Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF
a-AMYLASES FOR MALODOR STRIPPIN(~
TECHNICAL FIELD
The present invention relates to detergent compositions comprising a
combination of different a-amylases delivering improved malodor stripping
from soiled items in hard surface cleaning, dishwashing and laundry
applications.
BACKGROUND OF THE INVENTION
For a number of years amylase enzymes have been used for a variety
of different purposes, the most important of which are starch liquefaction,
textile desizing, starch modification in the paper and pulp industry, and for
brewing and baking. A further use of amylases which is becoming
25 increasingly important, is the removal of starch containing soils and stains
during the washing of fabrics, hard surfaces and dishes.
Indeed, amylase enzymes have long been recognised in dishwashing,
hard surface cleaning and laundry compositions to provide the removal of
30 starchy food residues or starchy films from dishware, flatware, glasses and
hard surfaces or to provide cleaning performance on starchy soils as well as
other soils typically encountered in laundry applications.
W094/02597, Novo Nordisk A/S published February 03, 1994,
35 describes cleaning compositions which incorporate mutant amylases. See
also WO94/18314, Genencor, published August 18, 1994 and
WO95/10603, Novo Nordisk A/S, published April 20,1995.
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Other amylases known for use in cleaning compositions include both
a- and ~-amylases. o~-Amylases are known in the art and include those
disclosed in US Pat. no. 5,003,257; EP 252,666; W091 /00353; FR
2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent
specification no. 1,296,839 (Novo).
Examples of commercial a-amylases products are Termamyl~, Ban~
and Fungamyl~, all available from Novo Nordisk A/S Denmark.
Recently new amylases have been identified and are described in
W095/26397, Novo Nordisk A/S, published October 05, 1995, disclosing
an a-amylase having a specific activity superior than Termamyl~.
Combinations of an a-amylase with a starch debranching enzyme
selected from pullulanase, isopullulanase and iso amylase are described in
EP 368 341, J04065494 and J06172796 for enhanced detergency against
dirt containing starch, fat, oils and proteins in laundry and automatic
dishwashing .
It has now been discovered that odorous materials are entrapped into
different types of amylase-susceptible and everyday stains found on fabrics,
dishware, hard surfaces and the like and that an uncomplete and unefficient
removal of such stains leads to malodor formation.
It has now surprisingly been found that the combined use of different
a-amylases improves the removal of malodor coming from different types of
amylase-susceptible and everyday stains. Especially good malodor control
on everyday stains such as body soils is obtained when the amylases are
30 further combined with a cellulase.
It is therefore an object of the present invention to provide detergent
compositions containing a-amylases which exhibit a good malodor control
on amylase-susceptible and everyday stains.
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It is another object of the present invention to provide detergent
compositions containing a-amylase enzymes which exihibit a good malodor
control on body soils.
SUMMARY OF THE INVENTION
The present invention relates to detergent compositions comprising a
combination of different a-amylases delivering improved malodor stripping
from soiled items in hard surface cleaning, dishwashing and laundry
0 applications.
DETAILED DESCRIPTION OF THE INVENTION
a-AmYlase Enzvmes
Essential components of the detergent compositions of the present
20 invention are a-amylase enzymes.
Without wishing to be bound by any theory, it is believed that a
combination of several a-amylases provides a more effective activity in
solution and/or a broader hydrolytic cleavage pattern than a single amylase
25 type as different amylases show different hydrolytic activity on various
substrates. Odorous materials are entrapped into these substrates and a
rapid and effective hydrolysis achieved on several different cleavage points
allows a more effective suspension and dissolution of the odorous materials
therein entrapped.
Suitable a-amylases inc~ude those disclosed in US Pat. no.
5,003,257; EP 252,666; W091 /00353; FR 2,676,456; EP 285,123; EP
525,610; EP 368,341; and British Patent specification no. 1,296,839
(Novo). Examples of commercial a-amylases products are Termamyl~, Ban'~
35 and Fungamyl@', all available from Novo Nordisk A/S Denmark. Other
suitable a-amylases are derived from B. Subtilis or B. stearothermophilvs.
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Other a-amylases herein have the commonality of being derived using
site-directed mutagenesis from one or more of the Bacillus a-amylases,
regardless of whether one, two or multiple amylases strains are the
immediate precursors.
a-Amylases of this invention include those amylases having improved
stability in detergents, especially improved oxidative stability. In general, the
stability-enhanced amylases can be obtained from Novo Nordisk A/S or from
Genencor International:
~a) An amylase according the W094/02597, Novo Nordisk A/S published
Feb. 3, 1994:
~i) a variant a-amylase wherein one or more of the Met amino
residues is exchanged with any amino acid residue except for Cys
and Met,
(ii) a Bacillus a-amylase acording to ~i),
(iii) a variant a-amylase according to (i-ii) wherein one or more Met
amino acid residues is exchanged with a Leu, Thr, Ala, Gly, Ser, lle,
or Asp amino acid residue, preferably a Leu, Thr, Ala or Gly amino
acid residue,
(iv) a variant a-amylase according to (i) in which substitution is made,
- using preferably Ala or Thr (more preferably Thr), of the Met residue
located in position 197 of the B. Iichenformis a-amylase, or the
homologous position variation of as similar parent amylase, such as
B. amyloliquefaciens, B. Subtilis, or B. ste~rothermophilus;
(b) Stability-enhanced amylases, including Purafact Ox AM(~), as described
in W094/18314, published August 18, 1994. Therein it was noted that
improved oxidative stability amylases have been made by Genencor from B.
licheniformjs NCIB8061. Met was identified as the most likely residue to be
modified. Met was substitued, one at a time, in positions 8, 15, 197, 256,
304, 366 and 438 leading to specific mutants, particulary important being
M 1 97L and M 1 97T with the M 1 97T variant being the most stable
expressed variant; corresponding a-amylases will therefore include:
(i) a variant a-amylase that is the expression product of a mutated
DNA sequence encoding an a-amylase, the mutated DNA sequence
being derived from a precursor a-amylase by the deletion or
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substitution of one or more oxidisable acids seiected from the group
consiting of Met, Trp, Cys and Tyr amino acid residues, in the
precursor a-amylase,
(ii) a variant a-amylase according to (i) wherein the oxidisable amino
acid residue to be deleted or substitued is a Met in the precursor a-
amylase equivalent to ~8, +15, +197, +256, +304, +366 or
+ 438 in Bacillus licheniformis a-amylase,
(iii) a variant a-amylase according to (ii) which is M197T;
10 (c) Preferred herein are amylase variants having additional modification in
the immediate parent available from Novo Nordisk A/S. These amylases are
disclosed in W095/10603, published April 1995:
(i) A variant of a parent a-amylase enzyme having an improved
washing and/or dishwashing performance as compared to the parent
enzyme, wherein one or more amino acid of the parent enzyme has
been replaced by a different amino acid and/or wherein one or more
amino acid have been deleted and/or wherein one or more amino acid
have been added to the parent a-amylase enzyme, provided that the
variant is different from one in which the Met in position 197 of
parent B. Iicheniformis a-amylase has been replaced by Ala or Thr
amino acid residue, as the only modification being made,
(ii) A variant according to (i) comprising a C-terminal part of an a-
amylase derived from B. Iicheniformis and a N-terminal part of an a-
amylase derived from B. amyloliquefaciens or from B.
stearothermophilus,
(iii) A variant known as Duramyl(~) according to (ii) wherein the Met
amino acid residue at position 197 has been substitued preferably by
a Leu, Thr, Ala, Gly, Ser, lle or Asp amino acid residue;
(d) W095/26397 Novo Nordisk, published October 05, 1995 describes
other suitable amylases: a-amylases characterised by having a specific
activity at least 25% higher than the specific activity of Termamyl~ at a
temperature range of 25~C to 55~C and at a pH value in the range of 8 to
10, measured by the Phadebas~ a-amylase activity assay. Such Phadebas~
a-amylase activity assay is described at pages 9-10, W095/26397.
Variants of these new amylases demonstrating at least one of the following
properties relative to the parent enzymes: 1) improved thermal stability, 2)
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oxidation stability and 3) reduced calcium ion dependency properties.
Examples of other desirable improvements or modifications of properties
(relative to the parent-a-amylase) which may be achieved with a variant
according to the present invention are: increased stability and/or a-
amylolytic activity at neutral to relatively high pH values, increased a-
amylolytic activity at relatively high temperature and increase or decrease of
the isoelectric point (pl) so as to better match the pl value for a-amylase
variant to the pH of the medium, have been described in the co-pending
application by Novo Nordisk W096/23873.
(e) Amylolytic enzymes with improved properties with respect to the
activity level and the combination of thermostability and a higher activity
level are described in W095/35382. These improved properties render the a
-amylases more suitable for more acidic or alkaline conditions and allow the
reduction of the calcium concentration withoùt a loss of performance of the
enzyme:
(i) Said a-amylase is derived from an a-amylase of B~cillus
licheniformis or an enzyme having at least 70~/0 amino acid identity
therewith which comprises one or more amino acid changes at positions
20 selected from the group consisting of positions 104, 128, 187 and 188 of
the amino acid sequence of the a-amylase of Bacillus licheniformis,
(ii) A variant according to (i) wherein at least one additional amino
acid change selected from the group consisting of His at position 133 to
Tyr, and Thr at position 149 to lle.
~f) An amylase according to W096/23874, Novo Nordisk A/S published
August 08, 1996 describing variants of a parent Termamyl-like a-amylase,
in which variant at least one amino acid residue of the parent a-amylase,
which is/are present in a fragment corresponding to the amino acid
30 fragments 44-57 of the amino acid sequence of SEQ. ID No. 4, has been
deleted or replaced with one or more amino acid residues which is/are
present in a fragment corresponding to the amino acid fragment 66-84 of
the amino acid sequence shown in SEQ. ID No.10, or in which one or more
additional amino acid residues has been added using the relevant part of
35 SEQ. ID No. 10 or a corresponding part of another Fungamyl-like a-amylase
as a template. Preferred is the parent hybrid a-amylase comprising at least
430 amino acid residues of the C-terminal part of the B. Iicheniformis a-
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amylase and an amino acid segment corresponding to the 37 N-terminal
amino acid residues of the B. ~myloliquefaciens a-amylase having the amino
acid sequence shown in SEQ. ID No. 4 and the amino acid segment
corresponding to the 445 C-terminal amino acid residues of the B.
Licheniformis a-amylase having the amino acid sequence shown in SEQ ID
No. 2.
Preferred combinations of a-amylases are combinations of a non-
modified ~-amylase derived from B. Iicheniformis, B. amyloliquefaciens, B.
10 Subtilis or B. stearothermophilus with a a-amylase as described herein
above under (a)-(c) and/or W095/26397 and/or W095/35382. More
preferred combination are the combination of an a-amylase as described in
W095/10603, known as Duramyl(~ and the a-amylase derived from B.
Iicheniformis, known as Termamyl(~) or with a variant of W095/26397 a-
amylases, preferably a variant demonstrating improved thermal stability, as
described in W096t23873. Other more preferred combinations are the
combination of the a-amylase derived from B. Iicheniformis, known as
Termamyl(~) with a variant of W095/26397 a-amylases, preferably
demonstrating improved thermal stability, as described in W096/23873;
20 with a Purafact OX AM~ ~W094/18314) andtor with the parent hybrid a-
amylase described in W096t23874. The detergent compositions of the
present invention can comprise a combination of more than two a-
amylases .
A cellulase can be added to such combinations.
These enzymes are incorporated into detergent compositions at a
level from 0.0001% to 0.1% total pure a-enzymes by weight of the total
composition, preferably from 0.0002% to 0.06%, more preferably from
30 0.0003% to 0.05% total pure a-amylase enzymes by weight of total
composition. The a-amylases are preferably incorporated into the detergent
compositions of the present invention in the range of from 1:3 to 3:1, more
preferred ratios are 1:1, 3:7 or 7:3.
Cellulase Enzvme
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The cellulases usable in the present invention include both bacterial or
fungal cellulases. Preferably, they will have a pH optimum of between ~ and
12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
J61078384 and W096/02653 which discloses fungal cellulase produced
respectively from Humicola insolens, Trichoderma, Thielavia and
Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus
species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275; DE-OS-2.247.832 and W095/26398.
Examples of cellulase components which may be usable in the
present invention are:
The complexe of cellulases commercailly available under the tradename
Celluzyme(g), or
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 antibody
20 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. WO91/17244, or
25 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
30 activity; a preferred endoglucanase component has the amino acid sequence
disclosed in PCT Patent Application No. W091/17244, or
any of the cellulases 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
35 not less than 7 or whose relative activity at a pH of not less than 8 is 50%
or over of the activity under optimum conditions when carboxy methyl
cellulose (CMC) is used as a substrate, or
. .
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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. W0 91/17243, or
an endoglucanase component which is immunoreactive with an antibody
raised against a highly purified -60kD endoglucanase derived from Bacillus
lautus, NCIMB 40250, or which is a homologue or derivative of the -60kD
0 endoglucanase exhibiting cellulase activity; a preferred endoglucanase
component has the amino acid sequence disclosed in PCT Patent
Application No. W0 91/10732.
Especially suitable cellulases are the cellulases having color care
benefits. Examples of such cellulases are cellulases described in European
patent application No. 91202879.2, filed November 6, 1991 (Novo).
According to the present invention, preferred cellulases are those as
described in Danish Patent Application 1159/90 or PCT patent application
W091/17243 which is also known as carezyme(TMl available from Novo
Nordisk A/S in Bagsvaerd, in Denmark. The cellulase preparation described
in these publications and the Carezyme~TM) consistent with this
description, can consist essentially of a homogeneous endoglucanase
component, which is immunoreactive with an anti-body raised against a
highly purified 43 kD cellulase derived from Humicola Insulens, DSM 1800,
or which is homologous to said 43 kD endoglucanase. An alternative
screening for appropriate cellulases for use in the laundry detergent
composition according to the present invention is the method specified in
EP-A-495 258 or more specifically in EP-A-350 098.
For industrial production of the cellulase preparation herein, however,
it is preferred to employ recombinant DNA techniques or other techniques
involving adjustments of fermentations or mutation of the microorganisms
involved to ensure overproduction of the desired enzymatic activities. Such
methods and techniques are known in the art and may readily be carried out
by persons skilled in the art.
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Preferred cellulases to be used in the present invention are 50 kD
endoglucanase and 43kD endoglucanase.
5 Detergent 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
0 form of the composition, and the nature of the cleaning operation for which
it is to be used.
The cleaning compositions according to the invention can be liquid,
paste, gels, bars, tablets, powder or granular forms. Granular compositions
15 can also be in "compact" form, the liquid compositions can also be in a
"concentrated" form.
The compositions of the invention may for example, be formulated as
hard surface cleaner, hand and machine dishwashing compositions, hand
20 and 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.
When formulated as compositions for use in manual dishwashing
25 methods the compositions of the invention preferably contain a surfactant
and preferably other detergent compounds selected from organic polymeric
compounds, suds enhancing agents, group 11 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.
.
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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.
0 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
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 15% of the total composition, preferably not exceeding 10%,
most preferably not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the present compositions
are selected from the alkali and alkaline-earth-metal salts of sulphates and
chlorides .
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
preferably less than 40%, more preferably less than 30%, most preferably
less than 20% by weight of the detergent composition.
Surfactant svstem
The detergent compositions according to the present invention
comprise a surfactant system wherein the surfactant can be selected from
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12
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 detergent compositions in
accord with the invention.
The surfactant is preferably formulated to be compatible with enzyme
10 components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at least
does not degrade, the stability of any enzyme in these compositions.
Preferred surfactant systems to be used according to the present
invention comprise as a surfactant one or more of the nonionic and/or
anionic surfactants described herein.
Polyethylene, polypropylene, and polybytylene oxide condensates of
alkyl phenols are suitable for use as the nonionic surfactant of the
20 surfactant systems of the present invention, with the polyethylene oxide
condensates being preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from about 6 to
about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms,
in either a straight-chain or branched-chain configuration with the alkylene
25 oxide. In a preferred embodiment, the ethylene oxide is present in an
amount equal to from about 2 to about 25 moles, more preferably from
about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
Commercially available nonionic surfactants of this type include IgepalTM
C0-630, marketed by the GAF Corporation; and TritonTM X-4~, X-114, X-
30 100 and X-102, all marketed by the Rohm & Haas Company. These
surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl
phenol ethoxylates).
The condensation products of primary and secondary aliphatic
alcohols with from about 1 to about 25 moles of ethylene oxide are suitable
35 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
... .
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W O 97/43385 13 PCTrUS97/08103
about 8 to about 22 carbon atoms. Preferred are the condensation products
of alcohols having an alky! 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 TergitolTM 1 5-S-9 ~the condensation
product of C1 1-C1 5 linear alcohol with 9 moles ethylene oxide), TergitolTM
0 24-L-6 NMW (the condensation product of C12-C14 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 C 1 4-C 1 5 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
C 1 4-C 1 5 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5
(the condensation product of C 1 4-C 1 5 linear alcohol with 5 moles of
ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the
condensation product of C 1 3-C 1 5 alcohol with 9 moles ethylene oxide),
20 marketed by The Procter & Gamble Company, and Genapol LA 030 or 050
(the condensation product of C 1 2-C 1 4 alcohol with 3 or 5 moles of
ethylene oxide) marketed by Hoechst. Preferred range of HLB in these
products is from 8-1 1 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 danuary 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,
30 hydrophilic group containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties ~optionally the hydrophobic group is
35 attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactoseas opposed to a glucoside or galactoside). The intersaccharide bonds can
CA 022~4069 1998-ll-12
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14
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(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from about 10 to about 18, preferably from about 12 to
0 about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,preferably 0; and x is from about 1.3 to about 10, preferably from about
1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl
is preferably derived from glucose. To prepare these compounds, the
alcohol or alkylpolyethoxy alcohol is formed first and then reacted with
glucose, or a source of glucose, to form the glucoside (attachment at the 1-
position). The additional glycosyl units can then be attached between their
1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably predominately the 2-position.
The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene glycol
are also suitable for use as the additional nonionic surfactant systems of the
present invention. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1500 to about 1800 and
will exhibit water insolubility. The addition of polyoxyethylene moieties to
this hydrophobic portion tends to increase the water solubility of the
molecule as a whole, and the liquid character of the product is retained up
to the point where the polyoxyethylene content is about 50% of the total
weight of the condensation product, which corresponds to condensation
with up to about 40 moles of ethylene oxide. Examples of compounds of
this type include certain of the commercially-available 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
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W O 97143385 15 PCTrUS97/08103-
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
5 80% by weight of polyoxyethylene and has a molecular weight of from
about 5,000 to about 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available 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-C 14
15 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C1g
alcohol ethoxylates (preferably C1 0 avg.) having from 2 to 10 ethoxy
groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy fatty acid
20 amide surfactants of the formula.
R2 - C - N - z
Il I
O Rl
wherein R 1 is H, or R 1 is C 1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5 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
30 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.
Suitable anionic surfactants to be used are linear alkyl benzene
sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20
carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03
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16
according to "The Journal of the American Oil Chemists Society", 52
(1975), pp. 323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
5 applications, comprise alkyl ester sulfonate surfactants of the structural
formula:
R3 - CH - C - oR4
I
SO3M
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
ester sulfonate. Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or unsubstituted
ammonium cations, such as monoethanolamine, diethanolamine, and
triethanolamine. Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or
isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is
C 1 o-C 1 6 alkyl.
Other suitable anionic surfactants include the linear alkyl benzene
sulfonate, alkyl sulfate surfactants which are water soluble salts or acids of
the formula ROS03M wherein R preferably is a C 1 0-C24 hydrocarbyl,
preferably an alkyl or hydroxyalkyl having a C 1 0-c20 alkyl component,
more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a cation,
e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium
or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium
cations and quaternary ammonium cations such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived
from alkylamines such as ethylamine, diethylamine, triethylamine, and
mixtures thereof, and the like). Typically, alkyl chains of 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) .
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Other anionic surfactants useful for detersive purposes can also be
included in the detergent compositions of the present invention. These can
include salts (including, for example, sodium, potassium, ammonium, and
5 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 citrates, e.g., as described in
British patent specification No. 1,082,179, Cg-C24
0 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, alkylphosphates, isethionates such as the acyl isethionates, N-acyl taurates,
alkyl succinamates snd sulfosuccinates, monoesters of sulfosuccinates
5 (especially saturated and unsaturated C12-C1g monoesters~ and diesters of
sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates
20 such as those of the formula RO(CH2CH20)k-CH2COO-M + 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.
25 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).
30 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.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
35 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 o-C24 alkyl component, preferably a C 1 2-C20 alkyl or
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18
hydroxyalkyl, more preferably C1 2-C1 8 alkyl or hydroxyalkyl, A is an
ethoxy or propoxy unit, m is greater than zero, typically between about 0.5
and about 6, more preferably between about 0.5 and about 3, and M is H
or a cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-
ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated
sulfates are contemplated herein. Specific ex~mples of substituted
ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations
and quaternary ammonium cations such as tetramethyl-ammonium and
0 dimethyl piperdinium cations and those derived from alkylamines such as
ethylamine, diethylamine, triethylamine, rnixtures thereof, and the like.
Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-
C1gE(1.0)M~, C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-
C18E(2 25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-
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 selected from sodium and
potassium.
The detergent compositions of the present invention may also contain
20 cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the
nonionic and/or anionic surfactants other than those already described
hereln.
Cationic detersive surfactants suitable for use in the detergent
25 compositions of the present invention are those having one long-chain
hydrocarbyl group. Examples of such cationic surfactants include the
ammonium surfactants such as alkyltrimethylammonium halogenides, and
those surfactants having the formula:
IR2(0R3)yllR4(0R3)yl2R5N + 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-,
35 and mixtures thereof; each R4 is selected from the group consisting of C1-
C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the
two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any
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19
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; each y is from 0 to about 10 and the sum of the y values is from
5 0 to about 15; and X is any compatible anion.
Quaternary ammonium surfactant suitable for the present invention
has the formula (I):
R1~o J~ 'R~
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the
formula (Il):
o
Formula ll
y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
20 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~ is a counterion, preferably a halide, e.g. chloride or
methylsulf ate.
R6
2~ ~o7zH
Formula lll
R6 is C1-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as defined in formula
30 I whereby
R1 is Cg, C10 or mixtures thereof, x=o,
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R3, R4 = CH3 and Rs = CH2CH20H.
Highly preferred cationic surfactants are the water-soluble
quaternary ammonium compounds useful in the present composition having
5 the formula:
R1 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
o 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-C1s particularly where the
alkyl group is a mixture of chain lengths derived from coconut or palm
kernel fat or is derived synthetically by olefin byild up or OXO alcohols
5 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:
20 coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C1 2-1 5 dimethyl hydroxyethyl ammonium chloride or bromide;
25 coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-O-C-C12_14 alkyl and R2R3R4 are methyl).
o
di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also described in U.S.
Patent 4,228,044, Cambre, issued October 14, 1980 and in European
Patent Application EP 000,224.
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When included therein, the detergent compositions of the present
invention typically comprise from 0.2% to about 25%, preferably from
about I % to about 8% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the detergent
compositions of the present invention. These surfactants can be broadly
described as aliphatic derivatives of secondary or tertiary amines, or
aliphatic derivatives of heterocyclic secondary and tertiary amines in which
o the aliphatic radical can be straight- or branched-chain. One of the aliphaticsubstituents contains at least about 8 carbon atoms, typically from about 8
to about 18 carbon atoms, and at least one contains an anionic water-
solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19,
5 lines 18-35, for examples of ampholytic surfactants.
When included therein, the 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 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
25 phosphonium or tertiary sulfonium compounds. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line
38 through column 22, line 48, for examples of zwitterionic surfactants.
When included therein, the detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from
30 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
35 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
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W O 97/43385 22 PCTAUS97/08103
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
5 of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon
atoms.
Semi-poiar nonionic detergent surfactants include the amine oxide
surfactants having the formula
0
R3 (oR4)xN(Rs)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene
15 or hydroxyalkylene group containing from about 2 to about 3 carbon atoms
or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a
polyethylene oxide group containing from about 1 to about 3 ethylene oxide
groups. The R5 groups can be attached to each other, e.g., through an
20 oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C1o-C18 alkyl
dimethyl amine oxides and Cg-C 12 alkoxy ethyl dihydroxy ethyl amine
oxides.
When included therein, the detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from
about 1% to about 10% by weight of such semi-polar nonionic surfactants.
The detergent composition of the present invention may further
comprise a cosurfactant selected from the group of primary or tertiary
amines.
Suitable primary amines for use herein include amines according to the
formula R1NH2 wherein R1 is a C6-C12 preferably C6-C10 alkyl chain or
R4X(CH2)n, X is -0-,-C(O)NH- or -NH-, R4 is a C6-C1 2 alkyl chain n is
between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched
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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-
5 octylamine, 1-decylamine and laurylamine. Other preferred primary amines
include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines havin~
0 the formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or
R5
- (CH2 - CH - O ~H
R3 is either a C6-C12 preferably C6-C1o 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 .
5 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 R1R2R3N where R1 is a C6-C12 alkyl
chain, R2 and R3 are C1-C3 alkyl or
- (CH2 - CH - O ~H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
R1--C--NH--~ CH2 )--N--( R2 )2
wherein R1 is C6-C1 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-lOoxypropylamine, N coco
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24
1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis~hydroxyehtyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10
5 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-
hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially
desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine
and oleylamine 7 times ethoxylated, lauryl amido propylamine and
0 cocoamido propylamine.
OPtional deterqent ingredients:
Other detergent enzymes
The detergent compositions can in addition to the combination of a-
amylase enzymes and eventually cellulases further comprise one or more
enzymes which provide cleaning performance and/or fabric care benefits.
Said enzymes include enzymes selected from hemicellulases,
peroxidases, proteases, gluco-amylases, other amylases, xylanases, lipases,
esterases, cutinases, pectinases, reductases, oxidases, phenoloxidases,
lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases,
13-glucanases, arabinosidases chondroitinase, laccase or mixtures thereof.
A preferred combination is a cleaning composition having a cocktail
of conventional applicable enzymes like protease, amylase, lipase, cutinase
and/or cellulase in conjunction with one or more plant cell wall degrading
enzymes.
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
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W O 97/43385 PCTrUS97/08103
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 peroxidases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of
the detergent composition.
0 Preferred commercially available protease enzymes include those sold
under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase
by Novo Nordisk A/S ~Denmark), those sold under the tradename Maxatase,
Maxacal, Maxapem and Properase by Gist-Brocades, those sold by
Genencor International, and those sold under the tradename Opticlean and
Optimase by Solvay Enzymes. Also proteases described in patent
applications EP 251 446, WO91/06637, W094/10591 and US serial
number 08/322676 can be included in the detergent composition of the
invention. Protease enzyme may be incorporated into the compositions in
accordance with the invention at a level of from 0.0001 % to 2% active
20 enzyme by weight of the composition.
It has been found that the addition of proteases to the combination of
a-amylases according to the present- invention, enhance the malodor
stripping from soiled items.
Other preferred enzymes that can be included in the detergent
compositions of the present invention include lipases. Suitable lipase
enzymes for detergent usage include those produced by microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
30 disclosed in British Patent 1,372,034. Suitable lipases inciude 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,
~apan, under the trade name Lipase P "Amano," hereinafter referred to as
35 "Amano-P". Especially suitable lipases are lipases such as M1 LipaseR and
LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which
CA 022~4069 1998-ll-12
W O 97t43385 PCT~US97/08103
26
have found to be very effective when used in combination with the
compositions of the present invention.
It has been found that the addition of lipases to the
combination of a-amylases according to the present invention, enhance the
malodor stripping from soiled items.
Also suitable are cutinases [EC 3.1.1.50~ which can be considered as
a special kind of lipase, namely lipases which do not require interfacial
0 activation. Suitable cutinases are described in WO 94/14963 and WO
94/14964. Addition of cutinases to detergent compositions have been
described in e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the
detergent composition at levels from 0.0001% to 2% of active enzyme by
weight of the detergent composition.
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 %
20 to 2% of active enzyme by weight of the detergent composition. They can
be added as separate ingredients ( prills, granulates,...) or as cogranulate of
two or more enzymes.
Other suitable detergent ingredients that can be added are enzyme
25 oxidation scavengers which are described in the copending European patent
application 92870018.6 filed on January 31, 1992. Examples of such
enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
Color care benefits
Technologies which provide a type of color care benefit can also be
included. 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.
35 94870206.3.
Bleaching agenf
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WO 97/43385 2 7 PCT/US97/08103
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,
- 5 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%.
The bleaching agent component for use herein can be any of the
0 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
20 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.
25 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
30 product, preferably 1 -5 % by weight.
The hydrogen peroxide releasing agents can be used in combination
with bleach activators such as tetraacetylethylenediamine (TAED),
nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591),
Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS,
described in W094/28106) or pentaacetylglucose (PAG), which are
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W O 97/43385 PCTAUS97/08103
28
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,
0 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
20 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
25 and, consequently, the substrate is bleached. Preferred zinc phthalocyanine
and a photoactivated bleaching process are described in U.S. Patent
4,033,718. Typically, detergent compositions will contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
30 Bvilder 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
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W O 97/43385 PCT~US97/08103
pentamethyleneacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene
phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
Phosphate builders as sodium tripolyphosphate can also be used herein.
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.
0 SKS-6 (Hoechst) . SKS-6 is a crystalline layered silicate consisting of
sodium silicate (Na2Si20s).
Suitable polycarboxylates containing one carboxy group include lactic
acid, glycolic acid and ether derivatives thereof as disclosed in Belgian
Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing
two carboxy groups include the water-soluble salts of succinic acid, malonic
acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid,
tartronic acid and fumaric acid, as well as the ether carboxylates described
in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent
No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups include, in
particular, water-soluble citrates, aconitrates and citraconates as well as
succinate derivatives such as the carboxymethyloxysuccinates described in
British Patent No. 1,379,241, lactoxysuccinates described in Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-
1,1,3-propane tricarboxylates described in British Patent No.1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,082,179, while
polycarboxylates containing phosphone substituents are disclosed in British
Patent No. 1,439,000.
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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-
5 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
disciosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
0 containing up to three carboxy groups per molecule, more particularly
citrates.
Preferred builder systems for use in the present compositions include
a mixture of a water-insoluble aluminosilicate builder such as zeolite A,
5 zeolite MAP 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
accordance with the invention is ethylenediamine-N,N'-disuccinic acid
20 ~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 of such preferred magnesium salts of EDDS include MgEDDS and
25 Mg2EDDS. 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
aluminosilicate builder such as zeolite MAP, zeolite A, and a watersoluble
30 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 phosphonates, amino polyalkylene phosphonates and amino
35 polycarboxylates.
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Other suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts, in which the polycarboxylic acid comprises at
least two carboxyl radicals separated from each other by not more than two
carbon atoms.
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.
0 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.
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
divided forms exemplified by silica aerogels and xerogels and hydrophobic
20 silicas of various types. These materials can be incorporated as particulatesin which the suds suppressor is advantageously releasably incorporated in a
water-soluble or water-dispersible, substantially non-surface-active
detergent impermeable carrier. Alternatively the suds suppressor can be
dissolved or dispersed in a liquid carrier and applied by spraying on to one or
2s more of the other components.
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.
Such suds suppressor system are described in Copending European Patent
application N 92870174.7 filed 10 November, 1992.
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3 2
Especially preferred silicone suds controlling agents are described in
Copending European Patent application N~92201649.8. Said compositions
can comprise a silicone/silica mixture in combination with fumed nonporous
silica such as AerosilR.
The suds suppressors described above are normally employed at
levels of from 0.001% to 2% by weight of the composition, preferably from
0.01% to 1% by weight.
to
Others
Other components used in detergent compositions may be employed,
such as soil-suspending agents, soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents, and/or
encapsulated or non-encapsulated perfumes.
Especially suitable encapsulating materials are water soluble capsules
which consist of a matrix of polysaccharide and polyhydroxy compounds
20 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
25 dextrins are,preferably, prepared from such starches as waxy maize, waxy
sorghum, sago, tapioca and potato. Suitable examples of said encapsulating
materials include N-Lok manufactured by National Starch. The N-Lok
encapsulating material consists of a modified maize starch and glucose. The
starch is modified by adding monofunctional substituted groups such as
30 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
35 their salts. Polymers of this type include the polyacrylates and maleic
anhydride-acrylic acid copolymers previously mentioned as builders, as well
as copolymers of maleic anhydride with ethylene, methylvinyl ether or
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methacrylic acid, the maleic anhydride constituting at least 20 mole percent
of the copolymer. These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most preferably
from 1% to 6% by weight of the composition.
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-
0 (2,4-dianilino-s-triazin-6-ylamino~stilbene-2:2' - disulphonate, monosodium
4',4" -bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate, disodium
4,4 ' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-
ylamino~stilbene-2,2' - disutphonate, 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 brighteners of copending European Patent application No.
95201 943.8.
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
0.20% to 5% more preferably from 0.25% to 2.5% by weight. These
25 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,
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
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34
3(pEG)43)o.75(poH)o.25[T-po)2.8(T-pEG)o.4]T(
H~0.25((pEG)43cH3)o.7!~
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
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,
0 "primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be
less than fully capped, and therefore their end groups may consist of
monoester of ethylene glycol and/or propane 1-2 diol, thereof consist
"secondarily" of such species.
The selected polyesters herein contain about 46% by weight of
dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about
10% by weight ethylene glycol about 13 % by weight of dimethyl
sulfobenzoic acid and about 15 % by weight of sulfoisophthalic acid, and
20 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,
25 using chlorine scavenger such as perborate, ammonium sulfate, sodium
sulphite or polyethyleneimine at a level above 0.1% by weight of total
composition, in the formulas will provide improved through the wash
stability of the a-amylase enzymes. Compositions comprising chlorine
scavenger are described in the European patent application 92870018.6
30 filed January 31, 1992.
Softening agents
Fabric softening agents can also be incorporated into laundry
35 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
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5,019,292. Organic fabric softening agents include the water insoluble
tertiary amines as disclosed in GB-A1 51 4 276 and EP-B0 011 340 and
their combination with mono C1 2-C14 quaternary ammonium salts are
disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides
as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric
softening systems include high molecular weight polyethylene oxide
materials as disclosed in EP-A-0 299 575 and 0 313 146.
Levels of smectite clay are normally in the range from 2% to 20%,
0 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
20 solid components of the composition.
Dye transfer inhibition
The detergent composition of the present invention can also include
25 compounds for inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric laundering
operations involving colored fabrics.
Polymeric dye transfer inhibiting agents
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
35 incorporated into detergent compositions in order to inhibit the transfer of
dyes from colored fabrics onto fabrics washed therewith. These polymers
have the ability to complex or adsorb the fugitive dyes washed out of dyed
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36
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,
5 polyvinylpyrrolidone polymers, polyvinyloxazolidones and
polyvinylimidazoles or mixtures thereof.
Addition of such polymers also enhances the performance of the enzymes
according the invention.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having
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 ~1
A is NC, co, c, -o-,-s-, -N-; x is 0 or li
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen
of the N-0 group can be attached or wherein the nitrogen of the
N-0 group is part of these groups.
The N-0 group can be represented by the following general structures
O o
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(Rl)x -N- (R2)y =N- (Rl)x
I
(R3)Z
wherein R 1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is O
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
o 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.
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.
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
alicyclic groups wherein the nitrogen of the N-O functional group is part of
30 said R group.
Examples o,f these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole 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
35 alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups.
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Examples of these classes are polyamine oxides wherein R groups
can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide
5 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.
0 The amine N-oxide po~ymers of the present invention typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the
amount of amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to
1: 1000000. More preferably from 1 :4 to 1: 1000000, most preferably from
1: 7 to 1: 1000000. The polymers of the present invention actually
encompass random or block copolymers where one monomer type is an
amine N-oxide and the other monomer type is either an amine N-oxide or
not. The amine oxide unit of the polyamine N-oxides has a PKa < 10,
preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material has the desired water-solubility and dye-suspending power.
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
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-
3~ 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.
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39
The average molecular weight range was determined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern
- Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
- 5 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
0 inhibiting properties while not adversely affecting the cleaning performance
of detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention
has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2,
more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
The detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of from
about 2,500 to about 400,000, preferably from about 5,000 to about
200,000, more preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York, NY and Montreal, Canada under the product names PVP K-15
(viscosity molecular weight of 10,000), PVP K-30 (average molecular
weight of 40,000), PVP K-60 (average molecular weight of 160,000), and
PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF
Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the detergent field (see for
example EP-A-262,897 and EP-A-256,696).
d) Polyvinyloxazolidone:
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
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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.
5 e) Polyvinylimidazole:
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.
f) Cross-linked polymers:
Cross-linked polymers are polymers whose backbone are
interconnected to a certain degree; these links can be of chemical or
~5 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
Method of washing
The compositions of the invention may be used in essentially any
30 washing or cleaning methods, including soaking methods, pretreatment
methods and methods with rinsing steps for which a separate rinse aid
composition may be added.
The process described herein comprises contacting fabrics with a
35 laundering solution in the usual manner and exemplified hereunder.
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The process of the invention is conveniently carried out in the course
of the cleaning process. The method of cleaning is preferably carried oùt at
5 ~C to 95 ~C, especially between 1 0~C and 60~C. However, specific
amylase enzymes within the specified enzymatic concentration, have
5 demonstrated superior starch cleaning even for wash cycles occuring at
very low temperatures (between 10~C and 25~C). The pH of the treatment
solution is preferably from 7 to 11.
A preferred machine dishwashing method comprises treating soiled
0 articles with an aqueous solution of the machine diswashing or rinsing
composition. A conventional effective amount of the machine dishwashing
composition means from 8-60 9 of product dissolved or dispersed in a wash
volume from 3-10 litres.
15 According to a manual dishwashing method, soiled dishes are contacted
with an effective amount of the diswashing composition, typically from 0.5-
209 (per 25 dishes being treated). Preferred manual dishwashing methods
include the application of a concentrated solution to the surfaces of the
dishes or the soaking in large volume of dilute solution of the detergent
20 composition.
The compositions of the invention may also be formulated as hard
surface cleaner compositions.
The following examples are meant to exemplify compositions of the
present invention, but are not necessarily meant to limit or otherwise define
the scope of the invention.
In the detergent compositions, the enzymes levels are expressed in
pure enzyme by weight of the total composition and the abbreviated
component identifications have the following meanings:
LAS : Sodium linear C12 alkyl benzene sulphonate.
TAS : Sodium tallow alkyl sulphate.
.
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42
XYAS : Sodium c1x - C1y alkyl sulfate.
SAS : C12-C14 secondary (2,3) alkyl sulfate in the
form of the sodium salt.
AEC : Alkyl ethoxycarboxylate surfactant of formula
C12 ethoxy (2) carboxylate.
SS : Secondary soap surfactant of formula 2-bytyl
octanoic acid.
25EY : A C 1 2-C 1 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 : C 1 2-C 1 5 mixed ethoxylated and/or
propoxylated fatty alcohol with an average
degree of ethoxylation of 3 to 7 and an average
degree of propoxylation of 4.5.
CFAA : C 1 2-C 1 4 alkyl N-methyl glucamide
TFAA : C16-C18 alkyl N-methyl glucamide.
Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio =
2.0)
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NaSKS-6 : Crystalline layered silicate of formula ~-
Na2Si205
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.
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(A1~2SiO2)12- 27H20 having a primary
particle size in the range from 1 to 10
micrometers
Citrate : Tri-sodium citrate dihydrate
Citric : Citric Acid
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Perborate : Anhydrous sodium perborate monohydrate
bleach, empirical formula NaBO2.H202
PB4 : Anhydrous sodium perborate tetrahydrate
Percarbonate : Anhydrous sodium percarbonate bleach of
empirical formula 2Na2C03.3H2O2
TAED : Tetraacetyl ethylene diamine
Paraffin : Paraffin oil sold under the tradename Winog 70
by Wintershall.
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 : Proteolytic enzyme sold under the tradename
Savinase, Alcalase, Durazym by Novo Nordisk
A/S, Maxapem and Maxacal sold by Gist-
Brocades and proteases described in patent
applications WO91/06637 and/or WO95/10591
and/or EP 251 446.
Lipase : Lipolytic enzyme sold under the tradename
Lipolase and Lipolase Ultra by Novo Nordisk
A/S.
Peroxidase : Peroxidase enzyme.
Cellulase 1, ll : Endoglucanase 50 kD, endoglucanase 43 kD.
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Amylase 1, ll : a-amylase enzyme derived from B.
Licheniformis, known as Termamyl~, o~-amylase
enzyme known as Duramyl(~ and a-amylase
enzyme described in W095/10603,
W096/23873 and W096/23874.
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.
EDDS : Ethylenediamine -N, N'- disuccinic acid, [S,S~
isomer in the form of the sodium salt.
Granular Suds : t2% Silicone/silica, 18% stearyl alcohol,70%
Suppressor starch in granular form
SCS : Sodium cumene sulphonate
Sulphate : Anhydrous sodium sulphate.
HMWPE0 : High molecular weight polyethylene oxide.
PGMS : Polyglycerol monostearate having a tradename
of Radiasurf 248.
TAE 25 : Tallow alcohol ethoxylate (25).
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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.
Example 1
Granular fabric cleaning compositions in accord with the invention
were prepared as follows:
11 111 lV V
LAS 22.0 22.0 22.0 22.0 22.0
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
DETPM P 0.4 0.4 0.4 0.4 0.4
Sodium sulfate 5.5 5.5 5.5 5.5 5.5
Amylase 1 0.0035 0.01 0.005 0.003 0.014
Amylase ll 0.0025 0.01 0.005 0.007 0.006
Cellulase 1 0.001 - - 0.00i
Cellulase ll - - 0.001 0.001
Protease 0.01 0.02 0.01 0.005 -
Pectinase 0.02 - - - -
Xylanase - - 0.01 0.02
Lipase 0.005 0.01
Water & minors Up to 100%
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Example 2
Granular fabric cleaning compositions in accord with the invention
were prepared as follows:
11 111 lV V
LAS 12.0 12.0 12.0 12.0 12.0
Zeolite A 26.0 26.0 26.0 26.0 26.0
SS 4.0 4.0 4.0 4.0
SAS 5.0 5.0 5.0 5.0 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 - 16.0
TAED 5.0 5.0 5.0 - 5.0
Protease 0.06 0.03 0.02 0.08
Lipase 0.005 0.01
Cellulase I - 0.001 - - 0.001
Cellulase ll - - - 0.001 0.001
11 111 lV V
Amylase 1 0.01 0.0045 0.05 0.014 0.005
Amylase ll 0.01 0.0105 0.05 0.006 0.005
Water & minors Up to 100%
ExamPle 3
Granular fabric cleaning compositions in accord with the invention
10 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
45E7 4.0 4.0
25E3S - - 3.0
68E11 1.8 1.8
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25E5 - - 8.0
Citrate 14.0 1 5.0 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
Ceilulase I - - 0.001
Cellulase ll 0.002 - 0.001
Amylase 1 0.015 0.020.0025
Amylase ll 0.015 0.010.0035
Silicate 2.0 2.5
Sulphate 3.5 5.2 3.0
PVP 0.3 0.5
Poly (4-vinylpyridine~-N-oxide/copolymer - - 0.2
of vinyl-imidazole and vinyl-pyrrolidone
ll lll
Perborate 0. 5 1 .0
Peroxidase 0.01 0.01
Phenol sulfonate 0.1 0.2
Water/Minors Up to 1 00%
- ExamDle 4
Granular fabric cleaning compositions in accord with the invention
were prepared as follows:
ll
LAS 6.5 8.0
Sulfate 15.0 18.0
Zeolite A 26.0 22.0
Sodium nitrilotriacetate 5.0 5.0
PVP 0.5 0.7
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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
Silicate 5.0 5.0
Carbonate 15.0 15.0
Peroxidase 0.1 0.1
Pectinase 0.02
Cellulase 1 0.005 0.002
Cellulase ll - 0.001
Amylase 1 0.005 0.01
Lipase 0.01
Amylase ll 0.005 0.003
Water/minors Up to 100%
Example 5
A compact granular fabric cleaning composition in accord with the
invention was prepared as follows:
45AS 8.0
25E3S 2.0
25E5 ~ 3 0
25E3 3.0
TFAA 2.5
Zeolite A 17.0
NaSKS-6 12.0
Citric acid 3.0
Carbonate 7.0
MA/AA 5.0
CMC 0 4
Poly (4-vinylpyridine)-N-oxide/ 0.2
copolymer of vinylimidazole and vinylpyrrolidone
Protease 0 05
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Lipase 0.001
Celiulase 1 0.01
Cellulase ll
Amylase 1 0.005
Amylase ll 0.005
TAED 6.0
Percarbonate 22.0
EDDS 0.3
Granular suds suppressor 3.5
water/minors Up to 100%
Exam~le 6
A granular fabric cleaning compositions in accord with the invention
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
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 1 1 .0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
Perborate 1 5.0
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay l O . 0 10 0
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HMWPE0 - 0.1
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 1 0.015 0.0035
Amylase ll 0.015 0.0025
Cellulase 1 0.001
Cellulase ll 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
Liquid fabric cleaning compositions in accord with the invention were
prepared as follows:
11 111 lV V Vl
AS 12.0 18.0 15.0 15.0 10.0 15.0
AE3S 8.0 4.0 5.0 4.0 5.0 4.0
Polyhydroxy fatty 3.0 3.0 4.0 4.0 4.0 6.0
acid amide
Nonionic 2.5 3.0 5.0 6.0 2.0 4.0
Amido propyl 1.5 1.5 1.5 1.0 2.5 2.5
amine
Tallow palm 5.0 9.0 7.0 7.0 5.0 7.0
kernel FA
Rapeseed FA 2.0 3.0 4.0 3.0 3.0 3.0
Citric acid 2.0 1.0 1.0 2.0 3.0 1.0
Protease 0.03 0.03 0.03 0.03 0.03 0 03
Lipase 0.003 0.003 0.003 0.003 0 003 0 003
Amylase 1 0.006 0.007 0.008 0.009 0.006 0.006
Amylase ll 0.006 0.003 0.005 0.004 0.009 0.007
Cellulase 1 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003
Cellulase ll 0.008 0.008 0.008 0.008 0.008 0.008
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Ethoxylated 0. 7 O. 7 O. 7 0.7 0.7 0.7
tetraethylene
pentaimine
1,2 Propylene 0.1 0.1 0.1 0.1 0.1 0.1
glycol, methyl
capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0 2.2
Propanediol 9.0 8.0 9.0 9.0 10.0 9.0
MeA 4.5 3.5 4 5 5 5 4 5 4 5
NaOH 2.5 3.5 2.5 1.5 2.5 2.5
Borax-Ca Format 2.0 3.0 2.0 1.5 2.0 2.0
Brightener 36 0.1 0.1 0.1 0.1 0.1 0.1
DETPMP 0.7 0.9 1.3 0.9 0.9 0.9
Water and minors Balance to 100%
ExamPle 8
Liquid fabric cleaning compositions in accord with the invention were
prepared as follows:
11 111 lV V
AS 12.0 15.0 15.0 10.0 15.0
AE3S 2.0 2.0 2.0 2.0 2.0
Polyhydroxy fatty acid 4.0 5.0 5.0 4.0 5.0
amide
Nonionic 5.0 5.0 6.0 4.0 5.0
Tallow palm kernel FA 6.0 7.0 4.5 7.0 7.0
Rapeseed FA 3.0 2.0 5.0 3.0 3.0
Citric acid 1.0 2.0 3.0 1.0 2.0
Protease 0.03 0.03 0.03 0.03 0.03
Lipase 0 003 0 003 0 003 0 003 0 003
Amylase 1 0.006 0.007 0.008 0.009 0.006
Amylase ll 0.006 0.003 0.005 0.004 0.009
Cellulase 1 0.0003 0.0003 0.0003 0.0003 0.0003
Cellulase ll 0.008 0.008 0.008 0.008 0.008
Ethoxylated tetraethylene 0.7 0.7 0.7 0.7 0.7
pentaimine
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1,2 Propylene glycol, 0.1 0.1 0.1 0.1 0.1
methyl capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0
Propanediol 9.0 8.0 9.0 9.0 10.0
MeA 4-5 3 5 4-5 5 5 4 5
NaOH 2.5 3.5 2.5 1.5 2.5
Borax-Ca Format 2.0 3.0 2.0 1.5 2.0
Brightener 36 0.1 0.1 0.1 0.1 0.1
Silicone 0.2 0.2 0.2 0.2 0.2
DETPMP 0.7 0.9 1.3 0.9 0.9
Water and minors Balance to 100%
ExamPle 9
Liquid fabric cleaning compositions in accord with the invention were
prepared as follows:
11 111 lV V
AS 12.0 12.0 12.0 15.0 14.0
AE3S 7-5 7-5 7 5 5.0 4.0
Polyhydroxy fatty acid 4.0 6.0 3.0 5.0 4.0
amide
Nonionic 2.5 2.5 2.5 4.0 4.5
Amido propyl amine 1.0 1.0 1.0 1.5 1.0
Tallow palm kernel FA 4.5 4.5 4.5 8.0 7.5
Rapeseed FA 3.0 3.0 3.0 3.0 3.0
Citric acid 2.0 3.5 2.0 1.0 1.0
Protease 0.03 0.03 0.03 0.03 0.03
Lipase 0.003 0.003 0.003 0.003 0.003
Amylase 1 0.015 0.006 0.007 0.008 0.009
Amylase ll 0.014 0.006 0.003 0.005 0.004
Cellulase 1 0.0005 0.0003 0.0003 0.0003 0.0003
Cellulase ll 0.008 0.008 0.008 0.008 0.008
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Ethoxylated tetraethylene 0.7 0.7 0.7 0.7 0.7
pentaimine
1,2 Propylene glycol, 0.1 0.1 0.1 0.1 0.1
methyl capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0
Propanediol 9.0 8.0 9.0 9.0 10.0
MeA 4-5 3-5 4-5 5-5 4 5
NaOH 2.5 3.5 2.5 1.5 2.5
Borax-Ca Format 2.0 3.0 2.0 1.5 2.0
Brightener 36 0.1 0.1 0.1 0.1 0.1
Silicone 0.2 0.2 0.2 0.2 0.2
DETPMP 0.7 0.9 1.3 0.9 0.9
Water and minors Balance to 100%
ExamPle 10
Heavy duty liquid fabric cleaning compositions suitable for use in the
pretreatment of stained fabrics, and for use in a machine laundering
method, in accord with the invention were prepared as follows:
-10
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
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
Protease 0.005 0.03 0.02 0.04 0.01
Lipase 0.002 0.01 0.02 - 0.004
Amylase 1 0.005 0.005 0.001 0.01 0.002
Amylase ll 0.0025 0.002 0.001 0.007 0.002
Cellulase 1 0.04 - 0.01
Cellulase ll - 0.02 0.01 - 0.001
Pectinase 0.02 0.02 - - -
Water/propylene glycol/ethanol 1100:1 :1 )
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Example 11
Heavy duty liquid fabric cleaning compositions in accord with the
invention were prepared as follows:
11 111 lV
LAS acid form - - 25.0
C12 14 alkenyl succinic 3.0 8.0 10.0
acid
Citric acid 10.0 15.0 2.0 2.0
25AS acid form 8.0 8.0 - 15.0
25AE2S acid form - 3.0 - 4.0
25AE7 - 8.0 - 6.0
25AE3 8.0 - - -
CFAA - - - 6.0
DETPMP 0.2 - 1.0 1.0
Fatty acid - - - 10.0
Oleic acid 1.8 - 1.0
Ethanol 4.0 4.0 6.0 2.0
Propanediol 2.0 2.0 6.0 10.0
1. Il 111 lV
Protease 0.02 0.02 0.02 0.01
Cellulase 1 0.04 - - 0.01
Cellulase ll - 0.001 0.0010.001
Amylase 1 0.002 0.007 0.0030.005
Amylase ll 0.002 0.003 0.0020.005
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
NaOH Up to pH 7.5
Waters/minors Up to 100%
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Exampie 1 2
The following rinse added fabric softener composition, in accord with
the invention, was prepared (parts by weight).
Softener active 24. 6
PGMS 2.0
TAE 25 1.5
Amylase 1 0.0005
Amylase 1 0.0005
Cellulase 1 0.001
Cellulase ll
HCL 0. 12
Antifoam agent 0.01 9
Blue dye 80ppm
CaC12 0.35
Perfume 0 90
0
Example 1 3
Syndet bar fabric cleaning compositions in accord with the invention
were prepared as follows:
11 111 lV
C12-16 alkyl sulfate, Na 20.0020.00 20.00 20.00
CFAA 5.0 5.0 5.0 5 0
C1 1-13 alkyl benzene 10.0 10.0 10.0 10.0
sulphonate, Na
Sodium carbonate 25.0 25.0 25.0 25.0
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
CMC 0.2 0.2 0.2 0.2
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Polyacryiate ~MW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Amylase 1 0.01 0.006 0.007 0.01
Amylase 11 0.005 0.014 0.003 0.005
Cellulase I - 0.004 - 0.01
Cellulase ll 0.001 - - 0.001
Protease 0.3 - 0.5 0.05
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.
Example 14
The following compact high density (0.96Kg/l) dishwashing detergent
0 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
Metasilicate - 2.50 2.50
Perborate 1.94 9.74 7.79 14.28 9.74
PB4 8.56
Percarbonate - - - - - 6.70
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
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Paraffin 0.50 0.50 0.50 0.50 - 0.20
Protease 0.0750.05 0.10 0.10 0.08 0.01
Lipase - 0.001 - 0.005
Amylase 1 0.0050.003 0.0050.01 0.005 0.0007
Amylase ll 0.0050.002 0.01 0.005 0.005 0.0018
Cellulase 1 0.001 - 0.005 - - 0.001
Cellulase ll0.001 - - - 0.001
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 11.0010.90 10.80 10.90 9.60
Example 15
5The following granular dishwashing detergent compositions examples
I 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
Silicate 7.40 7.40 7.40 12.00 8.00 20.34
Perborate 4.40 4.40 4.40 - 4.40
NaDCC - - - 2.00 - 1.50
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
Lipase 0.005 - 0.001
Amylase 1 0.002 0.001 0.005 0.006 0.007 0.01
Amylase ll 0.001 0.001 0.005 0.014 0.003 0.005
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Cellulase I 0.0010 005 0 001
Cellulase ll - - - 0.001 - 0.001
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
Example 16
The following detergent composition tablets of 25g weight were
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
Lipase 0.005 - -
Amylase 1 0.005 0.002 0.001
ll lll
Amylase ll 0.005 0.003 0.001
cellulase I - 0.01 0.01
Cellulase ll 0.004 0.01
Perborate 1.56 7.79
PB4 6.92 - 11.40
Nonionic 1.Z0 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
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Example 17
The following liquid dishwashing detergent compositions in accord
5 with the present invention I to ll, 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
Nonionic 2.50 1.00
Paraffin 2.20
Protease 0.03 0.02
Amylase 1 0.0025 0.0018
Amylase ll 0.00025 0.0007
Cellulase 1 0.04 0.01
cellulase ll - 0.005
480N 0.50 4.00
KOH - 6.00
Sulphate 1.60
pH (1% solution) 9.10 10.00
Examcle 18
0 The following liquid hard surface cleaning compositions were
prepared in accord with the present invention:
11 111 lV V Vl
Amylase 1 0.01 0.002 0.005 0.006 0.0007 0.003
Amylase ll 0.01 0.003 0.005 0.014 0.0003 0.002
Cellulase 1 0.01 - - 0.01
Cellulase ll 0.005 0.01
Protease 0.05 0.01 0.02 0.03 0.005 0.005
EDTA* - - 2.90 2.90
Na Citrate - - - - 2.90 2.90
,
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NaC12 Alkyl benzene 1.95 - 1.95 - 1.95
sulfonate
NaC12 Alkyl sulfate - 2.20 - 2.20 - 2.20
NaC1 2~ethoxy) - 2.20 - 2.20 - 2.20
* *sulfate
C12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
SCS 1.30 - 1.30 - 1.30
Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30
Water Balance to 100%
*Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
***AII formulas adjusted to pH 7
ExamPle 1 9
The following spray composition for cleaning of hard surfaces and
removing household mildew was prepared in accord with the present
invention:
Amylase 1 0.005
Amylase ll 0 005
Cellulase I
Cellulase ll 0.01
Protease 0.01
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
Sodium hydroxide 0.80
Silicate (Na) 0.04
Perf ume 0 3 5
Water/minors up to 100%
