Field of the Invention
[0001] The present invention relates to cleaning compositions, including laundry compositions
containing a keratanase enzyme.
[0002] More in particular, the invention relates to compact detergent compositions, granules
and liquids as well having said enzyme in the composition.
Background of the invention
[0003] Performance of a detergent product, for use in washing or cleaning method, such as
a laundry method, is judged by a number of factors, including the ability to remove
soils, and the ability to prevent the redeposition of the soils, or the breakdown
products of the soils on the articles in the wash.
[0004] Stains comprising body soils like skin flakes and sebum based stains are often difficult
to remove effectively from a soiled substrate.
[0005] The substrates can be fabrics like collar, sleeve, underwear, but also towels, sheets
or clothes.
[0006] Keratan sulphate is known to be present in skins. Mucopolysaccharides (proteoglycans)
e.g. keratan sulphate, and dermatan sulphate are found in the skin as lubricants having
a total MW of 2x10
5 to 2x10
6. They contain 20 to 60 polysaccharide chains per molecule.
[0007] It is known that keratanase enzymes have the ability to degrade the complex polysaccharide
chains found in keratan sulphates. In the art keratanases are used in the pharmaceutical
or medical field.
[0008] In EP 493 533 is disclosed that compositions of keratan sulphate can inhibit neurite
outgrowth, i.e. axonal growth and glial cell migration or invasion.
[0009] Keratanase enzyme can destroy or antagonise the growth inhibiting function of these
compounds.
[0010] However, benefits for use of keratanase in cleaning compositions have not been previously
recognized.
Summary of the invention
[0011] We have now found that keratanase enzyme may valuably be incorporated into cleaning
compositions, specifically at a level of from 0.0001% to 2% of the composition by
weight of active enzyme. The inclusion of such enzyme provides stain/soil removal
benefits. Removal of soils/stains, and in particular the removal of body soils/stains
and/or sebum based stains is enabled. We now have surprisingly found that application
of keratanase at above-mentioned levels in cleaning compositions delivers an important
boost of the cleaning performance.
[0012] It is an object of the present invention to provide cleaning compositions containing
keratanase enzyme and in particular to provide laundry detergent compositions containing
said enzyme providing enhanced body soil removal from fabrics.
Detailed description of the invention
[0013] An essential component of the cleaning compositions of the invention is a keratanase
enzyme. This enzyme is incorporated into the compositions in accordance with the invention
at a level of from 0.0001% to 2%, preferably from 0.0005% to 1.0%, more preferably
from 0.001% to 0.2% active enzyme by weight of the composition.
[0014] By keratanase enzyme it is meant herein any enzyme which degrade, for instance hydrolyze
and/or modify, complex polysaccharide chains found for instance in keratan sulphates.
[0015] Keratanase
R is also called endo-beta-galactosidase and classified as EC 3.2.1.103.
[0016] Keratanase variants either naturally occuring or made via genetic engineering as
part of the present invention may be specifically designed with regard to the optimization
of performance efficiency in the detergent compositions of the invention. For example,
variants may be designed such that the compatibility of the enzyme to commonly encountered
components of such compositions is increased.
[0017] Alternatively, the variant may be designed such that the optimal pH, bleach stability,
catalytic activity and the like of the enzyme variant is tailored to suit the particular
detergent application.
Detergent components
[0018] The detergent compositions of the invention may also contain additional detergent
components. The precise nature of these additional components, and levels of incorporation
thereof will depend on the physical form of the composition, and the nature of the
cleaning operation for which it is to be used.
[0019] The compositions of the invention may for example, be formulated as hand and machine
laundry detergent compositions including laundry additive compositions and compositions
suitable for use in the pretreatment of stained fabrics, rinse added fabric softener
compositions, and compositions for use in general household hard surface cleaning
operations.
[0020] When formulated as compositions suitable for use in a machine washing method, the
compositions of the invention preferably contain both a surfactant and a builder compound
and additionally one or more detergent components preferably selected from organic
polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants,
soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions
can also contain softening agents, as additional detergent components.
[0021] If needed the density of the laundry detergent compositions herein ranges from 550
to 1000 g/liter, preferably 600 to 950 g/liter of composition measured at 20°C.
[0022] The "compact" form of the compositions herein is best reflected by density and, in
terms of composition, by the amount of inorganic filler salt; inorganic filler salts
are conventional ingredients of detergent compositions in powder form; in conventional
detergent compositions, the filler salts are present in substantial amounts, typically
17-35% by weight of the total composition.
[0023] In the compact compositions, the filler salt is present in amounts not exceeding
15% of the total composition, preferably not exceeding 10%, most preferably not exceeding
5% by weight of the composition.
[0024] The inorganic filler salts, such as meant in the present compositions are selected
from the alkali and alkaline-earth-metal salts of sulphates and chlorides.
[0025] A preferred filler salt is sodium sulphate.
Surfactant system
[0026] The detergent compositions according to the present invention comprise a surfactant
system wherein the surfactant can be selected from nonionic and/or anionic and/or
cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
[0027] The surfactant is typically present at a level of from 0.1% to 60% by weight. More
preferred levels of incorporation are 1% to 35% by weight of laundry and rinse added
fabric softener compositions in accord with the invention.
[0028] The surfactant is preferably formulated to be compatible with enzyme components present
in the composition. In liquid or gel compositions the surfactant is most preferably
formulated such that it promotes, or at least does not degrade, the stability of any
enzyme in these compositions.
[0029] Preferred non-alkylbenzene sulfonate surfactant systems to be used according to the
present invention comprise as a surfactant one or more of the nonionic and/or anionic
surfactants described herein.
[0030] Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols
are suitable for use as the nonionic surfactant of the surfactant systems of the present
invention, with the polyethylene oxide condensates being preferred. These compounds
include the condensation products of alkyl phenols having an alkyl group containing
from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon
atoms, in either a straight-chain or branched-chain configuration with the alkylene
oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal
to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles,
of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants
of this type include Igepal™ CO-630, marketed by the GAF Corporation; and Triton™
X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants
are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
[0031] The condensation products of primary and secondary aliphatic alcohols with from about
1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant
of the nonionic surfactant systems of the present invention. 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. Preferred are the condensation products
of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms,
more preferably from about 10 to about 18 carbon atoms, with from about 2 to about
10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene
oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol
are present in said condensation products. Examples of commercially available nonionic
surfactants of this type include Tergitol™ 15-S-9 (the condensation product of C
11-C
15 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation
product of C
12-C
14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution),
both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product
of C
14-C
15 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (the condensation product
of C
12-C
13 linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (the condensation
product of C
14-C
15 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (the condensation product
of C
14-C
15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company,
Kyro™ EOB (the condensation product of C
13-C
15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and
Genapol LA O5O (the condensation product of C
12-C
14 alcohol with 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB
in these products is from 8-11 and most preferred from 8-10.
[0032] Also useful as the nonionic surfactant of the surfactant systems of the present invention
are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January
21, 1986, having 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 10, preferably from about 1.3
to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic
group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose
as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g.,
between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or
6- positions on the preceding saccharide units.
[0033] The preferred alkylpolyglycosides have the formula
R
2O(C
nH
2nO)
t(glycosyl)
x
wherein R
2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl,
and mixtures thereof in which the alkyl groups contain from about 10 to about 18,
preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is
from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl
is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy
alcohol is formed first and then reacted with glucose, or a source of glucose, to
form the glucoside (attachment at the 1-position). The additional glycosyl units can
then be attached between their 1-position and the preceding glycosyl units 2-, 3-,
4- and/or 6-position, preferably predominately the 2-position.
[0034] The condensation products of ethylene oxide with a hydrophobic base formed by the
condensation of propylene oxide with propylene glycol are also suitable for use as
the additional nonionic surfactant systems of the present invention. The hydrophobic
portion of these compounds will preferably have a molecular weight of from about 1500
to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water solubility of the
molecule as a whole, and the liquid character of the product is retained up to the
point where the polyoxyethylene content is about 50% of the total weight of the condensation
product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
Examples of compounds of this type include certain of the commercially-available Pluronic™
surfactants, marketed by BASF.
[0035] Also suitable for use as the nonionic surfactant of the nonionic surfactant system
of the present invention, are the condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic
moiety of these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from about 2500 to about
3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that
the condensation product contains from about 40% to about 80% by weight of polyoxyethylene
and has a molecular weight of from about 5,000 to about 11,000. Examples of this type
of nonionic surfactant include certain of the commercially available Tetronic™ compounds,
marketed by BASF.
[0036] Preferred for use as the nonionic surfactant of the surfactant systems of the present
invention are polyethylene oxide condensates of alkyl phenols, condensation products
of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of
ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C
8-C
14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C
8-C
18 alcohol ethoxylates (preferably C
10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
[0037] Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants
of the formula.
wherein R
1 is H, or R
1 is C
1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R
2 is C
5-31 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, R
1 is methyl, R
2 is a straight C
11-15 alkyl or C
16-18 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.
[0038] When included in such laundry detergent compositions, the nonionic surfactant systems
of the present invention act to improve the greasy/oily stain removal properties of
such laundry detergent compositions across a broad range of laundry conditions.
[0039] Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants
hereof are water soluble salts or acids of the formula RO(A)
mSO3M wherein R is an unsubstituted C
10-C
24 alkyl or hydroxyalkyl group having a C
10-C
24 alkyl component, preferably a C
12-C
20 alkyl or hydroxyalkyl, more preferably C
12-C
18 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
cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl
piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate (C
12-C
18E(1.0)M), C
12-C
18 alkyl polyethoxylate (2.25) sulfate (C
12-C
18E(2.25)M), C
12-C
18 alkyl polyethoxylate (3.0) sulfate (C
12-C
18E(3.0)M), and C
12-C
18 alkyl polyethoxylate (4.0) sulfate (C
12-C
18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
[0040] Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including
linear esters of C
8-C
20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO
3 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.
[0041] The preferred alkyl ester sulfonate surfactant, especially for laundry applications,
comprise alkyl ester sulfonate surfactants of the structural formula :
wherein R
3 is a C
8-C
20 hydrocarbyl, preferably an alkyl, or combination thereof, R
4 is a C
1-C
6 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,
R
3 is C
10-C
16 alkyl, and R
4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates
wherein R
3 is C
10-C
16 alkyl.
[0042] Other suitable anionic surfactants include the alkyl sulfate surfactants which are
water soluble salts or acids of the formula ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C
10-C
20 alkyl component, more preferably a C
12-C
18 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 piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C
12-C
16 are preferred for lower wash temperatures (e.g. below about 50°C) and C
16-18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
[0043] 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 triethanolamine salts) of soap, C
8-C
22 primary of secondary alkanesulfonates, C
8-C
24 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, C
8-C
24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl 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
C
12-C
18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated
C
6-C
12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates
of alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of
the formula RO(CH
2CH
2O)
k-CH
2COO-M+ wherein R is a C
8-C
22 alkyl, k is an integer from 1 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.
[0044] 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 3% to about 20%
by weight of such anionic surfactants.
[0045] The laundry detergent compositions of the present invention may also contain cationic,
ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or
anionic surfactants other than those already described herein.
[0046] Cationic detersive surfactants suitable for use in the laundry detergent compositions
of the present invention are those having one long-chain hydrocarbyl group. Examples
of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium
halogenides, and those surfactants having the formula :
[R
2(OR
3)
y][R
4(OR
3)
y]
2R
5N+X-
wherein R
2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in
the alkyl chain, each R
3 is selected from the group consisting of -CH
2CH
2-, -CH
2CH(CH
3)-, -CH
2CH(CH
2OH)-, -CH
2CH
2CH
2-, and mixtures thereof; each R
4 is selected from the group consisting of C
1-C
4 alkyl, C
1-C
4 hydroxyalkyl, benzyl ring structures formed by joining the two R
4 groups, -CH
2CHOH-CHOHCOR
6CHOHCH
2OH wherein R
6 is any hexose or hexose polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R
5 is the same as R
4 or is an alkyl chain wherein the total number of carbon atoms of R
2 plus R
5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to about 15; and X is any compatible anion.
[0047] Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds
useful in the present composition having the formula :
R
1R
2R
3R
4N
+X
- (i)
wherein R
1 is C
8-C
16 alkyl, each of R
2, R
3 and R
4 is independently C
1-C
4 alkyl, C
1-C
4 hydroxy alkyl, benzyl, and -(C
2H
40)
xH where x has a value from 2 to 5, and X is an anion. Not more than one of R
2, R
3 or R
4 should be benzyl. The preferred alkyl chain length for R
1 is C
12-C
15 particularly where the alkyl group is a mixture of chain lengths derived from coconut
or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols
synthesis.
[0048] Preferred groups for R
2R
3 and R
4 are methyl and hydroxyethyl groups and the anion x may be selected from halide, methosulphate,
acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
alkyl and R2R3R4 are methyl).
di-alkyl imidazolines (compounds of formula (i)].
[0049] Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044,
Cambre, issued October 14, 1980 and in European Patent Application EP 000,224.
[0050] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by
weight of such cationic surfactants.
[0051] Ampholytic surfactants are also suitable for use in the laundry detergent compositions
of the present invention. These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
One of the aliphatic substituents contains at least about 8 carbon atoms, typically
from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing
group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin
et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic
surfactants.
[0052] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by
weight of such ampholytic surfactants.
[0053] Zwitterionic surfactants are also suitable for use in laundry detergent compositions.
These surfactants can be broadly described as derivatives of secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives
of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19,
line 38 through column 22, line 48, for examples of zwitterionic surfactants.
[0054] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by
weight of such zwitterionic surfactants.
[0055] Semi-polar nonionic surfactants are a special category 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 3 carbon atoms; water-soluble
phosphine 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 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 the group consisting of alkyl and hydroxyalkyl moieties of from about
1 to about 3 carbon atoms.
[0056] Semi-polar nonionic detergent surfactants include the amine oxide surfactants having
the formula
wherein R
3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from
about 8 to about 22 carbon atoms; R
4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon
atoms or mixtures thereof; x is from 0 to about 3; and each R
5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms
or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
The R
5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to
form a ring structure.
[0057] These amine oxide surfactants in particular include C
10-C
18 alkyl dimethyl amine oxides and C
8-C
12 alkoxy ethyl dihydroxy ethyl amine oxides.
[0058] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by
weight of such semi-polar nonionic surfactants.
Optional detergent ingredients :
[0059] Preferred detergent compositions of the present invention may further comprise an
enzyme which provides cleaning performance and/or fabric care benefits. Said enzymes
include enzymes selected from cellulases, hemicellulases, peroxidases, proteases,
gluco-amylases, amylases, lipases, cutinases, pectinases, reductases, oxidases, phenoloxidases,
lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases,
arabinosidases or mixtures thereof.
[0060] A preferred combination is a cleaning composition having cocktail of conventional
applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction
with keratanase enzyme according to the invention.
[0061] 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.
[0062] Examples of such cellulases are cellulases produced by a strain of Humicola insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. 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).
[0063] 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.
[0064] 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.
[0065] 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.
[0066] Other preferred enzymes that can be included in the detergent compositions of the
present invention include lipases. 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 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 fluorescent 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". Especially
suitable lipases are lipases such as M1 Lipase
R and Lipomax
R (Gist-Brocades) and Lipolase
R (Novo) which have found to be very effective when used in combination with the compositions
of the present invention.
[0067] 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).
[0068] 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.
[0069] Amylases (α and/or β) can be included for removal of carbohydrate-based stains. Suitable
amylases are Termamyl
R (Novo Nordisk), Fungamyl
R and BAN
R (Novo Nordisk).
[0070] The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin.
[0071] 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.
[0072] 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.
[0073] Especially preferred detergent ingredients are combinations with technologies which
also provide a type of color care benefit. Examples of these technologies are metallo
catalysts for color maintenance. Such metallo catalysts are described in copending
European Patent Application No. 92870181.2.
[0074] Additional optional detergent ingredients that can be included in the detergent compositions
of the present invention include bleaching agents such as PB1, PB4 and percarbonate
with a particle size of 400-800 microns. These bleaching agent components can include
one or more oxygen bleaching agents and, depending upon the bleaching agent chosen,
one or more bleach activators. When present oxygen bleaching compounds will typically
be present at levels of from about 1% to about 25%. In general, bleaching compounds
are optional components in non-liquid formulations, e.g. granular detergents.
[0075] The bleaching agent component for use herein can be any of the bleaching agents useful
for detergent compositions including oxygen bleaches as well as others known in the
art.
[0076] The bleaching agent suitable for the present invention can be an activated or non-activated
bleaching agent.
[0077] One category of oxygen bleaching agent that can be used encompasses percarboxylic
acid bleaching agents and salts thereof. Suitable examples of this class of agents
include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934. Highly preferred
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in
U.S. Patent 4,634,551.
[0078] Another category of bleaching agents that can be used encompasses the halogen bleaching
agents. Examples of hypohalite bleaching agents, for example, include trichloro isocyanuric
acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished
product, preferably 1-5% by weight.
[0079] The hydrogen peroxide releasing agents can be used in combination with bleach activators
such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described
in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in
EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid
as the active bleaching species, leading to improved bleaching effect. In addition,
very suitable are the bleach activators C
8(6-octanamido-caproyl)oxybenzenesulfonate, C
9(6-nonamido caproyl) oxybenzenesulfonate and C
10(6-decanamido caproyl) oxybenzenesulfonate or mixtures thereof. Also suitable activators
are acylated citrate esters such as disclosed in Copending European Patent Application
No. 91870207.7.
[0080] Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach
activators and peroxygen bleaching compounds for use in cleaning compositions according
to the invention are described in our co-pending application USSN 08/136,626.
[0081] The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an
enzyme and a substrate therefore) which is capable of generating hydrogen peroxide
at the beginning or during the washing and/or rinsing process. Such enzymatic systems
are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
[0082] Bleaching agents other than oxygen bleaching agents are also known in the art and
can be utilized herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. These materials can be deposited upon the substrate during the washing
process. Upon irradiation with light, in the presence of oxygen, such as by hanging
clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated
and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a
photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically,
detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated
zinc phthalocyanine.
[0083] 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
tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
Though less preferred for obvious environmental reasons, phosphate builders can also
be used herein.
[0084] Suitable builders can be an inorganic ion exchange material, commonly an inorganic
hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B, HS or MAP.
[0085] Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst).
SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na
2Si
2O
5).
[0086] Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic
acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369
and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,
diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S.
Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups include, in particular,
water-soluble citrates, aconitrates and citraconates as well as succinate derivatives
such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate
materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent
No. 1,387,447.
[0087] Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates
containing phosphone substituents are disclosed in British Patent No. 1,439,000.
[0088] Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates,
2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates,
1,2,3,4,5,6-hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include
mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British
Patent No. 1,425,343.
[0089] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up
to three carboxy groups per molecule, more particularly citrates.
[0090] Preferred builder systems for use in the present compositions include a mixture of
a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate
(SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
[0091] A suitable chelant for inclusion in the detergent compositions in accordance with
the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium
salt thereof. Examples of such preferred sodium salts of EDDS include Na
2EDDS and Na
4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg
2EDDS. The magnesium salts are the most preferred for inclusion in compositions in
accordance with the invention.
[0092] Preferred builder systems include a mixture of a water-insoluble aluminosilicate
builder such as zeolite A, and a watersoluble carboxylate chelating agent such as
citric acid.
[0093] Other builder materials that can form part of the builder system for use in granular
compositions include inorganic materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic phosphonates, amino polyalkylene
phosphonates and amino polycarboxylates.
[0094] Other suitable water-soluble organic salts are the homo- or co-polymeric acids or
their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
[0095] Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 20,000 to 70,000, especially about 40,000.
[0096] Detergency builder salts are normally included in amounts of from 10% to 80% by weight
of the composition preferably from 20% to 70% and most usually from 30% to 60% by
weight.
[0097] Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone
mixtures. Silicones can be generally represented by alkylated polysiloxane materials
while silica is normally used in finely divided forms exemplified by silica aerogels
and xerogels and hydrophobic silicas of various types. These materials can be incorporated
as particulates in which the suds suppressor is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed
in a liquid carrier and applied by spraying on to one or more of the other components.
[0098] A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S.
Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying
silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published
April 28, 1977. An example of such a compound is DC-544, commercially available from
Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling
agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols.
Suitable 2-alkyl-alkanols are 2-butyl-octanol which are commercially available under
the trade name Isofol 12 R.
[0099] Such suds suppressor system are described in Copending European Patent application
N 92870174.7 filed 10 November, 1992.
[0100] Especially preferred silicone suds controlling agents are described in Copending
European Patent application N°92201649.8. Said compositions can comprise a silicone/silica
mixture in combination with fumed nonporous silica such as Aerosil
R.
[0101] The suds suppressors described above are normally employed at levels of from 0.001%
to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
[0102] Other components used in detergent compositions may be employed, such as soil-suspending
agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish
inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.
[0103] Especially suitable encapsulating materials are water soluble capsules which consist
of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616.
[0104] Other suitable water soluble encapsulating materials comprise dextrins derived from
ungelatinized starch acid-esters of substituted dicarboxylic acids such as described
in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches
as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating
materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material
consists of a modified maize starch and glucose. The starch is modified by adding
monofunctional substituted groups such as octenyl succinic acid anhydride.
[0105] Antiredeposition and soil suspension agents suitable herein include cellulose derivatives
such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo-
or co-polymeric polycarboxylic acids or their salts. Polymers of this type include
the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned
as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl
ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent
of the copolymer. These materials are normally used at levels of from 0.5% to 10%
by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight
of the composition.
[0106] Preferred optical brighteners are anionic in character, examples of which are disodium
4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate,
disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate,
disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate,
monosodium 4',4'' - bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate,
disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'
- disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2' disulphonate,
di-so-dium 4,4'bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylami-no)stilbene-2,2'disulphonate,
sodium 2(stilbyl-4''-(naphtho-1',2':4,5)-1,2,3 - triazole-2''-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl.
[0107] Other useful polymeric materials are the polyethylene glycols, particularly those
of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably
about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25%
to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric
polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash
deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in
the presence of transition metal impurities.
[0108] Soil release agents useful in compositions of the present invention are conventionally
copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene
glycol units in various arrangements. Examples of such polymers are disclosed in the
commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent
Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0
272 033 has the formula
(CH
3(PEG)
43)
0.75(POH)
0.25[T-PO)
2.8(T-PEG)
0.4]T(PO H)
0.25((PEG)
43CH
3)
0.75
where PEG is -(OC
2H
4)O-,PO is (OC
3H
6O) and T is (pcOC
6H
4CO).
[0109] Also very useful are modified polyesters as random copolymers of dimethyl terephthalate,
dimethyl sulfoisophthalate, ethylene glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate
groups, "primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of monoester of ethylene glycol
and/or propane 1-2 diol, thereof consist "secondarily" of such species.
[0110] The selected polyesters herein contain about 46% by weight of dimethyl terephthalic
acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol
about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic
acid, and have a molecular weight of about 3.000. The polyesters and their method
of preparation are described in detail in EPA 311 342.
Softening agents
[0111] Fabric softening agents can also be incorporated into laundry detergent compositions
in accordance with the present invention. These agents may be inorganic or organic
in type. Inorganic softening agents are exemplified by the smectite clays disclosed
in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the
water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and
their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0
026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919.
Other useful organic ingredients of fabric softening systems include high molecular
weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
[0112] Levels of smectite clay are normally in the range from 5% to 15%, more preferably
from 8% to 12% by weight, with the material being added as a dry mixed component to
the remainder of the formulation. Organic fabric softening agents such as the water-insoluble
tertiary amines or dilong chain amide materials are incorporated at levels of from
0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight
polyethylene oxide materials and the water soluble cationic materials are added at
levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials
are normally added to the spray dried portion of the composition, although in some
instances it may be more convenient to add them as a dry mixed particulate, or spray
them as molten liquid on to other solid components of the composition.
Dye transfer inhibition
[0113] The present invention also relates to a process for inhibiting dye transfer from
one fabric to another of solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
Polymeric dye transfer inhibiting agents
[0114] The detergent compositions according to the present invention also comprise from
0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight
of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting
agents are normally incorporated into detergent compositions in order to inhibit the
transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers
have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics
before the dyes have the opportunity to become attached to other articles in the wash.
[0115] Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone
polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
[0116] Addition of such polymers also enhances the performance of the enzymes according
the invention.
a) Polyamine N-oxide polymers
[0117] The polyamine N-oxide polymers suitable for use contain units having the following
structure formula :
- wherein
- P is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the
R-N-O group forms part of the polymerisable unit or a combination of both.
A is
-O-,-S-, -N- ; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups
or any combination thereof whereto the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group is part of these groups.
[0118] The N-O group can be represented by the following general structures :
- wherein
- R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or
combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the
N-O group can be attached or wherein the nitrogen of the N-O group forms part of these
groups.
[0119] The N-O group can be part of the polymerisable unit (P) or can be attached to the
polymeric backbone or a combination of both.
[0120] Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable
unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic
or heterocyclic groups.
[0121] One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein
the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole,
pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
[0122] Another class of said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group is attached to the R-group.
[0123] Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group
is attached to the polymerisable unit.
[0124] Preferred class of these polyamine N-oxides are the polyamine N-oxides having the
general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-O functional group is part of said R group.
[0125] Examples of these classes are polyamine oxides wherein R is a heterocyclic compound
such as pyrridine, pyrrole, imidazole and derivatives thereof.
[0126] Another preferred class of polyamine N-oxides are the polyamine oxides having the
general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-0 functional group is attached to said R groups.
[0127] Examples of these classes are polyamine oxides wherein R groups can be aromatic such
as phenyl.
[0128] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof.
[0129] The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by appropriate copolymerization
or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from
1:7 to 1:1000000. The polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-oxide and the other monomer
type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides
has a PKa < 10, preferably PKa < 7, more preferred PKa < 6. The polyamine oxides can
be obtained in almost any degree of polymerisation. The degree of polymerisation is
not critical provided the material has the desired water-solubility and dye-suspending
power.
[0130] Typically, the average molecular weight is within the range of 500 to 1000,000; preferably
from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000
to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
[0131] The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have
an average molecular weight range from 5,000-1,000,000, preferably from 20,000-200,000.
[0132] Highly preferred polymers for use in detergent compositions according to the present
invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers
wherein said polymer has an average molecular weight range from 5,000 to 50,000 more
preferably from 8,000 to 30,000, most preferably from 10,000 to 2O,000. The average
molecular weight range was determined by light scattering as described in Barth H.G.
and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".
[0133] Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular
weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably
from 10,000 to 20,000.
[0134] The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average
molecular weight range provide excellent dye transfer inhibiting properties while
not adversely affecting the cleaning performance of detergent compositions formulated
therewith.
[0135] The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably
from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
[0136] The detergent compositions of the present invention may also utilize polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably
from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000,
and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones
are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada
under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30
(average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones
which are commercially available from BASF Cooperation include Sokalan HP 165 and
Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field
(see for example EP-A-262,897 and EP-A-256,696).
d) Polyvinyloxazolidone :
[0137] The detergent compositions of the present invention may also utilize polyvinyloxazolidone
as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average
molecular weight of from about 2,500 to about 400,000, preferably from about 5,000
to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably
from about 5,000 to about 15,000.
e) Polyvinylimidazole :
[0138] The detergent compositions of the present invention may also utilize polyvinylimidazole
as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average
about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably
from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
Method of washing
[0139] The process described herein comprises contacting fabrics with a laundering solution
in the usual manner and exemplified hereunder.
[0140] The process of the invention is conveniently carried out in the course of the cleaning
process. The method of cleaning is preferably carried out at 5 °C to 95 °C, especially
between 10°C and 60°C. The pH of the treatment solution is preferably from 7 to 11,
especially from 7.5 to 10.5.
[0141] The following examples are meant to exemplify compositions of the present invention,
but are not necessarily meant to limit or otherwise define the scope of the invention.
[0142] In the detergent compositions, the abbreviated component identifications have the
following meanings:
- LAS
- : Sodium linear C12 alkyl benzene sulphonate
- TAS
- : Sodium tallow alkyl sulphate
- XYAS
- : Sodium C1X - C1Y alkyl sulfate
- SAS
- : C12-C14 secondary (2,3) alkyl sulfate in the form of the sodium salt.
- APG
- : Alkyl polyglycoside surfactant of formula C12 - (glycosyl)x, where x is 1.5,
- AEC
- : Alkyl ethoxycarboxylate surfactant of formula C12 ethoxy (2) carboxylate.
- SS
- : Secondary soap surfactant of formula 2-butyl octanoic acid
- 25EY
- : A C12-C15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene
oxide
- 45EY
- : A C14 - C15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene
oxide
- XYEZS
- : C1X - C1Y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole
- Nonionic
- : C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation
of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafax
LF404 by BASF Gmbh
- CFAA
- : C12-C14 alkyl N-methyl glucamide
- TFAA
- : C16-C18 alkyl N-methyl glucamide.
- Silicate
- : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0)
- NaSKS-6
- : Crystalline layered silicate of formula δ-Na2Si2O5
- Carbonate
- : Anhydrous sodium carbonate
- Phosphate
- : Sodium tripolyphosphate
- MA/AA
- : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000
- Polyacrylate
- : Polyacrylate homopolymer with an average molecular weight of 8,000 sold under the
tradename PA30 by BASF GmbH
- Zeolite A
- : Hydrated Sodium Aluminosilicate of formula Na12(A1O2SiO2)12. 27H2O having a primary particle size in the range from 1 to 10 micrometers
- Citrate
- : Tri-sodium citrate dihydrate
- Citric
- : Citric Acid
- Perborate
- : Anhydrous sodium perborate monohydrate bleach, empirical formula NaBO2.H2O2
- PB4
- : Anhydrous sodium perborate tetrahydrate
- Percarbonate
- : Anhydrous sodium percarbonate bleach of empirical formula 2Na2CO3.3H2O2
- TAED
- : Tetraacetyl ethylene diamine
- Paraffin
- : Paraffin oil sold under the tradename Winog 70 by Wintershall.
- Keratanase
- : Enzyme as described in this application
- Protease
- : Proteolytic enzyme sold under the tradename Savinase by Novo Nordisk A/S.
- Amylase
- : Amylolytic enzyme sold under the tradename Termamyl by Novo Nordisk A/S
- Lipase
- : Lipolytic enzyme sold under the tradename Lipolase by Novo Nordisk A/S
- Peroxidase
- : Peroxidase enzyme
- Cellulase
- : Cellulosic enzyme sold under the tradename Carezyme or Celluzyme by Novo Nordisk
A/S.
- CMC
- : Sodium carboxymethyl cellulose
- HEDP
- : 1,1-hydroxyethane diphosphonic acid
- DETPMP
- : Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under
the Trade name Dequest 2060
- PVP
- : Polyvinyl pyrrolidone polymer
- EDDS
- : Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium
salt.
- Suds Suppressor
- : 25% paraffin wax Mpt 50°C, 17% hydrophobic silica, 58% paraffin oil.
- Granular Suds Suppressor
- : 12% Silicone/silica, 18% stearyl alcohol, 70% starch in granular form
- SCS
- : Sodium cumene sulphonate
- Sulphate
- : Anhydrous sodium sulphate.
- HMWPEO
- : High molecular weight polyethylene oxide
- PGMS
- : Polyglycerol monostearate having a tradename of Radiasurf 248
- TAE 25
- : Tallow alcohol ethoxylate (25)
Keratanase activity
[0143] One unit will liberate 1.0 micromole of reducing sugar (measured as galactose) from
keratan sulphate per hour at pH 7.4 at 37°C.
In the following examples all levels of enzyme quoted are expressed as % active enzyme
by weight of the composition:
Example 1
[0144] Granular fabric cleaning compositions in accord with the invention were prepared
as follows:
|
I |
II |
III |
IV |
LAS |
22.0 |
22.0 |
22.0 |
22.0 |
Phosphate |
23.0 |
23.0 |
23.0 |
23.0 |
Carbonate |
23.0 |
23.0 |
23.0 |
23.0 |
Silicate |
14.0 |
14.0 |
14.0 |
14.0 |
Zeolite A |
8.2 |
8.2 |
8.2 |
8.2 |
DETPMP |
0.4 |
0.4 |
0.4 |
0.4 |
Sodium sulfate |
5.5 |
5.5 |
5.5 |
5.5 |
Protease |
0.01 |
0.02 |
0.01 |
0.005 |
Keratanase |
0.04 |
0.06 |
0.1 |
0.006 |
Lipase |
0.005 |
0.01 |
- |
- |
Cellulase |
0.001 |
- |
- |
0.001 |
Amylase |
0.01 |
- |
0.01 |
- |
Water/minors |
Up to 100% |
Example 2
[0145] Granular fabric cleaning compositions in accord with the invention were prepared
as follows:
|
I |
II |
III |
IV |
LAS |
12.0 |
12.0 |
12.0 |
12.0 |
Zeolite A |
26.0 |
26.0 |
26.0 |
26.0 |
SS |
4.0 |
4.0 |
4.0 |
4.0 |
SAS |
5.0 |
5.0 |
5.0 |
5.0 |
Citrate |
5.0 |
5.0 |
5.0 |
5.0 |
Sodium Sulfate |
17.0 |
17.0 |
17.0 |
28.0 |
Perborate |
16.0 |
16.0 |
16.0 |
- |
TAED |
5.0 |
5.0 |
5.0 |
- |
Keratanase |
0.20 |
0.01 |
0.02 |
0.008 |
Protease |
0.06 |
0.03 |
0.02 |
0.08 |
Lipase |
0.005 |
0.01 |
- |
- |
Cellulase |
0.001 |
- |
- |
0.001 |
Amylase |
0.01 |
- |
0.01 |
- |
Water/minors |
Up to 100% |
Example 3
[0146] Granular fabric cleaning compositions in accord with the invention which are especially
useful in the laundering of coloured fabrics were prepared as follows :
LAS |
11.4 |
10.7 |
- |
TAS |
1.8 |
2.4 |
- |
TFAA |
- |
- |
4.0 |
45AS |
3.0 |
3.1 |
10.0 |
45E7 |
4.0 |
4.0 |
- |
25E3S |
- |
- |
3.0 |
68E11 |
1.8 |
1.8 |
- |
25E5 |
- |
- |
8.0 |
Citrate |
14.0 |
15.0 |
7.0 |
Carbonate |
- |
- |
10 |
Citric acid |
3.0 |
2.5 |
3.0 |
Zeolite A |
32.5 |
32.1 |
25.0 |
Na-SKS-6 |
- |
- |
9.0 |
MA/AA |
5.0 |
5.0 |
5.0 |
DETPMP |
1.0 |
0.2 |
0.8 |
Keratanase |
0.01 |
0.05 |
0.02 |
Protease |
0.02 |
0.02 |
0.01 |
Lipase |
0.03 |
0.04 |
0.005 |
Amylase |
0.03 |
0.03 |
0.005 |
Pectinase |
0.01 |
- |
0.01 |
Cellulase |
0.005 |
- |
0.001 |
Silicate |
2.0 |
2.5 |
- |
Sulphate |
3.5 |
5.2 |
3.0 |
PVP |
0.3 |
0.5 |
- |
Poly (4-vinylpyridine)-N-oxide/copolymer of vinylimidazole and vinylpyrrolidone |
- |
- |
0.2 |
Perborate |
0.5 |
1.0 |
- |
Peroxidase |
0.01 |
0.01 |
- |
Phenol sulfonate |
0.1 |
0.2 |
- |
Water/Minors |
Up to 100% |
Example 4
[0147] Granular fabric cleaning compositions in accord with the invention were prepared
as follows:
LAS |
6.5 |
8.0 |
Sulfate |
15.0 |
18.0 |
Zeolite A |
26.0 |
22.0 |
Sodium nitrilotriacetate |
5.0 |
5.0 |
PVP |
0.5 |
0.7 |
TAED |
3.0 |
3.0 |
Boric acid |
4.0 |
- |
Perborate |
0.5 |
1.0 |
Phenol sulphonate |
0.1 |
0.2 |
Protease |
0.06 |
0.02 |
Keratanase |
0.01 |
0.02 |
Silicate |
5.0 |
5.0 |
Carbonate |
15.0 |
15.0 |
Peroxidase |
0.1 |
0.1 |
Lipase |
0.01 |
- |
Amylase |
0.01 |
0.01 |
Pectinase |
0.02 |
- |
Cellulase |
0.005 |
0.002 |
Water/minors |
Up to 100% |
Example 5
[0148] A compact granular fabric cleaning composition in accord with the invention was prepared
as follows:
45AS |
8.0 |
25E3S |
2.0 |
25E5 |
3.0 |
25E3 |
3.0 |
TFAA |
2.5 |
Zeolite A |
17.0 |
NaSKS-6 |
12.0 |
Citric acid |
3.0 |
Carbonate |
7.0 |
MA/AA |
5.0 |
CMC |
0.4 |
Poly (4-vinylpyridine)-N-oxide/copolymer of vinylimidazole and vinylpyrrolidone |
0.2 |
Keratanase |
0.05 |
Protease |
0.05 |
Lipase |
0.005 |
Cellulase |
0.001 |
Amylase |
0.01 |
TAED |
6.0 |
Percarbonate |
22.0 |
EDDS |
0.3 |
Granular suds suppressor |
3.5 |
water/minors |
Up to 100% |
Example 6
[0149] A granular fabric cleaning compositions in accord with the invention which provide
"softening through the wash" capability were prepared as follows:
45AS |
- |
10.0 |
LAS |
7.6 |
- |
68AS |
1.3 |
- |
45E7 |
4.0 |
- |
25E3 |
- |
5.0 |
Coco-alkyl-dimethyl hydroxyethyl ammonium chloride |
1.4 |
1.0 |
Citrate |
5.0 |
3.0 |
Na-SKS-6 |
- |
11.0 |
Zeolite A |
15.0 |
15.0 |
MA/AA |
4.0 |
4.0 |
DETPMP |
0.4 |
0.4 |
Perborate |
15.0 |
- |
Percarbonate |
- |
15.0 |
TAED |
5.0 |
5.0 |
Smectite clay |
10.0 |
10.0 |
HMWPEO |
- |
0.1 |
Protease |
0.02 |
0.01 |
Lipase |
0.02 |
0.01 |
Amylase |
0.03 |
0.005 |
Keratanase |
0.03 |
0.005 |
Cellulase |
0.02 |
0.001 |
Pectinase |
0.01 |
0.02 |
Silicate |
3.0 |
5.0 |
Carbonate |
10.0 |
10.0 |
Granular suds suppressor |
1.0 |
4.0 |
CMC |
0.2 |
0.1 |
Water/minors |
Up to 100% |
Example 7
[0150] Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment
of stained fabrics, and for use in a machine laundering method, in accord with the
invention were prepared as follows:
|
I |
II |
III |
IV |
V |
24AS |
20.0 |
20.0 |
20.0 |
20.0 |
20.0 |
SS |
5.0 |
5.0 |
5.0 |
5.0 |
5.0 |
Citrate |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
12E3 |
13.0 |
13.0 |
13.0 |
13.0 |
13.0 |
Monethanolamine |
2.5 |
2.5 |
2.5 |
2.5 |
2.5 |
Keratanase |
0.02 |
0.01 |
0.05 |
0.001 |
0.004 |
Protease |
0.005 |
0.03 |
0.02 |
0.04 |
0.01 |
Lipase |
0.002 |
0.01 |
0.02 |
- |
0.004 |
Amylase |
0.005 |
0.005 |
- |
- |
0.004 |
Cellulase |
0.04 |
- |
0.01 |
- |
- |
Pectinase |
0.02 |
0.02 |
- |
- |
- |
Water/propylene glycol/ethanol (100:1:1) |
Example 8
[0151] Heavy duty liquid fabric cleaning compositions in accord with the invention were
prepared as follows:
|
I |
II |
III |
IV |
LAS acid form |
- |
- |
25.0 |
- |
C12-14 alkenyl succinic acid |
3.0 |
8.0 |
10.0 |
- |
Citric acid |
10.0 |
15.0 |
2.0 |
2.0 |
25AS acid form |
8.0 |
8.0 |
- |
15.0 |
25AE2S acid form |
- |
3.0 |
- |
4.0 |
25AE7 |
- |
8.0 |
- |
6.0 |
25AE3 |
8.0 |
- |
- |
- |
CFAA |
- |
- |
- |
6.0 |
DETPMP |
0.2 |
- |
1.0 |
1.0 |
Fatty acid |
- |
- |
- |
10.0 |
Oleic acid |
1.8 |
- |
1.0 |
- |
Ethanol |
4.0 |
4.0 |
6.0 |
2.0 |
Propanediol |
2.0 |
2.0 |
6.0 |
10.0 |
Keratanase |
0.05 |
0.01 |
0.005 |
0.02 |
Protease |
0.02 |
0.02 |
0.02 |
0.01 |
Amylase |
0.005 |
0.01 |
0.005 |
0.01 |
Cellulase |
0.005 |
- |
- |
- |
Pectinase |
0.02 |
- |
- |
- |
Coco-alkyl dimethyl hydroxy ethyl ammonium chloride |
- |
- |
3.0 |
- |
Smectite clay |
- |
- |
5.0 |
- |
PVP |
1.0 |
2.0 |
- |
- |
Perborate |
- |
1.0 |
- |
- |
Phenol sulphonate |
- |
0.2 |
- |
- |
Peroxidase |
- |
0.01 |
- |
- |
NaOH |
Up to pH 7.5 |
Waters/minors |
Up to 100% |
Example 9
[0152] The following rinse added fabric softener composition, in accord with the invention,
was prepared (parts by weight).
Softener active |
24.5 |
PGMS |
2.0 |
TAE 25 |
1.5 |
Keratanase |
0.001 |
Cellulase |
0.001 |
HCL |
0.12 |
Antifoam agent |
0.019 |
Blue dye |
80ppm |
CaCl2 |
0.35 |
Perfume |
0.90 |
Example 10
[0153]
A/ Model beaker tests were carried out for keratanase. Activities are expressed v's
model substrates keratan sulphate. Since these enzymes are biological enzymes, activities
are specified at pH7. Keratanase activity is specified at 37°C. 0.25g of heavily stained
collar was exposed to 1 unit of enzyme. Tests were run at pH7 (TRIS buffer) and at
pH 10.5 (bicarbonate/carbonate buffer) and at ambient room temperature (20°C) and
at 37°C for both enzymes. Collar swatches was also washed in deionised water. Swatches
were left in solution for 1 hour with gentle agitation, then left to air dry.
Enzyme activity :
[0154] Unit definition (Sigma) of keratanse : one unit will liberate 1.0 µmole of reducing
sugar (measured as galactose) from keratan sulphate per hour at pH 7.4 at 37°C.
B/ In addition, dip tests were carried out on unwashed collar soils at pH conditions
of regular granular and liquid detergents, respectively, at 20°C and 37°C.
We have also found that increasing temperature from 20°C to 37°C gives improved benefits.
At pH 10.5, 37°C keratanase give improved stain removal benefits over alkaline pH
alone.
Example 11
[0155] Performance data using keratanase versus reference.
Body soil on |
with keratanase vs nil keratanase |
|
PSU |
Preference |
Pillows |
+ 0.2 |
55 : 45 |
Collars |
+ 0.8s |
64 s 36 |
Socks |
+ 0.4 |
56 : 46 |
[0156] The enzyme level used is 10 units/litre.
[0157] Test method: The enzyme keratanase was brought in 1L water, buffered to pH 10.4. Soiled garments
are soaked in this enzyme solution for 40 min.
[0158] The stained items are then dried and washed in Ariel Futur® (ex P&G) product without
keratanase.
[0159] The reference is a soak in nil enzyme solution (pH 10.4) followed by a wash with
Ariel Futur® (ex P&G) under the same conditions as for the test legs.
[0160] Ariel Futur® concentration in wash is 75 gram/12L and the wash was done at 40°C,
city water, Miele wash machine and using a short cycle.