Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING SPECIFIC
YTIC ENZYME AND ZEOLITE MAP
TECHNICAL FIELD
The present invention relates to detergent
compositions comprising a specific lipolytic enzyme and
zeolite MAP. In particular, the present invention relates
to improvements in the detergency performance of laundry,
diswashing and hard surface cleaning detergent compositions
comprising a specific lipolytic enzyme and zeolites as
sequestering agent for water hardness.
BACKGROUND OF THE INVENTION
The inclusion of lipolytic enzyme (e.g. lipase) in
detergent compositions for improved cleaning performance is
known, e.g. enhancement of removal of triglycerides
containing soils and stains from fabrics. Examples are US
Patent 4,769,173, Cornelissen et al. issued August 29,
1989; US Patent 5,069,809, Lagerwaard et al., issued
December 3, 1991; PCT application W094/03578 and HAPPI
(Household & Personal Products Industry) No. 28/1991.
In USP 4,769,173 is disclosed a certain class of
lipases consisting of fungal lipases ex Humicola lanuginosa
together with strong bleaching agents in detergent
compositions.
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An example of a fungal lipase in this patent is the
lipase ex Humicola lanuginosa, available from Amano under
the tradename Amano-CE.
In USP 5,069,809 is disclosed the combination of
strong bleaching agents with a lipase enzyme produced by
cloning the gene encoding the lipase produced by Humicola
lanuginosa and expressing the gene in Aspergillus oryzae as
host for use in detergent compositions.
In WO 94/03578 is disclosed an enzymatic detergent
composition containing 10 to 20 000 LU (Lipolytic units)
per gram of detergent composition of a lipase showing a
substantial lipolytic activity during the main cycle of a
wash process. This lipase is selected in particular on its
inactivation behaviour with Diisopropyl Fluoro Phosphate
(DFP).
In spite of the large number of publications on lipase
enzymes only the lipase derived from Humicola lanuginosa
strain DSM 4106 and produced in Aspergillus oryzae as host
has so far found wide-spread application as additive for
fabric washing products. It is available from Novo Nordisk
under the tradename Lipolase (TM). Gormsen and Malmos
describe in HAPPI this enzyme with trademark "Lipolase" as
being the first detergent lipase with a commercially
relevant cost performance based on the use of recombinant
DNA technology on an industrial scale.
In HAPPI is disclosed that Lipolase is the most
effective during the drying step rather than the washing
process itself. During the drying of the fabric, the
conditions like water level are more favourable for
lipolytic hydrolysis than during the actual wash cycle.
In order to optimize the stain removal performance of
Lipolase, Novo Nordisk have made a number of variants.
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As described in WO 92/05249 D96L variant of the native
Humicola lanuginosa lipase improves the lard stain removal
efficiency by a factor 4.4 over the wild-type lipase
(enzymes compared in an amount ranging from 0.075 to 2.5 mg
protein per liter).
In Research Disclosure No. 35944 published on March
10, 1994, by Novo Nordisk is disclosed that the lipase
variant (D96L) may be added in an amount corresponding to
O.OO1-lOOmg (5-500.000 LU/l) lipase variant per liter of
wash liquor.
Detergent compositions conventionally contain
detergency builders which lower the concentration of
calcium and magnesium water hardness ions in the wash
liquor and thereby provide good detergency effect in both
hard and soft water. Conventionally, inorganic phosphates,
such as sodium tripolyphosphate, have been used as builders
for laundry detergents. More recently, alkali metal
aluminosilicate ion-exchangers, particularly crystalline
sodium aluminosilicate zeolite A, have been proposed as
replacements for the inorganic phosphates.
For example, EP 21 491A (Procter & Gamble) discloses
detergent compositions containing a building system which
includes zeolite A, X or P (B) or a mixture thereof. EP
384070A (Unilever) discloses specific zeolite P materials
having an especially low silicon to aluminium ratio not
greater than 1.33 (hereinafter referred to as zeolite MAP)
and describes its use as a detergency builder. To date,
however, zeolite A is the preferred aluminosilicate
detergency builder in commercially available products.
However, it is known that there are certain problems
in the use of zeolites as detergency builders, as compared
with phosphates. For example, zeolites work relatively
slowly to sequester the calcium ions which reduces the
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detergency effect. One proposal which has been made to
overcome this problem is to introduce certain co-~uilders
to provide better and quicker hardness control. For
example, GB 1429143 (Procter & Gamble) and GB 1470250
(Procter & Gamble) describe a detergency building system
comprising an alkali metal aluminosilicate and citrates.
Moreover, it has been found that high levels of
soluble builders, for example, phosphates and citrates, can
have a negative effect on the performance of certain
lipases.
The problem associated with the use of high levels of
water soluble builders such as citrate or phosphates is
that they prevent calcium from inhibiting the well known
deactivation of lipase by the free fatty acids formed upon
the hydrolysis of triglycerides by lipase. These high
levels of water soluble builders are therefore detrimental
to the performance contribution of the lipase.
It has been found that lipase has only a limited
benefit as a detergent component, incorporating a
detergency builder such as zeolite A, due to the formation
of the calcium fatty acid crust which hardens the stain and
prevents its removal by the other detergent ingredients.
Consequently, the benefits of incorporating a lipase in a
liquid detergent composition comprising an aluminosilicate
detergency builder such as zeolite A are mainly observable
under multiple cycle conditions and pretreatments, not in
single wash conditions.
The overall performance of a detergent is indeed
judged by not only its ability to remove soils and stains,
e.g. greasy/oily soils, but also its ability to prevent
redeposition of the soils, or the breakdown products of the
soils or of any insoluble salt, on the article washed.
Redeposition effects results in the articles being coated
,
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in an unseemly film, appearing streaked or being covered in
visible spots which remain lntact at the end of the wash
process.
Therefore, there remains a substantial technical
challenge in formulating detergent compositions in such a
manner to meet the consumer's need for superior overall
detergency performance.
The above ob~ective has been met by detergent
compositions including laundry, dishwashing and hard
surface cleaner, containing specific lipolytic enzymes and
zeolite MAP.
It has now surprisingly been found that the
combination of specific lipolytic enzyme with a builder
system comprising zeolite MAP improves the overall
detergency performance e.g. whiteness maintenance on
fabrics and reduced spotting, filming and/or redeposition
of greasy/oily substances on dishware, hard surfaces and
the like.
This finding allows either improved performance or a
reduction of the surfactant/lipolytic enzyme levels while
keeping the same detergency performance.
SUMMARY OF THE INVENTION
The present invention relates to detergent
compositions comprising a specific lipolytic enzyme and
zeolite MAP. In particular, the present invention relates
to improvements in the overall detergency performance of
laundry, dishwashing and hard surface cleaning detergent
compositions comprising a specific lipolytic enzyme for
whiteness maintenance, reduced redeposition and greasy/oily
stains removal and zeolites as sequestring agent for water
hardness.
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DETAILED DESCRIPTION OF THE INVENTION
Specific lipolytic enzyme
An essential component of the detergent composition
according to the invention is a specific lipolytic enzyme.
In the present context, the term "lipolytic enzyme" is
intended to indicate an enzyme exhibiting a lipid degrading
capability, such as a capability of degrading a
triglyceride, a phospholipid, a wax-ester or cutin. The
lipolytic enzyme may, e.g., be a lipase, a phospholipase,
an esterase or a cutinase.
The specific lipolytic enzymes suitable for the present
invention are those lipolytic enzymes which provide a
significantly improved whiteness maintenance performance
when compared to an identical hydrolytic activity ~same
amount of LU per liter of wash solution) of the LipolaseTM
enzyme.
The significant whiteness maintenance performance as used
herein can be visually evaluated by expert graders using
the 0~4 panel score units ~PSU) Scheffé scale (0 stands
for no difference and 4 represents a very large
difference).
The specific lipolytic enzyme suitable for the present
invention is incorporated into the detergent composition in
accordance with the invention at a level of from 50 LU to
8500 LU per liter wash solution. Preferably said lipolytic
enzyme is present at a level of from 100 LU to 7500 LU per
liter of wash solution. More preferably at a level of from
150 LU to 5000 LU per liter of wash solution.
Suitable specific lipolytic enzymes for use herein
include those of bacterial and fungal origin. The lipolytic
enzymes from chemically or genetically modified mutants are
included herein.
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Preferred lipolytic enzymes include variants of lipolytic
enzymes producible by Humicola lanuginosa and Thermomyces
lanuginosus, or by cloning and expressing the gene
responsible for producing said variants into a host
organism, e.g. Aspergillus oryzae as described in European
Patent Application 0 258 068, incorporated herein by
reference.
Highly preferred lipolytic enzymes are variants of the
native lipase derived from Humicola lanuginosa as described
in US Serial No. 08/341,826. Preferably the Humicola
lanuginosa strain DSM 4106 is used. An example of said
variants is D96L lipolytic enzyme.
By D96L lipolytic enzyme variant is meant the lipase
variant as described in patent application WO 92/05249 viz.
wherein the native lipase ex Humicola lanuginosa the
aspàrtic acid (D) residue at position 96 is changed to
Leucine (L). According to this nomenclature said
substitution of aspartic acid to Leucine in position 96 is
shown as : D96L.
To determine the activity of the enzyme D96L the
standard LU assay was used (Analytical method, internal
Novo Nordisk number AF 95/6-GB 1991.02.07). A substrate for
D96L was prepared by emulsifying glycerine tributyrate
(Merck) using gum-arabic as emulsifier. Lipase activity was
assayed at pH 7 using pH stat. method.
One unit of lipase activity (LU/mg) is defined as the
amount needed to liberate one micromole fatty acid per
minute.
Builder System
According to the present invention the detergency
builder system is based on zeolite MAP, optionally in
conjunction with one or more supplementary builders. The
amount of zeolite MAP employed may range, for example, from
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1 to 80 wt.%, preferably from 5 to 60 wt.~, more preferably
from 15 to 40 wt.%.
Zeolite MAP is described in EP 384070A (Unilever). It
is defined as an alkali metal alumino-silicate of the
zeolite P type having a silicon to aluminium ratio not
greater than 1.33, preferably within the range from 0.9 to
1.33 and more preferably within the range of from 0.9 to
1.2. Of particular interest is zeolite MAP having a silicon
to aluminium ratio not greater than 1.15 and, more
particularly, not greater than 1.07.
Zeolite P having a Si:Al ratio of 1.33 or less may be
prepared by the following steps:
(i) mixing together a sodium aluminate having a mole
ratio Na20:Al203 within the range of from 1.4 to 2.0
and a sodium silicate having a mole ratio SiO2:Na20
within the range of from 0.8 to 3.4 with vigorous
stirring at a temperature within the range of from 25~
C to boiling point usually 95~C, to give a gel having
the following composition; Al203: (1.75-3.5) -SiO2
(2.3-7.5) Na20 :P (80-450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours,
preferably 2 to 5 hours, at a temperature within the
range of from 70~C to boiling point, usually to 95~C,
with sufficient stirring to maintain any solids
present in suspension;
(iii) separating the crystalline sodium
aluminosilicate thus formed, washing to a pH within
the range of from 10 to 12.5, and drying, preferably
at a temperature not exceeding 150~C, to a moisture
content of not less than 5 wt.~.
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Preferred drying methods are spray-drying and flash
drying. It appears that oven drying at too high a
temperature may adversely affect the calcium binding
capacity of the product under certain circumstances.
Commercial sodium metasilicate pentahydrate dissolved
in water and commercial sodium silicate solution
(waterglass) are both suitable silica sources for the
production of zeolite P in accordance with the invention.
The reactants may be added together in any order either
rapidly or slowly. Rapid addition at ambient temperature,
and slow addition at elevated temperature (90-95~C) both
give the desired product.
Vigorous stirring of the gel during the addition of
the reactants, and at least moderate stirring during the
subsequent ageing step, however, appear to be essential for
the formation of pure zeolite P. In the absence of
stirring, various mixtures of crystalline and amorphous
materials may be obtained.
Zeolite MAP generally has a calcium binding capacity
of at least 150 mg CaO per g of anhydrous aluminosilcate,
as measured by the standard method described in GB 1473201
(Henkel). The calcium binding capacity is normally 160 mg
CaO/g and may be as high 170 mg CaO/g.
Although zeolite MAP like other zeolites contains
water of hydration, for the purposes of the present
invention amounts and percentages of zeolite are expressed
in terms of the notional anhydrous material.
The amount of water present in hydrated zeolite MAP at
ambient temperature and humidity is generally about 20
wt.%-
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Preferred zeolite MAP for use in the present invention
is finely divided and has a d50 (as defined hereinafter)
within the range of from 0.1 to 10.0 micrometres. A
preferred zeolite MAP for use according to the present
invention has a d50 of from 1.0 to 10.0 micrometres, for
example 2.2 to 7.0 micrometres, more particularly 2.5 to
5.0 micrometres. The quantity "d50" indicates that 50 wt.%
of the particles have a diameter smaller than that figure.
The particule size may, in particular be determined by
conventional analytical techniques such as microscopic
determination using a scanning electron microscope or by
means of a laser granulometer. Other methods of
establishing dso values are disclosed in EP 384 070.
According to one embodiment of the invention the
zeolite MAP detergent builder is in powder form. For
convenience in handling, however, the material may be
granulated by conventional techniques such as spray drying
or by a non-tower method to form larger particles.
Cobuilders
In addition to zeolite MAP, the builder sytem may
contain an organic or inorganic cobuilder.
Suitable organic cobuilders can be monomeric or
polymeric carboxylates such as citrates or polymers of
acrylic, methacrylic and/or maleic acids in neutralised
form. Suitable inorganic cobuilders include carbonates and
amorphous and crystalline lamellar sodium silicates.
Crystalline layered silicates are most preferred.
Suitable lamellar silicates have the composition:
NaMSixO2x+1 , yH20
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11
where M is sodium or hydrogen, preferably sodium; x is a
number from 1.9 to 4; and y is a number from 0 to 20. Such
materials are described in US Patents No. 4664839; No.
4728443 and No. 4820439 (Hoechst AG). Especially preferred
are compounds in which x = 2 and y = O. The synthetic
material is commercially available from Hoechst AG as S-Na2
Si205 (SKS6) and is described in US Patent No. 4664830.
The cobuilder may include an aluminosilicate zeolite A
material, but where present such zeolite A builder is at a
level of no more than 2~ by weight of the detergent
composition.
The total amount of detergency builder in the granular
composition typically ranges from 1 to 80 wt.~, more
preferably from 15 to 60 wt.% and most preferably from 10
to 45 wt.~.
The objective of the washing process of soiled fabrics
is to clean these, i.e. to remove soils and stains from the
soiled clothes. However, as soon as the removed soils
appear in the wash solution, they can redeposit onto the
fabrics being washed. Especially for white garments the
redeposition of soil has a strong negative impact on the
whiteness of the fabric. But also the brightness and
freshness of colored fabrics is reduced by such
redeposition.
Whiteness maintenance is the monitoring of the
whiteness of wash & wear fabrics over a number of washing
cycles. A good performing detergent has a good whiteness
maintenance profile, i.e. it ensures that the whiteness of
washed fabrics is maintained at a high level during the
complete life cycle of wearing & washing by preventing as
much as possible the redeposition onto white fabrics of
removed soils.
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Without wishing to be bound by theory, it is believed
that the zeolite MAP provides a better control of the rate
of accumulation of calcium fatty acid complex at the
water/stain interface than zeolite A. Importantly, zeolite
MAP only requires low levels of water soluble cobuilders
which do not deactivate the specific lipolytic enzyme.
It has indeed been surprisingly found that the
incorporation into detergents of the specific lipolytic
enzymes according to the present invention together with
zeolite MAP delivers a significant benefit in whiteness
maintenance.
In addition, under hard surfaces cleaning and dishcare
conditions the use of said specific lipolytic enzymes with
zeolite MAP, shows a reduced spotting, filming and/or
redeposition of greasy/oily substances on dishes, plates,
hard surfaces and the like.
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 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 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 and machine laundry
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13
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 methods the compositions of the invention
preferably contain a surfactant and preferably other
detergent compounds selected from organic polymeric
compounds, suds enhancing agents, group II 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
release polymer, soil suspension and anti-redeposition
agents and corrosion inhibitors. Laundry compositions can
also contain softening agents, as additional detergent
components.
The compositions of the invention can also be used as
detergent additive products. Such additive products are
intended to supplement or boost the performance of
conventional detergent compositions.
If needed the density of the granular laundry
detergent compositions herein ranges from 400 to 1200
g/litre, preferably 600 to 950 g/litre of composition
measured at 20~C.
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
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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 17-3~ 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 system
The detergent compositions according to the present
invention can additionally comprise a surfactant system
wherein the surfactant can be selected from anionic and/or
nonionic 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
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1% to 30~ by weight of detergent compositions in accordance
with the present invention.
Preferred 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 surfactant systems of the
present invention, with the polyethylene oxide condensates
being preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing
from about 6 to about 14 carbon atoms, preferably from
about 8 to about 14 carbon atoms, in either a straight-
chain or branched-chain configuration with the alkylene
oxide. In a preferred embodiment, the ethylene oxide is
present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of
ethylene oxide per mole of alkyl phenol. Commercially
available nonionic surfactants of this type include
IgepalTM C0-630, marketed by the GAF Corporation; and
TritonTM X-45, X-114, X-100 and X-102, all marketed by the
Rohm & Haas Company. These surfactants are commonly
referred to as alkylphenol alkoxylates ~e.g., alkyl phenol
ethoxylates).
The condensation products of primary and secondary
aliphatic alcohols with from about 1 to about 25 moles of
ethylene oxide are suitable for use as the nonionic
surfactant of the nonionic surfactant systems of the
present invention. The alkyl chain of the aliphatic alcohol
can either be straight or branched, primary or secondary,
and generally contains from about 8 to about 22 carbon
atoms. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20
carbon atoms, more preferably from about 10 to about 18
carbon atoms, with from about 2 to about 10 moles of
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16
ethylene oxide per mole of alcohol. ~bout 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 15-S-9 (the condensation product of C11-C1s
linear alcohol with 9 moles ethylene oxide), TergitolTM 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
C14-C1s linear alcohol with 9 moles of ethylene oxide),
NeodolTM 23-3 (the condensation product of C12-C13 linear
alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7
(the condensation product of C14-C1s linear alcohol with 7
moles of ethylene oxide), NeodolTM 45-5 (the condensation
product of C14-C1s linear alcohol with 5 moles of ethylene
oxide) marketed by Shell Chemical Company, KyroTM EOB (the
condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company,
and Genapol LA 030 or 050 (the condensation product of C12-
C14 alcohol with 3 or 5 moles of ethylene oxide) marketed
by Hoechst. Preferred range of H~B in these products is
from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the
surfactant systems of the present invention are the
alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic
group containing from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g. a polyglycoside, hydrophilic group
containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most 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
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17
the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or galactose as opposed to a glucoside or
galactoside). The intersaccharide bonds can be, e.g.,
between the one position of the additional saccharide units
and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide units.
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 lO to
about 18, preferably from about 12 to about 14, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
preferably 0; and x is from about 1.3 to about lO,
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 pre~ominately 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
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18
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
consists of the reaction product of ethylenediamine and
excess propylene oxide, and generally has a molecular
weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that
the condensation product contains from about 40% to about
80% by weight of polyoxyethylene and has a molecular weight
of from about 5,000 to about 11,000. Examples of this type
of nonionic surfactant include certain of the commercially
available TetronicTM compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the
surfactant systems of the present invention are
polyethylene oxide condensates of alkyl phenols,
condensation products of primary and secondary aliphatic
alcohols with from about 1 to about 25 moles of ethylene
oxide, alkylpolysaccharides, and mixtures thereof. Most
preferred are Cg-C14 alkyl phenol ethoxylates having from 3
to 15 ethoxy groups and Cg-C1g alcohol ethoxylates
~preferably C1o avg.) having from 2 to 10 ethoxy groups,
and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy
fatty acid amide surfactants of the formula.
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19
R2 - C - N - Z,
Il I
O Rl
wherein R1 is H, or R1 is Cl_4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C~ 5
alkyl or C16_1g alkyl or alkenyl chain such as coconut
alkyl or mixtures thereof, and Z is derived from a reducing
sugar such as glucose, fructose, maltose, lactose, in a
reductive amination reaction.
When included in such detergent compositions, the
nonionic surfactant systems of the present invention act to
improve the greasy/oily stain removal properties of such
detergent compositions across a broad range of cleaning
conditions.
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 SO3
according to "The Journal of the American Oil Chemists
Society", 52 (1975), pp. 323-329. Suitable starting
materials would include natural fatty substances as derived
from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry applications, comprise alkyl ester sulfonate
surfactants of the structural formula :
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W O 97/43380 PCT~US96/07097
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is
C1o-C16 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R3 is Clo-C16 alkyl.
Other suitable anionic surfactants include the alkyl
sulfate surfactants which are water soluble salts or acids
of the formula ROSO3M wherein R preferably is a C1o-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a
C1o-C20 alkyl component, more preferably a C12-C1g alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
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 C12-C16 are preferred for lower
wash temperatures (e.g. below about 50~C) and C16_1g alkyl
chains are preferred for higher wash temperatures (e.g.
above about 50~C).
.
CA 022~4068 1998-11-12
W097/43380 PCT~S96/07097
21
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
substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, Cg-C22 primary of secondary
alkanesulfonates, Cg-C2~ 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 alkylpolyglycolethersulfates (containing up to 10
moles of ethylene oxide); alkyl glycerol sulfonates, fatty
acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated 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 such as those of the
formula RO(CH2CH2O)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.
Further examples are described in "Surface Active Agents
and Detergents" (Vol. I and II by Schwartz, Perry and
Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference~.
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W097/43380 PCT~S96/070s7
22
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO~A)mSO3M wherein R is an
unsubstituted C1o-C24 alkyl or hydroxyalkyl group having a
C10-C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-Cl8 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically between about 0.5 and about 6, more
preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated
sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted
ammonium cations include methyl-, dimethyl, trimethyl-
ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and
those derived from alkylamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-Cl8 alkyl
polyethoxylate (1.0) sulfate (C12-C18E(1.O)M)~ C12-C18
alkyl polyethoxylate (2.25) sulfate (C12-C1gE~2.25)M), C12-
C1g alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M),
and C12-C1g alkyl polyethoxylate (4.0) sulfate (C12-
C1gE(4.0)M), wherein M is conveniently selected from sodium
and potassium.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
those having one long-chain hydrocarbyl group. Examples of
such cationic surfactants include the ammonium surfactants
such as alkyltrimethylammonium halogenides, and those
surfactants having the formula :
[R2(oR3)y]~R4(OR3)y]2R5N+X~
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W097/43380 PCT/U~ ~7~7
23
wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chaln, each
R3 is selected from the group consisting of -CH2CH2-, -
CH2CH(CH3)-, -CH2CH~CH2OH)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of
C1-C4 alkyl, Cl-C4 hydroxyalkyl, benzyl ring structures
formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R5 is the same as R4 or is an
alkyl chain wherein the total number of carbon atoms of R2
plus R5 is not more than about 18; each y is from 0 to
about 10 and the sum of the y values is from 0 to about 15;
and X is any compatible anion.
Highly preferred cationic surfactants are the water-
soluble quaternary ammonium compounds useful in the
present composition having the formula :
RlR2R3R4N+X- ( i )
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is
independently C1-C4 alkyl, Cl-C4 hydroxy alkyl, benzyl, and
-(C2H40)XH where x has a value from 2 to 5, and X is an
anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-Cls
particularly where the al~yl 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
synthesis.
Preferred groups for R2R3 and R4 are methyl and
hydroxyethyl groups and the anion X may be selected from
halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or
bromide;
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W O 97143380 pcTrus96lo7o97
24
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12_1s dimethyl hydroxyethyl ammonium chloride or
bromide;
coconut dimethyl hydroxyethyl ammonium chloride or
bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
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.
Quaternary ammonium surfactants suitable for the present
invention have the formula (I):
R2 IR3
~0~ Rs X~
Formula I
whereby Rl is a short chainlength alkyl (C6-Cl0) or
alkylamidoalkyl of the formula (II) :
C6-C~ C~
Formula II
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,
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WOg7/43380 PCT~9~1~7~37
whereby R3, R4 and R5 are either the same or different and
can be either a short chain alkyl (Cl-C3) or alkoxylated
alkyl of the formula III,
whereby X~ is a counterion, preferably a halide, e.g.
chloride or methylsulfate.
R6
~Z
Formula III
R6 is Cl-C4 and z is l or 2.
Preferred quat ammonium surfactants are those as
defined in formula I whereby
Rl is Cg, Clo or mixtures thereof, x=o,
R3, R4 - CH3 and Rs = C~2CH2OH.
When included therein, the detergent compositions of
the present invention typically comprise from 0.2~ to about
25%, preferably from about 1% to about 8% by weight of such
cationic surfactants.
Ampholytic surfactants are also suitable for use in
the detergent compositions of the present invention. These
surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines
in which the aliphatic radical can be straight- or
branched-chain. One of the aliphatic substituents contains
at least about 8 carbon atoms, typically from about 8 to
about 18 carbon atoms, and at least one contains an anionic
water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column l9, 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
CA 022~4068 1998-11-12
W097/43380 PCT~S96/07097
26
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, ~uaternary
phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December
30, lg75 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 about 1% to about 10% by weight of
such zwitterionic sùrfactants.
Semi-polar nonionic surfactants are a special category
of nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-
soluble phosphine oxides containing one alkyl moiety of
from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and
a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties of from about 1 to about 3 carbon
atoms.
Semi-polar nonionic detergent surfactants include the
amine oxide surfactants having the formula
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27
R3(oR4)xN(R5)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 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 oxygen or
nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include
C1o-C1g alkyl dimethyl amine oxides and Cg-C12 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
preferably 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-Clo alkyl chain or R4X~CH2)n, X is -O-,-
C(O)NH- or -NH-, R4 is a C6-C12 alkyl chain n is between 1
to 5, preferably 3. R1 alkyl chains may be straight or
branched and may be interrupted with up to 12, preferably
less than ~ ethylene oxide moieties.
Preferred amines according to the formula herein above are
n-alkyl amines. Suitable amines for use herein may be
selected from 1-hexylamine, 1-octylamine, 1-decylamine and
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W097/43380 PCT~S96/07097
28
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 having the formula R1R2R3N 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 R4XtCH2)n, whereby X is -O-, -CtO)NH- or -NH-,R4 is a
C4-C12, n is between l to 5, preferably 2-3. Rs is H or C1-
C2 alkyl and x is between 1 to 6 .
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
R5
--(CH2 C~ H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
Rl -C-NH-~CH2~-N-~R2)2
wherein Rl is C6-C12 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-
10oxypropylamine, N coco 1-3diaminopropane, coconut-
alkyldimethylamine,lauryldimethylamine,lauryl bis(hydroxy-
ethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2
.
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W097/43380 PCT~S96/07097
29
moles propoxylated, octyl amine 2 moles propoxylated,
lauryl amidopropyldimethylamine, C8-10
amidopropyldimethylamine and C10 amidopropyldimethylamine.
The most preferred amines for use in the compositions
herein are 1-hexylamine, l-octylamine, 1-decylamine, 1-
dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine
and oleylamine 7 times ethoxylated, lauryl amido
propylamine and cocoamido propylamine.
Optional detergent ingredients :
0th er d e t ergen t enzymes
The detergent compositions can in addition to specific
lipolase enzymes further comprise one or more enzymes which
provide cleaning performance and/or fabric care benefits.
Said enzymes include enzymes selected from cellulases,
hemicellulases, peroxidases, proteases, gluco-amylases,
amylases, xylanases, other lipases, other esterases, other
cutinases, pectinases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases, pentosanases, malanases, ~-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.
The cellulases usable in the present invention include
both bacterial or fungal cellulase. Preferably, they will
have a pH optimum of between 5 and 9.5. Suitable cellulases
CA 022~4068 1998-11-12
W O 97143380 PCT~US96/07097
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by
a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM lB00.
Other suitable cellulases are cellulases originated from
Humicola insolens having a molecular weight of about 50KDa,
an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulases are the cellulases having
color care benefits. Examples of such cellulases are
cellulases described in European patent application No.
91202879.2, filed November 6, 1991 (Novo).
Peroxidase enzymes are used in combination with oxygen
sources, e.g. percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "solution bleaching", i.e.
to prevent transfer of dyes or pigments removed from
substrates during wash operations to other substrates in
the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase,
ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO
89/099813 and in European Patent application EP No.
91202882.6, filed on November 6, 1991.
Said cellulases and/or peroxidases are normally
incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent
composition.
Preferred commercially available protease enzymes
include those sold under the tradenames Alcalase, Savinase,
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31
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 and W094/10591 and USSN 08/322 676 can be
included in the detergent composition of the invention.
Protease enzyme may be incorporated into the compositions
in accordance with the invention at a level of from 0.0001
to 2% active enzyme by weight of the composition.
The detergent compositions of the present invention
can include other lipases. Suitable lipase enzymes for
detergent usage include those produced by microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. Suitable
lipases include those which show a positive immunological
cross-reaction with the antibody of the lipase, produced by
the microorganism Pseudomonas fluorescent IAM 1057. This
lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P". Especially suitable
lipases are lipases such as M1 LipaseR and LipomaxR (Gist-
Brocades) and LipolaseR(Novo) which have found to be very
effective when used in combination with the compositions of
the present invention.
Also suitable are cutinases [EC 3.1.1.50] which can be
considered as a special kind of lipase, namely lipases
which do not require interfacial activation. 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 other lipases and/or cutinases are normally
incorporated in the detergent composition at levels from
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W O 97/43380 PCT~US~ 7
0.0001~ to 2~ of active enzyme by weight of the detergent
composition.
Amylases ~a and/or ~) can be included for removal of
carbohydrate-based stains. WO/94/02597, Novo Nordisk A/S
published February 03, 1994, describes cleaning
compositions which incorporate mutant amylases. See also
WO/94/18314, Genencor, published August 18, 1994 and
WO/95/10603, Novo Nordisk A/S, published April 20,1995.
Other amylases known for use in cleaning compositions
include both a- and ~-amylases. a-Amylases are known in
the art and include those disclosed in US Pat. no.
5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent
specification no. 1,296,839 (Novo). Other suitable amylase
are stability-enhanced amylases including Purafact Ox AmR
described in WO 94/18314, published August 18, 1994 and
amylase variants having additional modification in the
immediate parent available from Novo Nordisk A/S, disclosed
in WO 95/10603, published April 95. Examples of
commercial a-amylases products are Termamyl~, Ban~
,Fungamyl~ and Duramyl~, all available from Novo Nordisk
A/S Denmark. W095/26397 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. Other 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.
The above-mentioned enzymes may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and
yeast origin. Said enzymes are normally incorporated in
the detergent composition at levels from 0.0001% to 2% of
active enzyme by weight of the detergent composition. The
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W O 97/43380 PCTrUS96/07097
33
enzymes can be added as single ingredients (prills,
granulates, stabilised liquids, etc...) or as mixture of
two or more enzymes (e.g. cogranulates).
Other suitable detergent ingredients that can be added
are enzyme oxidation scavengers which are described in the
copending European patent application 92870018.6 filed on
January 31, 1992. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
Color care benefits
Technologies which also provide a type of color care
benefit can be included. Examples of these technologies
are metallo catalysts for color maintenance. Such metallo
catalysts are described in the European patent EP 0 596 184
and in the copending European Patent Application No.
94870206.3.
Bleaching agent
Bleach systems that can be included in the detergent
compositions of the present invention include bleaching
agents such as PB1, PB4 and percarbonate with a particle
size of 400-800 microns. These bleaching agent components
can include one or more oxygen bleaching agents and,
depending upon the bleaching agent chosen, one or more
bleach activators. When present oxygen bleaching compounds
will typically be present at levels of from about 1% to
about 25%.
The bleaching agent component for use herein can be
any of the bleaching agents useful for detergent
compositions including oxygen bleaches as well as others
known in the art.
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W O 97/43380 PCTrUS96/07097
34
The bleaching agent suitable for the present invention can
be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be
used encompasses percarboxylic acid bleaching agents and
salts thereof. Suitable examples of this class of agents
include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of meta-chloro perbenzoic acid, 4-
nonylamino-4-oxoperoxybytyric acid and
diperoxydodecanedioic acid. Such bleaching agents are
disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S.
Patent 4,412,934. Highly preferred bleaching agents also
include 6-nonylamino-6-oxoperoxycaproic acid as described
in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of
hypohalite bleaching agents, for example, include trichloro
isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10%
by weight of the finished product, preferably 1-5% by
weight.
The hydrogen peroxide releasing agents can be used in
combination with bleach activators such as
tetraacetylethylenediamine (TAED), nonanoyloxybenzene-
sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in
EP 120,591), pentaacetylglucose (PAG) or Phenolsulfonate
ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS,
described in W094/28106), which are perhydrolyzed to form a
peracid as the active bleaching species, leading to
improved bleaching effect. Also suitable activators are
acylated citrate esters such as disclosed in Copending
European Patent Application No. 91870207.7.
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W O 97/43380 PCTAUS~ 7~7
It has been found that combination of specific
lipolytic enzyme a bleaching agent and especially with
nonanoyloxybenzene-sulfonate (NOBS) and Phenolsulfonate
ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS) as
bleach activator, reduce the spotting, filming and/or
redeposition thereby enhancing the whiteness maintenance
and the greasy/oily stain removal performance.
Useful bleaching agents, including peroxyacids and
bleaching systems comprising bleach activators and
peroxygen bleaching compounds for use in detergent
compositions according to the invention are described in
our co-pending applications USSN 08/136,626,
PCT/US95/07823, W095/27772, W095/27773, W095/27774 and
W095/27775.
The hydrogen peroxide may also be present by adding an
enzymatic system (i.e. an enzyme and a substrate therefore)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process.
Such enzymatic systems are disclosed in EP Patent
Application 91202655.6 filed October 9, 1991.
Bleaching agents other than oxygen bleaching agents
are also known in the art and can be utilized herein. One
type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. These
materials can be deposited upon the substrate during the
washing process. Upon irradiation with light, in the
presence of oxygen, such as by hanging clothes out to dry
in the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached.
Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033,718.
Typically, detergent compositions will contain about 0.025
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36
to about 1.25%, by weight, of sulfonated zinc
phthalocyanine.
Addi tional Builder system
The compositions according to the present invention
may comprise an additional builder system.
Any conventional builder system is suitable for use
herein including aluminosilicate materials, silicates,
polycarboxylates and fatty acids, materials such as
ethylenediamine tetraacetate, diethylene triamine
pentamethyleneacetate, metal ion 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 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.
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37
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.
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, l,2,3,4,5,6-hexane -hexacar-boxylates
and and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. Aromatic poly-
carboxylates include mellitic acid, pyromellitic acid and
the phthalic acid derivatives disclosed in British Patent
No. 1,425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
A suitable chelant for inclusion in the detergent
compositions in accordance with the invention is
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or
magnesium salt thereof. Examples of such preferred sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such
preferred magnesium salts of EDDS include MgEDDS and
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38
Mg2EDDS. The magnesium salts are the most preferred for
inclusion in compositions in accordance with the invention.
Other builder materials that can form part of the
builder system for use in granular compositions include
inorganic materials such as alkali metal carbonates,
bicarbonates, silicates, and organic materials such as the
organic phosphonates, amino polyalkylene phosphonates and
amino polycarboxylates.
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.
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. The total amount of detergency builder in the
granular composition ranges preferably from 15 to 60 wt~
and most preferably from 10 to 45 wt.%.
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 silicas of various types. These
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39
materials can be incorporated as particulates in which the
suds suppressor is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-
surface-active detergent impermeable carrier. Alternatively
the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of
the other components.
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.
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.
Others
Other components used in detergent compositions may be
employed, such as soil-suspending agents, soil-release
agents, optical brighteners, abrasives, bactericides,
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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 such as described
in GB 1,464,616.
other suitable water soluble encapsulating materials
comprise dextrins derived from ungelatinized starch acid-
e~ters of substituted dicarboxylic acids such as described
in US 3,455,838. These acid-ester dextrins are,preferably,
prepared from such starches as waxy maize, waxy sorghum,
sago, tapioca and potato. Suitable examples of said
encapsulating materials include N-Lok manufactured by
National Starch. The N-Lok encapsulating material consists
of a modified maize starch and glucose. The starch is
modified by adding monofunctional substituted groups such
as octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable
herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric
polycarboxylic acids or their salts. Polymers of this type
include the polyacrylates an~ maleic anhydride-acrylic acid
copolymers previously mentioned as builders, as well as
copolymers of maleic anhydride with ethylene, methylvinyl
ether or methacrylic acid, the maleic anhydride
constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.5% to
10% by weight, more preferably from 0.75% to 8%, most
preferably from 1% to 6% by weight of the composition.
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-
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41
anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate,
disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-
ylamino)stilbene-2:2' - disulphonate, monosodium 4',4'' -
bis-(2,4-dianilino-s-tri-azin-6 ylamino~stilbene-2-
sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-2-
hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'
disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-
2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-
anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl-4''-
(naphtho-1',2':4,5)-1,2,3 - triazole-2''-sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred
brighteners are the specific brighteners of copending
European Patent application No. 95201943.8.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about
4000. These are used at levels of from 0.20~ to 5~ more
preferably from 0.25% to 2.5% by weight. These polymers and
the previously mentioned homo- or co-polymeric
polycarboxylate salts are valuable for improving whiteness
maintenance, fabric ash deposition, and cleaning
performance on clay, proteinaceous and oxidizable soils in
the presence of transition metal impurities.
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
ass~gned US Patent Nos. 4116885 and 4711730 and European
Published Patent Application No. 0 272 033. A particular
preferred polymer in accordance with EP-A-0 272 033 has the
formula
(cH3(pEG)43)o.75(poH)o.25ET-po)2.8(T-pEG)o.4]T(
H)0.2s((pEG)43cH3)o~75
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42
where PEG is -(OC2H4)O-,PO is (OC3H6O) and T is
(pcOC6H4CO).
Also very useful are modified polyesters as random
copolymers of dimethyl terephthalate, dimethyl
sulfoisophthalate, ethylene glycol and 1-2 propane diol,
the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at
both end by sulphobenzoate groups, "primarily", in the
present context most of said copolymers herein will be end-
capped by sulphobenzoate groups. However, some copolymers
will be less than fully capped, and therefore their end
groups may consist of monoester of ethylene glycol and/or
propane 1-2 diol, thereof consist "secondarily" of such
species.
The selected polyesters herein contain about 46% by
weight of dimethyl terephthalic acid, about 16% by weight
of propane -1.2 diol, about 10% by weight ethylene glycol
about 13~ by weight of dimethyl sulfobenzoic acid and about
15~ by weight of sulfoisophthalic acid, and have a
molecular weight of about 3.000. The polyesters and their
method of preparation are described in detail in EPA 311
342.
Is is well known in the art that free chlorine in tap
water rapidly deactivates the enzymes comprised in
detergent compositions. Therefore, using chlorine scavenger
such as perborate, ammonium sulfate, sodium sulphite or
polyethyleneimine at a level above 0.1% by weight of total
composition, in the formulas will provide improved through
the wash stability of the amylase enzymes. Compositions
comprising chlorine scavenger are described in the European
patent application 92870018.6 filed January 31, 1992.
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43
Softening agents
Fabric softening agents can also be incorporated into
laundry detergent compositions in accordance with the
present invention. These agents may be inorganic or organic
in type. Inorganic softening agents are exemplified by the
smectite clays disclosed in GB-A-1 400 898 and in USP
5,019,292. Organic fabric softening agents include the
water insoluble tertiary amines as disclosed in GB-Al 514
276 and EP-BO 011 340 and their combination with mono C12-
C14 quaternary ammonium salts are disclosed in EP-B-O 026
527 and EP-B-O 026 528 and di-long-chain amides as
disclosed in EP-B-0 242 919. Other useful organic
ingredients of fabric softening systems include high
molecular weight polyethylene oxide materials as disclosed
in EP-A-O 299 575 and 0 313 146.
Levels of smectite clay are normally in the range from
2% to 20%, more preferably from 5% to 15% by weight, with
the material being added either spray-dried or as a dry
mixed component. Organic fabric softening agents such as
the water-insoluble tertiary amines or dilong chain amide
materials are incorporated at levels of from 0.5% to 5% by
weight, normally from 1% to 3% by weight whilst the high
molecular weight polyethylene oxide materials and the water
soluble cationic materials are added at levels of from 0.1%
to 2%, normally from 0.15% to 1.5% by weight. These
materials are normally added to the spray dried portion of
the composition, although in some instances it may be more
convenient to add them as a dry mixed particulate, or spray
them as molten liquid on to other solid components of the
composition.
Dye transfer inhibi tion
The detergent composition of the present invention can
also include compounds for inhibiting dye transfer from one
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44
fabric to another of solubilized and suspended dyes
encountered during fabric laundering operations involving
colored fabrics.
Polymeric dye tr~nsfer inhibiting agents
The detergent compositions according to the present
invention also comprise from 0.001~ to 10 %, preferably
from 0.01% to 2~, more preferably from 0.05% to 1% by
weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally
incorporated into detergent compositions in order to
inhibit the transfer of dyes from colored fabrics onto
fabrics washed therewith. These polymers have the ability
to complex or adsorb the fugitive dyes washed out of dyed
fabrics before the dyes have the opportunity to become
attached to other articles in the wash.
Especially suitable polymeric dye transfer inhibiting
agents are polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, 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 :
~I) Ax
I
R
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wherein P is a polymerisable unit, whereto the R-N-O group
can be attached to or wherein the R-N-O group forms
part of the polymerisable unit or a combination of
both.
O O O
Il 11 11
A is NC, CO, C, -O-,-S-, -N- ; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any
combination thereof whereto the nitrogen of the N-O
group can be attached or wherein the nitrogen of
the N-O group is part of these groups.
The N-O group can be represented by the following
general structures :
O O
(Rl)x -N- (R2)y =N- (Rl)x
I
(R3)z
wherein R1, 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 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.
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46
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-0 functional group is part of said R
group.
Examples of 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 alicyclic groups wherein the
nitrogen of the N-0 functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein
R groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine
oxide polymer formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric
backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and
mixtures thereof.
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47
The amine N-oxide polymers of the present invention
typically have a ratio of amine to the amine N-oxide of
10:1 to 1:1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The
polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-
oxide and the other monomer type is either an amine N-oxide
or not. The amine oxide unit of the polyamine N-oxides has
a PKa < 10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree
of polymerisation. The degree of polymerisation is not
critical provided the material has the desired water-
solubility and dye-suspending power.
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-vinylimidazole N-vinylpyrrolidone
copolymers wherein said polymer has an average molecular
weight range from S,000 to 50,000 more preferably from
8,000 to 30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light
scattering as described in Barth H.G. and Mays J.W.
Chemical Analysis Vol 113,"Modern Methods of Polymer
Characterization".
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48
Highly preferred N-vinylimidazole N-vinylpyrrolidone
copolymers have an average molecular weight range from
5,000 to 50,000; more preferably from 8,000 to 30,000; most
preferably from 10,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers
characterized by having said average molecular weight range
provide excellent dye transfer inhibiting properties while
not adversely affecting the cleaning performance of
detergent compositions formulated therewith.
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).
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49
d) Polyvinyloxazolidone :
The detergent compositions of the present invention
may also utilize polyvinyloxazolidone as a polymeric dye
transfer inhibiting agent. Said polyvinyloxazolidones have
an average molecular weight of from about 2,500 to about
400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000.
e) Polyvinylimidazole :
The detergent compositions of the present invention
may also utilize polyvinylimidazole as polymeric dye
transfer inhibiting agent. Said polyvinylimidazoles have an
average
about 2,500 to about 400,000, preferably from about 5,000
to about 200,000, more preferably from about 5,000 to about
50,000, and most preferably from about 5,000 to about
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 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-~imensional structure. In another embodiment, the
cross-linked polymers entrap the dyes by swelling.
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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 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 laundering solution in the usual manner and
exemplified hereunder.
The process of the invention is conveniently carried
out in the course of the cleaning process. The method of
cleaning is preferably carried out at 5 ~C to 95 ~C,
especially between 10~C and 60~C. The pH of the treatment
solution is preferably from 7 to 11. Typically, the
following dosing quantities under european and american
washing conditions are respectively : 4-10 g and 1-2 g of
the detergent composition per litre.
A preferred machine dishwashing method comprises
treating soiled 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 g of product dissolved or dispersed in a
wash volume from 3-10 litres.
According to a manual dishwashing method, soiled dishes are
contacted with an effective amount of the diswashing
composition, typically from 0.5-20g (per 25 dishes being
treated). Preferred manual dishwashing methods include the
application of a concentrated solution to the surfaces of
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51
the dishes or the soaking in large volume of dilute
solution of the detergent 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 level of the
enzymes other than the specific lipolytic enzyme of the
present invention, are expressed in pure enzyme by weight
of total composition and the abbreviated component
identifications have the following meanings :
LAS : Sodium linear C12 alkyl benzene
sulphonate
TAS : Sodium tallow alkyl sulphate
XYAS : Sodium C1x ~ C1y alkyl sulfate
SAS : C12-C14 secondary (2,3) alkyl sulfate
in the form of the sodium salt.
AEC : Alkyl ethoxycarboxylate surfactant of
formula C12 ethoxy (2) carboxylate.
SS : Secondary soap surfactant of formula
2-bytyl octanoic acid
25EY : A C12_Cls predominantly linear
primary alcohol condensed with an
average of Y moles of ethylene oxide
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52
45EY : A C14 - C1s predominantly linear
primary alcohol condensed with an
average of Y moles of ethylene oxide
XYEZS : C1x ~ C1y sodium alkyl sulfate
condensed with an average of Z moles
of ethylene oxide per mole
Nonionic : C13-C15 mixed
ethoxylated/propoxylated fatty
alcohol with an average degree of
ethoxylation of 3.8 and an average
degree of propoxylation of 4.5 sold
under the tradename Plurafac LF404 by
BASF Gmbh
CFAA : C12-C14 alkyl N-methyl glucamide
TFAA : C16-C1g alkyl N-methyl glucamide.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O
ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of
formula ~-Na2Si2Os
Carbonate : Anhydrous sodium carbonate
Metasilicate : Sodium metasilicate (SiO2:Na2O ratio =
2.0)
Phosphate or STPP : Sodium tripolyphosphate
~A/AA : Copolymer of 1:4 maleic/acrylic acid,
average molecular weight about 80,000
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PA3~ : 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
4 8 0N ~ n ~ om 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 Nal2~Alo2sio2)12- 27H20
having a primary particle size in the
range from 1 to 10 micrometers.
Zeolite MAP : Alkali metal alumino-silicate of the
zeolite P type having a silicon to
aluminium ratio not greater than 1.33
according to the present invention.
Citrate : Tri-sodium citrate dihydrate.
Citric : Citric Acid
Perborate : Anhydrous sodium perborate
monohydrate bleach, empirical formula
NaB02 ~ H2~2
PB4 Anhydrous sodium perborate
tetrahydrate.
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Percarbonate : Anhydrous sodium percarbonate bleach
of empirical for~ula 2Na2C03.3H202
TAED : Tetraacetyl ethylene dlamine.
NOBS : Nonanoyloxybenzene-sulfonate.
NACA-OBS : Phenolsulfonate ester of N-nonanoyl-
6-aminocaproic acid.
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 by Gist-
Brocades or Optipulp or Xylanase by
Solvay.
Protease : Proteolytic enzyme sold under the
tradename Savinase, Alcalase, Durazym
by Novo Nordisk A/S, Maxacal, Maxapem
sold by Gist-Brocades and proteases
described in patents WO91/06637
and/or W095/10591 and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the
tradename Purafact Ox AmR described
in WO 94/18314, sold by Genencor;
Termamyl~, Fungamyl~ and Duramyl~, all
available from Novo Nordisk A/S and
those described in W095/26397.
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Specific Lipolytic : Lipolytic enzyme sold under the
enzyme tradename Lipolase Ultra by Novo
Nordisk A/S.
Peroxidase : Peroxidase enzyme.
Cellulase : Cellulosic enzyme sold under the
tradename Carezyme or Celluzyme by
Novo Nordisk A/S.
CMC : Sodium carboxymethyl cellulose
HEDP : 1,1-hydroxyethane diphosphonic acid
DETPMP Diethylene triamine penta (methylene
phosphonic acid), marketed by
Monsanto under the Trade name Dequest
20~0.
PAAC pentaamine acetate cobalt ~III) sal.
BzP Benzoyl peroxide.
PVP Polyvinyl pyrrolidone polymer.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
SRP : Sulfonated poly-e~hoxy/propoxy end
capped ester oligomer and/or short
block polymer synthetised from
Dimethyl-terephtalate, 1,2 propylene
Glycol, methyl capped PEG or
sulfoethoxylate.
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LSD : C16-Clg dimethyl amine oxide, C12-Clg
alkyl ethoxysulfates etoxylation
degree 1-5, and the C13-C15
ethoxylated alcohols 12 or 30, sold
under the trade names Lutensol A012
and Lutensol A030 respectively, by
BASF GmbH.
EDDS : Ethylenediamine -N, N'- disuccinic
acid, [S,S] isomer in the form of the
sodium salt.
Granular Suds : 12% Silicone/silica, 18~ stearyl
Suppressor alcohol,70% 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 298
TAE 25 : Tallow alcohol ethoxylate (25)
PEG~-6) : Polyethylene glycol ~having a
molecular weight of 600).
BTA : Benzotriazole
Bismuth nitrate : Bismuth nitrate salt
NaDCC : Sodium dichloroisocyanurate
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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:
I II III IV 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 MAP 8.2 8.2 8.2 8.2 8.2
DETPMP 0.4 0.4 0.4 0.4 0.4
Sodium sulfate 5.5 5.5 5.5 5.5 5.5
Amylase 0.005 0.02 0.01 0.01 0.02
Protease 0.01 0.02 0.01 0.005 -
Pectinase 0.02 - - - -
Xylanase - - 0.01 0.02
Specific lipolytic enzyme 0.005 0.01 0.002 0.005 0.003
Cellulase 0.001 - - 0.001 -
Water & minors Up to 100
Example 2
Granular fabric cleaning compositions in accord with
the invention were prepared as follows:
I II III IV V
LAS 12.0 12.0 12.0 12.0 12.0
Zeolite MAP 26.0 26.0 26.0 26.0 26.0
SS 4.0 4.0 4.0 4.0 4.0
SAS 5.0 5.0 5.0 5.0 5.0
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Citrate 5.0 5.0 5.0 5.0 5.0
Sodium Sulfate 17.0 17.0 17.0 28.017.0
Perborate 16.0 16.0 16.0 - 16.0
TAED 5,0 - - - 5 o
NOBS - 3.0
NACA-OBS - - 4.0 - 2. 5
Protease 0.06 0.03 0.02 0. 08
Specific lipolytic 0.004 0. 005 0.008 0.10 0. 002
enzyme
Amylase 0.01 0. 015 0.01 0. 02 0. 005
Water ~ minors Up to 100%
Example 3
Granular fabric cleaning compositions in accord with
the invention which are especially useful in the laundering
of coloured fabrics were prepared as follows :
I II III
LAS 11.4 10.7
TAS 1.8 2.4
TFAA - - 4 0
45AS 3.0 3.1 10.0
45E7 4.0 4.0
25E3S ~ ~ 3.0
68E11 1.8 1.8
25E5 - - 8.0
Citrate 14.0 15.0 7.0
Carbonate - - 10
Citric 3.0 2.5 3.0
Zeolite MAP 32.5 32.1 25.0
Na-SKS-6 - - g,o
MA/AA 5.0 5.0 5.0
DETPMP 1.0 0.2 0.8
Protease 0.02 0.02 0.01
Specific lipolytic enzyme 0.002 0.008 0.002
Amylase 0.01
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Silicate 2.0 2.5
Sulphate 3.5 5.2 3.0
PVP 0.3 0.5
Poly (4-vinylpyridine)-N- - - 0.2
oxide/copolymer of vinyl-
imidazole and vinyl-
pyrrolidone
Perborate 0.5 1.0
Peroxidase 0.01 0.01
Phenol sulfonate 0.1 0.2
Water/Minors Up to 100%
Example 4
Granular fabric cleaning compositions in accord with
the invention were prepared as follows:
I II III IV
LAS 6.5 8.0 9.0 8.0
25AE3S - - 1.0 1.0
AS 15.0 18.0 7.5 7.0
23E6.5 - - 2.0 3.0
Zeolite MAP 26.0 22.0 24.0 28.0
Sodium nitriloacetate 5.0 5.0
PVP 0.5 0.7 _ _
NOBS ~ ~ 3-0
DTPA ~ ~ 0-3
Perborate 0.5 1.0 2.0 1.0
Boric acid 4.0 - - -
Phenol sulfonate 0.1 0.2
PEG - - 1.0 1.0
Polyacrylate - - 3.0 3.0
Protease 0.06 0.02 0.02 0.01
Silicate 5.0 5.0 1.0 1.0
Carbonate 15.0 15.0 15.0 30.0
Peroxidase 0.1 0.1
Pectinase 0.02
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Cellulase 0.005 0.002 0.0005 0.002
Specific lipolytic enzyme0.0010.0005 0.001 0.001
Amylase 0.01 0.01 0.01
SRP - - 0.2 0.2
Sulfate - - 19.5 6.5
Water/minors Up to 100
Example 5
A compact granular fabric cleaning composition in
accord with the invention was prepared as follows:
I II
LAS 0.0 8.0
TAS 0.0 2.0
45AS 8.0 0.0
25E3S 2.0 0.5
25E5 3 0 5 0
25E3 3.0
TFAA 2.5 0.0
Coco-alkyl-dimethyl hydroxy- 0.0 1.0
ethyl ammonium chloride
Zeolite MAP 17.0 15.0
NaSKS-6 12.0 10.0
Citric acid 3.0 2.0
Carbonate 7.0 8.0
MA/AA 5.0 1.0
CMC 0.4 0.4
Poly (4-vinylpyridine)-N-oxide/ 0.2 0.0
copolymer of vinylimidazole and
vinylpyrrolidone
Protease 0.05 0.03
Specific lipolytic enzyme 0.002 0.004
Cellulase 0.001 0.001
Amylase 0.01 0.006
TAED 6.0 3.0
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Percarbonate 22.0 20.0
NACA-OBS 0.0 3.0
EDDS 0.3 0.2
Granular suds suppressor 3.5 3,0
water/minors/sulfate Up to 100%
Example 6
A granular fabric cleaning compositions in accord with
the invention which provide "softening through the wash"
capability were prepared as follows:
I II
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 - 10.0
Zeolite MAP 15.0 12.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
Perborate 15.0
Percarbonate - 14.0
TAED 5.0 5.0
NACA-OBS - 2.0
Smectite clay 10.0 10.0
HMWPEO - O.1
Protease 0.02 0.01
Specific lipolytic enzyme0.0005 0.01
Amylase 0.03 0.005
Cellulase 0.001
Silicate 3.0 5.0
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Carbonate10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors/sulfate Up to 100%
Example 7
Heavy duty liquid fabric cleaning compositions
suitable for use in the pretreatment of stained fabrics,
and for use in a machine laundering method, in accord with
the invention were prepared as follows:
I II III IV V
24AS 20.0 20.0 20.0 20.0 20.0
SS 5.0 5.0 5.0 5.0 5.0
Citrate 1.0 1.0 1.0 1.0 1.0
Zeolite MAP 10.0 10.0 10.0 15.0 15.0
12E3 13.0 13.0 13.0 13.0 13.0
Monoethanolamine 2.5 2.5 2.5 2.5 2.5
Protease 0.005 0.03 0.02 0.04 0.01
Specific lipolytic 0.008 0.01 0.007 0.0005 0.004
enzyme
Amylase 0.005 0.005 0.001 0.01 0.004
Cellulase 0.04 - 0.01
Pectinase 0.02 0.02
Water/propylene glycol/ethanol (100:1:1)
Example 8
Heavy duty liquid fabric cleaning compositions in
accord with the invention were prepared as follows:
I II III IV
LAS acid form - - 25.0
C12_14 alkenyl succinic 3.0 8.0 10.0
acid
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Citric acid 10.0 10.0 2.0 2.0
25AS acid form 8.0 8.0 - 10.0
25AE3S acid form - 3.0 - 4.0
25AE7 - 8.0 - 6.0
25AE3 8.0 - 4.0
CFAA - - 4.0 6.0
DETPMP 0.2 - 1.0 1.0
Fatty acid - - - 15.0
Oleic acid 1.8 - 1.0
Ethanol 4.0 4.0 6.0 2.0
Propanediol 2.0 2.0 6.010.0
Zeolite MAP 10.0 15.0 10.015.0
Protease 0.02 0.02 0.020.01
Specific Lipolytic enzyme 0.005 0.010.005 0.01
Coco-alkyl dimethyl - - 3.0
hydroxy ethyl ammonium
chloride
Smectite clay - - 5.0
SRP - - 0.2 0.1
PVP 1.0 2.0
Perborate - 1.0
Phenol sulphonate - 0.2
Peroxidase - 0.01
NaOH Up to pH 7.5
Waters/minors Up to 100%
Example 9
Heavy duty liquid fabric cleaning compositions in
accord with the invention were prepared as follows:
I II III
Mono ethanol amine 1.0 1.1 0.7
C12HLAS - - 9.6
C25AE2.5S 19.019.0 13.8
Propane diol 6.2 6.3 4.9
23E9 2.0 2.0 2.2
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Sodium toluene sulfonate 2.5 2.8 1.5
NaOH 3.4 3.1 6.6
Polyhydroxy fatty acid 3.5 3.5
amide
Citric acid 3.0 3.0 7.1
Fatty acid 2.0 2.0
Specific lipolytic enzyme 0.004 0.01 0.01
Zeolite MAP 5.0 5.0 5.0
Borax 2.5 2.5 2.2
Ethanol 3.4 3.4 1.9
SRP 0.2 0.1 0.3
E15-18 ethoxylated 1.2 1.3 1.2
tetraethylene pentaimine
Glycerine - - 3.0
Water & Minors Up to 100%
Example 10
Bleach-containing non-aqueous fabric cleaning
composition in accord with the invention was prepared as
follows:
C12-15 alkyl ether (EO=3) sulfate Na Salt 14.0
CFAA 8.0
C12-14, Eo=5 alcohol ethoxylate 14.0
N-butoxy propoxy propanol 20.0
Perfume ~~7
Zeolite MAP 10.0
Topped palm kernel fatty acid Na salt 5.7
Trisodium citrate 1.9
Sodium percarbonate 9.4
Sodium carbonate 7.5
Sodium hydroxyethyl diphosphonate Na salt 1.7
[4-[N-nonanoyl-6-aminohexanoyloxy]benzene 4.7
sulfonate]2 Ca salt
Brightener 0.2
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Silicone oil DB-10 0 5
Specific lipolytic enzyme 0.005
Amylase 0 05
Protease 0.01
Cellulase 0.001
Minors Up to 100
Example 11
The following rinse added fabric softener composition,
in accord with the invention, was prepared (parts by
weight).
Softener active 24.5
PGMS 1.5
Alkyl sulfate 3.5
TAE 25 1.5
Specific lipolytic enzyme 0.001
Cellulase 0.001
Zeolite MAP 6.0
HCL 0.12
Antifoam agent 0.019
Blue dye 8Oppm
CaCl2 0.35
Perfume 0.90
Example 12
Syndet bar fabric cleaning compositions in accord with
the invention were prepared as follows:
I II IIIIV
C12-16 alkyl sulfate, Na 10.0 10.0 10.0 10.0
CFAA 5.0 5 0 5 0 5 o
C11-13 alkyl benzene 10.0 10.0 10.0 10.0
sulphonate, Na
Sodium carbonate 25.025.0 25.0 25.0
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Sodium pyrophosphate 7.0 7.0 7.0 7 0
Sodium tripolyphosphate 7.0 7.0 7.0 7.o
Zeolite MAP 5 0 5.0 5 0 5 0
Carboxymethylcellulose 0.2 0.2 0.2 0.2
Polyacrylate tMW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Specific lipolytic enzyme0.01 0.01 0.005 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
MgSO4 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 13
The following compact high density (0.96Kg/l)
dishwashing detergent compositions I to VI were prepared in
accord with the invention:
I II III IV V VI
STPP - - 18.0 15.0 - -
Zeolite MAP 15.0 12.0 25.0 20.0 12.0 20.0
Citrate 16.0 12.0 - - 12.0 15.0
Carbonate - 10.0 - 20.00 10.0 15.0
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
Alkyl sulfate 3.00 3.00 3.00 3.00 3.00 3.00
Nonionic 1.50 2.00 1.50 1.50 2.00 2.60
TAED 4.78 - 2.39 - 2.0 4.00
NOBS - 4.00 - - - 4 o
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NACA-OBS - - 2.50 - - -
HEDP 0.83 1.00 0.46 - 0.83
DETPMP 0. 6 5 0. 65 - - - -
PAAC - - - 0.20
BzP ~ ~ ~ 4-44
Paraffin 0. 50 0.50 O.S0 0. 50 - 0.20
Protease 0. 075 0.05 0.10 0.10 0.08 0.01
Specific 0.0005 0.001 0.0010.005 0.0004 0.001
lipolytic enzyme
Amylase 0.01 0.005 0.0150.015 0.005 0.0025
BTA 0.30 0 30 0 30 0 30
Bismuth Nitrate - 0.30
PA30 4.02
Terpolymer - - - 4,00 _ _
480N - 6.00 2.77 - 6.67
LSD - - 2.5 - - 10.0
Sulphate 5.0 17.0 3.0 - 23.0 1.00
pH (1~ solution)10.80 11.00 10.9010.80 10.90 9.60
Water and minors Up to 100%
Example 14
The following granular dishwashing detergent
compositions examples I to IV of bulk density 1.02Kg/L were
prepared in accord with the invention:
I II III IV V VI
STPP 23.0 20.0 30.0027.0 18.0 22.0
Zeolite MAP 10.0 15.0 10.0 15.0 20.0 8.0
Carbonate 30. 50 25.5 20.0 15.0 15.0 2.80
Silicate 7.40 7.40 7.40 12.00 8.00 14.0
Perborate 4.40 4.40 4.40 - 4.40
NaDCC - - - 2.00 - 1.50
Alkyl sulfate 1.0 1.0 1.0 2.0 2.0 1.5
Nonionic 0.75 0.75 0.75 1.90 1.20 0.50
TAED 1.00 1.00 - - 1.00
PAAC -- -- ~~~04
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BzP - 1.40 - - - -
Paraffin 0. 25 0.25 0.25
Protease 0.05 0.05 0.05 - 0.1
Specific 0. 005 0.001 0.001 0.0005 0.0008 0.001
lipolytic enzyme
Amylase 0.003 0.001 0.01 0 .02 0.01 0.015
BTA 0.15 - 0.15
LSD - - - 5.0 - 10.0
Sulphate 18.0 18.0 20.0 21.0 12.0
pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30
Water and minors Up to 100%
Example 15
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:
II III
STPP - 30.0 24.0
Zeolite MAP 12.0 20.0 16.0
Citrate 20.0
Carbonate - 5.00
Silicate 20.0 12.0 20.0
Protease 0. 03 0. 075 0.01
Specific lipolytic enzyme 0.005 0.001 0.0005
Amylase 0.01 0.005 0.001
Perborate 1.56 7.79
PB4 6.92 - 11.40
Alkyl sulfate 2.00 3.00 2.00
Nonionic 1.20 2.00 1.10
TAED 4.33 2.39 0.80
HEDP O . 67
DETPMP O . 65
Paraffin 0.42 0.50
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BTA 0.24 0.30
PA30 3.2 - -
LSD 10.0
Sulphate 10.0 10. 5 3.20
pH (1% solution) 10.60 10.60 11.00
Water and minors Up to 100%
Example 16
The following liquid dishwashing detergent
compositions in accord with the present invention I to II,
of density 1.40Kg/L were prepared:
I II
STPP 25.0 20.00
Zeolite MAP 10.0 6.0
Car~onate 2.70 2.00
Silicate - 4.40
NaDCC 1.10 1.15
Alkyl sulfate 3.00 1. 50
Nonionic 2.50 1.00
Paraffin 2.20
Protease 0. 03 0. 02
Specific Lipolytic Enzyme 0.005 0.0025
480N 0.50 4.00
KOH - 6.00
LSD 2.0
Sulphate 1.60
pH ~1% solution) 9.10 10.00
Water and minors Up to 100%
Example 17
The following liquid hard surface cleaning
compositions were prepared in accord with the present
invention :
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II III IV V VI
Specific lipolytic 0.01 0.002 0.0050.02 0.001 0.005
enzyme
Protease 0.05 0.01 0.02 0.03 0.005 0.005
Zeolite MAP 10.0 10.0 5.0 5.0 5.0 5.0
EDTA* - - 2.90 2.90
Na Citrate - - - - 2.90 2.90
NaC12 Alkyl 1.95 - 1.95 - 1.95
benzene sulfonate
NiEO9 1.50 2.00 1.50 2.00 1.50 2.00
NaC12 Alkyl - 2.20 - 2.20 - 2.20
sulfate
NaC12(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 and minors Balance to 100%
*Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
***All formulas adjusted to pH 7
Example 18
The following spray composition for cleaning of hard
surfaces and removing household mildew was prepared in
accord with the present invention:
Amylase 0.01
Specific lipolytic enzyme 0.01
Protease 0.01
Zeolite MAP 10.0
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
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NiEO9 2.00
Sodium hydroxide 0.80
Silicate ~Na) 0.04
Perfume 0.35
Water/minors up to 100
