Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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~ DETERGENT COMPOSITION COMPRISING A CELLULASE ENZYME
AND A LACCASE ENZYME
TECHNICAL FIELD
The present invention relates to detergent compositions comprising a
cellulase enzyme and a laccase enzyme.
BACKGROUND of the INVENTION
The detergency performance of enzymes in detergent products is
judged by a number of factors, including the ability to remove soils and stains
present in the typical load of the laundry.
In particular, coloured stains are problematic to remove. Coloured
stains are based on carotenoids compounds such as a-"~- and y-carotene and
Iycopene and xanthophyls, on porphyrins such as chlorophyll and on
flavonoid pigments and dye components. This latter group of natural
flavonoid based dye components comprises the highly coloured anthocyanins
dyes and pigments based on pelargonidin, cyanidin, delphidin and their
methyl esters and the antoxanthins. These compounds are the origin of most
of the orange, red, violet and blue colours occurring in fruits and are
abundant in all berries, cherry, red and black currents, grapefruits, passion
fruit, oranges, lemons, apples, pears, pomegranate, red cabbage, red beets
and also flowers. Derivatives of cyanidin are present in up to 80% of the
pigmented leaves, in up to 70% of fruits and in up to 50% of flowers. These
stains typically originate from red wine, fruit such as black currant, cherry,
strawberry and tomato (in particular ketchup and spaghetti sauce),
. .
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vegetables such as carrots and beetroot, tea, coffee, spices such as curry
and paprika, grass, or ball pens/ink.
Commercial detergents normally include bleaching agents to solve the
above mentioned problem. Traditionally, high levels of bleaching agents,
optionally with bleach precursors, are incorporated in detergent compositions.
Bleaching agents are compounds which are precursors of hydrogen peroxide;
hydrogen peroxide is then formed in the course of the washing procedure.
Perborates and percarbonates are the most important examples of such
hydrogen peroxide precursors.
In addition, in recent years consumer desirability for fabric conditioning
compositions has risen. Fabric care includes softening compositions which
impart several desirable properties to treated garments including softness and
static control. Fabric softness of laundered garments is typically achieved by
delivering a quaternary ammonium compound to the surface of the fabric.
Consumer desirability for durable press fabric garments, particularly cotton
fabric garments, has also risen. Durable press garments include those
garments which resist wrinkling of the fabric both during wear and during the
laundering process. Colour maintenance is also desirable.
Cellulolytic enzymes have been found to be particularly effective to
meet these needs since these enzymes exhibit both cleaning and fabric care
properties such as colour rejuvenation and depilling (EP-A-269 168,
W089109259, EP-A-177 165, EP-A-495 257 and EP-A-495 258). Defining a
cellulase selection criterion relevant for detergent application was made
possible by the C14MC-method described in EP-A-350 098.
Given the foregoing, there is clearly a continuing need to provide
detergent compositions which have an excellent overall detergency and fabric
care performance.
Accordingly, it is an object of the present invention to formulate
detergent compositions which provide effective and efficient cleaning of
coloured stains and soils. It is a further object of the present invention to
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provide a laundry detergent composition which achieves excellent fabric care
and cleaning.
It has now been surprisingly found that the bleaching performance of
the laccase is synergistically enhanced by the presence of a cellulase. In
addition, it has been found that the overall detergency and fabric care
performance of the cellulase is synergistically enhanced by a laccase.
It has also been found that the detergent composition of the present
invention provide sanitisation of the treated surfaces.
W091/05839 describes enzymes exhibiting a suitable oxidase activity
or peroxidase activity for the inhibition of textile dye transfer from a dyed
fabric to another fabric during the wash process. In particular, W095/01426
provides a detergent additive and a detergent composition comprising an
enzyme exhibiting laccase activity, oxygen and an enhancing agent, which
are capable of inhibiting the transfer of a textile dye from a dyed fabric to
another fabric when said fabrics are washed together in a wash liquor.
Hospital laundry detergents containing an oxidase and a protease enzymes
are disclosed in J64-60693. W093/13193 describes detergent compositions
comprising a protease derived from Nocardiopsis and enzymes exhibiting a
suitable oxidase activity or peroxidase activity, for stain bleaching and/or dyetransfer inhibition.
However, the combined use of a laccase and a cellulase for effective
and efficient cleaning of coloured stains and soils has not been recognised;
nor the combined use of a laccase and a cellulase for excellent fabric care
and cleaning properties.
SUMMARY of the INVENTION
The present invention relates to detergent compositions comprising a
laccase enzyme and a cellulase enzyme, which provide effective and efficient
cleaning of coloured stains and soils and sanitisation of the treated surfaces.
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In a preferred embodiment, the present invention relates to a laundry
detergent composition comprising a laccase enzyme and a cellulase enzyme
for excellent fabric care and cleaning properties.
DETAILED DESCRIPTION of the INVENTION
Laccase and Laccase related enzymes
Laccase and laccase related enzymes are an essential component of
the detergent compositions of the present invention. It has been surprisingly
found that the bleaching performance of the laccase is enhanced by the
presence of a cellulase. Accordingly, the detergent compositions of the
present invention provide effective and efficient cleaning of coloured stains
and soils.
Without wishing to be bound by theory, it is believed that the cellulase
enzymatic activity on the cellulolytic components of a coloured stain/soil and
on cellulose based fibers and fabrics, renders the colour-bodies more
accessible to the bleaching action of the laccase enzyme, resulting in
improved removal of coloured stains and soils.
In addition, the detergent compositions of the present invention
provide sanitisation of the treated surfaces.
Sanitisation includes all positive effects obtained by the inhibition or
reduction of microbial activity on fabrics and other surfaces, such as the
prevention of malodour development and bacterial/fungal growth. For
example, it provides prevention of malodour development on stored and
weared fabrics, on stored dishware, especially plastic kitchen gear and in
toilets. In particular, the composition of the invention will inhibit or at least
reduce the bacterial and/or fungal development on moist fabric waiting for
further laundry processing and thereby preventing the formation of malodour.
In addition, bacterial and/or fungal growth on hard surfaces such as tiles and
their silicone joints, sanitary installations, will be prevented.
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The sanitisation potential of the detergent compositions of the present
invention can be enhanced by the addition of chemical sanitisers such as
Triclosan and/or hexemidine. Parfums Cosmétiques Actualités No 125, Nov,
1995, 51-4 describes suitable chemical sanitisers.
The sanitisation benefits of the detergent compositions of the present
invention can be evaluated by the Minimum Inhibitory Concentration (MIC) as
described in Tuber. Lung. Dis. 1994 Aug; 75(4~:286-90; J. Clin. Microbiol.
1994 May; 32(5):1261-7 and J. Clin. Microbiol. 1992 Oct; 30(10):2692-7.
According to the present invention, laccases and laccase related
enzymes comprise any laccase enzyme comprised by the enzyme
classification (EC 1.10.3.2), any catechol oxidase enzyme comprised by the
enzyme classification (EC 1.10.3.1), any bilirubin oxidase enzyme comprised
by the enzyme classification (EC 1.3.3.5) or any monophenol
monooxygenase enzyme comprised by the enzyme classification (EC
1.14.99.1~.
Suitable enzymes are the laccase enzymes obtainable from
Coprinaceae disclosed in W096/06930.
The above mentioned enzymes may be derived from plants, bacteria or
fungi (including filamentous fungi and yeasts) and suitable examples include a
laccase derivable from a strain of Apergillus, Neurospora, e.g. N. crassa,
Podospora, Botrytis, Collybia, Fomes, Lentinus, Pleurotus, Trametes, e.g. T.
villosa and T. versicolor, Rhizoctonia, e.g. R. solani, Coprinus, e.g. C.
plicatilis and C. cinereus, Psatyrella, Myceliophthora, e.g. M. thermophila,
Schytalidium, Polyporus, e.g. P. pinsitus, Phlebia, e.g. P. radita (W0
92/01046) or Coriolus, e.g. C. hirsutus ~JP 2-238885).
The laccase or the laccase related enzyme may furthermore be one
which is producible by a method comprising cultivating a host cell
transformed with a recombinant DNA vector which carries a DNA sequence
encoding said laccase as well as DNA sequences encoding functions
permitting the expression of the DNA sequence encoding the laccase, in a
culture medium under conditions permitting the expression of the laccase
enzyme, and recovering the laccase from the culture.
.. . . . .. . . . . ..
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Especially suitable laccases that function at a pH above 7 are
obtainable from a strain of Coprinus, Myceliophtora. Most preferred are
laccases active at solution pH above 7 from Coprinus cinereus or
Myce/iophtora thermophila.
According to the invention laccases displaying immunochemical cross-
reactivity with an antibody raised against above described laccases are also
included.
The detergent composition of the present invention comprise a laccase
at a level generally from 0.0001% to 2%, preferably from 0.003% to 0.06%
pure enzyme by weight of the total composition. The ratio of active laccase
to active cellulase varies from 1:1000 to 1000:1, preferably from 1:100 to
100:1, more preferably from 1 :10 to 20:1 .
Determination of Laccase Activitv ILACU)
Laccase activity is determined from the oxidation of syringaldazin
under aerobic conditions. The violet colour produced is photometered at
530nm. The analytical conditions are 1911M syringaldazin, 23.2mM acetate
buffer, pH 5.5, 30~C, 1 min. reaction time.
1 lacc~se unit (LACU) is the amount of enzyme that catalyses the
conversion of 1.0 ~mole syringaldazin per minute at these conditions.
Enhancing agents
The detergent compositions according to the present invention may
contain an enhancing agent.
According to the invention an enhancing agent is any compound that
enhances the oxidation of the target soil or stain. The enhancing agent will
typically be an oxidizable compound, e.g. a metal ion or a phenolic compound
such as 7-hydroxycoumarin, vanillin, or p-hydroxybenzenesulfonate, (for
reference see W0 92/18683, W0 92/18687 and Kato M and Shimizu S,
Plant Cell Physiol. 1985 26 (7), pp. 1291-1301 (cf. Table 1 in particular).
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Particularly useful enhancing agents may be described by the following
formula:
OH
R2~,, OR3
l =O
R~
where R1 is H, OH, CnH2n+1, in which n is an integer of from 1 to 10; and
R2 and R ~ are the same or different and selected from CmH2m + 1, in which
m is an integer of from 1 to 10. R1, R2 and R3 may also contain double
bonds or cyclic groups.
In preferred embodiments, the enhancing agent is alkylsyringate in
particular methyl, ethyl, propyl, butyl, hexyl syringate. Other suitable
enhancing agents for the present invention are the new group of organic
chemical substances performing excellently as enhancers of phenol oxidising
enzymes, such as acetosyringone; described in W096/10079.
Other particularly useful enhancing agents may be described by the
following formula:
Rl R4
R3~ 1 ~R7
R4 Rs R6
in which formula X represents ~-O-) or (-S-), and the substituent groups
R1-R9, which may be identical or different, independently represents any of
the following radicals: hydrogen, halogen, hydroxy, formyl, carboxy and
esters and salts hereof, carbamoyl, sulfo, and esters and salts hereof,
sulfamoyl, nitro, amino, phenyl, C1-C14-alkyl, C1-Cs-alkoxy, carbonyl-C1-
Cs-alkyl, aryl-C1-Cs-alkyl; which carbamoyl, sulfamoyl, and amino groups
. .
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may furthermore be unstubstituted or substituted once or twice with a
substituent group R10; and which phenyl may furthermore be unsubstituted
or substituted with one or
more substituent groups R 10; and which C 1 -C 1 4-alkyl, C 1 -Cs-alkoxy,
carbonyl-C 1 -Cs-alkyl, and aryl-C 1 -Cs-alkyl groups may be saturated or
unsaturated, branched or unbranched, and may furthermore be unsubstitued
or substituted with one or more substituent groups R10;
which substituent groups R10 represents any of the following radicals
: halogen, hydroxy, formyl, carboxy and esters and salts hereof, carbamoyl,
sulfo and esters and salts hereof, sulfamoyl, nitro, amino, phenyl, aminoalkyl,
piperidino, piperazinyl, pyrrolidin-1-yl, C1-Cs-alkyl, C1-C6-alkoxy; which
carbamoyl, sulfamoyl and amino groups may furthermore be unsubstituted or
substituted once or twice with hydroxy, C1-Cs-alkyl, C1-Cs-alkoxy; and
which phenyl may furthermore be substituted with one or more of the
following radicals: halogen, hydroxy, amino, formyl, carboxy and esters and
salts hereof, carbamoyl, sulfo and esters and salts hereof, and sulfamoyl; and
which C1-Cs-alkyl, and C1-Cs-alkoxy groups may furthermore be saturated
or unsaturated, branched or unbranched and may furthermore be substituted
once or twice with any of the following radicals: halogen, hydroxy, amino
formyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and
salts hereof, and sulfamoyl;
or in which general formula two of the substituent groups R1-R9 may
together form a group -B-, in which B represents any of the following groups
: ~-CHR1 0-N--N-~,
(-Cll=CH-)n, (-CH=N-)n or (-N-CR10-NR1l-), in which groups n represents
an integer of from 1 to 3, R10 is a substituent group as defined above and
R11 is defined in the same way as R10 (it is to be understood that if the
above mentioned formula comprises two or more R10-substituent groups,
these R10-substituent groups may be the same or different).
In particular embodiments, the enhancing agent is 10-
methylphenothiazine, phenothiazine-10-propionic acid, N-hydroxysuccinimide
phenothiazine- 1 0-propionate, 1 0-ethyl-phenothiazine-4-carboxylic acid, 1 0-
ethylphenothiazine, 1 0-propylphenothiazine, 1 0-isopropylphenothiazine,
methyl-phenothiazine-1 0-propionate, 1 0-phenylphenothiazine, 10-
allylphenothiazine, 10-(3-(4-methylpiperazin-1-yl)propyl) phenothiazine, 10-(2-
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pyrrolidin-1 -yl-ethyl)phenothiazine, 2-methoxy-1 0-methylphenothiazine, 1-
methoxy-10-methyl-phenothiazing, 3-methoxy-10-methylphenothiazine, 3,10-
dimethylphenothiazine, 3,7,1 0-trimethylphenothiazine, 1 0-(2-
hydroxyethyl)phenothiazine, 1 0-(3-hydroxypropyl) phenothiazine, 3-~2-
hydroxyethyl)- 1 0-methylphenothiazine, 3-hydroxymethyl- 10-
methylphenothiazine, 3,7-dibromopheno-thiazine-1 0-propionic acid,
phenothiazine-1 O-propionamide, chlorpromazine, 2-chloro-10-
methylphenothiazine, 2-acetyl- 1 0-methylphenothiazine, 10-
methylphenoxazine, 1 0-ethyl-phenoxazine, phenoxazine-1 0-propionic acid,
10-(2-hydroxyethyl)phenoxazine or 4-carboxyphenoxazine-10-propionic acid.
The enhancing agents may be obtained from Sigma-Aldrich, Janssen
Chimica, Kodak, Tokyo Kasai Organic Chemicals, Daiichi Pure Chemicals Co.
or Boehringer Mannheim; N-methylated derivatives of phenothiazine and
phenoxazine may be prepared by methylation with methyliodide as described
by Cornel Bodea and loan Silberg in "Recent Advances in the Chemistry of
Phenothiazines" (Advances in heterocyclic chemistry, 1968, Vol.9, pp.321-
460); B. Cardillo & G. Casnati in Tetrahedron, 1967, Vol. 23, p.3771.
Phenothiazine and phenoxazine propionic acids may be prepared as described
in J.Org. Chem. 15, 1950, pp. 1125-1130. Hydroxyethyl and hydroxypropyl
derivatives of phenothiazine and phenoxazine may be prepared as described
by G.Cauquil in Bulletin de la Society Chemique de France, 1960, p.1049.
The enhancing agent may be present in concent-alions of from 0.01 to
50011M, preferably in concentrations of from 0.1 to 250',1M in the wash
solution. The enhancing agent is present in the detergent compositions at a
level of 0.1 % to 5 % by weight of the total detergent composition.
Cellulase enzYmes
The second essential element of the detergent composition of the
present invention is a cellulase. It has been surprisingly found that the overall
detergency and fabric care performance of the cellulase is synergistically
enhanced by a laccase. Accordingly, the laundry detergent compositions of
the present invention achieve excellent fabric care and cleaning.
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Without wishing ~o be bound by theory, it is believed that the bleach
activity of the laccase enzyme enhances the cellulolytic activity on cellulose
based cotton substrate. This enhanced cellulolytic activity results in enhanced
fabric care and soil removal at the cotton fabric surface. The increased
removal of worn cotton fibrils from the cotton fabric surface results in
improved fabric feel and removal of the entrapped soils, especially particulate
soils such as clay particles and carbon black particles. In addition, the
accessibility of the soils and stains entrapped on the cotton fabric surface is
enhanced and allows better laccase bleaching activity.
The cellulases usable in the present invention include both bacterial or
fungal cellulases. Preferably, they will have a pH optimum of between 5 and
12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
J61078384 and W096/02653 which discloses fungal cellulase produced
respectively from Humicola insolens, Trichoderma, Thielavia and
Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus
species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275; DE-OS-2.247.832 and W095/26398.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the
Humicola strain DSM 1800.
Preferred cellulases are cellulases originated from Humicola insolens having a
molecular weight of about 50KDa, an isoelectric point of 5.5 and containing
415 amino acids; and a ~43kD endoglucanase derived from I lumicola
insolens, DSM 1800, exhibiting cellulase activity. Another 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, 1994. 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 WO91/17244 and WO91/21801. Other suitable
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11
cellulases for fabric care and/or cleaning properties are described in
W096/34092, W096/17994 and W095/24471.
Said cellulases are normally incorporated in the detergent composition
at levels from 0.0001% to 2%, preferably 0.00015% to 0.6% of pure
enzyme by weight of total composition.
Deter4~l-t comPonents
The detergent compositions of the invention may also contain
additional detergent components. The precise nature of these additional
components, and levels of incorporation thereof will depend on the physical
form of the composition, and the nature of the cleaning operation for which it
is to be used.
The detergent compositions according to the invention can be liquid,
paste, gels, bars, tablets, spray, foam, powder or granular forms. Granular
compositions can also be in "compact" form, the liquid compositions can also
be in a "concentrated" form.
In a prefer,ed embodiment, the present invention relates to a laundry
and/or fabric care composition comprising a laccase and a cellulase (Examples
1-11). It has been found that the incorporation of a laccase enzyme and a
cellulase enzyme in a softener matrix does also deliver effective and efficient
cleaning of coloured stains and soils during the rinse cycle, with colour
safety. In a second embodiment, the present invention relates to
dishwashing or household detergent compositions ~Examples 12-20).
The compositions of the invention may for example, be formulated as
hand and machine dishwashing compositions, hand and machine laundry
detergent compositions including laundry additive compositions and
compositions suitable for use in the soaking and/or pretreatment of stained
fabrics, rinse added fabric softener compositions, and compositions for use in
general household hard surface cleaning operations. Compositions comprising
... . .. ...
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12
a laccase enzyme and a cellulase enzyme can also be formulated as
sanitisation products.
Such compositions containing a laccase and a cellulase 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 ll metal ions, solvents,
hydrotropes and additional enzymes.
When formulated as compositions suitable for use in a laundry machine
washing method, the compositions of the invention preferably contain both a
surfactant and a builder compound and additionally one or more detergent
components preferably selected from organic polymeric compounds,
bleaching agents, additional enzymes, suds suppressors, dispersants, lime-
soap dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors. Laundry compositions can also contain softening agents, as
additional detergent components.
The compositions of the invention can also be used as detergent
additive products. Such additive products are intended to supplement or
boost the performance of conventional detergent compositions.
If needed the density of the 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
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13
filler salts are conventional ingredients of detergent compositions in powder
form; in conventional detergent compositions, the filler saits are present in
substantial amounts, typically 17-35% by weight of the total composition.
In the compact compositions, the filler salt is present in amounts not
exceeding 15% of the total composition, preferably not exceeding 10%,
most preferably not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the present compositions
are selected from the alkali and alkaline-earth-metal salts of sulphates and
chlorides .
A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can
also be in a "concentrated form", in such case, the liquid detergent
compositions according the present invention will contain a lower amount of
water, compared to conventional liquid detergents.
Typically the water content of the concentrated liquid detergent is
preferably less than 40%, more preferably less than 30%, most preferably
less than 20% by weight of the detergent composition.
Suffactant s~t,,~
The detergent compositions according to the present invention comprise a
surfactant system wherein the surfactant can be selected from nonionic
and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or
semi-polar surfactants.
The surfactant is typically present at a level of from 0.1% to 60% by
weight. More preferred levels of incorporation are 1% to 35% by weight,
most preferably from 1% to 30% by weight of detergent compositions in
accord with the invention.
The surfactant is preferably formulated to be compatible with enzyme
components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at least
does not degrade, the stability of any enzyme in these compositions.
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14
Preferred surfactant systems to be used according to the present invention
comprise as a surfactant one or more of the nonionic and/or anionic
surfactants described herein.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use as the nonionic surfactant of the surfactant
systems of the present invention, with the polyethylene oxide condensates
being preferred. These compounds include the condensation products of alkyl
phenols having an alkyl group containing from about 6 to about 14 carbon
atoms, preferably from about 8 to about 14 carbon atoms, in either a
straight-chain or branched-chain configuration with the alkylene oxide. In a
preferred embodiment, the ethylene oxide is present in an amount equal to
from about 2 to about 25 moles, more preferably from about 3 to about 15
moles, of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic surfactants of this type include IgepalTM C0-630, marketed by the
GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed
by the Rohm & Haas Company. These surfactants are commonly referred to
as alkylphenol alkoxylates ~e.g., alkyJ 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 generaliy 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 ~teferal~ly from about 10 to about 18 carbon atoms, with from about 2
to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7
moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene
oxide per mole of alcohol are present in said condensation products.
Examples of commercially available nonionic surfactants of this type include
TergitolTM 1 5-S-9 (the condensation product of C1 1-C1 5 linear alcohol with
9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product
of C 1 2-C 1 4 primary alcohol with 6 moles ethylene oxide with a narrow
molecular weight distribution), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9
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moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-
C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the
condensation product of C 1 4-C 1 5 linear alcohol with 7 moles of ethylene
oxide), NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol
with 5 moles of ethylene oxide) marketed by Shell Chemical Company,
KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company, and Genapol
LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5
moles of ethylene oxide) marketed by Hoechst. Preferred range of 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 asopposed to a glucoside or galactoside~. The intersaccharide bonds can be,
e.g., between the one position of the additional saccharide units and the 2-,
3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R20~CnH2nO)t(9lycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from about 10 to about 18, preferably from about 12 to
about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
preferably O; 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
CA 022~4927 1998-ll-12
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16
alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source of glucose, to form the glucoside (attachment at the 1-position). The
additional glycosyl units can then be attached between their 1-position and
the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably
predominately the 2-position.
The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol are also
suitable for use as the additional nonionic surfactant systems of the present
invention. The hydrophobic portion of these compounds will preferably have
a molecular weight of from about 1500 to about 1800 and will exhibit water
insolubility. The addition of polyoxyethylene moieties to this hydrophobic
portion tends to increase the water solubility of the molecule as a whole, and
the liquid character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the
condensation product, which corresponds to condensation with up to about
40 moles of ethylene oxide. Examples of compounds of this type include
certain of the commercially-available 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 of from about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the extent that the
condensation product contains from about 40% to about 80% by weight of
polyoxyethylene and has a molecular weight of from about 5,000 to about
11,000. Exa.l,ples 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
.....
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17
mixtures thereof. Most preferred are Cg-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
Il I
o R1
wherein R1 is H, or R1 is C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C11 15 alkyl or C16 18
alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is
derived from a reducing sugar such as glucose, fructose, maltose, lactose, in
a reductive amination reaction.
Suitable anionic surfactants to be used are linear alkyl benzene sulfonate,
alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic
acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to
"The Journal of the American Oil Chemists Society", 52 (1975~, pp. 323-
329. Suitable starting materials would include natural fatty substances as
derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications, comprise alkyl ester sulfonate surfactants of the structural
formula:
o
Il
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination
.. ..
CA 022~4927 1998-ll-12
PCT~US97/08035
W O 97/43381
18
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,
~3 is C1 o-C1 6 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred
are the methyl ester sulfonates wherein R3 is C10-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 C 1 0-c24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C 1 0-c20 alkyl component, more preferably a C 1 2-C 1 8 alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium,potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-,
dimethyl-, and tri~elhyl ammonium cations and quaternary ammonium
cations such as tetramethyl-ammonium and dimethyl piperdinium cations and
quaternary ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like). Typically,
alkyl chains of C1 2-C1 6 are preferred for lower wash temperatures (e.g.
below about 50~C) and C16 18 alkyl chains are preferred for higher wash
temperatures (e.g. above about ~0~C).
Other anionic SU. ractants useful for detersive purposes can also be
included in the detergent compositions of the present invention. These can
include salts (including, for example, sodium, potassium, ammonium, and
substituted alnmonium salts such as mono-, di- and triethanolamine salts) of
soap, Cg-C22 primary of secondary alkanesulfonates, Cg-C24
olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of
the pyrolyzed product of alkaline earth metal citrates, e.g., as described in
British patent specification No. 1,082,179, Cg-C24
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkylphosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl
succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated C1 2-C1 8 monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl
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19
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates
such as those of the formula RO(CH2CH20)k-CH2COO-M+ wherein R is a
Cg-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming
cation. Resin acids and hydrogenated resin acids are also suitable, such as
rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tall oil.
Further examples are described in "Surface Active Agents and Detergents"
(Vol. I and ll by Schwartz, Perry and Berch). A variety of such surfactants
are also generally disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23
~herein incorporated by reference).
When included therein, the laundry detergent compositions of the present
invention typically comprise from about 1% to about 40%, preferably from
about 3 % to about 20 % by weight of such anionic surfactants.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula
RO(A)mS03M wherein R is an unsubstituted C1o-C24 alkyl or hydroxyalkyl
group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy
or propoxy unit, m is greater than zero, typically between about 0.5 and
about 6, more preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium, calcium, magnesium, etc. ), ammonium or substituted-ammonium
cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted ammonium cations
include methyl-, dimethyl, trimethyl-ammonium cations and quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium
cations and those derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like. Exemplary surfactants are C1 2-
C18 alkyl polyethoxylate (1.0) sulfate (C1 2-C1 8E(1 ~O)M), C1 2-C18 alkyl
polyethoxylate (2.25) sulfate (C1 2-C1 gE(2.25)M), C1 2-C1 8 alkyl
polyethoxylate (3.0) sulfate (C1 2-C1 gE(3.0)M), and C1 2-C1 8 alkyl
, . .
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polyethoxylate (4.0) sulfate (C1 2-C1 gE(4.0)M), wherein M is conveniently
selected from sodium and potassium.
The detergent compositions of the present invention may also contain
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 detergent
compositions of the present invention are those having one long-chain
hydrocarbyl group. Examples of such cationic surfactants include the
ammonium surfactants such as alkyltrimethylammonium h310genides, and
those surfactants having the formula:
~R2(0R3)y][R4(0R3)yl2R5N +X~
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-,
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 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 ~
R1~o~ ~R
Formula I
whereby Rl is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the
formula (11): .
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21
Formula ll
y is 2-4, preferably 3.
whereby R2 is It or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a
short chain alkyl (C1-C3) or alkoxylated alkyl of the formula lll,
whereby X~ is a counterion, preferably a halide, e.g. chloride or methylsulfate.
R6
~ ~Z
Formula lll
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,
R3, R4 - CH3 and Rs = CH2CH2OH.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the formula:
R1 R2R3R4N + X- (i)
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40lxH 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-C1s particularly where the
alkyl group is a mixture of chain lengths derived from coconut or palm kernel
fat or is derived synthetically by olefin build up or OX0 alcohols synthesis.
Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and
the anion X may be selected from halide, methosulphate, acetate and
phosphate ions.
. . .
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WO 97/43381 PCT/US97/08035
22
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;
C1 2-1 5 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula ~i) wherein R1 is
CH2-CH2-0-C-C1 2-14 alkyl and R2R3R4 are methyl).
Il
o
di-alkyl imidazolines [compounds of formula (i)~.
Other cationic surfactants useful herein are also described in U.S. Patent
4,228,044, Cambre, issued October 14, 1980 and in European Patent
Application EP 000,224.
Typical cationic fabric softening components include the water-insoluble
quaternary-ammonium fabric softening actives or their corresponding amine
precursor, 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) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
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W O 97/43381 23 PCTrUS97/08035
1 1 ) C1 2-18 alkyl dihydroxyethyl methylammonium chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallow-oxy-ethyl) dimethylammonium chloride;
1 4) ditallow imidazolinium methylsulfate;
1 5) 1 -(2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.
Biodegradable quaternary ammonium compounds have been presented
as alternatives to the traditionally used di-long alkyl chain ammonium
chlorides and methyl sulfates. Such quaternary ammonium compounds
contain long chain alk(en~yl groups interrupted by functional groups such as
carboxy groups. Said materials and fabric softening compositions containing
them are disclosed in numerous publications such as EP-A-0,040,562, and
EP-A-0,239,91 0.
The quaternary ammonium compounds and amine precursors herein have the
formula (I) or ~Il), below:
R3\ R3
R~ R2 + N--(CH2)n~CI H ~CH2 X
+ N--(C~--Q T 1 X R3 Q
T I T2
or
(I) (Il)
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -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 Cl-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C1 1-c22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X~ is a softener-compatible anion.
~ .
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W O 97/43381 PCTrUS97/08035
24
Non-limiting examples of softener-compatible anions include chloride ormethyl 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.
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 materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in
the aqueous fabric softening compositions herein include:
1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2~ N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl
ammonium
chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(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 detergent compositions of the present invention
typically comprise from 0.2% to about 25%, preferably from about 1% to
about 8% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the detergent
compositions of the present invention. These surfactants can be broadly
described as aliphatic derivatives of secondary or tertiary amines, or aliphaticderivatives of heterocyclic secondary and tertiary amines in which the
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W O 97/43381 PCT~US97/08035
aliphatic radical can be straight- or branched-chain. One of the aliphatic
substituents contains at least about 8 carbon atoms, typically from about 8
to about 18 carbon atoms, and at least one contains an anionic water-
solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines
18-35, for examples of ampholytic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to
about 10% by weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in detergent
compositions. These surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary amines, or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line
38 through column 22, line 48, for examples of zwitterionic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from 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
f~om about 1 to about 3 carbon atoms; water-soluble phosphine oxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and
2 moieties selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
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26
~r
R3(0R4)xNlR5)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 O 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-C1g alkyl dimethyl
amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included therein, the detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from about
1% to about 10% by weight of such semi-polar nonionic surfactants.
The detergent composition of the present invention may further
comprise a cosurfactant selected from the group of primary or tertiary
amines.
Suitable primary amines for use herein include amines according to the
formula R1NH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or
R4X(CH2)n, X is -O-,-C(O~NH- or -NH-, R4 is a C6-C1 2 alkyl chain n is
between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched
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-C 10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having
the formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or
.. ..
CA 022~4927 1998-11-12
W O 97/43381 PCTrUS97/08035
27
--( CH2--CH--O )XH
R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n,
whereby X is -O-, -C~O)NH- or -NH-,R4 is a C4-C12, n is between 1 to 5,
preferably 2-3. Rs is H or C1-C2 alkyl and x is between 1 to 6 .
R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted
with up to 12, preferably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl
chain, R2 and R3 are C1-C3 alkyl or
R5
- (CH2- CH - O ~H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
R1--C--NH--( CH2 )--N--( R2 )2
wherein R1 is C6-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,C8-1 Ooxypropylamine, 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, C8-1 O amidopropyldimethylamine and C1 O
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
, . , . . , . .... . ~
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28
oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido
propylamine .
.,.,ti~,~al detergent enzymes
The detergent compositions can in addition to the laccase and cellulase
enzymes further comprise one or more enzymes which provide cleaning
performance and/or fabric care benefits.
Said enzymes include enzymes selected from hemicellulases, peroxidases,
proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases,
esterases, cutinases, pectinases, keratanases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, 13-glucanases, arabinosidases, hyaluronidase,
chondroitinase or mixtures thereof.
A preferred combination is a detergent composition having cocktail of
conventional applicable enzymes like protease, amylase, lipase, cutinase
and/or cellulase in conjunction with one or more plant cell wall degrading
enzymes.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc and with use of a
phenolic substrate as bleach enhancing molecule. 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 W0 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.
Enhancers are generally comprised at a level of from 0.1% to 5% by
weight of total composition. Preferred enhancers are substitued phenthiazine
and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-
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WO 97/43381 PCT/US97/08035
29
4-carboxylic acid (EPC), 10-phenoxazinepropionic acid ~POP) and 10-
methylphenoxazine (described in WO 94/12621) and substitued syringates
(C3-C5 substitued alk~/l syringates) and phenols. Sodium percarbonate or
perborate are preferred sources of hydrogen peroxide.
Said peroxidases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of
the detergent composition.
Other preferred enzymes that can be included in the detergent
compositions of the present invention include lipases. Suitable lipase
enzymes for detergent usage include those produced by microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in British Patent 1,372,034. Suitable lipases include those which
show a positive immunological cross-reaction with the antibody of the lipase,
produced by the microorganism Pseudomonas f/uorescent IAM 1057. This
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-
P". Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscos~m, e.g. Chromob~cter viscosum v~r. Iipolyticum NRRLB
3673 from Toyo Jozo Co., Tagata, Japan; Chromob~cter viscosum lipases
from U.S. Biocl,en~ical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex Pseudomonas gl~dioli. Especially suitable lipases are lipases such
as M 1 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 suitables
are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO
95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO
96/00292 by Unilever.
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); WO 90/09446 (Plant Genetic
System) and WO 94/14963 and WO 94/14964 (Unilever~.
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.
.. . .. . . . . . ~ , .. _
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WO 97/43381 PCT/US97/0803S
Suitable proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. Iicheniformis (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 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 303761.8, filed April 28,
1987 (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. Suitable is what is called herein
"Protease C", which is a variant of an alkaline serine protease from Bacil/us inwhich Iysine replaced arginine at position 27, tyrosine replaced valine at
position 104, serine replaced asparagine at position 123, and alanine replaced
threonine at position 274. Protease C is described in EP 90915958:4,
corresponding to WO 91/06637, Published May 16, 1991. Genetically
modified variants, particularly of Protease C, are also included herein.
A preferred 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 for
a plurality of amino acid residues at a position in said carbonyi 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, +166, +195, +197, +204, +206,
+ 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or + 274 according
to the numbering of Bacil/us 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.
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31
Also suitable for the present invention are proteases described in patent
applications EP 251 446 and WO 91/06637, protease BLAP~ described in
W091/02792 and their variants described in WO 95/23221.
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. Other suitable proteases are
described in EP 516 200 by Unilever.
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 0.005% to 0.1%
pure enzyme by weight of the composition.
Amylases ~a and/or 13) 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 W095/10603, Novo Nordisk A/S, published April 20, 1995. Other
amylases known for use in cleaning compositions include both a- and ~-
amylases. a-Amylases are known in the art and include those disclosed in
US Pat. no. 5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent specification no.
1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases
described in W094/18314, published August 18, 1994 and W096/05295,
Genencor, published February 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. Also suitable are
amylases described in EP 277 216, W095126397 and W096/23873 (all by
Novo Nordisk~.
Examples of commercial a-amylases products are Purafect Ox Am~) from
Genencor and Termamyl(~), Ban@) ,Fungamyl@) and Duramyl~, all available
from Novo Nordisk AIS Denmark. W095126397 describes other suitable
amylases: a-amylases characterised by having a specific activity at least
25% higher than the specific activity of Termamyl(~) at a temperature range
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W O97/43381 32 PCTAUS97/08035
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. Suitable are variants of the above
enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic
enzymes with improved properties with respect to the activity level and the
combination of thermostability and a higher activity level are described in
W095/35382.
The amylolytic enzymes are incorporated in the detergent
compositions of the present invention a level of from 0.0001 % to 2%,
preferably from 0.00018% to 0.06%, more preferably from 0.00024% to
0.048% pure enzyme by weight of the composition.
The above-mentioned enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Origin can further
be mesophilic or extremophilic ~psychrophilic, psychrotrophic, thermophilic,
barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or 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 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 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 oftwo or more enzymes ( e.g. cogranulates ).
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
. , . .. , ~
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33
U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,101,457, 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. 4,261,868, 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 200,586, 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 and fabtic care benefits
Technologies which provide a type of color care benefit can also be
included. Examples of these technologies are metallo catalysts for color
maintenance. Such metallo catalysts are described in copending European
Patent Application No. 92870181.2. Dye fixing agents, polyolefin dispersion
for anti-wrinkles and improved water absorbancy, perfume and amino-
functional polymer for color care treatment and perfume substantivity are
further examples of color care / fabric care technologies and are described in
the co-pending Patent Application No. 96870140.9, filed November 07,
1996.
Fabric softening agents can also be incorporated into detergent
compositions in accordance with the present invention. These agents may be
inorganic or organic in type. Inorganic softening agents are exemplified by
the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292.
Organic fabric softening agents include the water insoluble tertiary amines as
disclosed in GB-A1 514 276 and EP-BO 011 340 and their combination with
mono C12-C14 quaternary ammonium salts are disclosed in EP-B-O 026 527
and EP-B-O 026 528 and di-long-chain amides as disclosed in EP-B-O 242
919. Other useful organic ingredients of fabric softening systems include high
molecular weight polyethylene oxide materials as disclosed in EP-A-O 299
575 and 0 313 146.
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34
Levels of smectite clay are normally in the range from 2% to 20%,
more preferably from 5% to 15% by weight, with the material being added
as a dry mixed component to the remainder of the formulation. Organic
fabric softening agents such as the water-insoluble tertiary amines or dilong
chain amide materials are incorporated at levels of from 0.5% to 5% by
weight, normally from 1% to 3% by weight whilst the high molecular weight
polyethylene oxide materials and the water soluble cationic materials are
added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by
weight. These materials are normally added to the spray dried portion of the
composition, although in some instances it may be more convenient to add
them as a dry mixed particulate, or spray them as molten liquid on to other
solid components of the composition.
Bleaching agent
Additional optional detergent ingredients that can be included in the
detergent 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%.
The bleaching agent cor."~onent for use herein can be any of the
bleaching agents useful for detergent compositions including oxygen bleaches
as well as others known in the art. The bleaching agent suitable for the
present invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this class of agents include magnesium monoperoxyphthalate hexahydrate,
the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching
. .
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agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S. Patent
4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-
oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used encompasses the
halogen bleaching agents. Examples of hypohalite bleaching agents, for
example, include trichloro isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such
materials are normally added at 0.5-10% by weight of the finished product,
preferably 1-5% by weight.
The hydrogen peroxide releasing agents can be used in combination with
bleach activators such as tetraacetylethylenediamine (TAED),
nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591)
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 08/136,626, PCT/US95/07823, W095/27772,
W095/27773, W095/27774 and W095/27775.
The hydrogen peroxide may also be present by adding an enzymatic
system (i.e. an enzyme and a substrate therefore) which is capable of
generating hydrogen peroxide at the beginning or during the washing and/or
rinsing process. Such enzymatic systems are disclosed in EP Patent
Application 91202655.6 filed October 9, 1991.
.
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36
Metal-containing catalysts for use in bleach compositions, include
cobalt-containing catalysts such as Pentaamine acetate cobalt(lll) salts and
manganese-containing catalysts such as those described in EPA 549 271;
EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416
and US 5,114,611. 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
tel, aacett.te, diethylene triamine pentamethyleneacetate, metal ion
sequealr~nts such as aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine
pentamethylenephosphonic acid. Phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly
an inorganic hydrated aluminosilicate material, more particularly a hydrated
synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
.. . .. .
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Another suitable inorganic builder material is layered silicate, e.g. SKS-
6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium
silicate (Na2Si2o5)-
Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent
Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two
carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid,
tartronic acid and fumaric acid, as well as the ether carboxylates described in
German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No.
3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups include, in
particular, water-soluble citrates, aconitrates and citraconates as well as
succinate derivatives such as the carboxymethyloxysuccinates described in
British Patent No. 1,379,241, lactoxysuccinates described in Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-
1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and
1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed
citrates described in British Patent No. 1,082,179, while polycarboxylates
containing phosphone substituents are disclosed in British Patent No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis -
dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-
hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in British Patent No. 1,425,343.
..... . ... ... .. ...
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38
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.
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 liquiddetergent compositions of the present invention are soaps and
polycarboxylates .
Other builder materials that can form part of the builder system for use
in granular compositions include inorganic materials such as alkali metal
carbonates, bicarbonates, silicates, and organic materials such as the organic
phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts, in which the polycarboxylic acid comprises at
least two carboxyl radicals separated from each other by not more than two
carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Exar~"~les of such
salts are polyacrylates of MW 2000-5000 and their copolymers with maleic
anhydride, such copolymers having a molecular weight of from 20,000 to
70,000, especially about 40,000.
~ etergency builder salts are normally included in amounts of from 5%
to 80% by weight of the composition preferably from 10% to 70% and most
usually from 30% to 60% by weight.
Chelating Agents
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VVO 97/43381 PCT~US97/0803 39
The detergent compositions herein may also optionally contain one or
more iron and/or manganese chelating agents. Such chelating agents can be
selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
- mixtures therein, all as hereinafter defined. Without intending to be bound by
theory, it is believed that the benefit of these materials is due in part to their
exceptional ability to remove iron and manganese ions from washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine-
hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali
metal, ammonium, and substituted ammonium salts therein and mixtures
therein.
Amino phosphonates are also suitable for use as chelating agents in
the compositions of the invention when at lease low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis Imethylenephosphonates) as DEQUEST. Preferred,
these amino phosphonates to not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful
in the compositions herein. See U.S. Patent 3,812,044, issued May 21,
1974, to Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1, 2-dihydroxy-3, 5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the IS,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine
diacetic acid IMGDA) salts (or acid form) as a chelant or co-builder useful
with, for example, insoluble builders such as zeolites, layered silicates and
the like.
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If utilized, these chelating agents will generally comprise from about
0.1% to about 15% by weight of the detergent compositions herein. More
preferably, if utilized, the chelating agents will comprise from about 0.1 % to
about 3.0% by weight of such compositions.
Suds su") r,ssor
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 inwhich the suds suppressor is advantageously releasably incorporated in a
water-soluble or water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds suppressor can be dissolved or
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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WO 97/43381 PCT/US97/08035
41
The suds suppressols described above are normally employed at levels
of from 0.001% to 2% by weight of the composition, preferably from 0.01%
to 1% by weight.
Others
Other components used in detergent compositions may be employed,
such as soil-suspending agents, soil-release agents, optical brighteners,
abrasives, bactericides, 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 3,455,838. These acid-ester dextrins are,preferably,
prepared from such starches as waxy maize, waxy sorghum, sago, tapioca
and potato. Suitable examples of said encapsulating materials include N-Lok
manufactured by National Starch. The N-Lok encapsulating material consists
of a modified maize starch and glucose. The starch is modified by adding
monofunctional substituted groups such as octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable herein include
cellulose derivatives such as methylcelluiose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or
their salts. Polymers of this type include the polyacrylates and maleic
anhydride-acrylic acid copolymers previously mentioned as builders, as well
as copolymers of maleic anhydride with ethylene, methylvinyl ether or
methacrylic acid, the maleic anhydride constituting at least 20 mole percent
of the copolymer. These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most preferably from
1% to 6% by weight of the composition.
,, ................. , . _ .
.
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WO 97/43381 PCT/US97/08035
42
Preferred optical brighteners are anionic in character, examples of
which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-
ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-
anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-
(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate, monosodium
4',4" -bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate, disodium
4,4' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,2' - disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-
triazol-2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-anilino-4-(1 -
methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no)stilbene-2,2'disulphonate,
sodium 2(stilbyl-4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific
brighteners of copending European Patent application No. 95201943.8.
Other useful polymeric materials are the polyethylene glycols,
particularly those of molecular weight 1000-10000, more particularly 2000
to 8000 and most preferably about 4000. These are used at levels of from
0.20% to 5% more preferably from 0.25% to 2.5% by weight. These
polymers and the previously mentioned homo- or co-polymeric
polycarboxylate salts are valuable for improving whiteness maintenance,
fabric ash deposition, and cleaning performance on clay, proteinaceous and
oxidizable soils in the presence of transition metal impurities.
Soil release agents useful in compositions of the present invention are
conventionally copoJymers or terpolymers of terephthalic acid with ethylene
glycol and/or propylene glycol units in various arrangements. Examples of
such polymers are disclosed in the commonly assigned US Patent Nos.
4116885 and 4711730 and European Published Patent Application No. O
272 033. A particular preferred polymer in accordance with EP-A-O 272 033
has the formula
(cH3(pEG)43)o.75(poH)o.25[T-po)2.8(T-pEG)o 4lT(
H)0.25((PEG)43CH3)0.75
where PEG is -(OC2H4)0-,PO is (OC3H60) and T is (pcOC6H4CO).
... .. .. , . ., ._,
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43
Also very useful are modified polyesters as random copolymers of
dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2
propane diol, the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or propane-diol. The target
is to obtain a polymer capped at both end by sulphobenzoate groups,
"primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be
less than fully capped, and therefore their end groups may consist of
monoester of ethylene glycol and/or propane 1-2 diol, thereof consist
"secondarily" of such species.
The selected polyesters herein contain about 46% by weight of
dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about
10% by weight ethylene glycol about 13% by weight of dimethyl
sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and
have a molecular weight of about 3.000. The polyesters and their method of
preparation are described in detail in EPA 311 342.
Is is well known in the art that free chlorine in tap water rapidly
deactivates the enzymes comprised in detergent compositions. Therefore,
using chlorine scavenger such as perborate, ammonium sulfate, sodium
sulphite or polyethyleneimine at a level above 0.1 % by weight of total
composition, in the formulas will provide improved through the wash stability
of the detergent enzymes. Compositions comprising chlorine scavenger are
described in the European patent application 92870018.6 filed January 31,
1 992.
Alkoxylated polycarboxylates such as those prepared from
polyacrylates are useful herein to provide additional grease removal
performance. Such materials are described in W0 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
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44
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 .
Dispersants
The detergent 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.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such
salts are polyacrylates of MW 2000-5000 and their copolymers with maleic
anhydride, such copolymers having a molecular weight of from 1,000 to
100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N
having a molecular weight of 4000, at a level from 0.5-20% by weight of
composition can be added in the detergent compositions of the present
invention.
The compositions of the invention may contain a lime soap peptiser
compound, which has preferably 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. 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) 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 example, in the following review articles; W.N.Linfield, Sur~actant science Series, Volume 7, page 3; W.N. Linfield, Tenside
surf. det., volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F.
_....
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Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The
LSDP is the % weight ratio of dispersing agent to sodium oleate required to
disperse the lime soap deposits formed by 0.0259 of sodium oleate in 30ml
of water of 333ppm CaCo3 ICa:Mg=3:2) equivalent hardness.
Surfactants having good lime soap peptiser capability will include certain
amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in
accord with the present invention include C 1 6-C 1 8 dimethyl amine oxide,
C12-C1g alkyl ethoxysulfates with an average degree of ethoxylation of from
1-5, particularly C1 2-C1 5 alkyl ethoxysulfate surfactant with a degree of
ethoxylation of amount 3 ~LSDP=4), and the C14-C1s 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.
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).
Hydrophobic bleaches such as 4-lN-octanoyl-6-aminohexanoyllbenzene
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 / hydrophobic bleach
formulations can also be used as lime soap peptisers compounds.
Dye transfer inhibition
The detergent compositions of the present invention can also include
compounds for inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric laundering
operations involving colored fabrics.
.. .. . . . . . . .
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Polymeric dye transfer inhibiting ~,e.)ts
The detergent compositions according to the present invention also
comprise from 0.001% to 10 %, preferably from 0.01% to 2 %, more
preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting
agents. Said polymeric dye transfer inhibiting agents are normally
incorporated into detergent compositions in order to inhibit the transfer of
dyes from colored fabrics onto fabrics washed therewith. These polymers
have the ability to complex or adsorb the fugitive dyes washed out of dyed
fabrics before the dyes have the opportunity to become attached to other
articles in the wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles
or mixtures thereof.
Addition of such polymers also enhances the performance of the enzymes
according the invention.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having
the following structure formula:
p
I
~I) Ax
I
R
wherein P is a polymerisable unit, whereto the R-N-0 group can be attached
to or wherein the R-N-0 group forms part of the polymerisable unit
or a combination of both.
O 00
Il 11 11
A is NC, C0, C, -0-,-S-, -N-; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen of
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47
the N-O group can be attached or wherein the nitrogen of the N-O
group is part of these groups.
The N-O group can be represented by the following general structures:
O O
(R1 )x -N- ~R2)y = N- (R1 )x
I
(R3)z
wherein R 1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is O or
1 and wherein the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group forms part of these groups.
The N-O group can be part of the polymerisable unit (P) or can be
attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine
and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine
N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto
the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides
having the general formula ~I) wherein R is an aromatic, heterocyclic or
alicyclic groups wherein the nitrogen of the N-O functional group is part of
said R group.
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48
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 alicyclicgroups 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 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; ~.referably from 1,000 to 50,000, more preferably from 2,000 to
30,000, most preferably from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
.. . . . . ...
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The N-vinylimidazole N-vinylpyrrolidone polymers used in the present
invention have an average molecular weight range from 5,000-1,000,000,
preferabiy from 5,000-200,000.
Highly preferred polymers for use in detergent compositions according
to the present invention comprise a polymer selected from N-vinylimidazole
N-vinylpyrrolidone copolymers wherein said polymer has an average molecular
weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000,
most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern
Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
average molecular weight range from 5,000 to 50,000; more preferably from
8,000 to 30,000; most preferably from 10,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by
having said average molecular weight range provide excellent dye transfer
inhibiting properties while not adversely affecting the cleaning performance of
detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention
has a molar ratio of N-vinylimidazole to N-vinyipyrrolidone from 1 to 0.2,
more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
The detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of from
about 2,500 to about 400,000, preferably from about 5,000 to about
200,000, more preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones
are commercially vailable from ISP Corporation, New York, NY and Montreal,
Canada under the product names PVP K-15 (viscosity molecular weight of
10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average
molecular weight of 160,000), and PVP K-90 (average molecular weight of
360,000). Other suitable polyvinylpyrrolidones which are commercially
available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12;
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polyvinylpyrrolidones known to persons skilled in the detergent field (see for
example FP-A-262,897 and Fp-A-256~696).
d) Polyvinyloxazolidone:
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about 2,500
to about 400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most preferably from
about 5,000 to about 15,000.
e) Polyvinylimidazole:
The detergent compositions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
polyvinylimidazoles have an average
about 2,500 to about 400,000, preferably from about 5,000 to about
200,000, more preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000.
f) Cross-linked polymers:
Cross-linked polymers are polymers whose backbone are interconnected to
a certain degree; these links can be of chemical or physical nature, possibly
with active groups n the backbone or on branches; cross-linked polymers
have been described in the Journal of Polymer Science, volume 22, pages
1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that
they form a three-dimensional rigid structure, which can entrap dyes in the
pores formed by the three-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 treal~"enl
solution is preferably from 7 to 12.
A prefer- ed 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 9 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 0.5-209
(per 25 dishes being treated). Preferred manual dishwashing methods include
the application of a concentrated solution to the surfaces of the dishes or the
soaking in large volume of dilute solution of the detergent composition.
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.
LAS : Sodium linear C12 alkyl benzene sulphonate.
. .
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TAS : Sodium tallow alkyl sulphate.
XYAS : Sodium C1X - C1y alkyl sulfate.
SAS : C12-C14 secondary (2,3) alkyl sulfate in the form
of the sodium salt.
AEC : Alkyl ethoxycarboxylate surfactant of formula C12
ethoxy (2) carboxylate.
SS : Secondary soap surfactant of formula 2-bytyl
octanoic acid.
25EY : A C12 C1s predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide.
45EY : A C14 - C1s predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide.
XYEZS : c1x - C1y sodium alkyl sulfate condensed with
an average of Z moles of ethylene oxide per mole.
Nonionic : C13-C1s mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxylation of
3.8 and an average degree of propoxylation of 4.5
sold under the tradename Plurafax LF404 by BASF
Gmbh.
AAPA : Cg-C1 o amidopropyldimethylamine.
CFAA : C12-C14 alkyl N-methyl glucamide.
TFAA : C 1 6-C 1 8 alkyl N-methyl glucamide.
DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
DEQA (1) : Di-~oleyloxyethyl) dimethyl ammonium
methylsulfate.
DEQA ~2) : Di-(soft-tallowyloxyethyl) hydroxyethyl methyl
ammonium methylsulfate.
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Wo 97/43381
53
DTDMAMS : Ditalllow dimethyl ammonium methylsulfate.
SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed
stearic acid.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by
Shell Chemical C0.
Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio =
2.0).
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si20s
Carbonate : Anhydrous sodium carbonate.
Metasilicate : Sodium metasilicate ~SiO2:Na20 ratio = 2.0).
Phosphate or STPP : Sodium tripolyphosphate.
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000.
PA30 : Polyacrylic acid of average molecular weight of
approximately 8,000.
Terpolymer : Terpolymer of average molecular weight approx.
7,000, comprising acrylic:maleic:ethylacrylic acid
monomer units at a weight ratio of 60:20:20.
480N : Random copolymer of 3:7 acrylic/methacrylic acid,
average molecular weight about 3,500.
Polyacrylate : Polyacrylate homopolymer with an average
molecular weight of 8,000 sold under the
tradename PA30 by BASF GmbH.
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na12(A1~2Si~2)12. 27H20 having a primary
particle size in the range from 1 to 10 micrometers
Zeolite MAP : Alkali metal alumino-silicate of the zeolite P type
having a silicon to aluminium ratio not greater than
1 .33
Citrate : Tri-sodium citrate dihydrate.
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Citric : Citric Acid.
Perborate : Anhydrous sodium perborate monohydrate
bleach, empirical formula NaBO2.H2O2
PB4 : Anhydrous sodium perborate tetrahydrate.
Percarbonate : Anhydrous sodium percarbonate bleach of
empirical formula 2Na2co3.3H2o2
TAED : Tetraacetyl ethylene diamine.
Paraffin : Paraffin oil sold under the tradename Winog 70 by
Wintershall .
Peroxidase : Peroxidase enzyme sold under the tradename
Guardzyme by Novo Nordisk A/S.
Pectinase : Pectolytic enzyme sold under the tradename
Pectinex AR by Novo Nordisk A/S.
Xylanase : Xylanolytic enzyme sold under the tradenames
Pulpzyme HB or SP431 by Novo Nordisk A/S or
Lyxasan ~Gist-Brocades) or Optipulp or Xylanase
(Solvay).
Protease : Protease B.
Lipase : Lipolytic enzyme sold under the tradename
Lipolase.
Cellulase I : Cellulolytic enzyme sold under the tradename
Carezyme or Celluzyme by Novo Nordisk A/S
43kD.
Cellulase ll : Endoglucanase 50kD, cellulolytic enzyme sold
under the tradename "Endolase" by Novo Nordisk.
~ccase : Laccase from Myceliophtora thermophila.
Enhancer : Butyl syringate.
CMC : Sodium carboxymethyl cellulose.
... .
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HEDP ~ hydroxyethane diphosphonic acid.
DETPMP Diethylene triamine penta (methylene phosphonic
acid), marketed by Monsanto under the Trade
name Dequest 2060.
PAAC pentaamine acetate cobalt (Ill) salt.
BzP : Benzoyl peroxide.
PVP : Polyvinyl pyrrolidone polymer.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
Soil Release Polymer : Sulfonated poly-ethoxy/propoxy end capped ester
oligomer.
EDDS : Ethylenediamine -N, N'- disuccinic acid, [S,S]
isomer in the form of the sodium salt.
Suds Suppressor : 25% paraffin wax Mpt 50~C, 17% hydrophobic
silica, 58% paraffin oil.
Granular Suds : 1 2 % Silicone/silica, 1 8 % stearyl alcohol, 70%
Suppressor starch in granular form.
SCS : Sodium cumene sulphonate.
Sulphate : Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethylene oxide.
PGMS : Polyglycerol monostearate having a tradename of
Radiasurf 248.
TAE 25 : Tallow alcohol ethoxylate (25)
PEG(-6) : Polyethylene glycol (having a molecular weight of
600).
BTA : Benzotriazole.
,
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Bismuth nitrate : Bismuth nitrate salt.
NaDCC : Sodium dichloroisocyanurate
KOH : 100% Active solution of Potassium Hydroxide
pH : Measured as a 1 % solution in distilled water at 20
~C.
Example 1
Granular fabric cleaning compositions in accord with the invention were
prepared as follows:
11 111 lV V
LAS 22.0 22.0 22.0 22.0 22.0
AE5 9 0 9 0 9 0 9
Phosphate 23.0 23.0 23.0 23.0 23.0
Carbonate 23.0 23.0 23.0 23.0 23.0
Silicate 14.0 14.0 14.0 14.0 14.0
Zeolite A 8.2 8.2 8.2 8.2 8.2
DETPMP 0.4 0.4 0.4 0.4 0.4
Sodium sulfate 5.5 5.5 5.5 5.5 5.5
Amylase 0.005 0.02 0.01 0.01 0.02
Protease 0.01 0.02 0.01 0.005 0.005
I aCc~ce 0.005 0.01 0.01 0.1 0.001
Enhancer 0.5 0.5 0.5 0.5 0.5
Pectinase 0.02
Xylanase - - 0.01 0.02
Lipase 0.005 0.01
Cellulase I 0.000 0.001 0.005 1.0 .0000
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Water & minors Up to 100%
ExamPle 2
Granular fabric cleaning compositions in accord with the invention were
prepared as follows:
11 111 lV V
AE 6.0 6.0 6.0 6.0 6.0
LAS 12.0 12.0 12.0 12.0 12.0
Zeolite A 26.0 26.0 26.0 26.0 26.0
SS 4.0 4.0 4.0 4.0 4.0
SAS 5.0 5.0 5.0 5.0 5.0
Citrate 5.0 5.0 5.0 5.0 5.0
Sodium Sulfate 17.0 17.0 17.0 28.0 17.0
Perborate 16.0 16.0 16.0 - -
TAED 5.0 5.0 5.0
Protease 0.06 0.03 0.02 0.08 0.01
11 111 lV V
I accase 0.09 0.001 0.04 0.04 0.02
Enhancer 0. 5 0. 5 0 . 5 0. 5 0 . 5
Cellulase I .0000 1.0 0.4 0.002 0.02
Lipase 0.005 0.01
Amylase 0.01 0.015 0.01 0.02 0.005
Water & minors Up to 100%
ExamPle 3
Granular fabric cleaning compositions in accord with the invention which
are especially useful in the laundering of coloured fabrics were prepared as
follows:
ll lll
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58
LAS 11.4 10.7
TAS 1.8 2.4
TFAA - 4.0
45AS 3.0 3.1 10.0
45E7 4.0 4.0
25~3S - - 3.0
68E11 1.8 1.8
25E5 - - 8.0
Citrate 14.0 15.0 7.0
Carbonate - - 10
Citric 3.0 2.5 3.0
Zeolite A 32.5 32.1 25.0
Na-SKS-6 - - 9.o
MA/AA 5.0 5.0 5.0
DETPMP 1.0 0.2 0.8
Cellulase 1 0.1 0.0004 0.005
Protease 0.02 0.02 0.01
Amylase 0.03 0.03 0.005
Silicate 2.0 2.5
Sulphate 3.5 5.2 3.0
PVP 0.3 0.5
PVN0/copolymer of vinyl- - - 0. 2
imidazole and vinyl-pyrrolidone
Perborate 0.5 1.0
Laccase 0.01 0.01 0.005
Enhancer 0.5 1.0 0.5
Water/Minors Up to 100%
ExamPle 4
Granular fabric cleaning compositions in accord with the invention
were prepared as follows:
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59
ll
LAS 6 . 5 8 .0
AE 8.0 8.0
Alkyl Sulfate 15.0 18.0
Zeolite A 26.0 22.0
Sodium nitrilotriacetate 5.0 5.0
PVP 0.5 0.7
TAED 3.0 3.0
Boric acid 4.0
Perborate 0. 5 1 . 0
Protease 0.06 0.02
Laccase 0.01 0.003
Enhancer 0.5 0.8
Silicate 5.0 5.0
Carbonate 15.0 15.0
Peroxidase - 0.1
Pectinase 0.02
Cellulase 1 0.005 0.002
Lipase 0.01
Amylase 0.01 0.01
Water/minors Up to 100%
Example 5
A compact granular fabric cleaning composition in accord with the
invention was prepared as follows:
45AS 8.0
25E3S 2.0
25E5 3.0
25E3 3 0
TFAA 2 . 5
Zeolite A 1 7.0
NaSKS-6 1 2.0
Citric acid 3 0
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Carbonate 7 0
MA/AA 5.0
CMC 0 4
PVN0 / copolymer of vinylimidazole and 0.2
vinylpyrrolidone
Protease 0.05
Laccase 0.06
Enhancer 0.8
Lipase 0.005
Cellulase 1 0.001
Amylase 0.01
TAED 6.0
Percarbonate 22.0
EDDS 0 3
Granular suds suppressor 3.5
water/minors Up to 100%
ExamPle 6
A granular fabric cleaning compositions in accord with the invention
which provide "softening through the wash" capability were prepared as
follows:
ll
45AS - 10.0
LAS 7.6
68AS 1.3
45E7 4.0
25E3 - 5.0
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 1 1 .0
Zeolite A 1 5 .0 1 5 . 0
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MA/AA 4 0 4 0
DETPMP 0 4 0 4
Perborate 15.0
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPE0 - 0.1
Protease 0.02 0.01
Laccase 0.02 0.02
Enhancer 1.0 1.0
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 1 0.001 0.2
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
Example 7
Heavy duty liquid fabric cleaning compositions suitable for use in the
pretreatment of stained fabrics, and for use in a machine laundering method,
in accord with the invention were prepared as follows:
11 111 lV V
24AS 20.0 20.0 20.0 20.0 20.0
SS 50 50 50 50
Citrate 1.0 1.0 1.0 1.0 1.0
12E3 13.0 13.0 13.0 13.0 13.0
Monethanolamine 2.5 2.5 2.5 2.5 2.5
Boric acid 2.75 5.75 1.5 1.5 1.5
Formic acid - - 1.0 1.0 1.0
Protease 0.005 0.03 0.02 0.04 0.01
Laccase 0.005 0.01 0.02 0.02 0.08
. .
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Enhancer 0.5 0.5 0.5 1.0 1.0
Lipase 0.002 0.01 0.02 - 0.004
Amylase 0.005 0.005 0.001 0.01 0.004
Cellulase 1 0.04 0.01 0.01 0.08 0.000
Pectinase 0.02 0.02 - - -
Water/propylene glycol/ethanol (100: 1: 1)
ExamPle 8
Heavy duty liquid fabric cleaning compositions in accord with the
invention were prepared as follows:
11 111 lV V
LAS acid form - - 25.0
C12 14 alkenyl succinic 3.0 8.0 10.0
acld
Citric acid 10.0 15.0 2.0 2.0 2
23AS acid form - - - - 8
25AS acid form 8.0 8.0 - 15.0 4
25AE3S acid form - 3.0 - 4.0
35AE35 acid form - - - - 8
25AE7 - 8.0 - 6.0
45AE7 - - - - 2.5
25AE3 8.0 - 4.0
CFAA - - - 6.0 4
11 111 lV V
AAPA 1.5
N-Cocoyl N-methyl glucamine - - 4.0
DETPMP 0.2 - 1.0 1.0 1.0
Fatty acid - - - 10.0 5.0
Oleic acid 1.8 - 1.0 - 3.0
Ethanol 4.0 4.0 6.0 2.0 1.0
Propanediol 2.0 2.0 6.0 10.0 12.0
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Boric acid 2.75 2.751.5 1.5 3.0
Formic acid - - 1.0 1.0
Protease 0.02 0.020.02 0.01 0.02
Laccase 0.003 0.010.02 0.1 0.001
Enhancer 0.3 0.4 0.8 1.0 0.3
Amylase 0.005 0.010.005 0.01 0.05
Cellulase 1 0.03 .0005 0 03
Cellulase ll - - 0.02 0.01 0.09
Coco-alkyl dimethyl hydroxy - - 3.0
ethyl ammonium chloride
Smectite clay - - 5.0
PVP 1.0 2.0
Perborate - 1.0
Phenol sulphonate - O. 2
Peroxidase - 0.01
Monoethanol amine 6.2
NaOH Up to pH 7.5
Water / minors Up to 100%
ExamDle 9
The following rinse added fabric softener composition, in accord with the
invention, was prepared (parts by weight).
DEQA 24.5
PGMS 1 5
Alkyl sulfate 3 . 5
TAE 25 1 . 5
Protease 0.005
Laccase 0.01
Enhancer 0. 8
Amylase 0.001
Cellulase 1 0.001
Boric acid 2.00
HCL 0. 12
Antifoam agent 0.01 9
.. . . . ..
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Blue dye 80ppm
CaCI2 0.35
Perfume 0 90
Example 10
The following fabric softener and dryer added fabric conditioner
compositions were prepared in accord with the present invention:
11 111 lV V
DEQA 2.6 19.0 - - -
DEQA(2) 51.8
DTMAMS - - - 26.0
SDASA - - 70.0 42.0 40.2
Stearic acid of IV = 0 0.3
Neodol 45-13 - - 13.0
Hydrochloride acid 0.02 0.02
Ethanol - - 1.0
Cellulase 1 0.02 0.0002 0.1 0.01 0.1
I acc~se 0.002 0.005 0.01 0.01 0.1
Enhancer 0.05 0.01 0.2 0.5 0.9
Perfume 1.0 1.0 0.75 1.0 1.5
Glycoperse S-20 - - - - 15.4
Glycerol monostearate - - - 26.0
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01
Electrolyte - 0.1
Clay - - - 3.0
Dye 1 Oppm 25ppm 0.01
Water and minors 100% 100%
ExamPle 1 1
Syndet bar fabric cleaning compositions in accord with the invention
were prepared as follows:
11 111 lV
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C 12- 16 alkyl sulfate, Na 10.0 10.0 10.0 10.0
C12-14 N-methyl glucamide 5.0 5.0 5.0 5.0
C11 -13 alkyl benzene 10.0 10.0 10.0 10.0
sulphonate, Na
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate 7.0 7.0 7.0 7 0
Sodium tripolyphosphate 7.0 7.0 7.0 7.0
Zeolite A 5 0 5 0 5 0 5 0
Carboxymethylcellulose 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Amylase 0.01 0.02 0.01 0.01
Protease 0.3 0.4 0 5 0 05
Cellulase 1 0.003 0.005 0.05 0.2
Laccase 0.3 0 05 0 1 0 05
Enhancer 1 0 0.5 0.5 0 8
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler *: balance to 100%
*Can be selected from convenient materials such as CaC03, talc, clay
(Kaolinite, Smectite), silicates, and the like.
ExamDle 12
The following compact high density (0.96Kg/l) dishwashing detergent
compositions I to Vl were prepared in accord with the invention:
11 111 lV V Vl
STPP - - 48.8 37.4
Citrate 32.9 17.0 - - 17.0 25.4
Carbonate 17.5 - 20.0 20.0 25.4
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Silicate 33.0 14.8 20.4 14.8 14.8
Metasilicate - 2 . 5 2. 50
PB1 1.9 9.7 7.79 14.3 9.7
PB4 8 . 6 - - - - -
Percarbonate - - - - - 6.7
Alkyl sulfate 3.0 3.0 3.0 3.0 3.0 3.0
Nonionic 1.5 2.0 1.5 1.5 2.0 2.6
TAED 4. 8 2.4 2.4 - - 4.0
HEDP 0.8 1.0 0.5 - 0.8
DETPMP 0.65 0.65
PAAC - - - 0.2
BzP 4.4
Paraffin 0.5 0.5 0.5 0.5 - 0.2
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Cellulase 1 0.005 - 0.004 0.05
Cellulase ll - 0.02 - 0.08 0.04
Laccase 0.01 0.01 0.04 0.04 0.08 0.005
Enhancer 0.5 0.5 0.8 1.0 1.5 0.3
Lipase - 0.001 - 0.005
Amylase 0.01 0.005 0.015 0.015 0.005 0.0025
BTA 0.3 0.3 0 3 0 3
Bismuth Nitrate - 0.3
PA30 4.0
Terpolymer - - - 4.0
480N - 6.0 2.8 - 6.7
Sulphate 7.1 20.8 8.4 - 26.3 1 .0
pH (1 % solution) 10.8 11.0 10.9 10.8 10.9 9.6
Exam Dle 13
The following granular dishwashing detergent compositions examples I
to IV of bulk density 1.02Kg/L were prepared in accord with the invention:
11 111 lV V Vl
STPP 30.00 30.00 30.00 27.90 34.50 26.70
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Carbonate 30.60 30.50 30.50 23.00 30.50 2.80
Silicate 7.40 7.40 7.40 12.00 8.00 20.34
PB1 4.40 4.40 4.40 - 4.40
NaDCC - - - 2.00 - 1.50
Alkyl sulfate 1.0 1.0 1.0 2.0 2.0 1.5
Nonionic 0.75 0.75 0.75 1.90 1.20 0.50
TAED 1.00 1.00 - - 1.00
PAAC - - 0-004
BzP - 1.40
Paraffin 0.25 0.25 0.25
Protease 0.05 0.05 0.05 0.1 0.1 0.2
Cellulase 1 0.05 0.075 0.001 0.02 0.02 0.08
Laccase 0.005 0.0075 0.01 0.02 0.04 0.04
Enhancer 0.2 0.3 0.4 0.4 0.4 0.8
Lipase 0.005 - 0.001
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.15 - 0.15
Sulphate 23.90 23.90 23.90 31.40 17.40
pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30
ExamDle 14
The following detergent composition tablets of 259 weight were
prepared in accord with the present invention by compression of a granular
dishwashing detergent composition at a pressure of 13KN/cm2 using a
standard 12 head rotary press:
ll lll
STPP - 48.8 47.5
Citrate 26.4
Carbonate - 5.0
Silicate 26.4 14.8 25.0
Protease 0.03 0.075 0.01
ll lll
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Cellulase 1 0.003 0 015 0 001
Laccase 0.00750.0075 0.01
Enhancer 0.3 0.6 1.0
Lipase 0.005 - -
Amylase 0.01 0.005 0.001
PB1 1.6 7.8
PB4 6.9 - 11.4
Alkyl sulfate 2.0 3.0 2.0
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
Sulphate 25.0 14.7 3.2
pH (1% solution) 10.6 10.6 11.0
ExamDle 1 5
The following liquid dishwashing detergent compositions in accord
with the present invention, of density 1.40Kg/L were prepared:
ll
STPP 33.30 20.00
Carbonate 2.70 2.00
Silicate - 4.40
NaDCC 1 .10 1 .1 5
Alkyl sulfate 3.00 1.50
Nonionic 2.50 1.00
Paraffin 2.20
Boric acid 1.0 2.0
Formic acid 1.0
ll
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Protease 0.03 0.02
Cellulase I 0 01 0 005
Laccase 0.01 0 01
Enhancer 0.2 0.5
Amylase 0.005 0.0025
480N O 50 4 0O
KOH - 6.00
Sulphate 1.60
pH (1 % solution) 9.10 10.00
ExamDle 16
The following liquid dishwashing compositions were prepared in accord
with the present invention:
11 111 lV V
Alkyl (1-7) ethoxy sulfate 28.5 27.4 19.2 34.1 34.1
Amine oxide 2.6 5.0 2.0 3.0 3.0
C12 glucose amide - - 6.0
Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0
Neodol C11 E9 - - 5.0 - -
Polyhydroxy fatty acid amide - - - 6.5 6.5
Sodium diethylene penta acetate - - 0.03
~40%)
Diethylenetriamine penta acetate - - - 0.06 0.06
Sucrose - - - 1.5 1.5
Ethanol 4.0 5.5 5.5 9.1 9.1
Alkyl diphenyl oxide disulfonate - - - - 2.3
Calcium formate - - - 0.5 1.1
Ammonium citrate 0.06 0.1
Sodium chloride - 1.0
Magnesium chloride 3.3 - 0.7
Calcium chloride - - 0.4
11 111 lV V
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Sodium sulfate - - 0.06 - -
Magnesium sulfate 0.08
Magnesium hydroxide - - - 2.2 2.2
Sodium hydroxide - - - 1.1 1.1
Hydrogen peroxide 200pp 0.16 0.006
m
Laccase0.01 0.02 0.03 0.06 0.08
Enhancer 0.5 0 5 0 5 1 0 1 5
Cellulase 1 0.001 0.2 0.03 0.03 0.1
Protease 0.017 0.005 .00350.003 0.00
Perfume 0.18 0.09 0.09 0.2 0.2
Water and minors Up to 100%
ExamDle 17
The following liquid hard surface cleaning compositions were prepared
in accord with the present invention:
11 111 lV V Vl
Amylase 0.01 0.002 0.005 0.02 0.001 0.005
Protease 0.05 0.01 0.02 0.03 0.005 0.005
Cellulase 1 0.05 0.000 0.02 - 0.003
Cellulase ll - - 0.1 0.001
Laccase 0.005 0.01 0.04 0.1 0.005 0.1
Enhancer 0.5 0.5 0.5 0.5 1.0 1.0
Boric acid 2.75 2.75 2.75 2.75 2.75 2.75
EO~A* - - 2.90 2.90
Na Citrate - - - - 2.90 2.90
NaC12 Alkyl benzene 1.95 - 1.95 - 1.95
sulfonate
NiE09 1.50 2.00 1.50 2.00 1.50 2.00
NaC12 Alkyl sulfate - 2.20 - 2.20 - 2.20
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NaC12~ethoxy) - 2.20 - 2.20 - 2.20
* *sulfate
11 111 lV V Vl
C 12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
Na Cumene sulfonate 1.30 - 1.30 - 1.30
Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30
Water Balance to 100%
*Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
***AII formulas adjusted to pH 7
ExamDle 18
The following spray composition for cleaning of hard surfaces and
removing household mildew was prepared in accord with the present
invention
Amylase 0.01
Protease 0.01
Celllulase 1 0.01
Laccase 0.01
Enhancer 0.5
Boric acid 2.0
Sodium octyl sulfate 2.0
Sodium dodecyl sulfate 4.0
NiE09 2.0
Sodium hydroxide 0.8
Silicate (Na) 0.04
Perfume 0.35
Water/minors up to 100% -
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ExamDle 19
The following lavatory cleansing block compositions were prepared in accord
with the present invention.
ll lll
C 16-1 8 fatty alcohol/50E0 80.0
LAS - - 80.0
Nonionic - 1.0
Oleoamide surfactant - 26.0
Partially esterified copolymer of vinylmethyl 5.0
ether and maleic anhydride, viscosity 0.1-
0.5
Polyethylene glycol MW 8000 - 39.0
Water-soluble K-polyacrylate MW 4000- - 12.0
8000
Water-soluble Na-copolymer of acrylamide - 19.0
~70%) and acryclic acid (30%) low MW
Na triphosphate 10.0
Carbonate - - 8.0
Cellulase 1 0.8 0.005 0.01
I accase 0.08 0.1 0.1
Enhancer 1.0 1.5 1.5
Dye 2.5 1.0 1.0
Perfume 3.0 - 7.0
KOH / HCL solution pH 6-1 1
ExamDle 20
The following toilet bowl cleaning composition was prepared in accord with
the present invention.
ll
C14-15 linear alcohol 7E0 2.0 10.0
Citric acid lo.o 5 o
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Cellulase 10.8 0.005
Laccase 0.08 0.1
Enhancer 1.0 1.0
DETPMP - 1.0
Dye 2.0 1.0
Perfume 3.0 3.0
NaOH pH 6-1 1
Water and minors Up to 1 00%
