositions is based on dodecenyl succinic acid and citric
acid.
Detergency builders are normally included in amounts of
from 3% to 50~ by weight of the composition preferably from
5% to 30% and most usually from 5% to 25% by weight.
Optional detergent ingredients :
Preferred detergent compositions of the present invention
may further comprise one or more enzymes which provide
cleaning performance and/or fabric care benefits. Said
enzymes include enzymes selected from cellulases,
hemicellulases, peroxidases, proteases, gluco-amylases,
àmylases, lipases, cutinases, pectinases, xylanases,
reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,
~-glucanases, arabinosidases or mixtures thereof.
A preferred combination is a detergent composition
having a cocktail of conventional applicable enzymes like
protease, amylase, lipase, cutinase and/or cellulase in
conjunction with the lipolytic enzyme variant D96L at a
level of from 50 LU to 8500 LU per liter wash solution.
The cellulases usable in the present invention include
both bacterial or fungal cellulase. Preferably, they will
have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by
a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800.
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16
Other suitable cellulases are cellulases originated from
Humicola insolens having a molecular weight of about 50KDa,
an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulases are the cellulases having
color care benefits. Examples of such cellulases are
cellulases described in European patent application No.
91202879.2, filed November 6, 1991 (Novo).
Peroxidase 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. Peroxidase 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
and in European Patent application EP No. 91202882.6, filed
on November 6, 1991.
Said cellulases and/or peroxidases are normally
incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent
composition.
Preferred commercially available protease enzymes
include those sold under the tradenames Alcalase, Savinase,
Primase, Durazym, and Esperase by Novo Nordisk A/S
(Denmark), those sold under the tradename Maxatase, Maxacal
and Maxapem by Gist-Brocades, those sold by Genencor
International, and those sold under the tradename Opticlean
and Optimase by Solvay Enzymes. Also proteases described in
our co-pending application USSN 08/136,797 can be included
in the detergent composition of the invention. Protease
enzyme may be incorporated into the compositions in
accordance with the invention at a level of from 0.0001% to
2% active enzyme by weight of the composition.
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17
A preferred protease herein referred to as "Protease D"
is a carbonyl hydrolase variant having an amino acid
sequence not found in nature, which is derived from a
precursor carbonyl hydrolase by substituting a different
amino acid for the amino acid residue at a position in said
carbonyl hydrolase equivalent to position +76, preferably
also in combination with one or more amino acid residue
positions equivalent to those selected from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105,
+109, +126, +128, +135, +156, +166, +195, +197, +204, +206,
+210, +216, +217, +218, +222, +260, +265, and/or +274
according to the numbering of Bacillus amyloliquefaciens
subtilisin, as described in the concurrently filed patent
application of A. Baeck et al. entitled "Protease-Containing
Cleaning Compositions" having U.S. Serial No. 08/322,676,
filed October 13, 1994, which is incorporated herein by
reference in its entirety.
Highly preferred enzymes that can be included in the
detergent compositions of the present invention include
lipases. It has been found that the cleaning performance on
greasy soils is synergistically improved by using lipases.
Suitable lipase enzymes include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. Suitable lipases include those which show a
positive immunological cross-reaction with the antibody of
the lipase, produced by the microorganism Pseudomonas
fluorescens IAM 1057. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name
Lipase P "Amano," hereinafter referred to as "Amano-P".
Further suitable lipases are lipases such as M1 LipaseR and
LipomaxR (Gist-Brocades). Highly preferred lipases are the
D96L lipolytic enzyme variant of the native lipase derived
from Humicola lanuginosa as described in US Serial No.
08/341,826. Preferably the Humicola lanuginosa strain DSM
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18
4106 is used. This enzyme is incorporated into the
composition in accordance with the invention at a level of
from 50 LU to 8500 LU per liter wash solution. Preferably
the variant D96L is present at a level of from 100 LU to
7500 LU per liter of wash solution. More preferably at a
level of from 150 LU to 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase
variant as described in patent application WO 92/05249 viz.
wherein the native lipase ex Humicola lanuginosa aspartic
acid (D) residue at position 96 is changed to Leucine ~L).
According to this nomenclature said substitution of aspartic
acid to Leucine in position 96 is shown as : D96L.
Also suitable are cutinases [EC 3.1.1.50] which can be
considered as a special kind of lipase, namely lipases which
-do not require interfacial activation. Addition of cutinases
to detergent compositions have been described in e.g. WO-A-
88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated
in the detergent composition at levels from 0.0001% to 2% of
active enzyme by weight of the detergent composition.
Amylases (& and/or ~) can be included for removal of
carbohydrate-based stains. Suitable amylases are TermamylR
(Novo Nordisk), FungamylR and BANR (Novo Nordisk).
The above-mentioned enzymes may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and
yeast origin.
Said enzymes are normally incorporated in the detergent
composition at levels from 0.0001% to 2% of active enzyme by
weight of the detergent composition.
Other suitable detergent ingredients that can be added are
enzyme oxidation scavengers which are described in Copending
European Patent application 92870018.6 filed on January 31,
1992. Examples of such enzyme oxidation scavengers are
ethoxylated tetraethylene polyamines.
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Other components used in detergent compositions may be
employed, such as soil-suspending agents, soil-release
polymers, abrasives, bactericides, tarnish inhibitors,
coloring agents, foam control agents, corrosion inhibitors
and perfumes.
Preferably, the liquid compositions according to the
present invention are in "concentrated form"i in such case,
the liquid detergent compositions according to the present
invention will contain a lower amount of water, compared to
conventional liquid detergents. The level of water is less
than 50%, preferably less than 30~ by weight of the
detergent compositons.
Said concentrated products provide advantages to the
consumer, who has a product which can be used in lower
amounts and to the producer, who has lower shipping costs.
The liquid compositions are especially effective when
applied directly to soils and stains in a pretreatment step.
The detergent compositions of the present invention can
also be used as detergent additive products. Such additive
products are intended to supplement or boost the performance
of conventional detergent compositions.
The detergent compositions according to the present
invention include compositions which are to be used for
cleaning of substrates, such as fabrics,fibers, hard
surfaces, skin etc., for example hard surface cleaning
compositions(with or without abrasives), laundry detergent
compositions, automatic and non-automatic dishwashing
compositions.
The following examples are meant to exemplify
compositions of the present inventions, but are not
necessarily meant to limit the scope of the invention.
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EXAMPLE I
The following liquid detergent compositions are made :
% by weight of the detergent compositions
A B C D
C12-C15 alkyl ethoxylated 2 8 11 5
sulfate
Cg-C10 hydroxyethyl dimethyl 2 2 2
quat
C12-C14 alkyldimethyl amine - - - 2
oxide
C12-C1s alkyl sulfate 17 12 7 8
C12-C14 N-methyl glucamide 5 4 4 3
C12-C14 fatty alcohol ethoxylate 6
C12-C1g fatty acid 11 4 4 3
Citric acid anhydrous 1 3 3 2
Diethylene triamine penta 1 1 1 0.5
methylene phosponic acid
Monoethanolamine 8 5 5 2
Sodium hydroxide 1 2.5 1 1.5
Propanediol 14.5 13.1 10.0 8
Ethanol 1.8 4.7 5. 4
Amylase (300KNU/g) O.1 0.1 0.1 0.1
Lipase D96/L (lOOKNlJ/g) O.15 0 .15 0.15 0.15
Protease (35g/l) 0.5 0.5 0.5 0.5)
Endo-A (5000 CEW/g) O. 05 0.05 0.05 0.5
Carezyme (5000 CEVU/g) O.09 0.09 0.09 0.9
Terephthalate-based polymer 0. 5 - 0. 3 0.3
Boric acid 2.4 2. 8 2. 8 2.4
Sodium xylene sulfonate - 3
DC 3225C 0.04 0.04 0.03 0.03 ~-
2-butyl-octanol
Branched silicone 0.3 0.3 0.3 0.3
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Water & minors Up to 100%
The above liquid detergent compositions (A-D) are found
to be very efficient in the removal of greasy/oily soils
under various usage conditions while having a controlled
suds profile.
