Note: Descriptions are shown in the official language in which they were submitted.
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. CLEANING COMPOSITIONS COMPRISING A
MYCODEXTRANASE
TECFiNTCAL FIELD
The present invention relates to cleaning compositions
including dishwashing, hard surface cleaning, toilet bowl
cleaning and laundry compositions containing a
mycodextranase enzyme.
BACKGROUND
The overall performance of cleaning compositions for use
in washing or cleaning such as dishwashing, hard surface
cleaning, toilet bowl cleaning and laundry, is judged by a
number of factors, including the ability.to remove soils and
the ability to prevent redeposition of the soils or the
breakdown product of the soils on the articles being washed.
Food soils are often difficult to remove effectively
from a soiled substrate. Highly colored soil derived from
foods and/or beverages for example, tea or coffee, are
particularly challenging to remove. Also body soils,
especially menstrual fluids are difficult to remove
completely and often build up on fabric, which leads to
yellowing. The substrates, for example, can be dishes, hard
surfaces, toilet bowls or fabrics.
Enzymes have been added to cleaning compositions as a
performance additive to improve cleaning performance.
Enzymes can be included in the present cleaning compositions
for a variety of purposes, including removal of
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carbohydrate-based stains from surfaces such as textiles,
for the prevention of refugee dye transfer in laundering,
and for fabric restoration.
It has now been found that cleaning compositions
comprising a mycodextranase enzyme improves specific or
broad stain removal, boosts overall cleaning performance and
provides sanitization for surfaces treated with the cleaning
compositions of the present invention.
SUI~IARY
The present invention relates to cleaning compositions
comprising a mycodextranase enzyme. In further embodiments,
the present invention further relates to cleaning
compositions comprising a mycodextranase enzyme in
combination with selected detergent ingredients such as
other enzymes, surfactants, bleaching agents and the like.
Such compositions satisfy the need for a cleaning
composition which provide improved specific or broad stain
removal, enhanced overall cleaning performance and
sanitization.
DETAILED DESCRIPTION
An essential component of the cleaning compositions of
the present invention is a mycodextranase enzyme.
This mycodextranase enzyme is incorporated into cleaning
compositions in accordance with the present invention at a
level of from about 0.00001% to about 1%, preferably from
about 0.0001o to about 0.5%, as a pure enzyme by weight of
composition.
Mycodextranase enzyme, which is 1,3- 1,4-alpha-D-Glucan
4-glucanohydrolase, is any enzyme which hydrolyzes 1,4-
alpha-D-glucosidic linkages in alpha-D-glucans containing
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both 1,3- and 1,4- bonds. For example, mycodextranase
enzyme hydrolyzes alpha-D-glucans into nigerose and 4-alpha-
D-nigerosylglucose. Mycodextranase enzyme does not
hydrolyze alpha-D-glucans containing only 1,3- or 1,4-
bonds. Also mycodextranase enzyme have no hydrolyzation on
the following glucans: alpha-1,4-(amlose), alpha-1,6-
(dextran); beta-1,2-; beta-1,3-(laminarin); beta-1,4-
(cellulose), beta-1,6-(pustulan). Mycodextranase enzyme is
described in the following publications which are hereby
incorporated by reference: E.T. Reese and M. Mandels,
Canadian Journal of Microbiology, volume l0, pages 103-114
(1964); K.K. Tung, J. Biol. Chem., volume 246, number 22,
pages 6722-673S (1971).
Mycodextranase enzyme can be derived from fungal origin
e.g. Penicillium species or can be expressed in any other
suitable host organism via cloning techniques known in the
art . This mycodextranase enzyme can be produced by the so
called wild-type organism or by any host organism in which
the gene responsible fox the production of the
mycodextranase enzyme, has been cloned and expressed.
Nowadays, it is common practice to modify wild-type
enzymes via protein / genetic engineering techniques in
order to optimize their performance efficiency in the
cleaning compositions of the invention. For example, the
variants may be designed such that the compatibility of the
enzyme to commonly encountered ingredients of such
compositions is increased. Alternatively, the variant may
be designed such that the optimal pH, bleach stability,
catalytic activity and the like, of the enzyme variant is
tailored to suit the particular cleaning application.
In particular, attention should be focused on amino
acids sensitive to oxidation in the case of bleach stability
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and on surface charges for the surfactant compatibility.
The isoelectric point of such enzymes may be modified by the
substitution of some charged amino acids, e.g, an increase
in isoelectric point may help to improve compatibility with
anionic surfactants. The stability of the enzymes may be
further enhanced by the creation of e.g. additional salt
bridges and enforcing calcium binding sites to increase
chelant stability. Special care must be paid to the
cellulases as most of the cellulases have separate binding
domains(CBD). Properties of such enzymes can be altered by
modifications in these domains.
One preferred type of mycodextranase enzyme is a
carbohydrase from the following EC category . EC 3.2.1.61,
which are commercially available by Sigma Chemicals. One DU
unit liberates 1 micro mole of reducing sugar (measured as
glucose) from nigeran per minute at pH 4.5 at 37~C.
Detergent components
The cleaning 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 hand and machine dishwashing compositions,
hand and machine laundry detergent compositions including
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laundry additive compositions and compositions suitable for
use in the soaking and/or pretreatment of stained fabrics,
rinse added fabric softener compositions, and compositions
for use in general household hard surface cleaning
5 operations. Compositions containing such mycodextranase
enzyme can also be formulated as sanitisation products,
contact lenses cleaner and health and beauty care products
such as oral/dental care and personal cleaning compositions.
Such compositions containing mycodextranase enzyme can
provide fabric cleaning, stain removal, whiteness
maintenance, softening, color appearance and dye transfer
inhibition when formulated as laundry detergent
compositions.
When formulated as compositions for use in manual
dishwashing methods the compositions of the invention
preferably contain a surfactant and preferably other
detergent compounds selected from organic polymeric
compounds, suds enhancing agents, group 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 suppressers,
dispersants, lime-soap dispersants, soil suspension and
anti-redeposition agents and corrosion inhibitors. Laundry
compositions can also contain softening agents, as
additional detergent components.
The compositions of the invention can also be used as
detergent additive products. Such additive products are
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intended to supplement or boost the performance of
conventional detergent compositions.
If the composition is a granule, the density of the
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 compositions herein is best
reflected by density and, in terms of composition, by the
amount of inorganic filler salt. Inorganic filler salts are
conventional ingredients of detergent compositions in powder
form. In conventional detergent compositions, the filler
salts are present in substantial amounts, typically 17-35%
by weight of the total composition.
In the compact compositions, the filler salt is present
in amounts not exceeding 150 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 sulfates and chlorides.
A preferred filler salt is sodium sulfate.
Liquid detergent compositions according to the present
invention can also be in a "concentrated form", in such
case, the liquid detergent compositions according to 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 400, more preferably less
than 30%, most preferably less than 20% by weight of the
detergent composition.
Surfactant system
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The cleaning compositions according to the present
invention comprise a surfactant system wherein the
surfactant can be selected from nonionic and/or anionic
and/or cationic and/or ampholytic and/or zwitterionic and/or
semi-polar surfactants.
The surfactant is typically present at a level of from
O.lo to 60% by weight. More preferred levels of
incorporation are to to 35% by weight, most preferably from
1% to 30o by weight of the cleaning composition in accord
with the invention.
The surfactant is preferably formulated to be compatible
with the mycodextranase enzyme present in the composition.
In liquid or gel compositions the surfactant is most
preferably formulated such that it promotes, or at least
does not degrade, the stability of the mycodextranase
enzyme, as well as other optional enzymes, in these
compositions.
Preferred surfactant systems to be used according to the
present invention comprise one or more of the nonionic
and/or anionic surfactants described herein.
Polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use as the
nonionic surfactant of the surfactant systems of the present
invention, with the polyethylene oxide condensates being
preferred. These compounds include the condensation products
of alkyl phenols having an alkyl group containing from about
6 to about 14 carbon atoms, preferably from about 8 to about
14 carbon atoms, in either a straight-chain or branched-
" chain configuration with the alkylene oxide. In a preferred
embodiment, the ethylene oxide is present in an amount equal
to from about 2 to about 25 moles, more preferably from
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about 3 to about 15 moles, of ethylene oxide per mole of
alkyl phenol. Commercially available nonionic surfactants of
this type include IgepalTM CO-630, marketed by the GAF
Corporation; and TritonTM X-45, X-l14, 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 ethylene oxide
per mole of alcohol. About 2 to about 7 moles of ethylene
oxide and most preferably from 2 to 5 moles of ethylene
oxide per mole of alcohol are present in said condensation
products. Examples of commercially available nonionic
surfactants of this type include TergitolTM 15-S-9 (the
condensation product of C11-C15 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 distribution), both
marketed by Union Carbide Corporation; NeodolTM 45-9 (the
condensation product of C14-C15 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-C15 linear
alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the
condensation product of C14-C15 linear alcohol with 5 moles
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of ethylene oxide) marketed by Shell Chemical Company,
KyroTM EOB (the condensation product of C13-C15 alcohol with
9 moles ethylene oxide), marketed by The Procter & Gamble
Company, and Genapol LA 030 or 050 (the condensation product
of C12-C14 alcohol with 3 or 5 moles of ethylene oxide)
marketed by Hoechst. Preferred range of HLB in these
products is from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the surfactant
systems of the present invention are the
alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably
from about 10 to about 16 carbon atoms and a polysaccharide,
e.g. a polyglycoside, hydrophilic group containing from
about 1.3 to about 10, preferably from about 1.3 to about 3,
most preferably from about 1.3 to about 2.7 saccharide
units. Any reducing saccharide containing 5 or 6 carbon
atoms can be used, e.g., glucose, galactose and galactosyl
moieties can be substituted for .the glucosyl moieties
(optionally the hydrophobic group is attached at the 2-, 3-,
4-, etc. positions thus giving a glucose or galactose as
opposed to a glucoside or galactoside). The intersaccharide
bonds can be, e.g., between the one position of the
additional saccharide units and the 2-, 3-, 4-, and/or 6-
positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R20 (CnH2n0) t (glycosyl) x
wherein R2 is selected from the group consisting of alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures
thereof in which the alkyl groups contain from about 10 to
about 18, preferably from about 12 to about 14, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
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preferably 0; and x is from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived
from glucose. To prepare these compounds, the alcohol or
5 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,
10 preferably predominately the 2-position.
The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol are also suitable for use as the
additional nonionic surfactant systems of the present
invention. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1S00 to
about 1S00 and will exhibit water insolubility. The addition
of polyoxyethylene moieties to this hydrophobic portion
tends to increase the water solubility of the molecule as a
whole, and the liquid character of the product is retained
up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product, which
corresponds to condensation with up to about 40 moles of
ethylene oxide. Examples of compounds of this type include
certain of the commercially-available PlurafacTM LF404 and
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
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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 80a 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 C8-C14 alkyl
phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-
Clg alcohol ethoxylates (preferably C10 avg.) having from 2
to 10 ethoxy groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy
fatty acid amide surfactants of the formula.
R2 - C - N - Z,
0 R1
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is C5-31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C11-15
alkyl or C16-18 alkyl or alkenyl chain such as coconut alkyl
or mixtures thereof, and Z is derived from a reducing sugar
such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
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Suitable anionic surfactants to be used are linear alkyl
benzene sulfonate, alkyl ester sulfonate surfactants
including linear esters of Cg-C20 carboxylic acids (i.e.,
fatty acids) which are sulfonated with gaseous S03 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 .
O
R3 - CH - C - OR4
S03M
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 Clp-C16 alkyl, and
R4 is methyl, ethyl or isopropyl. Especially preferred are
the methyl ester sulfonates wherein R3 is Clp-C16 alkyl.
Other suitable anionic surfactants include the alkyl
sulfate surfactants which are water soluble salts or acids
of the formula ROS03M wherein R preferably is a C10-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a
C10-C20 alkyl component, more preferably a C12-Clg alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
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ration (e.g. sodium, potassium, lithium), or ammonium or
substituted ammonium (e. g. methyl-, dimethyl-, and trimethyl
ammonium rations and quaternary ammonium rations such as
tetramethyl-ammonium and dimethyl piperdinium rations and
quaternary ammonium rations 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 C16-18 alkyl chains are preferred for higher wash
temperatures (e. g. above about 50~C).
Other anionic surfactants useful for detersive purposes
can also be included in the cleaning 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, C8-C22 primary of secondary alkanesulfonates, C8-
C24 olefinsulfonates, sulfonated polycarboxylic acids
prepared by sulfonation of the pyrolyzed product of alkaline
earth metal citrates, e.g., as described in British patent
specification No. 1,082,179, Cg-C24
alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene oxide); alkyl glycerol sulfonates, fatty aryl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl
phenol ethylene oxide ether sulfates, paraffin sulfonates,
alkyl phosphates, isethionates such as the aryl
isethionates, N-aryl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated C12-Clg monoesters) and diesters
of sulfosuccinates (especially saturated and unsaturated C6-
012 diesters), aryl 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
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RO (CH2CH20) k-0H2000-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).
When included therein, the laundry detergent
compositions of the present invention typically comprise
from about 1% to about 400, preferably from about 3o to
about 20o by weight of such anionic surfactants.
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted C10-C24 alkyl or hydroxyalkyl group having a
C10-024 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-Clg 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
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piperdinium cations and those derived from alkylamines such
as ethylamine, diethylamine, triethylamine, mixtures
thereof, and the like. Exemplary surfactants are C12-C18
alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)M), C12-C18
5 alkyl polyethoxylate (2.25) sulfate (C12-C18E(2.25)M), C12-
Clg alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M), and
C12-Clg alkyl polyethoxylate (4.0) sulfate (C12-C18E(4.0)M),
wherein M is conveniently selected from sodium and
potassium.
The cleaning compositions of the present invention may
also contain cationic, ampholytic, zwitterionic, and semi-
polar surfactants, as well as the nonionic and/or anionic
surfactants other than those already described herein.
Cationic detersive surfactants suitable for use in the
cleaning 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 .
LR2 (OR3 ) y] [R4 (OR3 ) y] 2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each R3
is selected from the group consisting of -CH2CH2-, -
CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of
C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures
formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer
having a molecular weight less than about 1000, and hydrogen
when y is not 0; R5 is the same as R4 or is an alkyl chain
wherein the total number of carbon atoms of R2 plus R5 is
not more than about 18; each y is from 0 to about 10 and the
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sum of the y values is from 0 to about 15; and X is any
compatible anion.
Quaternary ammonium surfactant suitable for the present
invention has the formula (I):
RZ ~ 3~~~~~~R4
R O+ N',
~~O ~Rs
X-
Formula I
whereby R1 is a short chainlength alkyl (C6-C10? or
alkylamidoalkyl of the formula (II) .
Cs C.~ N
~CH~
O
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,
whereby R3, R4 and R5 are either the same or different and
can be either a short chain alkyl (C1-C3? or alkoxylated
alkyl of the formula III,
whereby X- is a counterion, preferably a halide, e.g.
chloride or methylsulfate.
Rs
~H
O'~z
Formula III
R6 is C1-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as defined
in formula I whereby
R1 is Cg, C10 or mixtures thereof, x=o,
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R3, R4 - CH3 and R5 = CH2CH20H.
Highly preferred cationic surfactants are the water-
soluble quaternary ammonium compounds useful in the present
composition having the formula .
R1R2R3R4N+X- (i)
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is
independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and
-(C2H40)xH where x has a value from 2 to 5, and X is an
anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C15
particularly where the alkyl group is a mixture of chain
lengths derived from coconut or palm kernel fat or is
derived synthetically by olefin build up or OXO alcohols
synthesis. Preferred groups for R283 and R4 are methyl and
hydroxyethyl groups and the anion X may be selected from
halide, methosulfate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are .
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or
bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or
bromide;
myristyl trimethyl ammonium methyl sulfate;
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).
II
0
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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.
Typical cationic fabric softening components include the
water-insoluble quaternary-ammonium fabric softening
actives, the most commonly used having been di-long alkyl
chain ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the
following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dehydrogenated tallow dimethylammonium chloride;
3) dehydrogenated tallow dimethylammonium
methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium
chloride;
11) C12-18 alkyl dihydroxyethyl methylammonium
chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride
(DSOEDMAC);
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium
methylsulfate.
Biodegradable quaternary ammonium compounds have been
presented as alternatives to the traditionally used di-long
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19
alkyl chain ammonium chlorides and methyl sulfates. Such
quaternary ammonium compounds contain long chain alk(en)yl
groups interrupted by functional groups such as carboxy
groups. Said materials and fabric softening compositions
containing them are disclosed in numerous publications such
as EP-A-0,040,562, and EP-A-0,239,910.
The quaternary ammonium compounds and amine precursors
herein have the formula (I) or (II), below .
R3 R3
R NR2(C~2)II-Q"~T 1 x- +\j/ (CH2)n-CH -CH, X -
R3
RI T~ T'-
or
(I) (II)
wherein Q is selected from -0-C(O)-, -C(O)-0-, -O-C(O)-0-,
. -NR4-C (O) -, -C (O) -NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, TS are independently C11-C22 alkyl or
alkenyl;
n and m are integers from 1 to 4; and
X' is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include
chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must
contain at least 11 carbon atoms, preferably at least 16
carbon atoms. The chain may be straight or branched.
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Tallow is a convenient and inexpensive source of long
chain alkyl and alkenyl material. The compounds wherein T1,
T2, T3, T4, T5 represents the mixture of long chain
5 materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds
suitable for use in the aqueous fabric softening
compositions herein include .
10 1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)
ammonium methyl sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium
15 chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-
dimethyl ammonium chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-
ethyl)-N,N-dimethyl ammonium chloride;
20 6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-
ammonium chloride; and
8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2o to about 250,
preferably from about to to about 8% by weight of such
cationic surfactants.
Ampholytic surfactants are also suitable for use in the
cleaning 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
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21
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-
s solubilizing group, e.g. carboxy, sulfonate, sulfate. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, lines 18-35, fox examples of
ampholytic surfactants.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2% to about 15%,
preferably from about 1% to about 10% by weight of such
ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
cleaning compositions. These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivatives of heterocyclic secondary and tertiary amines,
or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S. Patent
No. 3,929,678 to Laughlin et al., issued December 30, 1975
at column 19, line 38 through column 22, line 48, for
examples of zwitterionic surfactants.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2% to about 15%,
preferably from about 1% to about 10% by weight of such
zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category
of nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to about
18 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-
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22
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
0
T
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 C10-
Clg alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2o to about 15%,
preferably from about to to about 10% by weight of such
semi-polar nonionic surfactants.
The cleaning composition of the present invention may
further comprise a cosurfactant selected from the group of
primary or tertiary amines. Suitable primary amines for use
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23
herein include amines according to the formula R1NH2 wherein
R1 is a C6-C12 preferably C6-C1~ 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 5 ethylene oxide moieties.
Preferred amines according to the formula herein above
are n-alkyl amines. Suitable amines for use herein may be
selected from 1-hexylamine, 1-octylamine, 1-decylamine and
laurylamine. Other preferred primary amines include C8-C10
oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido
propylamine.
Suitable tertiary amines for use herein include tertiary
amines having the formula R1R2R3N wherein R1 and R2 are C1-
Cg alkylchains or
Rs
-C CHz-CH-O ~H
R3 is either a C6-C12 preferably C6-Clp alkyl chain, or R3
is R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-~R4 is a C4-
C12~ n is between 1 to 5, preferably 2-3. R5 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
Rs
-C CHZ-CH-O ~H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
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24
O
R1-C-NH-( CHz )-N-(Rz )
n z
wherein R1 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-
l0oxypropylamine, N coco 1-3diaminopropane,
coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl
amine 2 moles propoxylated, octyl amine 2 moles
propoxylated, lauryl amidopropyldimethylamine, C8-10
amidopropyldimethylamine and C10 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein
are 1-hexylamine, 1-octylamine, 1-decylamine, 1-
dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine
and oleylamine 7 times ethoxylated, lauryl amido propylamine
and cocoamido propylamine.
Conventional detergent enzymes
The cleaning compositions can in addition to
mycodextranase enzyme 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, lipases, phospholipases, esterases,
cutinases, pectinases, keratanases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases, pentosanases, malanases, i3-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase or
mixtures thereof.
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A preferred combination is a cleaning composition
having cocktail of conventional applicable enzymes like
protease, amylase, lipase, cutinase and/or cellulase in
5 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
10 have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.09S.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from
Humicola insolens having a molecular weight of about 50KDa,
an isoelectric point of 5.5 and containing 41S amino acids;
and a ~43kD endoglucanase derived from Humicola insolens,
DSM 1800, exhibiting cellulase activity; a preferred
endoglucanase component has the amino acid sequence
disclosed in PCT Patent Application No. WO 91/17243. Also
suitable cellulases are the EGIII cellulases from
Trichoderma longibrachiatum described in W094/21801,
Genencor, published September 29, I994. 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). Carezyme and Celluzyme (Novo Nordisk A/S)
are especially useful. See also W091/17243.
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26
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,
W089/09813 and in European Patent application EP No.
91202882.6, filed on November 6, 1991 and EP No. 96870013.8,
filed February 20, 1996. Also suitable is the laccase
enzyme.
Preferred enhancers are substitued phenthiazine and
phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-
ethylphenothiazine-4-carboxylic acid (EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine
(described in WO 94/12621) and substitued syringates (C3-C5
substitued alkyl syringates) and phenols. Sodium
percarbonate or perborate are preferred sources of hydrogen
peroxide.
Said cellulases and/or peroxidases are normally
incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent
composition.
Other preferred enzymes that can be included in the
detergent compositions of the present invention include
lipases. Suitable lipase 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
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27
which show a positive immunological cross-reaction with the
antibody of the lipase, produced by the microorganism
Pseudamonas fluorescent IAM 10S7. This lipase is available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the
trade name Lipase P "Amano," hereinafter referred to as
"Amano-P". Other suitable commercial lipases include Amano-
CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata, Japan; Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands,
and lipases ex Pseudomonas gladioli. Especially suitable
lipases are lipases such as M1 LipaseR and LipomaxR (Gist-
Brocades) and LipolaseR and Lipolase UltraR(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. Addition of cutinases
to detergent compositions have been described in e.g. WO-A-
88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated
in the detergent composition at levels from 0.0001% to 2% of
active enzyme by weight of the detergent composition.
Suitable proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B.
licheniformis (subtilisin BPN and BPN'). One suitable
protease is obtained from a strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed
and sold as ESPERASE~ by Novo Industries A/S of Denmark,
hereinafter "Novo". The preparation of this enzyme and
analogous enzymes is described in GB 1,243,784 to Novo.
Other suitable proteases include ALCALASE~, DURAZYM~ and
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28
SAVINASE~ from Novo and MAXATASE~~ MAXACAL~, PROPERASE~ and
MAXAPEM~ (protein engineered Maxacal) from Gist-Brocades.
Proteolytic enzymes also encompass modified bacterial serine
proteases, such as those described in European Patent
Application Serial Number 87 30376l.8, filed April 28, l987
(particularly pages 17, 24 and 98), and which is called
herein "Protease B", and in European Patent Application
199,404, Venegas, published October 29, 1986, which refers
to a modified bacterial serine protealytic enzyme which is
called "Protease A" herein.
More preferred is what is called herein "Protease C",
which is a variant of an alkaline serine protease from
Eacillus in which lysine replaced arginine at position 27,
tyrosine replaced valine at position 104, serine replaced
asparagine at position 123, and alanine replaced threonine
at position 274. Protease C is described in EP 90915958:4,
corresponding to WO 91/06637, Published May 16, 1991.
Genetically modified variants, particularly of Protease C,
are also included herein. See also a high pH protease from
Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
Enzymatic detergents comprising protease, one or more
other enzymes, and a reversible protease inhibitor are
described in WO 92/03529 A to Novo. When desired, a
protease having decreased adsorption and increased
hydrolysis is available as described in WO 95/07791 to
Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 94/25583 to
Novo .
In more detail, protease referred to as "Protease D" is
a carbonyl' hydrolase variant having an amino acid sequence
not found in nature, which is derived from a precursor
carbonyl hydrolase by substituting a different amino acid
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29
for a plurality of amino acid residues at a position in said
carbonyl hydrolase equivalent to position +76, preferably
also in combination with one or more amino acid residue
positions equivalent to those selected from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105,
+109, +126, +128, +135, +156, +l66, +195, +197, +204, +206,
+210, +216, +217, +218, +222, +260, +265, and/or +274
according to the numbering of Bacillus amyloliquefaciens
subtilisin, as described in W095/10591 and in the patent
application of C. Ghosh, et al, "Bleaching Compositions
Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994.
Also suitable for the present invention are proteases
described in patent applications EP 251 446 and W091/06637
and protease BLAP~ described in W091/02792. The proteolytic
enzymes are incorporated in the detergent compositions of
the present invention a level of from 0.0001% to 2%,
preferably from 0.001% to 0.2%, more preferably from o.0050
to 0.1% pure enzyme by weight of the composition.
Amylases (a and/or f3) can be included for removal of
carbohydrate-based stains. W094/02597, Novo Nordisk A/S
published February 03, 1994, describes cleaning compositions
which incorporate mutant amylases. See also W094/18314,
Genencor, published August 18, 1994 and W095/10603, Novo
Nordisk A/S, published April 20, l995. Other amylases known
for use in cleaning compositions include both a- and (3-
amylases. a-Amylases are known in the art and include
those disclosed in US Pat. no. 5,003,257; EP 2S2,666;
W0/91/00353; 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, l994 and W096/05295, Genencor,
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published Februaury 22, 1996 and amylase variants having
additional modification in the immediate parent available
from Novo Nordisk A/S, disclosed in WO 95/10603, published
April 95.
5
Examples of commercial a-amylases products are Termamyl~
Ban~ ,Fungamyl~ and Duramyl~, a11 available from Novo
Nordisk A/S Denmark. W095/26397 describes other suitable
amylases . a-amylases characterised by having a specific
10 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
15 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
20 yeast origin.
Origin can further be mesophilic or extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic,
alkalophilic, acidophilic, halophilic, etc.). Purified or
25 non-purified forms of these enzymes may be used. Also
included by definition, are mutants of native enzymes.
Mutants can be obtained e.g. by protein and/or genetic
engineering, chemical and/or physical modifications of
native enzymes. Common practice as well is the expression of
30 the enzyme via host organisms in which the genetic material
responsible for the production of the enzyme has been
cloned.
Said enzymes are normally incorporated in the detergent
composition at levels from 0.0001% to 2% of active enzyme by
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31
weight of the detergent composition. The enzymes can be
added as separate single ingredients (prills, granulates,
stabilized liquids, etc... containing one enzyme ) or as
mixtures of two or more enzymes ( e.g. cogranulates ).
S
Other suitable detergent ingredients that can be added
are enzyme oxidation scavengers which are described in
Copending European Patent application 92870018.6 filed on
January 31, 1992. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials and means for their
incorporation into synthetic detergent compositions is also
disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. 3,553,139,
January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,l01,457, Place et al, July 18, 1978, and
in U.S. 4,507,219, Hughes, March 26, 1985.
Enzyme materials useful for liquid detergent
formulations, and their incorporation into such
formulations, are disclosed in U.S. 4,26l,868, Hora et al,
April 14, 1981. Enzymes for use in detergents can be
stabilised by various techniques. Enzyme stabilisation
techniques are disclosed and exemplified in U.S. 3,600,319,
August 17, 1971, Gedge et al, EP 199,405 and EP 20Q,586,
October 29, 1986, Venegas. Enzyme stabilisation systems are
also described, for example, in U.S. 3,519,570. A useful
Bacillus, sp. AC13 giving proteases, xylanases and
cellulases, is described in WO 9401532 A to Novo.
Color care benefits
Technologies which provide a type of color care benefit
can also be included. Examples of these technologies are
metallo catalysts for color maintenance. Such metallo
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32
catalysts are described in copending European Patent
Application No. 92870181.2.
Bleaching agent
S Additional optional detergent ingredients that can be
included in the cleaning compositions of the present
invention include bleaching agents such as hydrogen
peroxide, 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%.
1$
The bleaching agent component for use herein can be any
of the bleaching agents useful for cleaning compositions
including oxygen bleaches as well as others known in the
art. The bleaching agent suitable for the present invention
can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used
encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include
magnesium monoperoxyphthalate hexahydrate, the magnesium
salt of meta-chloro perbenzoic acid, 4-nonylamino-4-
oxvperoxybutyric 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
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33
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), nonanoyioxybenzene-
sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in
EP 120,591) or 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.
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/l36,626, 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, l991.
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34
Metal-containing catalysts for use in bleach
compositions, include cobalt-containing catalysts such as
Pentaamine acetate cobalt(III? salts and manganese-
containing catalysts such as those described in EPA 549 27l;
EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US
5,194,416 and US 5,l14,611. Bleaching composition comprising
a peroxy compound, a manganese-containing bleach catalyst
and a chelating agent is described in the patent application
No 94870206.3.
Bleaching agents other than oxygen bleaching agents are
also known in the art and can be utilized herein. One type
of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. These
materials can be deposited upon the substrate during the
washing process. Upon irradiation with light, in the
presence of oxygen, such as by hanging clothes out to dry in
the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached.
Preferred zinc phthalocyanine and a photoactivated bleaching
process are described in U.S. Patent 4,033,718. Typically,
detergent compositions will contain about 0.025% to about
1.25%, by weight, of sulfonated zinc phthalocyanine.
Builder system
The compositions according to the present invention may
further comprise a builder system. Any conventional builder
system is suitable for use herein including aluminosilicate
materials, silicates, polycarboxylates, alkyl- or alkenyl-
succinic acid 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
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pentamethylenephosphonic acid. Phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange
5 material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered
10 silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline
layered silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivatives
15 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, malefic acid,
diglycollic acid, tartaric acid, tartronic acid and fumaric
20 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
25 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
30 tricarboxylates described in British Patent No. l,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
35 tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
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Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
l,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,l79, 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,S-tetrahydrofuran -
tetracarboxylates, 1,2,3,4,5,6-hexane -hexacar-boxylates and
and carboxymethyl derivatives of polyhydric alcohols such as
sorbitol, mannitol and xylitol. Aromatic poly-carboxylates
include mellitic acid, pyromellitic acid and the phthalic
acid derivatives disclosed in British Patent No. 1,42S,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
Preferred builder systems for use in the present
compositions include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A or of a layered
silicate (SKS-6), and a water-soluble carboxylate chelating
agent such as citric acid.
A suitable chelant for inclusion in the detergent
compositions in 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
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EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The
magnesium salts are the most preferred for inclusion in
compositions in accordance with the invention.
Preferred builder systems include a mixture of a water-
insoluble aluminosilicate builder such as zeolite A, and a
watersoluble carboxylate chelating agent such as citric
acid. Preferred builder systems for use in liquid detergent
compositions of the present invention are soaps and
polycarboxylates.
Other builder materials that can form part of the
builder system fox 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 malefic 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 5o to 80% by weight of the composition
preferably from loo to 70% and most usually from 30% to 60%
by weight.
Suds suppressor
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Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in
finely divided forms exemplified by silica aerogels and
xerogels and hydrophobic silicas of various types. These
materials can be incorporated as particulates in which the
suds suppressor is advantageously releasably incorporated in
a water-soluble or water-dispersible, substantially non-
surface-active detergent impermeable carrier. Alternatively
the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of
the other components.
A preferred silicone suds controlling agent is disclosed
in Bartollota et al. U.S. Patent 3 933 672. Other
particularly useful suds suppressors are the self-
emulsifying silicone suds suppressors, described in German
Patent Application DTOS 2 646 126 published April 28, 1977.
An example of such a compound is DC-544, commercially
available from Dow Corning, which is a siloxane-glycol
copolymer. Especially preferred suds controlling agent are
the suds suppressor system comprising a mixture of silicone
oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-
butyl-octanol which are commercially available under the
trade name Isofol 12 R.
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.
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The suds suppressors described above are normally
employed at levels of from O.OOlo to 2% by weight of the
composition, preferably from O.Olo to 1% by weight.
Others
Other components used in cleaning compositions may be
employed, such as soil-suspending agents, soil-release
agents, optical brighteners, abrasives, bactericides,
tarnish inhibitors, coloring agents, and/or encapsulated or
non-encapsulated perfumes.
Especially suitable encapsulating materials are water
soluble capsules which consist of a matrix of polysaccharide
and polyhydroxy compounds such as described in GB 1,464,616.
Other suitable water soluble encapsulating materials
comprise dextrins derived from ungelatinized starch acid-
esters of substituted dicarboxylic acids such as described
in US 3,455,S38. 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 and malefic anhydride-acrylic acid
copolymers previously mentioned as builders, as well as
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copolymers of malefic anhydride with ethylene, methylvinyl
ether or methacrylic acid, the malefic anhydride constituting
at least 20 mole percent of the copolymer. These materials
are normally used at levels of from 0 . 5% to 10 o by weight,
5 more preferably from 0.7S% to 80, most preferably from to 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-
10 anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate,
disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-
ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-
(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' -
disulphonate, monosodium 4',4 " -bis-(2,4-dianilino-s-tri-
15 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-
20 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
25 application No. 9S201943.8.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about
30 4000. These are used at levels of from 0.20% to So 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
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on clay, proteinaceous and oxidizable soils in the presence
of transition metal impurities.
Soil release agents useful in compositions of the
present invention are conventionally copolymers or
terpolymers of terephthalic acid with ethylene glycol and/or
propylene glycol units in various arrangements. Examples of
such polymers are disclosed in the commonly assigned US
Patent Nos. 41l6885 and 4711730 and European Published
Patent Application No. 0 272 033. A particular preferred
polymer in accordance with EP-A-0 272 033 has the formula
(CH3 (PEG) 43) 0.75 (POH) 0.25 ~T-PO) 2.8 (T-PEG) 0.4] T (PO
H)0.25((PEG)43CH3)p.75
where PEG is -(OC2H4)O-, PO is (OC3H60) and T is
(pcOC6H4C0).
Also very useful are modified polyesters as random
copolymers of dimethyl terephthalate, dimethyl
sulfoisophthalate, ethylene glycol and 1-2 propane diol, the
end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at
both end by sulphobenzoate groups, "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
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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 31l 342.
Is is well known in the art that tree 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 detergent enzymes. Compositions
comprising chlorine scavenger are described in the European
patent application 92870018.6 filed January 31, 1992.
Alkoxylated polycarboxylates such as those prepared from
polyacrylates are useful herein to provide additional grease
removal performance. Such materials axe described in WO
91/08281 and PCT 90/01815 at p. 4 et seq., incorporated
herein by reference. Chemically, these materials comprise
polyacrylates having one ethoxy side-chain per every 7-8
acrylate units. The side-chains are of the formula
-(CH2CH20)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The
side-chains are ester-linked to the polyacrylate "backbone"
to provide a "comb" polymer type structure. The molecular
weight can vary, but is typically in the range of about 2000
to about 50,000. Such alkoxylated polycarboxylates can
comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
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
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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-0 026
527 and EP-B-0 026 528 and di-long-chain amides as disclosed
in EP-B-0 242 919. Other useful organic ingredients of
fabric softening systems include high molecular weight
polyethylene oxide materials as disclosed in EP-A-0 299 575
and 0 3l3 146.
Levels of smectite clay are normally in the range from
2% to 20%, more preferably from 5% to 15% by weight, with
the material being added as a dry mixed component to the
remainder of the formulation. Organic fabric softening
agents such as the water-insoluble tertiary amines or dilong
chain amide materials are incorporated at levels of from
0.5% to 5% by weight, normally from to to 3o 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 20, normally from 0.15% to 1.5o 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.
Dispersants
The cleaning composition of the present invention can
also contain dispersants . 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.
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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 malefic anhydride, such copolymers
having a molecular weight of from l,000 to 100,000.
S
Especially, copolymer of acrylate and methylacrylate
such as the 480N having a molecular weight of 4000, at a
level from 0.5-20o by weight of composition can be added in
the cleaning compositions of the present invention.
IO
The compositions of the invention may contain a lime
soap peptiser compound, which has a lime soap dispersing
power (LSDP), as defined hereinafter of no more than 8,
preferably no more than 7, most preferably no more than 6.
15 The lime soap peptiser compound is preferably present at a
level from 0% to 20% by weight.
A numerical measure of the effectiveness of a lime soap
peptiser is given by the lime soap dispersant power (LSDP)
20 which is determined using the lime soap dispersant test as
described in an article by H.C. Borghetty and C.A. Bergman,
J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This
lime soap dispersion test method is widely used by
practitioners in this art field being referred to, for
25 example, in the following review articles; W.N. Linfield,
Surfactant science Series, Volume 7, page 3; W.N. Linfield,
Tenside surf. det., volume 27, pages 159-163, (1990); and
M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries,
volume 104, pages 71-73, (1989). The LSDP is the % weight
30 ratio of dispersing agent to sodium oleate required to
disperse the lime soap deposits formed by 0.025g of sodium
oleate in 30m1 of water of 333ppm CaCo3 (Ca:Mg=3:2)
equivalent hardness.
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Surfactants having good lime soap peptiser capability
will include certain amine oxides, betaines, sulfobetaines,
alkyl ethoxysulfates and ethoxylated alcohols.
5 Exemplary surfactants having a LSDP of no more than 8
for use in accord with the present invention include C16-C18
dimethyl amine oxide, C12-C18 alkyl ethoxysulfates with an
average degree of ethoxylation of from 1-5, particularly
C12-C15 alkyl ethoxysulfate surfactant with a degree of
10 ethoxylation of amount 3 (LSDP=4), and the C14-C15
ethoxylated alcohols with an average degree of ethoxylation
of either 12 (LSDP=6) or 30, sold under the tradenames
Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.
15 Polymeric lime soap peptisers suitable for use herein
are described in the article by M.K. Nagarajan, W.F. Masler,
to be found in Cosmetics and Toiletries, volume 104, pages
71-73, (1989) .
20 Hydrophobic bleaches such as 4-[N-octanoyl-6-
aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-
aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]benzene sulfonate and mixtures thereof; and
nonanoyloxy benzene sulfonate together with hydrophilic j
25 hydrophobic bleach formulations can also be used as lime
soap peptisers compounds.
Dye transfer inhibition
The cleaning compositions of the present invention can
30 also include compounds for inhibiting dye transfer from one
fabric to another of solubilized and suspended dyes
encountered during fabric laundering operations involving
colored fabrics.
35 Polymeric dye transfer inhibiting agents
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The cleaning compositions according to the present
invention also comprise from 0.001% to 10 a, preferably from
0 . O1 o to 2%, more preferably from 0 . 05% to 1 o by weight of
polymeric dye transfer inhibiting agents. Said polymeric dye
transfer inhibiting agents are normally incorporated into
cleaning 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 .
P
(I) Ax
R
wherein P is a polymerisable unit, whereto the R-N-0 group
can be attached to or wherein the R-N-O group forms
part of the polymerisable unit or a combination of
both.
0 0 0
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A is NC, C0, 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- (R1)x
(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 0 or 1 and wherein
the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group forms part of
these groups.
The_N-O group can be part of the polymerisable unit (P)
or can be attached to the polymeric backbone or a
combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part
of the polymerisable unit comprise polyamine N-oxides
wherein R is selected from aliphatic, aromatic, alicyclic or
heterocyclic groups.
One class of said polyamine N-oxides comprises the group
of polyamine N-oxides wherein the nitrogen of the N-0 group
forms part of the R-group. Preferred polyamine N-oxides are
those wherein R is a heterocyclic group such as pyrridine,
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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.
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
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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 S0,000,
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 5,000 to 50,000 more preferably from 8,000
to 30,000, most preferably from 10,000 to 2O,000.
The average molecular weight range was determined by
light scattering as described in Barth H.G. and Mays J.W.
Chemical Analysis Vol 113,"Modern Methods of Polymer
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Characterization". Highly preferred N-vinylimidazole N-
vinylpyrrolidone copolymers have an average molecular weight
range from 5,000 to 50,000; more preferably from 8,000 to
30,000; most preferably from 10,000 to 20,000.
5
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
t0 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
IS 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
20 molecular weight of from about 2,500 to about 400,000,
preferably from about S,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
25 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
30 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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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,S00 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 103S-1039.
In one embodiment, the cross-linked polymers are made in
such a way that they form a three-dimensional rigid
structure, which can entrap dyes in the pores formed by the
three-dimensional structure. In another embodiment, the
cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-
pending patent application 94870213.9
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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.
A preferred machine dishwashing method comprises
treating soiled articles with an aqueous liquid having
dissolved or dispensed therein an effective amount 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
the dishes or the soaking in large volume of dilute solution
of the detergent composition.
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The following examples are meant to exemplify
compositions of the present invention, but are not
necessarily meant to limit or otherwise define the scope of
the invention.
In the detergent compositions, the enzymes levels are
expressed by pure enzyme by weight percentage of the total
composition and the detergent ingredients are expressed by
weight percentage of the total compositions, unless
otherwise specified. The abbreviated component
identifications therein have the following meanings:
LAS . Sodium linear C12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulfate
CXyAS . Sodium ClX - Cly alkyl sulfate
C25Ey . A C12_C15 Predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
CgyEZ . A ClX - Cly predominantly linear primary
alcohol condensed with an average of Z
moles of ethylene oxide
CXyEZS . Clg - Cly sodium alkyl sulfate condensed
with an average of Z moles of ethylene
oxide per mole
QAS . R2.N+(CH3)2(C2H40H) with R2 - C12-C14
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Soap . Sodium linear alkyl carboxylate derived
from a 80/20 mixture of tallow and coconut
oils.
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-C18 alkyl N-methyl glucamide.
TPKFA . C12-C14 topped whole cut fatty acids.
DEQA . Di-(tallow-oxy-ethyl) dimethyl ammonium
chloride.
SDASA . 1:2 ratio of stearyldimethyl amine:triple-
pressed stearic acid.
Neodol 45-13 . C14-C15 linear primary alcohol ethoxylate,
sold by Shell Chemical C0.
Tallow . Dihydrogenated tallowamidoethyl
hydroxyethylmonium methosulfate / glycol
distearate / cetyl alcohol.
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio
- 2.0)
NaSKS-6 . Crystalline layered silicate of formula 8-
Na2Si205.
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Carbonate . Anhydrous sodium carbonate with a particle
size between 200 ~tm and 900um.
Bicarbonate . Anhydrous sodium bicarbonate with a
particle size between 400 ~tm and I200~m.
STPP . Anhydrous sodium tripolyphosphate
MA/AA . Copolymer of 1:4 maleic/acrylic acid,
average molecular weight about 80,000
PA30 . Polyacrylic acid of average molecular
weight of approximately 8,000.
Terpolymer . Terpolymer of average molecular weight
approx. 7,000, comprising
acrylic:maleic:ethylacrylic acid monomer
units at a weight ratio of 60:20:20
480N . Random copolymer of 3:7
acrylic/methacrylic acid, average
molecular weight about 3,500.
Polyacrylate . Polyacrylate homopolymer with an average
molecular weight of 8,000 sold under the
tradename PA30 by BASF GmbH
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H2 having a primary
particle size in the range from 0.1 to 10
micrometers
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Citrate . Tri-sodium citrate dehydrate of activity
86,4o with a particle size distribution
between 425 ~m and 850 Vim.
Citric . Anhydrous citric acid
PB1 . Anhydrous sodium perborate monohydrate
bleach, empirical formula NaB02.H202
PB4 . Anhydrous sodium perborate tetrahydrate
Percarbonate . Anhydrous sodium percarbonate bleach of
empirical formula 2Na2C03.3H202
TAED . Tetraacetyl ethylene diamine.
NOBS . Nonanoyloxybenzene sulfonate in the form
of the sodium salt.
Photoactivated . Sulfonated zinc phtlocyanine encapsulated
Bleach in dextrin soluble polymer.
PAAC . Pentaamine acetate cobalt(III? salt.
Paraffin . Paraffin oil sold under the tradename
Winog 70 by Wintershall.
BzP . Benzoyl Peroxide.
Mycodextranase . 1,3-1,4-alpha-D-Glucan 4-glucanohydrolase
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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 W091/06637 and/or W095/10591
and/or EP 251 446.
Amylase . Amylolytic enzyme sold under the tradename
Purafact Ox AmR described in WO 94/18314,
W096/05295 sold by Genencor; Termamyl~,
Fungamyl~ and Duramyl~, all available from
Novo Nordisk A/S and those described in
W095/26397.
Lipase . Lipolytic enzyme sold under the tradename
Lipolase, Lipolase Ultra by Novo Nordisk
A/S
Cellulase . Cellulytic enzyme sold under the tradename
Carezyme, Celluzyme and/or Endolase 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 bequest 2060.
PVNO . Poly(4-vinylpyridine)-N-Oxide.
PVPVI . Poly (4-vinylpyridine)-N-oxide/copolymer
of vinyl-imidazole and vinyl-pyrrolidone.
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Brightener 1 . Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-
1.3.5-triazin-2-yl) stilbene-2:2"-
disulfonate.
Silicone . Polydimethylsiloxane foam controller with
antifoam siloxane-oxyalkylene copolymer as
dispersing agent with a ratio of said foam
controller to said dispersing agent of
10:1 to 100:1.
Granular Suds . 12o Silicone/silica, 18o stearyl
Suppressor alcoho1,70% starch in granular form
SRP 1 . Sulfobenzoyl end capped esters with
oxyethylene oxy and terephtaloyl backbone.
SRP 2 . Diethoxylated poly (1,2 propylene
terephtalate) short block polymer.
SCS . Sodium cumene sulphonate
Sulfate . Anhydrous sodium sulfate.
HMWPEO . High molecular weight polyethylene oxide
PEG . Polyethylene glycol.
BTA . Benzotriazole
Bismuth nitrate . Bismuth nitrate salt
NaDCC . Sodium dichloroisocyanurate
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Encapsulated . Insoluble fragrance delivery technology
perfume utilising zeolite 13x, perfume and a
particles dextrose/glycerin agglomerating binder.
KOH . 100% Active solution of Potassium
Hydroxide
Silica dental . Precipitated silica identified as Zeodent
abrasive 119 offered by J.M. Huber.
Carboxyvinyl . Carbopol offered by B.F. Goodrich Chemical
polymer Company.
Carrageenan . Iota Carrageenan offered by Hercules
Chemical Company.
pH . Measured as a 1% solution in distilled
water at 20~C.
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Example 1
The following laundry detergent compositions were prepared
in accord with the invention:
5
z iz izz zv v m
r~AS 8.a 8.0 8.o s.o s.o 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Mycodextranase 0.001 0.001 0.003 0.001 0.00I 0.003
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
Amylase - 0.0009 0.0009 0.0009 0.0009 0.0009
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm)
Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
~
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone 0.5 0.5 0.5 0.5 0.5 0.5
ant i foam
Misc/minors 1000
to
Density in 850 850 8S0 850 850 850
g/litre
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Example 2
The following granular laundry detergent compositions of
bulk density 7S0 g/litre were prepared in accord with the
S invention:
T II III
LAS 5.25 5.6l 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.2S - 5.0
C25E3 - 5.5 -
QAS 0.8 2.0 2.0
STPP 19.7 - -
Zeolite A - l9.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8 - -
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7 -
TAED 0 . S 3 . 1 -
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Mycodextranase 0.001 0.001 0.001
Protease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006
Amylases 0.0009 0.0009 0.0009
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated 15 ppm 27 ppm 27 ppm
bleach (ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.3
particles
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
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Examt~le 3
The following detergent formulations, according to the
present invention were prepared, where I is a phosphorus-
containing detergent composition, II is a zeolite-containing
detergent composition and III is a compact detergent
composition:
I II III
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0 -
C45AS 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0 - -
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated 0.02 0.02 0.02
bleach
Mycodextranase 0.001 0.001 0.001
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.002 0.003 0.00l
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
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Example 4
The following nil bleach-containing detergent formulations
of particular use in the washing of colored clothing,
according to the present invention were prepared:
I II III
Blown Powder
Zeolite A 15.0 15.0 -
Sodium sulfate 0.0 5.0 -
LAS 3.0 3.0 -
DETPMP 0.4 0.5 -
CMC 0.4 0.4 -
MA/AA 4.0 4.0 -
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0 -
TAS 3.0 2.0 -
Silicate 4.0 4.0 -
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
- Citrate 10.o - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Mycodextranase 0.1 0.1 0.1
Protease 0.026 0.016 0.047
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase 0.006 0.006 0.006
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
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Density (g/litre) 700 700 700
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Example 5
The following detergent formulations, according to the
present invention were prepared:
5
I II III IV
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 l8.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - -
DETPMP 0.7 1.0 - -
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Mycodextranase 0.001 0.001 0.003 0.003
Protease 0.008 0.0l 0.026 0.026
Amylase 0.00? 0.Q04 - 0.002
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0005 - -
Photoactivated 70ppm 45ppm, - lOppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PBl 6.0 2.0 -
NOBS 2.0 1.0 -
Balance 100 100 100 100
(Moisture and
Miscellaneous)
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Example 6
The following detergent according to the
formulations,
present invention were prepared:
I II III Iv
Blown Powder
Zeolite A 30.0 22.0 6.0 6.7
Na SkS-6 - - - 3.3
Polycarboxylate - - - 7.1
Sodium sulfate 19.0 5.0 7.0 -
MA/AA 3.0 3.0 6.0 -
LAS 14.0 l2.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - - - 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0 -
Brightener 1 0.2 0.2 0.2 -
Carbonate 8.0 l6.0 20.0 10.0
DETPMP - 0.4 0.4 -
Spray On
C45E7 1.0 1.0 1.0 3.2
Dry additives
PVPVI/PVNO 0.5 0.5 0.5 -
Mycodextranase 0.07 0.1 0.07 0.1
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - to
balance
Balance (Moisture 100 100 100
and Miscellaneous)
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Example 7
The following high density and bleach-containing detergent
formulations, according to the present invention were
prepared:
I II III
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0 -
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PBl 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Mycodextranase 0.001 0.001 0.001
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.0Q5
Cellulase 0.002 0.002 0.002
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
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Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 8S0
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Example 8
The following high density detergent formulations, according
to the present invention were prepared:
I II
Agglomerate
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Mycodextranase 0.001 0.003
Protease 0.014 0.014
Lipase 0.009 0.009
Cellulase 0.001 0.001
Amylase 0.005 0.005
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
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Example 9
The following granular detergent formulations, according to
the present invention were prepared:
5
I II III Iv v
LAS 21.0 2S.0 l8.0 18.0 -
Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
~
Decyl dimet - 0.4 0.7 0.7 0.8
hyl
hydroxyethyl NH4+Cl
Nonionic 1.2 - 0.9 0.5 -
Coco C12-14 Fatty - - - - 1.0
Alcohol
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
MA/AA - - 0.9 0.9 -
SRP1 0.3 0.1S 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.S 29.3 5.0 13.0 15.0
Silicate 2.0 - 7.6 7.9 -
Mycodextranase 0.003 0.001 0.001 0.003 0.003
Protease 0.007 0.007 0.007 0.007 0.007
Amylase - 0.004 0.004 0.004 0.004
Lipase 0.003 0.003 0.003 - -
Cellulase - 0.001 0.001 0.00l 0.001
NOBS - - - 1.2 1.0
PB1 - - - 2.4 1.2
Diethylene triamine - - - 0.7 1.0
penta acetic acid
Diethylene triamine - - 0.6 - -
penta methyl
phosphonic acid
Mg Sulfate - - 0.8 - -
Photoactivated bleach 45 50 15 45 42
ppm ppm ppm ppm ppm
Brightener 1 0.05 - 0.04 0.04 0.04
Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to 00
10
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Example 10
The following liqu id detergentformulations, according
to the present invention were prepared:
x x= xxx xv v vx vxx v=xi
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.018.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
QAS - - - - 3.0 1.0 - -
TPKFA 2.0 - 13.0 2.0 - 15.07,0 7.0
Rapeseed fatty - - - 5.0 - - 4.0 4.0
acids
Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl/ 12.0 10.0 - - 15.0 - - -
tetradecenyl
succinic acid
Oleic acid 4.0 2.0 1.0 - 1.0 - - -
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5.0 - - 9.0 9.0
Amine
Tri Ethanol - - B - - - - -
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3
tetraethylene
pentamine
DETPMP 1.0 i.0 O.S 1.0 2.0 1.2 1.0 -
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - _ - _ _ _ _
0.10
Mycodextranase 0.1 0.1 0.1 0.07 0.1 0.1 0.07 0.07
Protease_ ,005 ,005 .004 ,003 0.08 .005.003 .006
Lipase - .002 - .0002- - .003 .003
Amylase .002 .002 .Q05 .004 .d02 .008.005 .005
Cellulase - - - .0001- - .0004 .000
9
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na fortnate - - 1.0 - - - - -
Ca chloride - 0.015 - 0.01 - - - -
Bentonite clay - - - - 4.0 4.0 - -
Suspending clay - - - - 0.6 0.3 - -
SD3
Balance 100 100 100 100 100 1D0 100 100
Moisture and
Miscellaneous
Percarbonate 20.0 20.0
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Example 11
Granular fabric cleaning compositions which provide
"softening through the wash" capability were prepared in
accord with the present invention .
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 - 11.0
Zeolite A 15.0 1S.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
PB1 15.0 -
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - O.I
Mycodextranase 0.001 0.001
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.00I -
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 1000
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Example 12
The following rinse added fabric softener composition was
prepared in accord with the present invention .
Softener active 20.0
Mycodextranase 0.001
Amylase 0.001
Cellulase 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaCl2 0.20
Perfume 0.90
Water / minors Up to 100%
Example 13
The following fabric softener composition was prepared in
accord with the present invention .
I II III
DEQA 2.6 19.0 -
SDASA - - 70.0
Stearic acid of IV=0 0.3 - -
Neodol 45-13 - - 13.0
Hydrochloride acid 0.02 0.02 -
Ethanol - - 1.0
PEG - 0.6 -
Mycodextranase 0.1 0.1 0.05
Perfume 1.0 1.0 0.75
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01 -
Electrolyte - 600ppm -
Dye 100ppm 50ppm 0.01
Water and minors 100% l00% l00%
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Example 14
Syndet bar fabric cleaning compositions were prepared in
accord with the present invention .
I II III Iv
C26 AS 20.00 20.00 20.00 20.00
CFAA 5.0 S.0 5.0 5.0
LAS (C11-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 2S.0 2S.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
STPP 7.0 7.0 7.0 7.0
Zeolite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Mycodextranase 0.001 0.001 0.001 0.001
Amylase 0.001 0.001 0.001 0.001
Protease 0.03 - 0.0S 0.005
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler* . balanceto 1000
*Can be selected from convenient materials such as CaC03,
talc, clay (Kaolinite, Smectite), silicates, and the like.
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Examgle 15
The following compact high density (0.96Kg/1)
dishwashing detergent compositions I to VI were prepared in
S accord with the present invention:
I II III IV V VI
STPP - - 49.0 38.0 - -
Citrate ~ 33.0 17.5 - - 54.0 25.4
Carbonate - 17.5 - 20.0 14.0 25.4
Silicate 33.0 l4.8 20.4 14.8 14.8 -
Metasilicate - 2.5 2.5 - - -
PB1 1.9 9.7 7.8 14.3 7.8 -
PB4 8.6 - - - - -
Percarbonate - - - - - 6.7
Nonionic 1.5 2.0 1.5 1.5 1.5 2.6
TAED 4.8 2.4 2.4 - 2.4 4.0
HEDP 0.8 1.0 0.5 - -
DETPMP 0.6 0.6 - - -
PAAC - - - 0.2 -
BzP - - - 4.4 - -
Paraffin 0.5 0.5 0.5 0.5 0.5 0.2
Mycodextranase 0.01 0.05 0.01 0.05 0.01 0.05
Protease 0.075 0.05 0.10 0.l0 0.08 0.01
Lipase - 0.00l - Q.005 - -
Amylase 0.0l 0.005 0.0l5 0.015 0.01 0.0025
BTA 0.3 0.3 0.3 0.3 0.3 -
Bismuth Nitrate - 0.3 - - - -
PA30 4.0 - - - - -
Terpolymer - - - 4.0 - -
480N - 6.0 2.8 - - -
Sulfate 7.1 20.8 8.4 - 0.5 1.0
pH (1% solution) 10.8 11.0 10.9 l0.8 10.9 9.6
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Example 16
The following granular dishwashing detergent
compositions examples I to IV of bulk density 1.02Kg/L were
prepared in accord with the present invention .
I II III IV V VI
STPP 30.0 30.0 30.0 27.9 34.5 26.7
Carbonate 30.S 30.5 30.5 23.0 30.5 2.80
Silicate 7.4 7.4 7.4 12.0 8.0 20.3
PB1 4.4 4.4 4.4 - 4.4 -
NaDCC - - - 2.0 - 1.5
Nonionic 0.75 0.75 0.75 1.9 1.2 0.5
TAED 1.0 1.0 - - 1.0 -
PAAC - - 0.004 - - -
BzP - 1.4 - - - -
Paraffin 0.25 0.25 0.25 - - -
Mycodextranase 0.01 0.05 0.01 0.05 0.01 0.05
Protease 0.05 0.05 0.0S - 0.1 -
Lipase 0.005 - 0.001 - - -
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.l5 - 0.15 - - -
Sulfate 23.9 23.9 23.9 3l.4 17.4 -
pH (1% solution) 10.8 10.8 10.8 10.? 10.7 l2.3
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Example 17
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:
I II III
STPP - 48.8 47.5
Citrate 26.4 - -
Carbonate - 5.0 -
Silicate 26.4 14.8 25.0
Mycodextranase 0.01 0.05 0.01
Protease 0.03 0.075 0.01
Lipase 0.005 - -
Amylase 0.01 0.005 0.001
PB1 1.6 7.8 -
PB4 6.9 - 11.4
Nonionic 1.2 2.0 1.1
TAED 4.3 2.4 0.8
HEDP 0.7 - -
DETPMP 0.65 - -
Paraffin 0.4 0.5 -
BTA 0.2 0.3 -
PA30 3.2 - -
Sulfate 25.0 14.7 3.2
pH (1o solution) l0.6 10.6 11.0
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Example 18
The following liquid dishwashing detergent compositions
were prepared in accord with the present invention I to II,
of density 1.40Kg/L .
I II
STPP 33.3 20.0
Carbonate 2.7 2.0
Silicate - 4.4
NaDCC 1.1 1.15
Nonionic 2.5 1.0
Paraf f in 2 . 2 -
Mycodextranase Q.01 0.01
Protease 0.03 0.02
Amylase 0.005 0.0025
480N 0.50 4.00
KOH - 6.00
Sulfate 1.6 -
pH (1% solution) 9.1 l0.0
Example 19
The following liquid hard surface cleaning compositions
were prepared in accord with the present invention .
I II III IV V VI
Mycodextranase 0.002 0.005 0.001 0.005 0.001 0.005
Amylase 0.01 0.002 0.005 0.02 0.001 0.005
Protease 0.05 0.0l 0.02 0.03 0.005 0.005
EDTA* - - 2.90 2.90 - -
Citrate - - - - 2.90 2.90
LAS 1.95 - 1.95 - 1.95 -
C12 AS - 2.20 - 2.20 - 2.20
NaCl2(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 Balanceto 100%
*Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
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***Al1 formulas adjusted to pH 7
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Example 20
The following spray composition for cleaning of hard
surfaces and removing household mildew was prepared in
5 accord with the present invention .
Mycodextranase 0.01
Amylase 0.01
Protease 0.01
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
Sodium hydroxide 0.80
Silicate (Na) 0.04
Perf ume 0 . 3 5
Water/minors up to 1000
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Example 21
A two-layer effervescent denture cleansing tablet was
prepared in accord with the present invention .
Acidic Laver
Mycodextranase 0.1
Protease 0.1
Tartaric acid 24.0
Sodium carbonate 4.0
Sulphamic acid 10.0
PEG 20,000 4.0
Sodium bicarbonate 24.5
Potassium persulfate 15.0
Sodium acid pyrophosphate 7.0
Pyrogenic silica 2.0
Tetracetylethylene diamin.e 7.0
Ricin-oleylsulfosuccinate 0.5
Flavor 1.0
Alkaline layer
PB1 32.0
Bicarbonate 19.0
EDTA 3.0
STPP 12.0
PEG 20,000 2.0
Potassium persulfate 26.0
Sodium carbonate 2.0
Pyrogenic silica 2.0
Dye/flavor 2.0
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Example 22
Dentifrice compositions were prepared in accord with
the present invention .
I II III Iv
Sorbitol (70% aqueous 35.000 35.000 3S.000 3S.000
solution)
PEG-6 l.000 1.000 1.000 1.000
Silica dental abrasive 20.000 20.000 20.000 20.0Q0
Sodium fluoride 0.243 0.243 0.243 0.243
Titanium dioxide 0.500 0.500 0.500 0.S00
Sodium saccharin 0.286 Q.286 0.286 0.286
Mycodextranase 0.5 0.5 0.3 0.3
Protease 2.000 3.S00 1.500 2.000
Sodium alkyl sulfate 4.000 4.000 4.000 4.000
(27.9% aqueous solution)
Flavor 1.040 1.040 1.040 1.040
Carboxyvinyl polymer 0.300 0.300 0.300 0.300
Carrageenan 0.800 0.800 0.800 0.800
Water Balance to 100%
Example 23
Mouthwash compositions were prepared in accord with the
present invention .
I II III IV
SDA 40 8.00 8.00 8.00 8.00
Alcohol
_ 0.08 0.08 0.08 0.08
Flavor
Emulsifier 0.08 0.08 0.08 0.08
Sodium fluoride 0.05 0.05 0.05 0.05
Glycerin 10.00 10.00 10.00 10.00
Swe etener 0.02 0.02 0.02 0.02
Mycodextranase 0.5 0.3 0.5 0.3
Protease 3.00 7.50 1.00 5.00
Benzoic acid 0.05 0.05 0.05 0.05
Sodium hydroxide 0.20 0.20 0.20 0.20
Dye 0.04 0.04 0.04 0.04
Water Balance to 100%
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Example 24
A liquid personal cleansing composition containing soap
was prepared in accord with the present invention .
S
I II
Mycodextranase 0.1 0.1
Protease 0.10 -
Soap (K or Na) 15.00 -
30% Laurate -
30% Myristate -
25% Palmitate -
15% Stearate -
Fatty acids (above ratios) 4.50 -
Na Lauryl Sarcosinate 6.00 -
Sodium Laureth Sulfate 0.66 12.0
Cocamidopropylbetaine l.33 3.0
Glycerine 15.00 -
Propylene Glycol 9.00 -
Ethylene glycol distearate 1.50 0.3S
(EDTA)
Cocoamide MEA - 0.2
Perfume - 0.6
*Polyquaterium-7 - 0.08
DMDM hydantoin - 0.14
Sodium benzoate - 0.25
Tetrasodium EDTA dihydrate - 0.11
Citric - 0.09
Propylparaben 0.10 -
Methylparaben 0.20 -
Calcium sulfate 3 -
Acetic acid 3
Water and minors Up to 100%
KOH/NaOH (pH adjustment)
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* Copolymer of dimethyl dialkyl ammonium chloride and
acrylamide
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Example 25
A personal cleansing bar composition was prepared in
accord with the present invention .
5
Sodium Cocoyl Isethionate 47.20
Sodium Cetearyl sulfate 9.14
Paraffin g,05
Sodium Soap (in situ) 3.67
Sodium Isethionate 5.51
Sodium Chloride 0.45
Titanium Dioxide 0.4
Trisodium EDTA 0.1
Trisodium Etidronate 0.1
Perfume 1 . 20
Na2S04 0.87
Mycodextranase 0.5
Protease 0.10
Water Balance to 100
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Example 26
A shampoo composition was prepared in accord with the
present invention .
I II III IV V VI
NH4 laureth-3 sulfate 16.0 18.0 10.0 16.0 14.0 18.0
NH4 lauryl sulfate 5.0 6.0 3.0 3.0 4.0 6.0
Na lauryl sarcosinate - - 2.0 - - -
Cocoamide MEA 1.0 - - 1.0 0.6 -
Dimethicone 40/60 0.8 1.0 0.4 3.0 2.0 1.0
Polyguaternium-10 - - 0.01 - 0.2 -
Cetyl alcohol 0.5 0.4 - 0.4 0.4 0.1
Stearyl alcohol - 0.2 - 0.5 0.1 0.2
Panthenyl ethyl ether 0.2 - - 0.2 0.2 0.2
Panthenol 10% - 0.03 - 0.03 - -
Tallow _ - _ _ _ 0.5
Mineral oil - - - - 0.5 -
Tetrasodium EDTA 0.09 0.09 0.07 0.09 0.09 0.09
DMDM Hydantoin 0.14 0.14 0.14 0.12 0.14 0.Z4
Sodium benzoate 0.25 0.2S - 0.25 0.25 0.25
Citrate 1.0 - - 1.0 1.0 -
Citric 0.1 - 0.3 0.1 - -
Sodium hydroxide - - 0.3 - - -
Sodium phosphate - 0.6 - - - 0.6
Disodium phosphate - 0.2 - - - 0.2
Sodium chloride 1.5 1.5 3.0 1.5 2.0 1.5
PEG-12 - - 0.15 - - 0.4
NH4 xylene sulfonate 0.4 0.4 - 0.4 0.4 0.4
Glycol distearate 1.0 3.0 1.5 2.0 3.0 0.5
Zinc pyrithione - - 1.0 - - -
Mycodextranase 0.05 0.05 0.05 0.05 0.05 0.05
Perfume 0.2 0.6 0.6 0.2 0.4 0.6
Water and minors Up to 100%
