Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENTS WITH PROTEASE ENZYME
AND LACCASE ENZYME
TECHNICAL FIELD
The present invention relates to detergent compositions comprising a
serine protease and a laccase. Such compositions provide improved cleaning
and stain removal performance.
BACKGROUND of the INVENTION
The detergency performance of enzymes in detergent products is
judged by a number of factors, including the ability to remove soils and stains
present in the typical load of the laundry.
The complex nature of everyday 'skin' soils typically found on
pillowcases, T-shirts, collars and socks, provides a thorough cleaning
- challenge for detergents. These soils are difficult to remove completely and
often residues build up on fabric leading to dinginess and yellowing.
In addition, these soils or their breakdown products tend to redeposit on the
articles in the wash.
Proteases have been used in detergent compositions to provide
removal of soils. Indeed, their ability to hydrolyse proteins has been taken
advantage of by incorporating naturally occurring and protein engineered
proteases as an additive to hard surface cleaners, dishwashing compositions,
laundry compositions and the like. Many soils are proteinaceous and wide-
specifity proteases can substantially improve the removal of such stains.
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Stains, in particular coloured stains, are problematic to remove. These
stains typically originate from red wine, fruit such as black currant, cherry,
strawberry and tomato (in particular ketchup and spaghetti sauce),
5 vegetables such as carrots and beetroot, tea, coffee, spices such as curry
and paprika, grass, or ball pens/ink. Commercial detergents normally include
bleaching agents to solve the above mentioned problem.
Traditionally, high levels of bleaching agents, optionally with bleach
10 percursors, are incorporated in detergent compositions. Bleaching agents are
compounds which are precursors of hydrogen peroxide; hydrogen peroxide is
then formed in the course of the washing procedure. Perborates and
percarbonates are the most important examples of such hydrogen peroxide
precursors .
Given the foregoing, there is clearly a continuing need to provide
detergent compositions which have an excellent overall detergency
performance. Accordingly, it is an object of the present invention to
formulate detergent compositions which provide effective and efficient
20 cleaning of coloured and everyday "skin" stains and soils.
It has now been surprisingly found that the overall detergency
performance of serine proteases is synergistically enhanced by a laccase. In
addition, it has been found that the bleaching performance of the laccase is
25 synergistically enhanced by the presence of a serine protease.
This finding allows either improved cleaning and stain removal
performance or a reduction of the enzyme levels while keeping the same
cleaning and stain removal performance.
It has also been found that the detergent composition of the
present invention provide sanitisation of the treated surfaces.
W091/05839 describes enzymes exhibiting a suitable oxidase activity
35 or peroxidase activity for the inhibition of textile dye transfer from a dyedfabric to another fabric during the wash process. In particular, W095/01426
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WO 97/43384 PCT/US97/08048
provides a detergent additive and a detergent composition comprising an
enzyme exhibiting laccase activity, oxygen and an enhancing agent, which
are capabie of inhibiting the transfer of a textile dye from a dyed fabric to
~ another fabric when said fabrics are washed together in a wash liquor.
5 Hospital laundry detergents containing an oxidase and a protease enzymes
~ are disclosed in J64-60693. WO93tl3193 describes detergent compositions
comprising a protease derived from Nocardiopsis and enzymes exhibiting a
suitable oxidase activity or peroxidase activity, for stain bleaching and/or dyetransfer inhibition.
However, the use of a laccase and a serine protease for effective and
efficient cleaning of colou-ed and everyday "skin" stains and soils, has not
been recognised.
SUMMARY of the INVENTION
The present invention relates to detergent compositions comprising a
serine protease and a laccase. Such compositions provide improved cleaning
and stain removal performance.
DETAILE~ DESCRIPTION of the INVENTION
Serine Protease
Serine protease enzymes are an essential component of the detergent
compositions of the present invention. It has been surprisingly found that the
bleaching performance of the serine protease is enhanced by the presence of
a laccase. Accordingly, the detergent compositions of the present invention
provide effective and efficient cleaning of coloured and everyday "skin"
stains and soils.
The detergent compositions of the present invention comprise a
protease at a level from 0.0001% to 2%, preferably from 0.001% to 0.5%,
more preferably from 0.002% to 0.085% pure enzyme by weight of total
composition, in addition to the laccase.
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The serine proteolytic enzyme can be of animal, vegetable or
microorganism (preferred) origin. More preferred is serine proteolytic enzyme
of bacterial origin. Purified or non-purified forms of an enzyme may be used.
5Proteolytic enzymes produced by chemically or genetically modified mutants
are included by definition, as are close structural enzyme variants. Particularly
preferred by way of proteolytic enzyme is bacterial serine proteolytic enzyme
obtained from Bacillus, Bacil/~Js subtilis and/or Bacillus licheniformis. Suitable
commercial proteolytic enzymes which may be considered for inclusion in the
0present invention compositions include Alcalase(~), Esperase~', Durazym(~,
Savinase(~', Maxatase~', Maxacal@), Maxapem~' 15 ~protein engineered
Maxacal~; Purafect(~) and Substilin BPN and BPN'.
Serine proteolytic enzymes also encompass modified bacterial serine
15proteases, such as those described in European Patent Application No.
87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98~, and
which is called herein "Protease B", and in European Patent Application EP
199 404, Venegas, published October 29, 1986, which refers to a modified
bacterial serine protease which is called "Protease A" herein. More preferred
20is what is called herein "Protease C" being a variant of an alkaline serine
protease from Bacillus in which the Iysine replaced arginine at position 27,
tyrosine replaced valine at position 104, serine replaced asparagine at
position 123 and alanine replaced threonine at position 274. Protease C is
described in EP 909159~8.4, corresponding to WO 91/06637, published
25May 16, 1991. Genetically modified variants, particularly of Protease C, are
also included therein.
~efer,e~ proteolytic enzymes are selected from the group consisting
of Savinase~), Esperase~, Maxacal@~, Purafect~), BPN', Protase A and Protease
30B and mixtures thereof. Bacterial serine protease enzymes obtained from
Bacillus subtilis and/or Bacillus /icheniformis are preferred.
An especially preferred protease herein referred to as "Protease D" is a
carbonyl hydrolase variant having an amino acid sequence not found in
35nature, 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
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hydrolase equivalent to + 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 B~cillus ~myloliq~lefaciens substilisin, as described in thepatent application of A. Baeck et al. entitled "Protease-containing cleaning
compositions" having US serial No. 08/322,676, filed October 13, 1994.
0 Laccase and Laccase related enzvmes
Laccase and laccase related enzymes are an essential component of
the detergent compositions of the present invention. It has been surprisingly
found that the bleaching performance of the laccase is enhanced by the
presence of a serine protease. Accordingly, the detergent compositions of the
present invention provide effective and efficient cleaning of coloured and
everyday "skin" stains and soils.
In addition, the detergent compositions of the present invention
provide sanitisation of the treated surfaces.
Sanitisation includes all positive effects obtained by the inhibition or
reduction of microbial activity on fabrics and other surfaces, such as the
prevention of malodour development and bacterial/fungal growth. For
example, it provides prevention of malodour development on stored and
weared fabrics, on stored dishware, especially plastic kitchen gear and in
toilets. In particular, the composition of the invention will inhibit or at least
reduce the bacterial and/or fungal development on moist fabric waiting for
further laundry processing and thereby preventing the formation of malodour.
In addition, bacterial and/or fungal growth on hard surfaces such as tiles and
their silicone joints, sanitary installations, will be prevented.
The sanitisation potential of the detergent compositions of the present
invention can be enhanced by the addition of chemical sanitisers such as
Triclosan and/or hexemidine. Parfums Cosmétiques Actualités No 125, Nov,
1995, 51 -4 describes suitable chemical sanitisers.
The sanitisation benefits of the detergent compositions of the present
invention can be evaluated by the Minimum Inhibitory Concentration (MIC~ as
. ., .. ~, .. . ~
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described in Tuber. Lung. Dis. 1994 Aug; 75(4):286-90; J. Clin. Microbiol.
1994 May; 32(5):1261-7 and J. Clin. Microbiol. 1992 Oct; 30(10):2692-7.
According to the present invention, laccases and laccase related
5 enzymes comprise any laccase enzyme comprised by the enzyme
classification (EC 1.10.3.2), any catechol oxidase enzyme comprised by the
enzyme classification (EC 1.10.3.1), any bilirubin oxidase enzyme comprised
by the enzyme classification ~EC 1.3.3.5) or any monophenol
monooxygenase enzyme comprised by the enzyme classification (EC
1.14.99.1).
The above mentioned enzymes may be derived from plants, bacteria or
fungi (including filamentous fungi and yeasts) and suitable examples include a
laccase derivable from a strain of Apergillus, Neurospora, e.g. N. crassa,
Podospora, Botrytis, Collybia, Fomes, Lentinus, Pleurotus, Trametes, e.g. T.
villosa and T. versicolor, Rhizoctonia, e.g. R. solani, Coprinus, e.g. C.
plicatilis and C. cinereus, Psatyrella, Myceliophthora, e.g. M. thermophila,
Schytalidium, Polyporus, e.g. P. pinsitus, Phlebia, e.g. P. radita (W0
92/01046) or Coriolus, e.g. C. hirsutus (JP 2-238885).
The laccase or the laccase related enzyme may furthermore be one
which is producible by a method comprising cultivating a host cell
transformed with a recombinant DNA vector which carries a DNA sequence
encoding said laccase as well as DNA sequences encoding fucnctions
permitting the expression of the DNA sequence encoding the laccase, in a
culture medium under conditions permitting the expression of the laccase
enzyme, and recovering the laccase from the culture.
Especially suitable l~ccases that function at a pH above 7 are
obtainable from a strain of Coprinus and/or Myceliophtora.
According to the invention laccases displaying immunochemical cross-
reactivity with an antibody raised against above described laccases are also
included .
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The detergent composition of the present invention comprise a laccase
at a level from 0.0001% to 2%, preferably from 0.003% to 0.06% pure
enzyme by weight of the total composition.
The ratio of active laccase to active protease varies from 1:1000 to 1000:1,
preferably from 1:100 to 100:1, more preferably from 1:10 to 20:1.
Determination of Laccase ActivitY (LACU)
Laccase activity is determined from the oxidation of syringaldazin
under aerobic conditions. The violet colour produced is photometered at
530nm. The analytical conditions are 19~1M syringaldazin, 23.2mM acetate
buffer, pH 5.5, 30~C, 1 min. reaction time.
1 iaccase unit (LACU~ is the amount of enzyme that catalyses the
conversion of 1.0 llmole syringaldazin per minute at these conditions.
Enhancin~ agents
The detergent compositions according to the present invention may
contain an enhancing agent.
According to the invention an enhancing agent is any compound that
enhances the oxidation. The enhancing agent will typically be an oxidizable
compound, e.g. a metal ion or a phenolic compound such as 7-
hydroxycoumarin, vanillin, or p-hydroxybenzenesulfonate, (for reference see
WO 92/18683, WO 92/18687 and Kato M and Shimizu S, Plant Cell Physiol.
1985 26 (7), pp. 1291-1301 (cf. Table 1 in particular).
Particularly useful enhancing agents may be described by the following
formula:
OH
R2~ ~ ~OR3
f=o
Rl
where R1 is H, OH, CnH2n+ 1, in which n is an integer of from 1 to 10; and
R2 and R3 are the same or different and selected from CmH2m+ 1, in which
. .
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m is an integer of from 1 to 10. R1, R2 and R3 may also contain double
bonds or cyclic groups.
In preferred embodiments, the enhancing agent is alkylsyringate in
particular methyl, ethyl, propyl, butyl, hexyl syringate. Other suitable
5 enhancing agents for the present invention are the new group of organic
chemical substances performing excellently as enhancers of phenol oxidising
enzymes, such as acetosyringone; described in W096/10079.
Other particularly useful enhancing agents may be described by the
0 following formula:
Rl R9
R2~X~R8
E~4 Rs E~6
in which formula X represents (-O-) or (-S-), and the substituent groups
15 R1-R9, which may be identical or different, independently represents any of
the following radicals: hydrogen, halogen, hydroxy, formyl, carboxy and
esters and salts hereof, carbamoyl, sulfo, and esters and salts hereof,
sulfamoyl, nitro, amino, phenyl, C1 -C1 4-alkyl, C1 -Cs-alkoxy, carbonyl-C1-
Cs-alkyl, aryl-C1-Cs-alkyl; which carbamoyl, sulfamoyl, and amino groups
20 may furthermore be unstubstituted or substituted once or twice with a
substituent group R10; and which phenyl may furthermore be unsubstituted
or substituted with one or
more substituent groups R10; and which C1-C14-alkyl, C1-Cs-alkoxy,
carbonyl-C1-Cs-alkyl, and aryl-C1-Cs-alkyl groups may be saturated or
25 unsaturated, branched or unbranched, and may furthermore be unsubstitued
or substituted with one or more substituent groups R1 0;
which substituent groups R10 represents any of the following radicals
: halogen, hydroxy, formyl, carboxy and esters and salts hereof, carbamoyl,
sulfo and esters and salts hereof, sulfamoyl, nitro, amino, phenyl, aminoalkyl,
30 piperidino, piperazinyl, pyrrolidin-1-yl, C1-Cs-alkyl, C1-Cs-alkoxy; which
carbamoyl, sulfamoyl and amino groups may furthermore be unsubstituted or
. , . _ . _
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substituted once or twice with hydroxy, C 1 -Cs-alkyl, C 1 -Cs-alkoxy; and
which phenyl may furthermore be substituted with one or more of the
following radicals: halogen, hydroxy, amino, formyl, carboxy and esters and
salts hereof, carbamoyl, sulfo and esters and salts hereof, and sulfamoyl; and
which C1-Cs-alkyl, and C1-Cs-alkoxy groups may furthermore be saturated
or unsaturated, branched or unbranched and may furthermore be substituted
once or twice with any of the following radicals: halogen, hydroxy, amino
formyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and
salts hereof, and sulfamoyl;
0 or in which general formula two of the substituent groups R1-R9 may
together form a group -B-, in which B represents any of the following groups
: (-CHR 10-N = N-),
(-CH=CH-)n, (-CH=N-)n or (-N-CR10-NR11-), in which groups n represents
an integer of from 1 to 3, R10 is a substituent group as defined above and
R11 is defined in the same way as R10 (it is to be.understood that if the
above mentioned formula comprises two or more R 1 ~-substituent groups,
these R10-substituent groups may be the same or different).
In particular embodiments, the enhancing agent is 10-
methylphenothiazine, phenothiazine-10-propionic acid, N-hydroxysuccinimide
phenothiazine- 10-propionate, 10-ethyl-phenothiazine-4-carboxylic acid, 10-
ethylphenothiazine, 10-propylphenothiazine, 10-isopropylphenothiazine,
methyl-phenothiazine- 10-propionate, 10-phenylphenothiazine, 10-
allylphenothiazine, 10-(3-(4-methylpiperazin-1-yl)propyl) phenothiazine, 10-(2-
pyrrolidin-1 -yl-ethyl)phenothiazine, 2-methoxy-10-methylphenothiazine, 1 -
- methoxy- 10-methyl-phenothiazing, 3-methoxy- 10-methylphenothiazine, 3,10-
dimethylphenothiazine, 3,7,10-trimethylphenothiazine, 10-~2-
hydroxyethyl)phenothiazine, 10-(3-hydroxypropyl) phenothiazine, 3-(2-
hydroxyethyl)- 10-methylphenothiazine, 3-hydroxymethyl- 10-
methylphenothiazine, 3,7-dibromopheno-thiazine-10-propionic acid,
phenothiazine-10-propionamide, chlorpromazine, 2-chloro-10-
methylphenothiazine, 2-acetyl-10-methylphenothiazine, 10-
methylphenoxazine, 10-ethyl-phenoxazine, phenoxazine-10-propionic acid,
10-~2-hydroxyethyl)phenoxazine or 4-carboxyphenoxazine-10-propionic acid.
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The enhancing agents may be obtained from Sigma-Aldrich, Janssen
Chimica, Kodak, Tokyo Kasai Organic Chemicals, Daiichi Pure Chemicals Co.
or Boehringer Mannheim; N-methylated derivatives of phenothiazine and
phenoxazine may be prepared by methylation with methyliodide as described
by Cornel Bodea and loan Silberg in "Recent Advances in the Chemistry of
Phenothiazines" (Advances in heterocyclic chemistry, 1968, Vol.9, pp.321-
460); B. Cardillo & G. Casnati in Tetrahedron, 1967, Vol. 23, p.3771.
Phenothiazine and phenoxazine propionic acids may be prepared as described
in J.Org. Chem. 15, 1950, pp. 1125-1130. Hydroxyethyl and hydroxypropyl
10 derivatives of phenothiazine and phenoxazine may be prepared as described
by G.Cauquil in Bulletin de la Society Chemique de France, 1960, p.1049.
The enhancing agent may be present in concentrations of from 0.01 to
500~1M, preferably in concentrations of from 0.1 to 25011M in the wash
solution.
The enhancing agent is present in the detergent compositions at a level
of 0.1 % to 5 % by weight of the total detergent composition.
Deterqent comPonents
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.
In a preferred embodiment, the present invention relates to a laundry
and/or fabric care composition comprising a laccase and a serine protease
(Examples 1-11). It has been found that the incorporation of a laccase
enzyme and a serine protease in a softener matrix does also deliver effective
30 and efficient cleaning of coloured and everyday "skin" stains and soils during
the rinse cycle, with colour safety. In a second embodiment, the present
invention relates to dishwashing or household cleaning compositions
(Examples 12-20).
The compositions of the invention may for example, be formulated as
hard surface cleaner, hand and machine dishwashing compositions, hand and
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11
machine laundry detergent compositions including laundry additive
compositions and compositions suitable for use in the soaking and/or
pretreatment of stained fabrics, rinse added fabric softener compositions.
Compositions comprising a laccase and a serine protease enzymes can also
be formulated as sanitisation products.
The present invention also relates to a process for contacting fabrics
with a laundering solution as hereinbefore described. The washing process is
preferably carried out at 5~C to 75~C, especially 20 to 60~ The pH of the
0 treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5.The process and compositions of the invention can also be used as detergent
additive products. Such additive products are intended to supplement or
boost the performance of conventional detergent compositions.
When formulated as compositions for use in manual dishwashing
methods the compositions of the invention preferably contain a surfactant
and preferably other detergent compounds selected from organic polymeric
compounds, suds enhancing agents, group l l metal ions, solvents,
hydrotropes and additional enzymes.
When formulated as compositions suitable for use in a laundry 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, lime-
soap dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors. Laundry compositions can also contain softening agents, as
additional detergent components.
The compositions of the invention can also be used as detergent
additive products. Such additive products are intended to supplement or
boost the performance of conventional detergent compositions.
If needed the density of the granular laundry detergent compositions
herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of
composition measured at 20~C.
. . .
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12
The "compact" form of the granular laundry detergent compositions
herein is best reflected by density and, in terms of composition, by the
amount of inorganic filler salt; inorganic filler salts are conventional
5 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.
In the compact compositions, the filler salt is present in amounts not
exceeding 1 5% of the total composition, preferably not exceeding 10%,
10 most preferably not exceeding 5% by weight of the composition.
The inorganic filler salts are typically selected from the alkali and
alkaline-earth-metal salts of sulphates and chlorides.
A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can
also be in a "concentrated form", in such case, the liquid detergent
compositions according the present invention will contain a lower amount of
water, compared to conventional liquid detergents.
Typically the water content of the concentrated liquid detergent is
20 preferably less than 40%, more preferably less than 30%, most preferably
less than 20% by weight of the detergent composition.
Surfactant svstem
The detergGnt 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.
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,
most preferably from 1% to 20% by weight of laundry and rinse added fabric
softener compositions in accordance with the invention.
The surfactant is preferably formulated to be compatible with enzyme
components present in the composition. In liquid or gel compositions the
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13
surfactant is most preferably formulated such that it promotes, or at least
does not degrade, the stability of any enzyme in these compositions.
Preferred surfactant systems to be used according to the present
5 invention comprise as a surfactant one or more of the nonionic and/or anionic
surfactants described herein. Preferred surfactant systems comprise an
anionic to nonionic weight ratio of 1:1 to 10:1, preferably 1:1 to 3:1. It has
been found that said ratios of anionic to nonionic provide optimized stain
removal performance.
Polyethylene, polypropylene, and polybytylene 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
5 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 embodi,.,e..t, the ethylene oxide is present in an amount equal to
from about 2 to about 25 moles, more preferably from about 3 to about 1~
moles, of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic surfactants of this type include IgepalTM C0-630, marketed by the
GAF Corporation; and TritonTM 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 ethoxylatesi.
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
.. ~ , ., . .. . ~ .... ....
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14
TergitolTM 1 5-S-9 (the condensation product of C1 1-C1 5 linear alcohol with
9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product
of C 1 2-C 1 4 primary alcohol with 6 moles ethylene oxide with a narrow
molecular weight distribytion), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9
moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-
C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 ~the
condensation product of C14-C1s linear alcohol with 7 moles of ethylene
oxide), NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol
0 with 5 moles of ethylene oxide) marketed by Shell Chemical Company,
KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company, and Genapol
LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 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.
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 ,,~referably 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 asopposed 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.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(9lycosyl)x
wherein R2 js selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
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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
aikylpolyethoxy 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
0 predominately the 2-position.
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
20 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 PluronicTM surfactants, marketed by
BASF.
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
30 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
35 5,000 to about 11,000. Examples of this type of nonionic surfactant include
CA 022~494l l998-ll-l2
W O 97/43384 PCTAUS97/08048
16
certain of the commercially available TetronicTM compounds, marketed by
BASF .
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 Cg-C14 alkyl phenol ethoxylates having
from 3 to 15 ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C1o
0 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants of the formula.
R2 C-N-Z,
O Rl
wherein Rl is H, or R1 is C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is Cs 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, R1 is methyl, R2 is a straight C11 15 alkyl or C16 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.
When included in such laundry detergent compositions, the nonionic
su~actant 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.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula
RO(A)mS03M wherein R is an unsubstituted C1o-C24 alkyl or hydroxyalkyl
group having a C 1 0-C24 alkyl component, preferably a C 1 2-C20 alkyl or
hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy
CA 022~4941 1998-11-12
W O 97/43384 17 PCTAUS97/08048
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
5 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,
0 triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-
C18 alkyl polyethoxylate ~1.0) sulfate IC1 2-C1 gE(1 .O)M), C1 2-C1 8 alkyl
polyethoxylate ~2.25) sulfate (Cl 2-C1 gE(2.25)M), C1 2-C1 8 alkyl
polyethoxylate (3.0) sulfate (C1 2-C1 gE(3.0)M), and C1 2-C1 8 alkyl
polyethoxylate (4.0) sulfate (C1 2-C1 gE(4.0)M), wherein M is conveniently
5 selected from sodium and potassium.
Suitable anionic surfactants to be used are alkyl ester sulfonate
surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty
acids) which are sulfonated with gaseous S03 according to "The Journal of
20 the American Oil Chemists Society", 52 ( 1 975), 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
25 formula:
o
R3 - CH - C - oR4
I
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C 1 -C6 hydrocarbyl, preferably an alkyl, or combination
thereof, and M is a cation which forms a water soluble salt with the alkyl
35 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,
.
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18
R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred
are the methyl ester sulfonates wherein R3 is C1 0-C1 6 alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants
which are water soluble salts or acids of the formula ROSO3M wherein R
preferably is a C1 o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C1 0-c20 alkyl component, more preferably a C1 2-C1 8 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-,
0 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 C1 2-C1 6 are preferred for lower wash temperatures (e.g.
below about 50~C) and C16 18 alkyl chains are preferred for higher wash
temperatures ~e.g. above about 50~C).
Other anionic surfactants useful for detersive purposes can also be
included in the laundry deter~ent compositions of the present invention.
20 These can include salts (including, for example, sodium, potassium,
ammonium, and substituted ammonium salts such as mono-, di- and
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
25 citrates, e.g., as described in British patent specification No. 1,082,179, Cg-
C24 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-
30 acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinates (especially saturated and unsaturated C12-C1g monoesters)
and diesters of sulfosuccinates (especially saturated and unsaturated C6-C1 2
diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
35 described below), branched primary alkyl sulfates, and alkyl polyethoxy
carboxylates such as those of the formula RO(CH2CH20)k-CH2COO-M +
CA 022~4941 1998-11-12
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19
wherein R is a Cg-C22 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.
5 Further examples are described in "Surface Active Agents and Detergents"
(Vol. I and ll 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).
10 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.
The detergent composition of the present invention may further
5 comprise a cosurfactant selected from the group of primary or tertiary
amines.
Suitable primary amines for use herein include amines according to the
formula RlNH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or
R4X(CH2)n, X is -O-,-C(O)NH- or -NH-, R4 is a C6-C1 2 alkyl chain n is
20 between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched
and may be interrupted with up to 12, preferably less than 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-
25 octylamine, 1-decylamine and laurylamine. Other preferred primary amines
include C8-C 10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having
30 the formula R1 R2R3N wherein R1 and R2 are C1 -C8 alkylchains or
R5
--( CH2--CH--O )xH
R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n,
whereby X is -O-, -C(O)NH- or -NH-,R4 is a C4-C12, n is between 1 to 5,
preferably 2-3. Rs is H or C1-C2 alkyl and x is between 1 to 6 .
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R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted
with up to 12, preferably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R1 R2R3N where R1 is a C6-C12 alkyl
5 chain, R2 and R3 are C1-C3 alkyl or
R5
--( CH2--CH--O )xH
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
Rl--C--NH--( cH2 )--N--( R2 )2
wherein R 1 is C6-C 1 2 alkyl; n is 2-4,
preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine,
1 -hexylamine, 1 -decylamine, 1 -dodecylamine,C8-1 Ooxypropylsmine, N coco
1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl
20 bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
amidopropyidimethylamine, C8-10 amidopropyldimethylamine and C10
amidopropyldimethylamine .
The most preferred amines for use in the compositions herein are 1-
25 hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable
are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and
oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido
propylamine.
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
hereln .
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21
According to the present invention, it has been found that cationic
surfactants enchance the overall cleaning performance of the laccase.
Cationic detersive surfactants suitable for use in the laundry detergent
compositions of the present invention are those having one long-chain
5 hydrocarbyl group. Examples of such cationic surfactants include the
ammonium surfactants such as alkyltrimethylammonium halogenides, and
those surfactants having the formula:
[R2(oR3)y] [R4(oR3)y]2R5N + X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-,
and mixtures thereof; each R4 is selected from the group consisting of C1-C4
5 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two
R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose
or hexose polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein
the total number of carbon atoms of R2 plus R5 is not more than about 18;
20 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.
Quaternary ammonium surfactant suitable for the present invention has the
formula (I):
~0~ N~Rs
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the
formula (Il~:
C6~N~ ~
Formula ll
y is 2-4, preferably 3.
CA 022~4941 1998-11-12
W O 97/43384 rCT~US97/08048
22
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 lll, whereby X~ is5 a counterion, preferably a halide, e.g. chloride or methylsulfate.
R6
H
Formula lll
R6 is C1-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as defined in formula I
whereby
R 1 is Cg, C 10 or mixtures thereof, x = o,
R3, R4 = CH3 and Rs = CH2CH20H.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the formula:
R 1 R2R3R4N + X~ (i)
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40)XH where x has a value from
2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be
benzyl.
The preferred alkyl chain length for R1 is C12-C1~ particularly where the
aJkyl group is a mixture of chain lengths derived from coconut or palm kernel
fat or is derived synthetically by olefin byild up or OX0 alcohols synthesis.
Preferred groups for R2R3 and R4 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;
CA 022~4941 1998-11-12
W O 97/43384 PCTrUS97/08048
23
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;
5 lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula ~i) wherein R1 is
CH2-Ctl2-0-C-C12 14 alkyl and R2R3R4 are methyl).
Il
O
di-alkyl imidazolines [compounds of formula ~i)].
Other cationic surfactants useful herein are also described in lJ.S.
Patent 4,228,044, Cambre, issued October 14, 1980 and in European Patent
Application EP 000,224.
Typical cationic fabric softening components include the water-insoluble
quaternary-ammonium fabric softening actives or thei corresponding amine
precursor, the most commonly used having been di-long alkyl chain
20 ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the following:
1 ) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
1 1 ) C 1 2-1 8 alkyl dihydroxyethyl methylammonium chloride;
1 2) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallow-oxy-ethyl) dimethylammonium chloride;
1 4) ditallow imidazolinium methylsulf ate;
15) 1-(2-tallowylamidoethyl~-2-tallowyl imidazolinium methylsulfate.
,, . ~ . . ....
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Biodegradable quaternary ammonium compounds have been presented
as alternatives to the traditionally used di-long alkyl chain ammonium
chlorides and methyl sulfates. Such quaternary ammonium compounds
5 contain long chain alk(en)yl groups interrupted by functional groups such as
carboxy groups. Said materials and fabric softening compositions containing
them are disclosed in numerous publications such as EP-A-0,040,562, and
EP-A-0,239,91 0.
~o The quaternary ammonium compounds and amine precursors herein have the
formula ~I) or (Il), below:
R3~ R3
\ / + N -(CH2)n~CIH -CH2 X
+ N -(C ~ -Q--T 1 X- R3 Q
Rl Tl T2
-- Or
1 5 (I) (Il)
wherein Q is selected from -0-C(0)-, -C(0)-0-, -0-C(0)-0-, -NR4-C(o)-, -
C(o)-NR4-;
R 1 is (CH2) n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C1 1-C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X~ is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include chloride or
methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11
carbon atoms, preferably at least 16 carbon atoms. The chain may be
straight or branched.
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W O 97/43384 PCTnUS97/08048
Tallow is a convenient and inexpensive source of long chain alkyl and
alkenyl material. The compounds wherein T1, T2, ~3, T4, T5 represents the
mixture of long chain materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in
the aqueous fabric softening compositions herein include:
1 ) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di~tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl~ ammonium methyl
0 sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di~2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl
ammonium
chloride;
6) N,N,N-tri~tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-l 2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N, N-dimethyl-ammonium
chloride; and
8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
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.
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 heterocyciic 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 l 9, lines
18-3~, for examples of ampholytic surfactants.
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26
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.
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.
0 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line
38 through column 22, iine 48, for examples of zwitterionic surfactants.
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.
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.
Semi-polar nonionic detergent surfactants include the amine oxide
surfactants having the formula
o
R3(oR4)xN(R5)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof
35 containing from about 8 to about 22 carbon atoms; R4 is an alkylene or
hydroxyalkylene group containing from about 2 to about 3 carbon atoms or
CA 02254941 1998-11-12
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27
mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or
hydroxya!kyl 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 R5 groups can be attached to each other, e.g., through an
oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C1 o-C1 8 alkyl
dimethyl amine oxides and Cg-C 12 alkoxy ethyl dihydroxy ethyl amine
oxides.
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
surf actants .
Ootional deterqent inqredients:
Dispersant
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.
Polymers of this type are disclosed in GB-A-1,596,756. Exarnples of such
salts are polyacrylates of MW 2000-~000 and their copolymers with maleic
anhydride, such copolymers having a molecular weight of from 1,000 to
1 00,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N
having a molecular weight of 4000, at a level from 0.5-20% by weight of
composition can be added in the detergent compositions of the present
invention.
Other detergent enzymes
. .
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28
The detergent compositions can in addition to a laccase and serine
protease enzymes further comprise one or more enzymes which provide
cleaning performance and/or fabric care benefits.
Said enzymes include enzymes selected from cellulases, hemicellulases,
peroxidases, gluco-amylases, amylases, xylanases, lipases, esterases,
cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, 13-glucanases,
arabinosidases chondroitinase, or mixtures thereof.
A preferred combination is a cleaning composition having a cocktail of
conventional applicable enzymes like amylase, lipase, cutinase and/or
cellulase.
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 cellulase components which may be usable are:
A cellobiohydrolase component which is immunoreactive with an antibody
raised against a highly purified -70kD cellobiohydrolase ~EC 3.2.1.91) derived
from Humicola insolens, DSM 1800, or which is a homologue or derivative of
the -70kD cellobiohydrolase exhibiting cellulase activity, or
an endoglucanase component which is immunoreactive with an anitbody
raised against a highly purified -50kD endoglucanase derived from Humicola
insolens, DSM 1800, or which is a homologue or derivative of the -50kD
endoglucanase exhibiting cellulase activity; a preferred endoglucanase
component has the amino acid sequence disclosed in PCT Patent Application
No. W091/17244, or an endoglucanase component which is immunoreactive
with an antibody raised against a highly purified -50kD (apparent molecular
weight, the amino acid composition corresponds to 45kD with 2n
glycosylation sites) endoglucanase derived from Fusarium oxysporum, DSM
2672, or which is a homologue or derivative of the -50kD endoglucanase
exhibiting cellulase activity; a preferred endoglucanase component has the
.
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W O 97/43384 PCTnUS97/08048
amino acid sequence disclosed in PCT Patent Application No. WO91/17244,
or
any of the cellulase disclosed in the published European Patent Application
No. EP-A2-271 004, the cellulases having a non-degrading index (NDI) of not
less than 500 and being alkalophilic cellulases having an optimum pH not less
than 7 or whose relative activity at a pH of not less than 8 is 50% or over
the activity under opitmum conditions when carboxy methyl cellulose ~CMC)
is used as a substrate, or an endoglucanase component which is
immunoreactive with an antibody raised against a highly purified -43kD
endoglucanase derived from Humicola insolens, DSM 1800, or which is a
homologue or derivative of the -43kD endoglucanase exhibiting cellulase
activity; a preferred endoglucanase component has the amino acid sequence
disclosed in PCT Patent Application No. WO 90/17243, or an endoglucanase
component which is immunoreactive with an antibody raised against a highly
purified -60k~ endoglucanase derived from Bacillus lautus, NCIMB 40250, or
which is a homologue or derivative of the -60kD endoglucanase exhibiting
cellulase activity; a preferred endoglucanase component has the amino acid
sequence disclosed in PCT Patent Application No. WO 91/10732.
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.
Other preferred enzymes that can be included in the detergent
compositions of the present invention include lipases. Suitable lipase
. . .
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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, lapan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-
P". Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR
(Gist-Brocades) and LipolaseR- Also suitable are cutinases [EC 3.1.1.50]
0 which can be considered as a special kind of lipase, namely lipases which do
not require interfacial activation. Suitable cutinases are described in WO
94/14963 and WO 94114964. Addition of cutinases to detergent
compositions have been described in e.g. WO-A-88/09367 (Genencor).
The lipases andlor 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 (a and/or 13) can be included for removal of carbohydrate-
based stains. Suitable amylases are TermamylR~ (Novo Nordisk), FungamylR
20 and BANR (Novo Nordisk). Highly preferred amylases are amylase variants
disclosed in W095/10603.
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 the copending European patent
application 92870018.6 filed on January 31, 1992. Examples of such
35 enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
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31
Color care benefits
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 the European patent EP O 596 184 and in the
copending European Patent Application No. 94870206.3.
0 Ble~ching agent
Bleach systems that can be included in the detergent compositions of
the present invention include bleaching agents such as PB 1, 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%. Bleaching agents are preferred detergent
ingredients since the combination with laccase results in enhanced cleaning
and whiteness performance.
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.
The bleaching agent suitable for the present invention can be an activated or
non-activated bleaching agent.
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-oxoperoxybytyric 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.
. . .
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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.
The hydrogen peroxide releasing agents can be used in combination
with bleach activators such as tetraacetylethylenediamine (TAED),
0 nonanoyloxybenzene-sulfonate tNOBS, 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. Also
suitable activators are acylated citrate esters such as disclosed in Copending
European Patent Application No. 91870207.7.
Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
detergent compositions according to the invention are described in our co-
pending applications USSN 08/136,626, PCT/US95/07823, W095/27772,
W095/27773, W095/27774 and W095/27775.
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.
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
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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.
5 Builder system
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, diethylene triamine
pentamethyleneacetate, metal ion sequeslrants such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene
phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
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.
Another suitable inorganic builder material is layered silicate, e.g. SKS-
6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium
silicate (Na2si2o5)
Suitable polycarboxylates containing one carboxy group include lactic
acid, glycolic acid and ether derivatives thereo~ as disclosed in Belgian PatentNos. 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.
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Po!ycarboxylates 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.
0 1,439,000.
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 poly-carboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly
citrates.
Preferred builder systems for use in the present compositions include a
25 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.
A suitable chelant for inclusion in the detergent compositions in
30 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 Na2EDDS and Na4EDDS. Examples
35 of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS.
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The magnesium salts are the most preferred for inclusion in compositions in
accordance with the invention.
- Preferred builder systems include a mixture of a water-insoluble
5 aluminosilicate byilder such as zeolite A, and a watersoluble carboxylate
chelating agent such as citric acid.
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
10 phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
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
15 carbon atoms.
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.
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.
25 Suds suppressor
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
30 divided forms exemplified by silica aerogels and xerogels and hydrophobic
silicas of various types. These materials can be incorporated as particulates inwhich 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
35 dispersed in a liquid carrier and applied by spraying on to one or more of the
other components.
~ . . .
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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-bytyl-octanol which are commercially
available under the trade name Isofol 12 R.
0 Such suds suppressor system are described in Copending European Patent
application N 92870174.7 filed 10 November, 1992.
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
15 silica such as AerosilR.
The suds suppressors described above are normally employed at ievels
of from 0.001 % to 2% by weight of the composition, preferably from 0.01 %
to 1 % by weight.
Others
Other components used in detergent compositions may be employed,
such as soil-suspending agents, soil-release agents, optical brighteners,
25 abrasives, bactericides, tarnish inhibitors, coloring agents, and/or
encapsulated or non-encapsulated perfumes.
Especially suitable encapsulating materials are water soluble capsules
which consist of a matrix of polysaccharide and polyhydroxy compounds
30 such as described in GB 1,464,616.
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
35 and potato. Suitable examples of said encapsulating materials include N-Lok
manufactured by National Starch. The N-Lok encapsulating material consists
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37
of a modified maize starch and glucose. The starch is modified by adding
monofunctional substituted groups such as octenyl succinic acid anhydride.
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 byilders, as well
as copolymers of maleic anhydride with ethylene, methylvinyl ether or
methacrylic acid, the maleic anhydride constituting at least 20 mole percent
0 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.
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-
20 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. Highly preferred brighteners are the specific
25 brighteners of copending European Patent application No. 95201943.8.
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
30 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.
~5
., . =
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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
(CH3(PEG)43)0.75(PoH)o.25[T-po)2.8(T-pEG)o-4]T(
H~0.25~(PEG)43CH3)0.75
where PEG is -(OC2H4)0-,P0 is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers of
dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2
5 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
20 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.
The selected polyesters herein contain about 46% by weight of
25 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.
Is is well known in the art that free chlorine in tap water rapidly
deactivates the enzymes comprised in detergent compositions. Therefore,
using chlorine scavenger such as perborate, ammonium sulfate, sodium
sulphite or polyethyleneimine at a level above 0.1 % by weight of total
35 composition, in the formulas will provide improved through the wash stability of the specific amylase enzymes. Compositions comprising chlorine
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scavenger are described in the European patent application 92870018.6 filed
January 31, 1992.
Softening agents
Fabric softening agents are very suitable for incorporation 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
0 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-~-O 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 57~ and 0 313 146.
Levels of smectite clay are normally in the range from 2% to 20%,
more preferably from 5% to 15% 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
The detergent composition of the present invention can also include
compounds for inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric laundering
operations involving colored fabrics.
,
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Polymeric dye transfer inhibiting agents
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
0 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.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
15 polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles
or mixtures thereof.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having
20 the following structure formula:
p
I
(I) Ax
I
R
wherein P is a polymerisable unit, whereto the R-N-0 group can be attached
to or wherein the R-N-0 group forms part of the polymerisable unit
or a combination of both.
O O O
Il 11 11
A is NC, C0, C, -0-,-S-, -N-; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen
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41
of the N-O group can be attached or wherein the nitrogen of the N-
O group is part of these groups.
The N-O group can be represented by the following general structures:
O O
(R1)x-N- (R2)y =N- (R1~x
(R3)z
wherein R 1, R2, and R3 are aiiphatic 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.
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.
20 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.
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.
25 Preferred polyamine N-oxides are those wherein R is a heterocyclic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine
and derivatives thereof.
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.
Other suitable polyamine N-oxides are the polyamine oxides whereto
the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides
having the general formula ~I) wherein R is an aromatic, heterocyclic or
35 alicyclic groups wherein the nitrogen of the N-0 functional group is part of
said R group.
. ~, . . . . . .
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Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazoie and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides
having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic5 groups wherein the nitrogen of the N-0 functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein R groups can
be aromatic such as phenyl.
0 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.
The amine N-oxide polymers of the presel-t 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: 1 000000. 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.
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
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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 5,000-200,000.
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 20,000.
The average molecular weight range was determined by light scattering as
10 described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern
Methods of Polymer Characterization".
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.
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.
20 The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention
has a molar rstio 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
The detergent compositions of the present invention may also utilize
polyvinvlpyrrolidone ("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
30 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
laverage molecular weight of 160,000), and PVP K-90 ~average molecular
35 weight of 360,000). Other suitable polyvinylpyrrolidones which are
commercially available from BASF Cooperation include Sokalan HP 165 and
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44
Sokalan tlP 12; polyvinylpyrrolidones known to persons skilled in the
detergent field (see for example EP-A-262,897 and EP-A-256,696).
d~ Polyvinyloxazolidone:
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:
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
20 15,000.
f) Cross-linked polymers:
Cross-linked polymers are polymers whose backbone are
25 interconnected to a certain degree; these links can be of chemical or physical
nature, possibly with active groups n the backbone or on branches; cross-
linked polymers have been described in the Journal of Polymer Science,
volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way
that they form a three-dimensional rigid structure, which can entrap dyes in
the pores formed by the three-dimensional structure. In another embodiment,
the cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-pending patent
application 94870213.9.
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The following examples are meant to exemplify compositions of the
present invention, but are not necessarily meant to limit or otherwise define
5 the scope of the invention. In the detergent compositions, the level of the
enzymes are expressed in pure enzyme by weight of total composition and
the abbreviated component identifications have the following meanings:
LAS : Sodium linear C1 2 alkyl benzene sulphonate.
TAS : Sodium tallow alkyl sulphate.
XYAS : Sodium c1x - C1y alkyl sulfate.
SAS : C12-C14 secondary 12,3) alkyl sulfate in the form
of the sodium salt.
AEC : Alkyl ethoxycarboxylate surfactant of formula C1 2
ethoxy (2) carboxylate.
SS : Secondary soap surfactant of formula 2-bytyl
octanoic acid.
25EY : A C1 2 C1 5 predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide.
45EY : A C14 - C1s 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-C1s 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.
AAPA : C8-C10 amidopropyldimethylamine.
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CFAA : C 1 2-C 14 alkyl N-methyl glucamide.
TFAA : C 1 6-C 1 8 alkyl N-methyl glucamide.
DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
DEQA (1) : Di-(oleyloxyethyl) dimethyl ammonium
methylsulfate.
DEQA (2) : Di-(soft-tallowyloxyethyl) hydroxyethyl methyl
ammonium methylsulfate.
DTDMAMS : Ditalllow dimethyl ammonium methylsulfate.
SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed
stearic acid.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by
Shell Chemical C0.
Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio =
2.0~.
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si20s.
Carbonate : Anhydrous sodium carbonate.
Metasilicate : Sodium metasilicate (SiO2:Na20 ratio = 2.0~.
Phosphate or STPP : Sodium tripolyphosphate.
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000.
PA30 : Polyacrylic acid of average molecular weight of
approximately 8,000.
Terpolymer : Terpolymer of average molecular weight approx.
7,000, comprising acrylic:maleic:ethylacrylic acid
monomer units at a weight ratio of 60:20:20.
480N : Random copolymer of 3:7 acrylic/methacrylic acid,
average molecular weight about 3,500.
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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(A1~2Si~2)12- 27H20 having a primary
particle size in the range from 1 to 10
micrometers.
Zeolite MAP : Alkali metal alumino-silicate of the zeolite P type
having a silicon to aluminium ratio not greater than
1 .33.
Citrate : Tri-sodium citrate dihydrate.
Citric : Citric Acid.
Perborate : Anhydrous sodium perborate monohydrate bleach,
empirical formula NaB02.H202
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 .
Peroxidase : Peroxidase enzyme sold under the tradename
Guardzyme by Novo Nordisk A/S.
Pectinase : Pectolytic enzyme sold under the tradename
Pectinex AR by Novo Nordisk A/S.
Xylanase : Xylanolytic enzyme sold under the tradenames
Pulpzyme HB or SP431 by Novo Nordisk A/S or
Lyxasan (Gist-Brocades) or Optipulp or Xylanase
(Solvay) .
Protease : Protease B.
Lipase : Lipolytic enzyme sold under the tradename
Lipolase.
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Cellulase I : Cellulolytic enzyme sold under the tradename
Carezyme or Celluzyme by Novo Nordisk A/S
43kD.
Cellulase ll : Endoglucanase 50kD, cellulolytic enzyme sold
under the tradename "Endolase" by Novo Nordisk.
Laccase : Laccase from Myceliophtora thermophila.
Enhancer : Butyl syringate.
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.
PAAC : pentaamine acetate cobalt (Ill) salt.
BzP : Benzoyl peroxide.
PVP : Polyvinyl pyrrolidone polymer.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
Soil Release Polymer : Sulfonated poly-ethoxy/propoxy end capped ester
oligomer.
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
siiica, 58% paraffin oil.
Granular Suds : 1 2% Silicone/silica, 1 8% stearyl alcohol,70%
Suppressor starch in granular form.
SCS : Sodium cumene sulphonate.
Sulphate : Anhydrous sodium sulphate.
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HMWPEO : High molecular weight polyethylene oxide.
PGMS : Polyglycerol monostearate having a tradename of
Radiasurf 248.
TAE 25 : Tallow alcohol ethoxylate (25).
PEG(-6) : Polyethylene glycol (having a molecular weight of
600).
BTA : Benzotriazole.
Bismuth nitrate : Bismuth nitrate salt.
NaDCC : Sodium dichloroisocyanurate.
KOH : 100% Active solution of Potassium Hydroxide.
pH : Measured as a 1 % solution in distilled water at 20
~C.
ExamDle 1
Granular fabric cleaning compositions in accord with the invention were
5 prepared as follows:
11 111 lV V
LAS 22.0 22.0 22.0 22.0 22.0
AE5 9.0 9.0 9.0 9.0 9.0
Phosphate 23.0 23.0 23.0 23.0 23.0
Carbonate 23.0 23.0 23.0 23.0 23.0
Silicate 14.0 14.0 14.0 14.0 14.0
Zeolite A 8.2 8.2 8.2 8.2 8.2
DETPMP 0.4 0.4 0.4 0.4 0.4
Sodium sulfate 5.5 5.5 5.5 5.5 5.5
Amylase 0.005 0.02 0.01 0.01 0.02
Protease 0.01 0.02 0.01 0.005 0.005
.
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Laccase 0.005 0.01 0.01 0.01 0.005
Enhancer 0. 5 0. 5 0. 5 0. 5 0. 5
11 111 lV V
Pectinase 0.02
Xylanase - - 0.01 0.02
Lipase 0.005 0.01
Cellulase 1 0.001 - - 0.001
Water & minors Up to 100%
Exam~le 2
Granular fabric cleaning compositions in accord with the invention were
5 prepared as follows:
11 111 lV V
AE 6.0 6.0 6.0 6.0 6.0
LAS 12.0 12.0 12.0 12.0 12.0
Zeolite A 26.0 26.0 26.0 26.0 26.0
SS 40 40 40
SAS 5.0 5.0 5.0 5.0 5.0
Citrate 5.0 5.0 5.0 5.0 5.0
Sodium Sulfate 17.0 17.0 17.0 28.0 17.0
Perborate 16.0 16.0 16.0
TAED 5.0 5.0 5.0
Protease 0.06 0.03 0.02 0.08 0.01
Laccase 0.005 0.01 0.04 0.04 0.01
Enhancer 0 . 5 0 . 5 0. 5 0. 5 0 . 5
Lipase 0.005 0.01
Amylase 0.01 0.015 0.01 0.02 0.005
Water & minors Up to 100%
Exam~le 3
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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 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
Protease 0.02 0.02 0.01
Amylase 0.03 0.03 0.005
Silicate 2.0 2.5
Sulphate 3.5 5.2 3.0
PVP 0.3 0.5
PVN0/copolymer of vinyl- - - 0. 2
imidazole and vinvl-pyrrolidone
Perborate 0.5 1.0
Peroxidase 0.01 0.01
Laccase 0.01 0.01 0.02
Enhancer 0.5 1.0 0.5
Phenol sulfonate 0.1 0.2
Water/Minors Up to 100%
Exam~le 4
.
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Granular fabric cleaning compositions in accord with the invention
were prepared as follows:
ll
LAS 6. 5 8 .0
AE 8.0 8.0
Alkyl 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
Laccase 0.01 0.1
Enhancer 0. 5 0. 8
Silicate 5.0 5-0
Carbonate 15.0 15.0
Peroxidase - 0.1
Pectinase 0.02
Cellulase 1 0.005 0.002
Lipase 0.0 1
Amylase 0.01 0.01
Water/minors Up to 100%
ExamPle 5
A compact granular fabric cleaning composition in accord with the
0 invention was prepared as follows:
45AS 8.0
25E3S 2.0
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25E5 3.0
25E3 3.0
TFAA 2. 5
Zeolite A 1 7.0
NaSKS-6 1 2.0
Citric acid 3 0
Carbonate 7 o
MA/AA 5 0
CMC 0.4
PVN0/copolymer of vinylimidazole and 0.2
vinylpyrrolidone
Protease 0.05
Laccase 0.02
Enhancer 0.8
Lipase 0 005
Cellulase 1 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
A granular fabric cleaning compositions in accord with the invention
5 which provide "softening through the wash" capability were prepared as
follows:
ll
45AS - 10.0
LAS 7.6
68AS 1 . 3
45E7 4.0
25E3 - 5.0
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Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 1 1 .0
Zeolite A 1 5 .0 1 5.0
MAIAA 4.0 4.0
DETPMP 0.4 0 4
Perborate 1 5.0
ll
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPE0 - 0.1
Protease 0.02 0.01
Laccase 0.02 0.02
Enhancer 1.0 1.0
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 1 0.001
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
Heavy duty liquid fabric cleaning compositions suitable for use in the
5 pretreatment of stained fabrics, and for use in a machine laundering method,
in accord with the invention were prepared as follows:
11 111 lV V
24AS 20.0 20.0 20.0 20.0 20.0
SS 5.0 5.0 5.0 5.0 5.0
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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
Boric acid 2.75 5.75 1.5 1.5 1.5
Formic acid - - 1.0 1.0 1.0
Protease 0.005 0.03 0.02 0.04 0.01
Laccase 0.005 0.01 0.02 0.02 0.04
Enhancer 0.5 0.5 0.5 1.0 1.0
Lipase 0.002 0.01 0.02 - 0.004
11 111 lV V
Amylase 0.005 0.005 0.001 0.01 0.004
Cellulase 1 0.04 - 0.01
Pectinase 0.02 0.02
Water/propylene glycol/ethanol (100
ExamDle 8
Heavy duty liquid fabric cleaning compositions in accord with the
5 invention were prepared as follows:
11 111 lV V
LAS acid form - - 25.0
C 12- 14 alkenyl succinic 3 0 8.010.0
acid
Citric acid 10.0 16.0 2.0 2.0 2
23AS acid form - - - - 8
25AS acid form 8.0 8.0 - 15.0 4
25AE3S acid form - 3.0 - 4.0
35AE35 acid form - - - - 8
25AE7 - 8.0 - 6.0
45AE7 - - - - 2.5
25AE3 8.0 - 4.0
CFAA - - - 6.0 4
AAPA - - - - 1.5
. .. . . . . . . . ....
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N-Cocoyl N-methyl glucamine - - 4.0
DETPMP 0.2 - 1.0 1.0 1.0
Fatty acid - - - 10.0 5.0
Oleic acid 1.8 - 1.0 - 3.0
Ethanol 4.0 4.0 6.0 2.0 1.0
Propanediol 2.0 2.0 6.0 10.0 12.0
Boric acid 2.75 2.75 1.5 1.5 3.0
Formic acid - - 1.0 1.0
Protease 0.02 0.02 0.02 0.010.02
Laccase 0.00 0.01 0.02 0.040.008
11 111 lV V
Enhancer 0.3 0.4 0.8 1.0 0.3
Amylase 0.00 0.01 0.00 0.010.05
Cellulase I - - - - 0.03
Cellulass 11 - - - - O.Og
Coco-alkyl dimethyl hydroxy - - 3.0
ethyl ammonium chloride
Smectite clay - - 5.0
PVP 1.0 2.0
Perborate - 1.0
Phenol sulphonate - 0.2
Peroxidase - 0.01
Monoethanol amine 6.2
NaOH Up to pH 7.5
Water / minors Up to 100%
ExamDle 9
The following rinse added fabric softener composition, in accord with the
invention, was prepared (parts by weight).
DEQA 24. 5
PGMS 1.5
Alkyl sulfate 3.5
TAE 25 1.5
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Protease 0.005
Laccase 0.01
Enhancer 0.8
Amylase 0.001
Cellulase 10.001
Boric acid 2.00
HCL 0.12
Antifoam agent 0.01 9
Blue dye 80ppm
CaCI2 0.35
Perfume 0.90
.
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ExamPle 1 0
The following fabric softener and dryer added fabric conditioner
compositions were prepared in accord with the present invention:
11 111 lV V
DEQA 2.6 19.0 - - -
DEQA(2) - - 51.8
DTMAMS - - - 26.0
SDASA - - 70.0 42.0 40.2
Stearic acid of IV=O 0.3 - - - -
Neodol 45- 13 13 o
Hydrochloride acid 0.02 0.02
Ethanol - - 1.0
Protease 0.02 0.005 0.008 0.05 0.005
Laccase 0.002 0.005 0.01 0.01 0.1
Enhancer 0.05 0.01 0.2 0.5 0.9
Perfume 1.0 1.0 0.75 1.0 1.5
Glycoperse S-20 - - - - 15.4
Glycerol monostearate - - - 26.0
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01
Electrolyte - 0.1
Clay 3 0
Dye 1 Oppm 25ppm 0.01
Water and minors 100% 100%
ExamDle 1 1
Syndet bar fabric cleaning compositions in accord with the invention
10 were prepared as follows:
11 111 lV
C12-16 alkyl sulfate, Na 10.0 10.0 10.0 10.0
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C12-14 N-methyl glucamide 5.0 5.0 5.0 5.0
11 111 lV
C11-13 alkyl benzene 10.0 10.0 10.010.0
sulphonate, Na
Sodium carbonate 25.0 25.0 25.025.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
Sodium tripolyphosphate 7.0 7.0 7.0 7.0
Zeolite A 5.0 5 0 5 0 5 0
Carboxymethylcellulose 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2 0. 2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Amylase 0.01 0.02 0.010.01
Protease 0.3 0.4 0.5 0.05
Laccase 0.3 0.05 0.1 0.05
Enhancer 1.0 0.5 0.5 0.3
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler*: balance to 100%
*Can be selected from convenient materials such as CaC03, talc, clay
~Kaolinite, Smectite), silicates, and the like.
Exam~le 1 2
The following compact high density (0.96Kg/l) dishwashing detergent
compositions I to Vl were prepared in accord with the invention:
11 111 lV V Vl
STPP - - 48.80 37.39
Citrate 32.95 17.05 - - 17.05 25.40
Carbonate - 17. 50 - 20.00 20.00 25.40
Silicate 33.00 14.81 20.36 14.81 14.81
.
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Metasilicate - 2.50 2.50
PB1 1.94 9.74 7.79 14.28 9.74
11 111 lV V Vl
PB4 8.56
Percarbonate - - - - - 6.70
Alkyl sulfate 3.00 3.00 3.00 3.00 3.00 3.00
Nonionic 1.50 2.00 1.50 1.50 2.00 2.60
TAED 4.78 2.39 2.39 - - 4.00
HEDP 0.83 1.00 0.46 - 0.83
DETPMP 0.65 0.65
PAAC - - - 0.20
BzP - - - 4.44
Paraffin 0.50 0.50 0.50 0.50 - 0.20
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Laccase 0.01 0.01 0.04 0.04 0.08 0.005
Enhancer 0.5 0.5 0.5 1.0 1.5 0.3
Lipase - 0.001 - 0.005
Amylase 0.01 0.005 0.015 0.015 0.005 0.0025
BTA 0.30 0.30 0.30 0.30
Bismuth Nitrate - 0.30
PA30 4.02
Terpolymer - - - 4.00
480N - 6.00 2.77 - 6.67
Sulphate 7.11 20.77 8.44 - 26.24 1.00
pH ~1% solution)10.80 11.00 10.90 10.80 10.90 9.60
Example 13
The following granular dishwashing detergent compositions examples I
5 to IV of bulk density 1.02Kg/L were prepared in accord with the invention:
11 111 lV V Vl
STPP 30.00 30.00 30.00 27.90 34.50 26.70
Carbonate 30.50 30.50 30.50 23.00 30.50 2.80
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Silicate7.40 7.40 7.40 12.00 8.00 20.34
PB1 4.40 4.40 4.40 - 4.40
NaDCC - - - 2.00 - 1.50
11 111 lV V Vl
Alkyl sulfate 1.0 1.0 1.0 2.0 2.0 1.5
Nonionic 0.75 0.75 0.75 1.90 1.20 0.50
TAED 1.00 1.00 - - 1.00
PAAC - - 0-004
BzP - 1.40
Paraffin 0.25 0.25 0.25 - - -
Protease 0.05 0.05 0.05 0.1 0.1 0.2
Laccase 0.005 0.0075 0.01 0.02 0.04 0.04
Enhancer 0.2 0.3 0.4 0.4 0.4 0.8
Lipase 0.005 - 0.001
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.15 - 0.15
Sulphate 23.90 23.90 23.90 31.40 17.40
pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30
Exam~le 14
The following detergent composition tablets of 25g weight were
5 prepared in accord with the present invention by compression of a granular
dishwashing detergent composition at a pressure of 13KN/cm2 using a
standard 12 head rotary press:
ll lll
STPP - 48.80 47.50
Citrate 26.40
Carbonate - 5.00
Silicate 26.40 14.80 25.00
Protease 0.03 0.075 0.01
Laccase 0.0075 0.0075 0.01
Enhancer 0.3 0.6 1.0
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Lipase 0.005
Amylase 0.01 0.005 0.001
PB1 1.56 7.79
PB4 6.92 - 11.40
Alkyl sulfate 2.00 3.00 2.00
Nonionic 1.20 2.00 1.10
TAED 4.33 2.39 0.80
HEDP 0.67
DETPMP 0.65
Paraffin 0.42 0.50
BTA 0.24 0.30
PA30 3.2
Sulphate 25.05 14.70 3.20
pH (1% solution) 10.60 10.60 11.00
Exam~le 15
The following liquid dishwashing detergent compositions in accord
5 with the present invention, of density 1.40Kg/L were prepared:
ll
STPP 33.30 20.00
Carbonate 2.70 2.00
Silicate - 4.40
NaDCC 1.10 1.15
Alkyl sulfate 3.00 1.50
Nonionic 2.50 1.00
Paraffin 2.20
Boric acid 1.0 2.0
Formic acid 1.0
Protease 0.03 0.02
Laccase 0.01 0.01
Enhancer 0.2 0.5
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Amylase 0.005 0.0025
480N 0. 50 4.00
KOH - 6.00
Sulphate 1.60
pH (1% solution) 9.10 10.00
. .
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ExamPIe 16
The following liquid dishwashing compositions were prepared in accord
with the present invention:
11 111 lV V
Alkyl (1-7) ethoxy sulfate 28.5 27.4 19.2 34.1 34.1
Amine oxide 2.6 5.0 2.0 3.0 3.0
C12 glucose amide - - 6.0
Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0
Neodol C 11 E9 - - 5.0
Polyhydroxy fatty acid amide - - - 6.5 6.5
Sodium diethylene penta acetate - - 0.03
(40%)
Diethylenetriamine penta acetate - - - 0.06 0.06
Sucrose - - - 1 . 5 1 . 5
Ethanol 4.0 5.5 ~.5 9.1 9.1
Alkyl diphenyl oxide disulfonate - - - - 2.3
Calcium formate - - - 0.5 1.1
Ammonium citrate 0.06 0.1
Sodium chloride - 1 .0
Magnesium chloride 3.3 - 0.7
Calcium chloride - - 0.4
Sodium sulfate - - 0.06
Magnesium sulfate 0.08
Magnesium hydroxide - - - 2.2 2.2
Sodium hydroxide - - - 1.1 1.1
Hydrogen peroxide 200pp 0.16 0.006
m
Laccase 0.01 0.02 0.03 0.06 0.08
Enhancer 0.5 0.5 0.5 1.0 1.5
Protease 0.017 0.005 .0035 0.003 0.00
Perfume 0.18 0.09 0.09 0.2 0.2
CA 02254941 1998-11-12
W O 97/43384 PCT~US97108048
Water and minors Up to 100%
ExamPle 17
The following liquid hard surface cleaning compositions were prepared
in accord with the present invention:
11 111 lV V Vl
Amylase 0.01 0.002 0.005 0.02 0.001 0.005
Protease 0.05 0.01 0.02 0.03 0.005 0.005
Laccase 0.005 0.01 0.04 0.1 0.005 0.1
Enhancer 0.5 0.5 0.5 0.5 1.0 1.0
Boric acid 2.75 2.75 2.75 2.75 2.75 2.75
EDTA * - - 2.90 2.90
Na Citrate - - - - 2.90 2.90
NaC12 Alkyl benzene 1.95 - 1.95 - 1.95
sulfonate
NiE09 1.50 2.00 1.50 2.00 1.50 2.00
NaC12 Alkyl sulfate - 2.20 - 2.20 - 2.20
NaC12(ethoxy) - 2.20 - 2.20 - 2.20
* *sulfate
C 12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
Na Cumene sulfonate 1.30 - 1.30 - 1.30
Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30
Water Balance to 100%
0 *Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
***AII formulas adjusted to pH 7
ExamPle 18
CA 022~4941 1998-11-12
W O 97/43384 PCT~US97/08048
66
The following spray composition for cleaning of hard surfaces and
removing household mildew was prepared in accord with the present
Invention:
Amylase 0.01
Protease 0.01
Laccase 0.01
Enhancer 0. 5
Boric acid 2.00
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
NiE09 2.00
Sodium hydroxide 0.80
Silicate (Na) 0.04
Perfume 0.35
Watertminors up to 100%
ExamDle 1 9
The following lavatory cleansing block compositions were prepared in
10 accord with the present invention.
C16-18 fatty alcohol/50E0 80.0
LAS - - 80.0
Nonionic - 1.0
Oleoamide surfactant - 26.0
Partially esterified copolymer of vinylmethyl 5.0
ether and maleic anhydride, viscosity 0.1-
0.5
Polyethylene glycol MW 8000 - 39.0
CA 022~4941 1998-11-12
W 097/43384 67 PCTrUS97/08048
Water-soluble K-polyacrylate MW 4000- - 12.0
8000
Water-soluble Na-copolymer of acrylamide - 1 9.0
~70%) and acryclic acid (30%) low MW
Na triphosphate 10.0
Carbonate - - 8.0
Protease 0.8 0.005 0.01
Laccase 0.08 0.1 0.1
Enhancer 1.0 1 5 1 5
ll lll
Dye 2.5 1.0 1.0
Perfume 3.0 - 7.0
KOH / HCL solution pH 6-11
Example 20
The following toilet bowl cleaning composition was prepared in accord with
5 the present invention.
ll
C14-15 linear alcohol 7EO 2.0 10.0
Citric acid 10.0 5.0
Protease 0.8 0.005
Laccase 0.08 0.1
Enhancer 1.0 1.0
DETPMP - 1.0
Dye 2.0 1.0
Perfume 3.0 3.0
NaOH pH 6-1 1
Water and minors Up to 100%
