Note: Descriptions are shown in the official language in which they were submitted.
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WO 98/39402 PCTJUS97/03409
1
CLEANING COMPOSITIONS COMPRISING XYLAN DEGRADING
ALKALINE ENZYME AND BLEACHING AGENT
10
Field of the Invention
The present invention relates to cleaning compositions, including
laundry, dishwashing, household cleaning and oral/dental compositions,
comprising a xylan degrading alkaline enzyme and a bleaching agent.
Background of the invention
Performance of a detergent product, for use in washing or cleaning
method, is judged by a number of factors, including the ability to remove
soils, and the ability to prevent the redeposition of the soils, or the
breakdown products of the soils on the articles in the wash.
Removal by detergents of stains stemming from plants, wood, mould-
clay based soil and fruits is on of the thoughest cleaning challenge.
3o Especially in the laundry processes wherein the tendency is to move to low
wash temperatures and shorter washing cycles. These stains typically
- contain complex mixtures of fibrous material, based mainly on
carbohydrates and their derivatives, fibre and cell wall components.
Moreover, such stains are generally accompanied by amyiose, sugars and
their derivatives. Specific examples of such soils would include orange,
tomato, banana, tea, mango, broccoli, spinash soils and grass.
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In particular, food soils are often difficult to remove effectively from a
soiled item. Highly coloured or 'dried-on' soils derived from fruit and/or
vegetables are particularly challenging soils to remove. Indeed processed or
cocked vegetables and fruits often contain non-plant cell walls materials
used for the processing, cooking and flavouring of the food : butter, milk,
eggs, oils such as soya or olive oil, thickeners, sweeteners such as sugar.
These material are often based on proteins, fats and/or starches.
Moreover, the colored plant and fruit stains also contain highly
colored color-bodies associated with cell wall constituents. This color-
bodies are based on carotenoids compounds such as a-,~i- and y-carotene
and lycopene 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 colored anthocyanins
~ 5 dyes and pigments based on peiargonidin, cyanidin, delphidin and their
methyl esters and the antoxanthins. These compounds are the origin of
most of the orange, red, violet and blue colors 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
2o 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.
The items can be fabrics, hard surfaces, dishware such as
plasticware, glassware or chinaware, or teeth and mouth.
It is therefore an object of the present invention to provide a cleaning
composition which significantly improves the removal of a broad range of
plant based stains. It is another object of the present invention to provide a
cleaning composition which enhances fabric realistic items cleaning and
3o whitening.
The above objective has been met by formulating cleaning
compositions comprising a xylan degrading alkaline enzyme and bleaching
agent.
In a preferred embodiment, the present invention relates to a laundry
and/or fabric care composition comprising a xylan degrading alkaline enzyme
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and a bleaching agent, which enhances fabric realistic items cleaning and
whitening. In a second embodiment, the present invention relates to
dishwashing or household cleaning compositions comprising a xylan
degrading alkaline enzyme and a bleaching agent, and in a third
embodiment, the present invention relates to oral/dental care compositions
comprising a xylan degrading alkaline enzyme and a bleaching agent.
Xylan degrading enzymes like xylanase are commonly used in the
paper/pulp industry and to a lesser extent also in the starch/baking industry.
Examples of such xyian degrading enzymes are the commercial available
xylanases e.g. Pulpzyme HB, Pulpzyme HC and SP431 (Novo Nordisk A/S),
Lyxasan fGist-Brocades) Optipulp and Xylanase (Solvayl.
In WO 94/01532 is disclosed a method for producing enzymes from
~ 5 strains of the alkalophilic species Bacillus sp. AC13. Enzymes obtainable
from these strains are proteases, xylanases and cellulases as well. The
protease and cellulase enzymes are demonstrated to be valuable for use in
detergents while on the other hand xylanase is shown to be of use in
processes for treatment of lignocellulosic pulp i.e. the paper pulp industry.
In WO 92/06209 is disclosed that xylanase enzymes are
overexpressed by microbial strains constructed via genetic techniques free
of cellulolytic enzymes. These xylanase enzymes are described for use in a
variety of applications like the bleaching of wood pulps and the modification
of cereals and grains for use in baking and the production of animal feeds.
In WO 92/19726 are disclosed stabilised, modified enzymes. The
naturally occurring amino acids (other than proline) have been substituted
with a proline residue at one or more positions. Among the modified
3o enzymes, amylases, lipases, cellulases, xylanases and peroxidases are
mentioned. Said stabilised, modified enzymes can be used in detergent
compositions.
EP 709 452 recognises the benefits for use of xylanase enzymes at
low levels in cleaning formulations.
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WO 95/35362 describes cleaning compositions containing plant-cell-
walls degrading enzymes such as pectinases and/or hemicellulases and/or
optionally cellulases. The cleaning properties of the xylanases enzymes
were tested in bleach free detergents.
As can be seen from the above, cleaning benefits for the combined
use of xylan degrading alkaline enzymes with a bleaching agent have not
been previously recognised.
Summary of the invention
The present invention relates to cleaning compositions comprising an
xylan degrading alkaline enzyme and a bleaching agent, which significantly
~ 5 improve the removal of a broad range of plant based stains.
Detailed description of the invention
2o The xvlan degirading alkaline enzyme
An essential component of the detergent compositions of the
invention is a xylan degrading alkaline enzyme. The cleaning compositions
of the present invention significantly improve the removal of a broad range
25 of plant based stains. In addition, it has been found that the cleaning
compositions of the present invention enhance fabric realistic items cleaning
and whitening.
Without wishing to be bound by theory, it is believed that the xylan
3o degrading alkaline enzyme is capable of attacking specific parts of
piant/fruit
cell constituents, breaking them down and facilitating removal during the
wash process. This goes by random endo-hydrolysis of the xylan
component or by successive exo-hydrolysis of xylose residues from the non-
reducing end of the xylan polymer chain or by removal of substituents such
35 as acetyl, 4-O-methyl glucuronic side chains, the L-arabinose side chains
and ferulic acid cross linkages and p-coumaric side chains from the xylan
polymer of the plant/fruit cells. Moreover, the xyian degrading activity
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enhances the accessibility of other detergent ingredients at the stain/soil.
Indeed, it is believed that the access for the bleaching agent to the color
bodies from the colored plant and/or fruit stains is facilitated by the
enzymatic activity of the xylan degrading alkaline enzyme. The discoloration
and/or fragmentation of the color bodies in the colored plant and/or fruit
constituents and of particulates entrapped in such stains is thereby greatly
enhanced.
By xylan degrading enzyme it is meant herein any enzyme which
degrade, for instance hydrolyse and/or modify, xylan containing polymers
which are associated with hemicellulose and other plant polysaccharides.
By xylan degrading alkaline enzyme it is meant a xylan degrading
enzyme having an enzymatic activity of at least 10%, preferably at least
25%, more preferably at least 40% of its maximum activity at a pH ranging
~ 5 from 7 to 12. Preferably, a xylan degrading enzyme having its maximum
activity at a pH ranging from 7 to 12.
The xylan degrading alkaline enzyme can be a single xylan degrading
activity species or a mixture of the iso-enzymes obtained via the purification
20 of the crude xylan degrading alkaline enzyme mixure. The xylan degrading
enzymes of interest are the endo- and exo-Xylanases hydrolysing Xylan in
endo- or in exo fashion: endo-1,3 beta Xylosidase (E.C. 3.2.1.32) , the
endo-1,4-beta Xylanase (E.C. 3.2.1.8), 1,3-beta D Xylans
Xylohydrolase,(E.C. 3.2.1.72), 1,4 -beta D Xylans Xylohydrolase,(E.C.
25 3.2.1.37). Other Xylan degrading alkaline enzymes of interest remove
substitutions from the main xylan polymer such as Acetylxylan esterase ;
Glucuronoarabinoxylan endo-1,4-xylanase (E.C. 3.2.1.136), arabinosidase
(E.C.3.2.1.55) and ferulic esterase and coumaric acid esterase. These
enzymes remove respectively the acetylation , 4-0-methyl glucuronic side
3o chains ; the L-arabinose side chains and ferulic acid cross linkages and p-
coumaric side chains from the main xylan polymer.
- The xylan degrading alkaline enzymes can be produced as the wild
types by alkalophilic micro-organisms , but also the genes encoding the
35 xylan degrading alkaline enzymes can be cloned and expressed in suitable
hosts. The cloned xylan degrading alkaline enzymes are either the natural
wild types or the protein engineered enzymes for improved compatibility
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with detergents. Examples of micro-organisms suitable for the production
of the enzymes are listed : Bacillus species: AC13(NCIMB 40482); SD 902
(FERM P-13356); BX-1; BX-2; BX-3; BX-4 ; DSM 71 197; W2 (FERM P-
7221 ); W4 (FERM P-7223); C-%(-2 (FERM P-1698); TAR-1; V1-4; 41 M1;
K-12; B. stearothermophilus; B. polymyxa; B. circulars; Thermoto4a
species: T. neopolitama; T. thermarium.; Streptomvces species:
S.viridosporus (ATCC 39115) S. olivochromogenes; Asper4illus species: A.
phoenicis; Humicola species: H. insoiens; Trichoderma species: T. reesei
(VTT-D-86271-RUT C30); Actinomadura flexuosa; Microtetetraspora
to flexuosa ; Thermonaspora fusca KW 3 (DSM 6013); E.coli and variants
carrying plasmid pCX31 1; Cepholosporum f NCL 87.1 1.91; Actinomycetes.
Nowadays, it is common practice to modify wild-type enzymes via
~ 5 protein / genetic engineering techniques in order to optimise their
performance efficiency in the cleaning compositions of the invention. For
example, the variants may be designed such that the compatibility of the
enzyme to commonly encountered ingredients of such compositions is
increased. Alternatively, the variant may be designed such that the optimal
20 pH, bleach stability, catalytic activity and the like, of the enzyme
variant is
tailored to suit the particular cleaning application.
In particular, attention should be focused on amino acids sensitive to
25 oxidation in the case of bleach stability and on surface charges for the
surfactant compatibility. The isoelectric point of such enzymes may be
modified by the substitution of some charged amino acids, e.g. an increase
in isoelectric point may help to improve compatibility with anionic
surfactants. The stability of the enzymes may be further enhanced by the
30 creation of e.g. additional salt bridges and enforcing calcium binding
sites to
increase chelant stability.
Pulpzyme HB and Pulpzyme HC from Novo Nordisk and xylanase
35 L120000 from Solvay are commercial available xylan degrading alkaline
enzymes.
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Said xylan degrading alkaline enzyme is incorporated into the
compositions of the present invention preferably at a level of from
0.0001 % to 2%, more preferably from 0.0005% to 0.5%, most preferred
from 0.001 % to 0.05% pure enzyme by weight of the composition.
The bleaching! acLent
The bleaching agent according to the present invention can be any of
the bleaching agents useful for cleaning compositions including oxygen
bleaches as well as others known in the art. The bleaching agent suitable
for the present invention can be an activated or non-activated bleaching
agent.
~ 5 These bleaching agents can be such as hydrogen peroxide, PB 1, PB4
and percarbonate with a particle size of 400-800 microns. These bleaching
agent components can include one or more oxygen bleaching agents and,
depending upon the bleaching agent chosen, one or more bleach activators.
When present oxygen bleaching compounds will typically be present at
20 levels of from about 1 % to about 25%.
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,
25 the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching
agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S. Patent
4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-
30 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
35 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.
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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
~ 5 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
2o 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.
25 Peroxidase enzymes are used in combination with oxygen sources,
e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are
used for "solution bleaching", i.e. to prevent transfer of dyes or pigments
removed from substrates during wash operations to other substrates in the
wash solution. Peroxidase enzymes are known in the art, and include, for
3o example, horseradish peroxidase, ligninase and haloperoxidase such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International Application
WO 89/099813, W089/09813 and in European Patent application EP No.
91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed
35 February 20, 1996. Also suitable is the laccase enzyme.
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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.
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), i 0
ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid
(POP) and 10-methylphenoxazine (described in WO 94/12621 ) and
substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen
peroxide.
Metal-containing catalysts for use in bleach compositions, include
cobalt-containing catalysts such as Pentaamine acetate cobalt(III) salts and
~ 5 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 phthaiocyanine
and a photoactivated bleaching process are described in U.S. Patent
4,033,71$. Typically, detergent compositions will contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
Said bleaching agents are generally comprised at a level of from
0.001 % to 30%, preferably from 0.01 % to 25% by weight of total
composition.
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Cleaning components
The cleaning compositions of the invention may also contain
additional cleaning components. The precise nature of these additional
components, and levels of incorporation thereof will depend on the physical
form of
the composition, and the nature of the cleaning operation for which it is to
be used.
In a preferred embodiment, the present invention relates to a laundry
and/or fabric care composition comprising a xylan degrading alkaline enzyme
and a bleaching agent (Examples 1-1 1 ). In a second embodiment, the
present invention relates to dishwashing or household cleaning
compositions (Examples 12-18) and in a third embodiment, the present
~ 5 invention relates to oral/dental care compositions (Examples 19-21 ).
The cleaning compositions according to the invention can be liquid,
paste, gels, bars, tablets, powder or granular forms. Granular compositions
can also be in "compact" form, the liquid compositions can also be in a
2o "concentrated" form.
The compositions of the invention may for example, be formulated as
hand and machine dishwashing compositions, hand and machine laundry
detergent compositions including laundry additive compositions and
25 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
containing such xyian degrading enzyme can also be formulated as oral
/dental care compositions.
Such compositions containing xylan degrading alkaline enzyme can
provide fabric cleaning, stain removal, whiteness maintenance, softening,
color appearance and dye transfer inhibition when formulated as laundry
detergent compositions.
When formulated as compositions for use in manual dishwashing
methods the compositions of the invention preferably contain a surfactant
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and preferably other detergent compounds selected from organic polymeric
compounds, suds enhancing agents, group II metal ions, solvents,
hydrotropes and additional enzymes.
When formulated as compositions suitable for use in a laundry
machine washing method, the compositions of the invention preferably
contain both a surfactant and a builder compound and additionally one or
more detergent components preferably selected from organic polymeric
compounds, bleaching agents, additional enzymes, suds suppressors,
dispersants, lime-soap dispersants, soil 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
7 5 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
2o composition measured at 20 ° C.
The "compact" form of the compositions herein is best reflected by density
and, in terms of composition, by the amount of inorganic filler salt;
inorganic filler salts are conventional ingredients of detergent compositions
25 in powder form; in conventional detergent compositions, the filler salts
are
present in substantial amounts, typically 17-35% by weight of the total
composition.
In the compact compositions, the filler salt is present in amounts not
exceeding 15% of the total composition, preferably not exceeding 10%,
3o 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
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compositions according the present invention will contain a lower amount of
water, compared to conventional liquid detergents.
Typically the water content of the concentrated liquid detergent is
preferably less than 40%, more preferably less than 30%, most preferably
less than 20% by weight of the detergent composition.
Surfactant system
The cleaning compositions according to the present invention generally
comprise a surfactant system wherein the surfactant can be selected from
nonionic and/or anionic and/or cationic and/or ampholytic andlor zwitterionic
and/or semi-polar surfactants.
t 5 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 cleaning 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.
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
3o 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
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moles, of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic surfactants of this type include IgepaITM CO-630, marketed by the
GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all
marketed by the Rohm & Haas Company. These surfactants are commonly
referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of primary and secondary aliphatic alcohols
with from about 1 to about 25 moles of ethylene oxide are suitable for use
as the nonionic surfactant of the nonionic surfactant systems of the present
invention. The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secondary, and generally contains from about 8 to
about 22 carbon atoms. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20 carbon atoms,
more preferably from about 10 to about 18 carbon atoms, with from about
2 to about 10 moles of 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 TergitoITM 15-S-9 (the condensation product of C 1 1-C 15
linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the
condensation product of C12-C14 primary alcohol with 6 moles ethylene
oxide with a narrow molecular weight distribution), both marketed by Union
Carbide Corporation; NeodoITM 45-9 (the condensation product of C 14-C 15
linear alcohol with 9 moles of ethylene oxide), NeodoITM 23-3 (the
condensation product of C 12-C 13 linear alcohol with 3.0 moles of ethylene
oxide), NeodoITM 45-7 (the condensation product of C 14-C 15 linear alcohol
with 7 moles of ethylene oxide), NeodoITM 45-5 (the condensation product
of C 14-C 15 linear alcohol with 5 moles of ethylene oxide) marketed by
Shell Chemical Company, KyroTM EOB (the condensation product of C13-
3o C 15 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 8-1 1 and most
preferred from 8-10.
Also useful as the nonionic surfactant of the surfactant systems of the
present invention are the alkylpolysaccharides disclosed in U.S. Patent
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WO 98/39402 14 PCT/US97103409
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about
to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,
hydrophilic group containing from about 1.3 to about 10, preferably from
5 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
1 o as opposed to a glucoside or galactoside). The intersaccharide bonds can
be, e.g., between the one position of the additional saccharide units and the
2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R201CnH2n01t~91ycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
2o groups contain from about 10 to about 18, preferably from about 12 to
about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
preferably 0; and x is from about 1.3 to about 10, preferably from about
1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl
is preferably derived from glucose. To prepare these compounds, the
alcohol or alkylpolyethoxy alcohol is formed first and then reacted with
glucose, or a source of glucose, to form the glucoside (attachment at the 1-
positionl. 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 1 500 to about 1800 and
will exhibit water insolubility. The addition of poiyoxyethylene moieties to
this hydrophobic portion tends to increase the water solubility of the
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WO 98/39402 15 PCT/US97/03409
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
~ 5 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
1 1,000. Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
2o 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, alkylpoiysaccharides,
and mixtures thereof. Most preferred are Cg-C14 alkyl phenol ethoxylates
25 having from 3 to 15 ethoxy groups and Cg-C 1 g alcohol ethoxylates
(preferably C ~ p avg.1 having from 2 to 10 ethoxy groups, and mixtures
thereof.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
3o surfactants of the formula.
R2-C-N-Z,
O R1
35 wherein R 1 is H, or R 1 is C 1 _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5_3~ hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
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WO 98/39402 16 PCTIUS97/03409
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 S03
according to "The Journal of the American Oil Chemists Society", 52
(1975), pp. 323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications, comprise alkyl ester sulfonate surfactants of the structural
~ 5 formula:
O
R3 - CH - C - OR4
2o S03M
wherein R3 is a Cg-C2p hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C1-Cg hydrocarbyl, preferably an alkyl, or combination
thereof, and M is a cation which forms a water soluble salt with the alkyl
25 ester suffonate. Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or unsubstituted
ammonium cations, such as monoethanolamine, diethanolamine, and
triethanolamine. Preferably, R3 is C1p-C16 alkyl, and R4 is methyl, ethyl or
isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is
3o C1 p-C1 g 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 C1 p-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
35 having a C1p-C2p alkyl component, more preferably a C12-C1g alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
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WO 98/39402 1 ~ PCT/US97103409
methyl-, dimethyl-, and trimethyl ammonium cations and quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl
piperdinium cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and the like). Typically, alkyl chains of C12-C1 g are preferred for
lower wash temperatures (e.g. below about 50°C) and C16-18 alkyl chains
are preferred for higher wash temperatures (e.g. above about 50°C).
Other anionic surfactants useful for detersive purposes can also be
included in the cleaning compositions of the present invention. These can
include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of
soap, 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,
alkyl
2o phosphates, isethionates such as the acyl isethionates, N-acyl taurates,
alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates
(especially saturated and unsaturated C 12-C 1 g monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated C6-C 12 diesters), acyl
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below), branched primary alkyl sulfates, and alkyl poiyethoxy carboxylates
such as those of the formula RO(CH2CH20)k-CH2C00-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
3o 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 11 by Schwartz, Perry and Berch). A variety of such
surfactants are also generally disclosed in U.S. Patent 3,929,678, issued
December 30, 1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference).
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WO 98/39402 18 PCT/US97/03409
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 C10-C24 alkyl or hydroxyaikyl
group having a C1p-C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-C1 g 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,
2o diethylamine, triethylamine, mixtures thereof, and the like. Exemplary
surfactants are C 12-C 1 g alkyl poiyethoxylate 11.0) sulfate (C 12-
CIgE(1.0)M), C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-
C1 gE(2.25)M), C12-C1 g alkyl polyethoxylate (3.0) sulfate (C12-
ClgE(3.0)M), and C12-C1g alkyl polyethoxyiate (4.0) sulfate (C12-
C1 gE(4.OlM), wherein M is conveniently selected from sodium and
potassium.
The cleaning compositions of the present invention may also contain
cationic, amphoiytic, zwitterionic, and semi-polar surfactants, as well as the
3o nonionic andlor anionic surfactants other than those already described
herein.
Cationic detersive surfactants suitable for use in the cleaning
compositions of the present invention are those having one long-chain
hydrocarbyl group. Examples of such cationic surfactants include the
ammonium surfactants such as alkyltrimethylammonium halogenides, and
those surfactants having the formula
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WO 98/39402 19 PCT/US97/03409
(R2(OR3)yl(R4(OR3)y)zRSN+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 C 1-
C4 alkyl, C 1-C4 hydroxyalkyl, benzyl ring structures formed by joining the
two R4 groups, -CH2CHOH-CHOHCORSCHOHCH20H 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.
~ 5 Quaternary ammonium surfactant suitable for the present invention
has the formula (I):
R Rz
~~O ~Rs
X-
Formula I
whereby R 1 is a short chainlength alkyl (C6-C 10) or alkylamidoalkyl of the
2o formula (II)
Cs-C~~N~CH~
II z
O
Formula II
y is 2-4, preferably 3.
25 whereby R2 is H or a C 1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a
short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,
3o whereby X- is a counterion, preferably a halide, e.g. chloride or
methylsulfate.
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Rs
~H
O z
Formula III
Rfi is C 1-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as defined in formula
I whereby
R 1 is Cg, C 1 p or mixtures thereof, x = o,
Rg, R4 = CH3 and R5 = CH2CH20H.
1o Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the
formula
R 1 R2R3R4N + X- (i)
wherein R1 is Cg-C1 fi alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-Cq, hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value
from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should
be benzyl.
The preferred alkyl chain length for R 1 is C 12-C 15 particularly where the
alkyl group is a mixture of chain lengths derived from coconut or palm
kernel fat or is derived synthetically by olefin build up or OXO alcohols
synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl
groups and the anion X may be selected from halide, methosulphate,
acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for
use herein are
coconut trimethyf ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
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myristyl trimethyl ammonium methyl sulphate;
fauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxyl4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-o-C-C12-14 alkyl and R2R3R4 are methyl).
0
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-
~ 5 insolublequaternary-ammonium fabric softening actives, the
most
commonly used having been di-long alkyl chain ammonium chloride
or
methyl sulfate.
Preferred ationic softeners among these include the following:
c
1) ditallow dimethylammonium chloride (DTDMAC);
20 2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate
;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
25 7) stearyl benzyl dirnethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
11) C12-18 alkyl dihydroxyethyl methyiammonium chloride;
30 12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowyiamidoethyl)-2-tallowyl imidazolinium
meth ylsulfate.
Biodegradable quaternary ammonium compounds have been
presented as alternatives to the traditionally used di-long alkyl chain
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ammonium chlorides and methyl sulfates. Such quaternary ammonium
compounds contain long chain alk(en)yl groups interrupted by functional
groups such as carboxy groups. Said materials and fabric softening
compositions containing them are disclosed in numerous publications such
as EP-A-0,040,562, and EP-A-0,239,910.
The quaternary ammonium compounds and amine precursors herein have
the formula (I) or (II), below
R3 R2 R 3~ R s
N-(CHz)n-CH -CHz X
N-~~2)n-QJT 1 X -
R3 Q
R~ T~ Ti
or
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-0-, -NR4-C(O)-, -
C(01-NR4-;
~5 R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is C 1-C4 alkyl or C 1-C4 hydroxyalkyl or H;
R4 is H or C 1-C4 alkyl or C 1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C11-C22 alkyl or alkenyl;
2o n and m are integers from 1 to 4; and
X- is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include chloride or
methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11
carbon atoms, preferably at least 16 carbon atoms. The chain may be
straight or branched.
3o 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.
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Specific examples of quaternary ammonium compounds suitable for
use in the aqueous fabric softening compositions herein include
1 ) N,N-di(taliowyl-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-tailowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
5) N-(2-tailowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyll-N,N-dimethyl
ammonium
chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
~ 5 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.
2o When included therein, the cleaning 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 cleaning
25 compositions of the present invention. These surfactants can be broadly
described as aliphatic derivatives of secondary or tertiary amines, or
aliphatic derivatives of heterocyclic secondary and tertiary amines in which
the aliphatic radical can be straight- or branched-chain. One of the aliphatic
substituents contains at least about 8 carbon atoms, typically from about 8
3o 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.
35 When included therein, the cleaning compositions of the present
invention typically comprise from 0.2% to about 7 5%, preferably from
about 1 % to about 10% by weight of such ampholytic surfactants.
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WO 98/39402 2 4 PCT/US97103409
Zwitterionic surfactants are also suitable for use in cleaning
compositions. These surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary amines, or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line
38 through column 22, fine 48, for examples of zwitterionic surfactants.
When included therein, the cleaning compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from
about 1 % to about 10% by weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of nonionic
~ 5 surfactants which include water-soluble amine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected
from the group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-soluble phosphine
oxides containing one alkyl moiety of from about 10 to about 18 carbon
2o 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 hydroxyaikyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide
surfactants having the formula
0
T
R3 ( OR4 ) xN ( R5 ) 2
wherein R3 is an alkyl, hydroxyaikyl, or alkyl phenyl group or mixtures
therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene
or hydroxyalkylene group containing from about 2 to about 3 carbon atoms
or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a
polyethylene oxide group containing from about 1 to about 3 ethylene oxide
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WO 98/39402 2 5 PCT/IJS97103409
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
dimethyi amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine
oxides.
When included therein, the cleaning compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from
1 o about 1 % to about 10% by weight of such semi-polar nonionic surfactants.
The cleaning composition of the present invention may further
comprise a cosurfactant selected from the group of primary or tertiary
amines.
Suitable primary amines for use herein include amines according to
the formula R1 NH2 wherein R1 is a Cg-C12~ preferably Cg-C1 p alkyl chain
or R4X(CH2yn, X is -O-,-CIO1NH- or -NH-, R4 is a Cg-C12 alkyl chain n is
between 1 to 5, preferably 3. R 1 alkyl chains may be straight or branched
2o and may be interrupted with up to 12, preferably less than 5 ethylene oxide
moieties.
Preferred amines according to the formula herein above are n-alkyl
amines. Suitable amines for use herein may be selected from 1-hexylamine,
1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines
include C8-C10 oxypropyiamine, octyloxypropylamine, 2-ethylhexyl-
oxypropyfamine, tauryl amido propylamine and amido propylarnine.
Suitable tertiary amines for use herein include tertiary amines having
3o the formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or
Rs
i
-C CHz-CH-Q ~H
R3 is either a Cg-C12, preferably Cg-C10 alkyl chain, or R3 is R4X(CH2p,
whereby X is -O-, -C(O)NH- or -NH-~R4 is a C4-C12, n is between 1 to 5,
preferably 2-3. R5 is H or C 1-C2 alkyl and x is between 1 to 6 .
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WO 98/39402 2 6 PCTlUS97/03409
Rg and R4 may be linear or branched ; R3 alkyl chains may be interrupted
with up to 12, preferably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R1 R2RgN where R1 is a C6-C12 alkyl
chain, R2 and R3 are C 1-C3 alkyl or
Rs
-~ CH_,-CH-O~H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
O
I I
R i -C-NH-( CH2 )-N-( R2 )
n z
wherein R 1 is Cg-C 12 alkyl; n is 2-4,
preferably n is 3; R2 and R3 is C 1-C4
Most preferred amines of the present invention include 1-octylamine,
1-hexylamine, 1-decyiamine, 1-dodecylamine,CB-1 Ooxypropylamine, N coco
1-3diaminopropane, coconutalkyldimethyiamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyllamine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C 10
amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-
hexyiamine, 1-octylamine, 1-decylamine, 1-dodecyiamine. Especially
desirable are n-dodecyldimethylamine and bishydroxyethylcoconutaikylamine
and oieylamine 7 times ethoxylated, lauryl amido propylamine and
cocoamido propylamine.
3o Other detergent enzymes
The cleaning compositions can in addition to xylan degrading alkaline
enzyme further comprise one or more enzymes which provide cleaning
performance and/or fabric care benefits.
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WO 98/39402 2 ~ PCT/US97/03409
Said enzymes include enzymes selected from the group of protein
degrading enzymes such as proteases, Keratanase, from the group of
starch-and starch-derivatives degrading enzymes like: alfa-,beta- and iso-
amylases, pullulanase, from the group of polysaccharide degrading enzymes
such as isomaltase, glucoamylase, dextranase, mycodextranase, invertase,
lactase, insuiinase and from the group of oligosaccharide degrading
enzymes such as lysozym, endoglycosidaseH, alfa- and beta-N-
acetylgalactosaminidases, neuraminidase, chondroitinase, hesperinidase,
hyaluronidase and chitinase. Also suitable are enzymes selected from the
group of esters and fat's and wax-hydrolysing enzymes like lipase,
phoshpolipases, esterases and cutinases. Other plant-cell-walls degrading
enzymes can be selected from the group of cellulose and hemi-cellulose
degrading enzymes such as endo-and exo-cellulases and beta-giucosidases,
~ 5 the endo 1-3/ 1-4-beta glucanases and xyloglucanases, the pectin degrading
enzymes pectin esterase, pectin lyase, pectate lyase, endo-and exo-
polygalacturonase and rhamnogalacturonase and from the group of the
galactanases, arabinases, lichenases, mannanases and laminarinases.
Preferred are those enzymes being of the alkaline type.
Other preferred enzymes that can be included in the cleaning
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 fluorescent IAM
1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan, under the trade name Lipase P "Amano," hereinafter referred to as
"Amano-P". Other suitable commercial lipases include Amano-CES, lipases
ex Chromobacter viscosum, e.g. Chromobacter viscosum var, lipolyticum
NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscvsum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and iipases ex Pseudomonas gladioli. Especially suitable fipases
are lipases such as M 1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR
and Lipolase UItraR(Novo) which have found to be very effective when used
in combination with the compositions of the present invention. Also
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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 95135381
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 (Uniiever).
The iipases and/or cutinases are normally incorporated in the cleaning
composition at levels from 0.0001 % to 2% of pure enzyme by weight of
the detergent composition.
Suitable proteases are the subtilisins which are obtained from
~ 5 particular strains of B. subtilis and B. licheniformis (subtilisin BPN and
BPN'). One suitable protease is obtained from a strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed and sold as
ESPERASE° by Novo Industries A/S of Denmark, hereinafter "Novo".
The
preparation of this enzyme and analogous enzymes is described in GB
1,243,784 to Novo: Other suitable proteases include ALCALASE°,
DURAZYM° and 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 Bacillus in which lysine replaced arginine
at position 27, tyrosine replaced valine at position 104, serine replaced
asparagine at position 123, and alanine replaced threonine at position 274.
Protease C is described in EP 90915958:4, corresponding to WO
91 /06637, Published May 16, 1991. Genetically modified variants,
particularly of Protease C, are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl
hydroiase variant having an amino acid sequence not found in nature, which
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WO 98/39402 2 9 PCT/US97/03409
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
carbonyl hydrolase equivalent to position + 76, preferably also in
combination with one or more amino acid residue positions equivalent to
those selected from the group consisting of + 99, + i 01, + 103, + 104,
+ 107, + 123, + 27, + 105, + 109, + 126, + 7 28, + 135, + 156, + 1 fib,
+ 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260,
+ 265, and/or + 274 according to the numbering of Bacillus
amyioliquefaciens subtilisin, as described in W095/10591 and in the patent
application of C. Ghosh, et al, "Bleaching Compositions Comprising
Protease Enzymes" having US Serial No. 08/322,677, filed October 13,
1994.
Also suitable for the present invention are proteases described in
patent applications EP 251 446 and WO 91 /06637, protease BLAP°
~ 5 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
20 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.
25 The proteolytic enzymes are incorporated in the cleaning
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.
3o Amylases (a and/or f3) can be included for removal of carbohydrate-
based stains. W094/02597, Novo Nordisk A/S published February 03,
1994, describes cleaning compositions which incorporate mutant amylases.
See also W095/10603, Novo Nordisk A/S, published April 20, 1995.
Other amylases known for use in cleaning compositions include both a- and
35 (3-amylases. a-Amylases are known in the art and include those disclosed in
US Pat. no. 5,003,257; EP 252,666; W0/91 /00353; FR 2,676,456; EP
285,123; EP 525,fi10; EP 368,341; and British Patent specification no.
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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, W095/26397 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 A/S Denmark. W095/26397 describes other suitable
amylases : a-amylases characterised by having a specific activity of least
25% higher than the specific activity of Termamyl~ at a temperature range
of 25°C to 55°C and at a pH value in the range of 8 to 10,
measured by the
Phadebas~ a-amylase activity assay. Suitable are variants of the above
~ 5 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
W095135382.
2o The amylolytic enzymes are incorporated in the cleaning 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.
25 The celiulases usable in the present invention include both bacterial or
fungal celiuiase. Preferably, they will have a pH optimum of between 5 and
9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307,
Barbesgoard et al, which discloses fungal cellulase produced from Humicoia
insoiens. Suitable celiulases are also disclosed in GB-A-2.075.028; GB-A
30 2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the
Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicoia
35 insoiens having a molecular weight of about 50KDa, an isoelectric point of
5.5 and containing 415 amino acids; and a '43kD endoglucanase derived
from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred
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endoglucanase component has the amino acid sequence disclosed in PCT
Patent Application No. WO 91 /17243. Also suitable celfulases are the EGlil
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 ANSI
are especially useful. See also W091 /17243.
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,
barophiiic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-
purified
forms of these enzymes may be used. Also included by definition, are
~ 5 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 cleaning 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
(grills, granulates, stabilized liquids, etc... containing one enzyme ) or as
mixtures of two 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
3o enzyme oxidation scavengers are ethoxylated tetraethylene pofyamines.
A range of enzyme materials and means for their incorporation into
synthetic detergent compositions is also disclosed in WO 9307263 A and
WO 9307260 A to Genencor International, WO 8908694 A to Novo, and
U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.
4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
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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 fabric care benefits
Technologies which provide a type of color cars benefit can also be
included. Examples of these technologies are metallo catalysts for color
maintenance. Such metallo catalysts are described in copending European
~ 5 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
2o November 07, 1996.
Fabric softening agents can also be incorporated into laundry
detergent and/or fabric care compositions in accordance with the present
invention. These agents may be inorganic or organic in type. Inorganic
25 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-0 026 527 and EP-B-0 026 528 and
3o di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic
ingredients of fabric softening systems include high molecular weight
polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313
146.
35 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
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3 3 PCT/US97/03409
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.
Builder system
The compositions according to the present invention may further
~ 5 comprise a builder system. Any conventional builder system is suitable for
use herein including aluminosiiicate materials, silicates, polycarboxylates,
alkyl- or alkenyl-succinic acid and fatty acids, materials such as
ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate,
metal ion sequestrants such as aminopolyphosphonates, particularly
2o ethyfenediamine tetramethylene phosphonic acid and diethyiene triamine
pentamethylenephosphonic acid. Phosphate ~ builders can also be used
herein.
Suitable builders can be an inorganic ion exchange material,
25 commonly an inorganic hydrated aluminosilicate material, more particularly
a
hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g.
SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of
3o sodium silicate (Na2Si2051.
Suitable polycarboxylates containing one carboxy group include tactic
acid, glycolic acid and ether derivatives thereof as disclosed in Belgian
Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing
35 two carboxy groups include the water-soluble salts of succinic acid,
malonic
acid, (ethylenedioxy) diacetic acid, malefic acid, diglycollic acid, tartaric
acid,
tartronic acid and fumaric acid, as well as the ether carboxylates described
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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. Polycarboxyiates containing sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
~ 5 and 1,398,422 and in U.S. Patent No. 3,936,448, and the suifonated
pyrolysed citrates described in British Patent No. 1,082,179, while
polycarboxylates containing phosphone substituents are disclosed in British
Patent No. 1,439,000.
2o Alicyciic 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
25 alcohols such as sorbitol, mannitol and xyiitol. Aromatic poly-carboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxyiates
3o 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
35 a layered silicate ~SKS-6), and a water-soluble carboxylate chelating agent
such as citric acid.
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Preferred builder systems include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, and a watersoluble carboxylate
chelating agent such as citric acid. Preferred builder systems for use in
liquid detergent compositions of the present invention are soaps and
5 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-
poiymeric acids or their salts, in which the polycarboxylic acid comprises at
~ 5 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
2o malefic anhydride, such copolymers having a molecular weight of from
20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 5%
to 80% by weight of the composition preferably from 10% to 70% and
25 most usually from 30% to 60% by weight.
Chelating Agents
The detergent compositions herein may also optionally contain one or
3o 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
35 their exceptional ability to remove iron and manganese ions from washing
solutions by formation of soluble chelates.
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Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethyienediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, 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 (methylenephosphonates) as DEQUEST. Preferred,
these amino phosphonates to not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
~ 5 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.
2o A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,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
25 glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-
builder
useful with, for example, insoluble builders such as zeolites, layered
silicates and the like.
If utilized, these chelating agents will generally comprise from about
30 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 suppressor
Another optional ingredient is a suds suppressor, exemplified by
silicones, and silica-silicone mixtures. Silicones can be generally
represented
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PCT/US97/03409
by alkylated polysiloxane materials while silica is normally used in finely
divided forms exemplified by silica aerogels and xerogels and hydrophobic
silicas of various types. These materials can be incorporated as particulates
in which the suds suppressor is advantageously reieasably 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,
~ 5 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.
2o 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
25 can comprise a silicone/siiica mixture in combination with fumed nonporous
silica such as AerosilR.
The suds suppressors described above are normally employed at
levels of from 0.001 % to 2% by weight of the composition, preferably from
30 0.01 % to 1 % by weight.
Others
Other components used in cleaning compositions may be employed,
35 such as soil-suspending agents, soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents, and/or
encapsulated or non-encapsulated perfumes.
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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
i o sorghum, sago, tapioca and potato. Suitable examples of said encapsulating
materials include N-Lok manufactured by National Starch. The N-Lok
encapsulating material consists of a modified maize starch and glucose. The
starch is modified by adding monofunctional substituted groups such as
octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or
their salts. Polymers of this type include the polyacrylates and malefic
2o anhydride-acrylic acid copolymers previously mentioned as builders, as well
as copolymers of malefic anhydride with ethylene, methylvinyl ether or
methacrylic acid, the malefic anhydride constituting at least 20 mole percent
of the copolymer. These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most preferably
from 1 % to 6% by weight of the composition.
Preferred optical brighteners are anionic in character, examples of
which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-
ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-
anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-
(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate, monosodium
4',4" -bis-(2,4-dianifino-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-aniiino-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
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39
4,4'-bis(2-sulphostyryllbiphenyl. 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
~ 5 conventionally copolymers or terpolymers of terephthalic acid with
ethylene
glycol and/or propylene glycol units in various arrangements. Examples of
such polymers are disclosed in the commonly assigned US Patent Nos.
4116885 and 4711730 and European Published Patent Application No. 0
272 033. A particular preferred polymer in accordance with EP-A-0 272
20 033 has the formula
(CH3(PEG?43)0.75(POH)0.25~T-P012.8(T-PEG)0.41T(PO
H)0.25((PEG)43CH3)0.75
25 where PEG is -(OC2H4)O-,PO is (OC3Hg0) and T is (pcOCgH4C0).
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
3o secondarily of mono esters of ethylene glycol andlor 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
35 monoester of ethylene glycol and/or propane 1-2 diol, thereof consist
"secondarily" of such species.
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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
suifobenzoic 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 31 1 342.
Is is well known in the art that free chlorine in tap water rapidly
deactivates the enzymes comprised in detergent compositions. Therefore,
1o 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
~ 5 filed January 31, 1992.
Alkoxylated poiycarboxylates such as those prepared from
polyacrylates are useful herein to provide additional grease removal
performance. Such materials are described in WO 91 /08281 and PCT
20 90/01815 at p. 4 et ~seq., incorporated herein by reference. Chemically,
these materials comprise pofyacrylates 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 poiyacrylate "backbone" to provide a "comb" polymer
25 type structure. The molecular weight can vary, but is typically in the
range
of about 2000 to about 50,000. Such alkoxyiated polycarboxylates can
comprise from about 0.05% to about 10%, by weight, of the compositions
herein.
Dispersants
The cleaning composition of the present invention can also contain
dispersants : Suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts, in which the poiycarboxylic acid comprises at
least two carboxyl radicals separated from each other by not more than two
carbon atoms.
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41
Polymers of this type are disclosed in GB-A-1,596,756. Examples of
such salts are poiyacrylates of MW 2000-5000 and their copolymers with
malefic 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 cleaning compositions of the
present invention.
The compositions of the invention may contain a lime soap peptiser
compound, which preferably has a lime soap dispersing power (LSDP), as
defined hereinafter of no more than 8, preferably no more than 7, most
preferably no more than 6. 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
2o 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, Surfactant science Series, Volume 7, page 3;
W.N. Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and
M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages
71-73, (19891. The LSDP is the % weight ratio of dispersing agent to
sodium oleate required to disperse the lime soap deposits formed by 0.0258
of sodium oleate in 30m1 of water of 333ppm CaC03 (Ca:Mg = 3:2)
3o 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 g-C 1 g dimethyl amine oxide,
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C12-C1 g alkyl ethoxysulfates with an average degree of ethoxylation of
from 1-5, particularly C 12-C 15 alkyl ethoxysulfate surfactant with a degree
of ethoxylation of amount 3 (LSDP = 4), and the C 14-C 15 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-[N-octanoyl-6-aminohexanoyl]benzene
sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-
decanoyl-6-aminohexanoyl]benzene sulfonate and mixtures thereof; and
~ 5 nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic
bleach formulations can also be used as lime soap peptisers compounds.
Dye transfer inhibition
2o The cleaning 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.
25 Polymeric dye transfer inhibiting agents
The cleaning 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
3o agents. Said polymeric dye transfer inhibiting agents are normally
incorporated into cleaning compositions in order to inhibit the transfer of
dyes from colored fabrics onto fabrics washed therewith. These polymers
have the ability to complex or adsorb the fugitive dyes washed out of dyed
fabrics before the dyes have the opportunity to become attached to other
35 articles in the wash.
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WO 98/39402
4 3 PCT/US97/03409
Especially suitable polymeric dye transfer inhibiting agents are
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, polyvinyfpyrrolidone 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
2o wherein P is a polymerisable unit, whereto the R-N-O group can be
attached to or wherein the R-N-O group forms part of the
polymerisable unit or a combination of both.
0 0 0
II Il II
A is NC, CO, C, -O-,-S-, -N- ; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyciic or
alicyclic groups or any combination thereof whereto the nitrogen
of the N-0 group can be attached or wherein the nitrogen of the
3o N-O group is part of these groups.
The N-0 group can be represented by the following general structures
0 0
I I
(R1)x -N- (R2)y =N- (Rl)x
I
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WO 98/39402 ~ 4 PCTIUS97103409
( R3 ) z
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0
or 1 and wherein the nitrogen of the N-O group can be attached
or wherein the nitrogen of the N-O group forms part of these
groups.
The N-O group can be part of the polymerisable unit (P) or can be
1 o 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-0 functional group is part
of said R group.
Examples of these classes are polyamine oxides wherein R is a
heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives
thereof.
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Another preferred class of polyamine N-oxides are the polyamine
oxides having the general formula (I) wherein R are aromatic, heterocyclic or
alicyclic groups wherein the nitrogen of the N-0 functional group is attached
to said R groups.
Examples of these classes are poiyamine 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, polyalkyienes,
polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof.
~ 5 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
20 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from
1:7 to 1:1000000. The ~olvmers of the nraecnt ~r",o.,+;.,., .,..,.........
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,
25 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.
3o Typically, the average molecular weight is within the range of 500 to
1000,000; preferably from 1,000 to 50,000, more preferably from 2,000
to 30,000, most preferably from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
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The N-vinylimidazole N-vinylpyrrolidone polymers used in the present
invention have an average molecular weight range from 5,000-1,000,000,
preferably from 5,000-200,000.
Highly preferred polymers for use in detergent compositions
according to the present invention comprise a polymer selected from N-
vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000 more preferably
from 8,000 to 30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light
scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol
1 13,"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
2o having said average molecular weight range provide excellent dye transfer
inhibiting properties while not adversely affecting the cleaning performance
of detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present
invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1
to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinyipyrrolidone
3o 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
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weight of 40,0001, PVP K-60 (average molecular weight of 160,000), and
PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF
Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the detergent field (see for
example EP-A-262,897 and EP-A-256,696).
d? Polyvinyloxazolidone
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about
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
~ 5 from about 5,000 to about 15,000.
e) Polyvinylimidazole
The detergent compositions of the present invention may also utilize
2o polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
polyvinylirnidazoles have an average 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.
f) Cross-linked polymers
Cross-linked polymers are polymers whose backbone are
interconnected to a certain degree; these links can be of chemical or
3o 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-finked polymers entrap the dyes by swelling.
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48
Such cross-finked polymers are described in the co-pending patent
application 94870213.9
Method of washing
The compositions of the invention may be used in essentially any
washing or cleaning methods, including soaking methods, pretreatment
1 o methods and methods with rinsing steps for which a separate rinse aid
composition may be added.
The process described herein comprises contacting fabrics with a
laundering solution in the usual manner and exemplified hereunder.
The process of the invention is conveniently carried out in the course
of the cleaning process. The method of cleaning is preferably carried out at
5 ° C to 95 ° C, especially between 10 ° C and 60
° C. The pH of the
treatment solution is preferably from 7 to 12.
A preferred machine dishwashing method comprises treating soiled
articles with an aqueous liquid having dissolved or dispensed therein an
effective amount of the machine diswashing or rinsing composition. A
conventional effective amount of the machine dishwashing composition
means from 8-60 g of product dissolved or dispersed in a wash volume
from 3-10 litres.
According to a manual dishwashing method, soiled dishes are
contacted with an effective amount of the diswashing composition,
3o typically from 0.5-20g (per 25 dishes being treated). Preferred manual
dishwashing methods include the application of a concentrated solution to
the surfaces of the dishes or the soaking in large volume of dilute solution
of the detergent composition.
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.
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In the detergent compositions, the enzymes levels are expressed by
pure enzyme by weight of the tots! composition and unless otherwise
specified, the detergent ingredients are expressed by weight of the total
compositions. The abbreviated component identifications therein have the
following meanings:
LAS . Sodium linear C12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulphate
CXYAS : Sodium C 1 X - C 1 Y alkyl sulfate
25EY . A C12_C15 predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide
CXYEZ . A C1 X - C1 Y predominantly linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
XYEZS : C 1 X - C 1 Y sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
QAS . R2.N+/CH3)2/C2H40H) with R2 = C12-C14
Soap . Sodium linear alkyl carboxylate derived from a 80/20
mixture of tallow and coconut oils.
Nonionic . C13-C15 mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxylation of 3.8
and an average degree of propoxylation of 4.5 sold
under the tradename Plurafac LF404 by BASF Gmbh.
CFAA . C 12-C 14 alkyl N-methyl glucamide.
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TFAA : C 1 g-C 1 g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
Tallow . Dihydrogenated tallowamidoethyl hydroxyethylmonium
methosulfate / glycol distearate / cetyl alcohol.
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula 8-Na2Si205.
Carbonate . Anhydrous sodium carbonate with a particle size
between 200 ~m and 900pm.
Bicarbonate . Anhydrous sodium bicarbonate with a particle size
between 400 pm and 1200pm.
STPP . Anhydrous sodium tripolyphosphate
MA/AA . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000-80,000
PA30 . Polyacrylic acid of average molecular weight of
approximately 8,000.
Terpoiymer . Terpolymer of average molecular weight approx.
7,000, comprising acrylic:mafeic:ethylacrylic acid
monomer units at a weight ratio of 60:20:20
480N . Raridom 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
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Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12, 27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
Citrate . Tri-sodium citrate dihydrate of activity 86,4% with a
particle size distribution between 425 pm and 850 ~
m.
Citric . Anhydrous citric acid
PB1 . Anhydrous sodium perborate monohydrate bleach,
empirical formula NaB02.H202
PB4 ; Anhydrous sodium perborate tetrahydrate
Percarbonate : Anhydrous sodium percarbonate bleach of empirical
formula 2Na2C03.3H202
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
Photoactivated . Sulfonated zinc phtalocyanine encapsulated in dextrin
Bleach soluble polymer.
BUS . Butyl syringate CChem. Ber. 67 ( 1934) 67).
PPT . 10-propionic phenothiazine (J. Org. Chem. 15 ( 1950)
1 125-30).
PAAC . Pentaamine acetate cobalt(///) salt.
Paraffin : Paraffin oil sold under the tradename Winog 70 by
Wintershall.
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BzP . Benzoyl Peroxide.
Alkaline Xyianase . Xylan degrading alkaline enzyme sold under the
tradename Pulpzyme HC and Pulpzyme HB by Novo
Nordisk A/S, and Xylanase L120000 by Solvay.
Peroxidase : Peroxidase Guardzyme sold by Novo Nordisk.
Laccase . Laccase obtainable from Coprinaceae as described in
WO 96/06930 by Novo Nordisk.
Protease . Proteolytic enzyme sold under the tradename
Savinase, Alcalase, Durazym by Novo Nordisk A/S,
Maxacal, Maxapem sold by Gist-Brocades and
proteases described in patents W091 /06637 and/or
W095/10591 and/or EP 251 446.
Amylase . Amylolytic enzyme sold under the tradename Purafact
Ox AmR described in WO 94/18314, W096/05295
sold by Genencor; Termamyl~, Fungamyl~ and
Duramyl°, all available from Novo Nordisk A/S and
those described in W095/26397.
Lipase : Lipolytic enzyme sold under the tradename Lipolase,
Lipolase Ultra by Novo Nordisk A/S
Cellulase . Cellulytic enzyme sold under the tradename Carezyme,
Celluzyme and/or Endolase by Novo Nordisk A/S.
CMC . Sodium carboxymethyl cellulose.
DTPA . Pentasodium diethylene triamine tetraacetate.
HEDP . 1,1-hydroxyethane diphosphonic acid.
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53
DETPMP , Diethylene triamine penta (methylene phosphonic
acidl, marketed by Monsanto under the Trade name
bequest 2060.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
PVPVI . Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl
imidazole and vinyl-pyrrolidone.
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin
2-yl) stilbene-2:2'-disulfonate.
Silicone antifoam . Polydimethylsiioxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio
of said foam controller to said dispersing agent of
10:1 to 100:1.
Granular Suds . 12% Silicone/siiica, 18% stearyl alcohol,70% starch
Suppressor in granular form
SRP 1 : Sulfobenzoyl or sodium isethionate end capped esters
with oxyethylene oxy and terephtaloyl backbone.
SRP 2 . Diethoxylated poly ( 1,2 propylene terephtaiate) short
block polymer.
SCS . Sodium cumene sulphonate
Sulphate . Anhydrous sodium sulphate.
HMWPEO . High molecular weight polyethylene oxide
PEG . Polyethylene glycol.
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BTA : Benzotriazole.
Bismuth nitrate . Bismuth nitrate salt.
NaDCC . Sodium dichloroisocyanurate.
Encapsulated . Insoluble fragrance delivery technology utilising zeolite
perfume particles 13x, perfume and a dextrose/glycerin agglomerating
binder.
KOH . 100% Active solution of Potassium Hydroxide
Silica dental . Precipitated silica identified as Zeodent 1 19 offered by
abrasive J.M. Huber.
Carboxyvinyl . Carbopol offered by B.F. Goodrich Chemical Company.
polymer
Carrageenan . Iota Carrageenan offered by Hercules Chemical
' Company.
pH : Measured as a 1 % solution in distilled water at 20°C.
Example 1
The following laundry detergent compositions were prepared in accord with
the invention:
I II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
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Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
T'AED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Alkaline xylanase0.05 0.05 0.005 0.05 0.05 0.005
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
Amylase - 0.0009 0.0009 0.0009 0.0009 0.0009
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm)
Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to 100%
Density in g/litre 850 850 850 850 850 850
Example 2
The following granular laundry detergent compositions of bulk density 750
g/litre were prepared in accord with the invention:
1 11 III
LAS 5.25 5.6 4.8
TAS 1.25 1.9 1.6
C45AS ~ - 2.2 3.9
C25AE3S - 0.8 1.2
C45E7 3.25 - 5.0
C25E3 - 5.5 -
QAS 0.8 2.0 2.0
STPP 19.7 - _
Zeolite A - 19.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21 )
Carbonate 6.1 21.4 21.4
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WO 98139402 5 6 PCT/US97/03409
Bicarbonate - 2.0 2.0
Silicate 6.8 - -
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7 2.5
TAED 0.5 3.1 0.25
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Alkaline Xylanase 0.007 0.007 0.0007
Protease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
Cellulase - 0.0006 -
Amylase 0.0009 0.0009 0.0009
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach15 ppm 27 ppm 27 ppm
fppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.3
particles
Silicone antifoam 0.5 2.4 2.4
Minorslmisc to 100%
Example 3
The following detergent formulations, according to the present invention
were prepared, where I is a phosphorus-containing detergent composition, II
is a zeolite-containing detergent composition and III is a compact detergent
composition:
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0 -
C45AS 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0 - -
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 0.2 0.2 0.2
2 ~
Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2
Spray On
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C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15,0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 p
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Alkaline Xylanase 0.05 0.05 0.08
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.002 0.003 0.001
Dry mixed sodium sulfate3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 4
The following detergent formulations of particular use in the washing of
colored clothing, according to the present invention were prepared:
Blown Powder
Zeolite A 15.0 15.0 -
Sodium sulfate 0.0 5.0 -
LAS 3.0 3.0 -
DETPMP 0.4 0.5 -
CMC 0.4 0.4
MA/AA 4.0 4.0 -
I II III
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0 -
Silicate 4.0 4.0 -
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0' 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
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WO 98/39402 5 8 PCT/US97l03409
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVIlPVNO 0.5 0.5 0.5
Peroxidase 0.05 - -
Laccase - 0.05 0.02
PPT 0.5 - -
BUS - 0.8 1.5
PB1 1.0 - -
Alkaline Xylanase 0.001 0.005 0.007
Protease 0.026 0.016 0.047
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase - 0.006 -
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (gllitre) 700 700 700
Example 5
The following detergent formulations, according to the present invention
were prepared:
1 II III IV
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
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Bicarbonate - 7, 5 - -
DETPMP 0.7 1.0 - _
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Alkaline Xylanase 0.01 0.005 0.02 0.01
Protease 0.008 0.01 0.026 0.026
Amylase 0.007 0.004 - 0.002
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0005 - _
Photoactivated 70ppm 45ppm - l0ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0 1.0 1.0
NOBS 2.0 1.0 0.5 0.5
Balance (Moisture 100 100 100 100
and Miscellaneous)
Example 6
The following detergentformulations, to present invention
according the
were prepared:
I II III IV
Blown Pawder
Zeolite A 30.0 22.0 6.0 6.7
Na SkS-6 - - - 3.3
I II III IV
Pofycarboxylate- _ _ 7.1
Sodium sulfate19.0 5.0 7.0 _
MA/AA 3.0 3.0 6.0 -
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - _ _ 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0 -
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Brightener 1 0.2 0.2 0.2 -
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4 -
Spray On
C45E7 1.0 1.0 1.0 3.2
Dry additives
PVPVI/PVNO 0.5 0.5 0.5 -
Alkaline Xylanase 0.005 0.005 0.01 0.01
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0.0002 0.0002 - -
NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - to balance
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 7
The following high density and bleach-containing detergent formulations,
according to the present invention were prepared:
I II tll
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodium sulfate 0.0 5.0 0.0
I II III
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
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Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - _
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0 _
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
Polyethylene -
oxide of
MW
- 0.2
5,000,000
Bentonite clay - - 10.0
Alkaline Xylanase0.01 0.05 0.08
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase - - 0.002
Silicone antifoam5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture 100.0 100.0 100
and 0
Miscellaneous) .
Density (g/litre) 850 850 850
Example 8
The following high density detergent formulations, according to the present
invention were prepared:
Agglomerate
C45AS 1 1.0 14.0
Zeolite 15.0 6.0
A
Carbonate 4.0 g.0
MA/AA 4.0 2,p
CMC 0.5 0.5
DETPMP 0.4 0.4
Spray On
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C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Alkaline Xylanase 0.01 0.05
Protease 0.014 0.014
Lipase 0.009 0.009
Cellulase 0.001 -
Amylase 0.005 0.005
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litrel 850 850
Example 9
The following granular detergent formulations, according to the present
invention were prepared:
I II III IV V
LAS 21.0 25.0 18.0 18.0 -
Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decyl dimethyl - 0.4 0.7 0.7 0.8
hydroxyethyl NH4 + CI
Nonionic 1.2 - 0.9 0.5
Coco C12-14 Fatty Alcohol- - - - 1.0
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
MA/AA - - 0.9 0.9 -
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SRPi 0.3 0.15 0.2 0. i 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 13.0 15.0
Silicate 2.0 - 7.6 7,g _
Alkaline Xylanase 0.01 0.02 0.02 0.005 0.001
Protease 0.007 0.007 0.007 0.007 0.007
Amylase - 0.004 0.004 0.004 0.004
Lipase 0.003 0.003 0.003 - _
Cellulase - - - 0.001 0.001
NOBS 0.5 0.5 0.5 1.2 1.0
PB1 0.6 0.6 0.6 2.4 1.2
Diethylene triamine - - - 0.7 1.0
yenta
acetic acid
Diethylene triamine - - 0.6 - _
yenta
methyl phosphoric acid
Mg Sulfate _ _
0.8 - _
Photoactivated bleach 45 50 15 45 42
iPPml
Brightener 1 0.05 - 0.04 0.04 0.04
Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to
100%
Example 10
The followingliquid formulations,, according the
detergent to present
invention were prepared:
I II III IV V VI VII VIII
LAS 10.0 13.0 9.0 - 25.0 - _ _
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
1 II 111 IV V VI VII VIII
QAS - - - - 3.0 1.0 - -
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed fatty - - - 5.0 - - 4.0 4.0
acids
Citric 2.0 3.0 1.0 1.5 7.0 1.0 1.0 1.0
Dodecenyl/ 12.0 10.0 - - i 5,0 _ _ -
tetradecenyl
succinic acid
Oleic acid 4.0 2.0 1.0 - 1.0 - _ _
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Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5.0 - - 9.0 9.0
Amine
Tri Ethanol - - 8 - - - _ -
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3
tetraethylene
pentamine
DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 -
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
Laccase 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
BUS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Alkaline 0.01 0.02 0.02 .005 0.05 0.05 .005 0.02
Xylanase
Protease .005 .005 .004 .003 0.08 .005 .003 .006
Lipase - .002 - .000 - - .003 .003
2
Amylase .002 .002 .005 .004 .002 .008 .005 .005
Cellulase - - - .000 - - .000 .000
1 4 4
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - - - -
Ca chloride - 0.01 - 0.01 - - - -
5
Bentonite clay - - - - 4.0 4.0 -
Suspending clay - - - - 0.6 0.3 - -
SD3
Balance 100 100 100 100 100 100 100 100
Moisture and
Miscellaneous
Example 11
Granular fabric vide through
cleaning compositions "softening the
which pro
wash" capability
were prepared
in accord with
the present invention
I II
45AS - 10.0
LAS 7.6 -
68AS 1.3 -
45E7 4.0 -
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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
Zeoiite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
PB1 15.0 -
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - 0.1
Alkaline Xylanase 0.01 0.02
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001 -
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
Example 12
The following compact high density (0.96Kg/l) dishwashing detergent
compositions I to VI were prepared in accord with the present invention:
I II III IV V VI
STPP - - 49.0 38.0 - -
Citrate 33.0 i 7.5 - - 54.0 25.4
Carbonate - 17.5 - 20.0 14.0 25.4
Silicate 33.0 14.8 20.4 14.8 14.8 -
Metasilicate - 2.5 2.5 - - _
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PB1 1.9 9.7 7.8 14.3 7.8 -
PB4 8.6 - _ _ - -
Percarbonate - - - - - 6,7
Nonionic 1.5 2.0 1.5 1.5 1.5 2.6
TAED 4.8 2.4 2.4 - 2.4 4.0
HEDP 0.8 1.0 0.5 - - -
DETPMP 0.6 0.6 - - - -
PAAC - - - 0.2 - -
BzP - - - 4.4 -
Paraffin 0.5 0.5 0.5 0.5 0.5 0.2
Alkaline Xylanase0.01 0.005 0.01 0.02 0.02 0.04
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Lipase - 0.001 - 0.005 - -
Amylase 0.01 0.005 0.015 0.015 0.01 0.0025
BTA 0.3 0.3 0.3 0.3 0.3 -
Bismuth Nitrate- 0.3 - - - -
PA30 4.0 - - - - -
Terpolymer - - - 4.0 - -
480N - 6.0 2.8 - - -
Sulphate ' 7.1 20.8 8.4 - 0.5 1.0
pH ( 1 % solution)10.8 11.0 10.9 10.8 10.9 9.6
Examc~le 13
The following granular dishwashing detergent compositions examples I to IV
of bulk density 1.02Kg/L were prepared in accord with the present invention
I Il III IV V VI
STPP 30.0 30.0 30.0 27.9 34.5 26.7
Carbonate 30.5 30.5 30.5 23.0 30.5 2.80
Silicate 7.4 7.4 7.4 12.0 8.0 20.3
PB1 4.4 4.4 4.4 2.0 4.4 2.0
NaDCC - - - 2.0 - 1.5
Nonionic 0.75 0.75 0.75 1.9 1.2 0.5
TAED 1.0 1.0 - - 1.0 -
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PAAC - - 0.004 - _ _
BzP - 1.4 _ _
Paraffin 0.25 0.25 0.25 - -
Alkaline Xylanase0.008 0.08 0.01 0.01 0.1 0.05
Protease 0.05 0.05 0.05 - 0.1 -
Lipase 0.005 - 0.001 - -
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.15 - 0.15 - _ -
Sulphate 23.9 23.9 23.9 31.4 17.4 -
pH ( 1 % solution)10.8 10.8 10.8 10.7 10.7 12.3
Example 14
The following detergent composition tablets of 25g weight were prepared in
accord with the present invention by compression of a granular dishwashing
detergent composition at a pressure of 13KN/cm2 using a standard 12 head
rotary press:
I II III
STPP - 48.8 47.5
Citrate 26.4 - _
Carbonate - 5.0
Silicate 26.4 14.8 25.0
Alkaline Xylanase 0.01 0.05 0.1
Protease 0.03 0.075 0.01
Lipase 0.005 -
Amylase 0.01 0.005 0.001
PB1 1.6 7,g _
PB4 6.9 - 1 1.4
Nonionic 1.2 2.0 1.1
TAED 4.3 2.4 0.8
HEDP 0,7 - -
I II III
DETPMP 0.65 - ~ -
Paraffin 0.4 0.5 -
BTA 0.2 0.3 -
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PA30 3.2 - -
Sulphate 25.0 14.7 3.2
pH (1 % solution) 10.6 10.6 1 1.0
Example 15
The following liquid dishwashing detergent compositions were prepared in
accord with the present invention I to II, of density 1.40Kg/L
I II
STPP 33.3 20.0
Carbonate 2.7 2.0
Silicate - 4.4
NaDCC 1.1 1.15
Nonionic 2.5 1.0
Paraffin 2.2
Alkaline Xylanase 0.005 0.05
Protease 0.03 0.02
Amylase 0.005 0.0025
Laccase 0.02 0.02
BUS 0.5 0.5
480N 0.50 4.00
KOH - 6.00
Sulphate 1.6 -
pH (1 % solution) 9.1 10.0
Examale 16
The following liquid dishwashing compositions were prepared in accord with
the present invention
1 II 111 IV 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
C 12 glucose amide - - 6.0 - -
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Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0 -
Neodol C 1 1 E9 - - 5.0 - -
Polyhydroxy fatty acid amide-
- - 6.5 6.5
Sodium diethylene yenta - - 0.03 - -
acetate
(40%)
Diethylenetriamine yenta - -
acetate
- 0.06 0.06
Sucrose
- - - 1.5 1.5
Ethanol 4.0 5.5 5.5 9.1 9.1
Alkyl Biphenyl oxide disulfonate-
_ - - 2.3
Calcium formate - - - 0.5 1.1
Ammonium citrate 0.06 0.1 - _ _
Sodium chloride - 1.0 - - _
Magnesium chloride 3.3 _ 0.7 - -
Calcium chloride - - 0.4 -
~
Sodium sulfate - - 0.06 - -
Magnesium sulfate 0.08 - _ _ _
Magnesium hydroxide - -
- 2.2 2.2
Sodium hydroxide - -
- 1.1 1.1
Hydrogen peroxide 200pp 0.16 0.006 - -
m
BUS - - - 0.1 0.5
Laccase - - - 0.05 0.02
Protease 0.017 0.005 .0035 0.003 0.002
Alkaline xylanase 0.1 0.08 0.05 0.1 0.05
Perfume 0. i 0.09 0.09 0.2 0.2
8
Water and minors Up to 0%
10
Example 17
The following liquid hard surface cleaning compositions were prepared in
accord with the present invention
I II III IV V VI
Alkaline Xylanase 0.01 0.01 0.005 0.05 0.001 0.005
Amylase 0.01 0.002 0.005 0.02 0.001 0.005
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~ ~
Protease 0.05 0.01 0.02 0.03 0.005 0.005
Laccase 0.02 0.02 0.02 0.02 0.02 0.02
BUS 0.5 0.5 0.5 0.5 0.5 0.5
EDTA'" - - 2.90 2.90 - -
Citrate - - - - 2.90 2.90
LAS 1.95 - 1.95 - 1.95 -
C 12 AS - 2.20 - 2.20 - 2.20
NaC12iethoxy) - 2.20 - 2.20 - 2.20
'" '* sulfate
C 12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
SCS 1.30 - 1.30 - 1.30 -
Hexyl Carbitol ~" 6.30 6.30 6.30 6.30 6.30 6.30
~"
Water Balance 100%
to
'"Na4 ethylenediamine diacetic acid
* "Diethylene glycol monohexyl ether
~" ~" "All formulas adjusted to pH 7
ExamJ~le 18
The following spray composition for cleaning of hard surfaces and removing
household mildew was prepared in accord with the present invention
I
Alkaline Xylanase 0.01
Amylase 0.01
Protease 0.01
Laccase 0.08
BUS 1.0
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
Sodium hydroxide 0.80
1
Silicate (Na) 0.04
Perfume 0.35
Water/minors up to 100%
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Example 19
A two-layer effervescent denture cleansing tablet was prepared in accord
with the present invention
Acidic Layer
Protease 0.1
Tartaric acid 24.0
Sodium carbonate 4.0
Sulphamic acid 10.0
PEG 20,000 4.0
Sodium bicarbonate 24.5
Potassium persulfate 15.0
Sodium acid pyrophosphate
Pyrogenic silica 2.0
Tetracetylethylene diamine
Ricin-oleylsulfosuccinate 0.5
Flavor 1.0
Alkaline layer
Alkaline Xylanase 0.01
PB 1 32.0
Bicarbonate 19.0
EDTA 3.0
STPP 12.0
PEG 20,000 2.0
Potassium persulfate 26.0
Sodium carbonate 2.0
Pyrogenic silica 2.0
Dye/flavor 2.0
Example 20
1 o Dentifrice compositions were prepared in accord with the present invention
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I II III IV
Sorbitol (70% aqueous 35.0 35.0 35.0 35.0
solution)
PEG-6 1.0 1.0 1.0 1.0
Silica dental abrasive 20.0 20.0 20.0 20.0
Sodium fluoride 0.24 0.24 0.24 0.24
Titanium dioxide 0.5 0.5 0.5 0.5
Sodium saccharin 0.29 0.29 0.29 0.29
Alkaline Xylanase 0.005 0.5 0.01 0.02
Protease 0.2 0.35 0.15 0.2
PB 1 1.0 1.0 - -
Peroxidase - 0.05 - -
PPT - 0.5 - -
Laccase - - 0.05 0.01
BUS - - 0.7 1.0
Sodium alkyl sulfate 4.0 4.0 4.0 4.0
(27.9% aqueous solution)
Flavor 1.04 1.04 1.04 1.04
Carboxyvinyl polymer 0.3 0.3 0.3 0.3
Carrageenan 0.8 0.8 0.8 0.8
Water Balance to 100%
Example 21
Mouthwash compositions were prepared in accord with the present
invention
I II Ill IV
SDA 40 Alcohol 8.00 8.00 8.00 8.00
Flavor 0.08 0.08 0.08 0.08
Emulsifier 0.08 0.08 0.08 0.08
Sodium fluoride0.05 0.05 0.05 0.05
Glycerin 10.00 10.00 10.00 10.00
Sweetener 0.02 0.02 0.02 0.02
I II Ili IV
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Alkaline Xylanase 0.005 0.01 0.001 0.008
Protease 0.3 0.7 5 0.1 0.5
Laccase 0.05 0.05 0.05 0.05
BUS 0.5 0.5 0.5 0.5
Benzoic acid 0.05 0.05 0.05 0.05
Sodium hydroxide 0.20 0.20 0.20 0.20
Dye 0.04 0.04 0.04 0.04
Water Balance 0%
to 10
