Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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ORGANIC CATALYST WITH ENHANCED ENZYME COMPATIBLITY
FIELD OF INVENTION
This invention relates to cleaning compositions comprising organic catalysts
and
processes for making and using such cleaning products.
BACKGROUND OF THE INVENTION
Oxygen bleaching agents, for example hydrogen peroxide, are typically used to
facilitate
the removal of stains and soils from clothing and various surfaces.
Unfortunately such agents are
extremely temperature rate dependent. As a result, when such agents are
employed in colder
solutions, the bleaching action of such solutions is markedly decreased.
In an effort to resolve the aforementioned performance problem, the industry
developed a
class of materials known as "bleach activators". However, as such materials
rapidly lose their
effectiveness at solution temperatures of less than 40 C, new organic
catalysts such as 3,4-
dihydro-2-[2-(sulfooxy)decyl]isoquinolimium, inner salt were developed. In
general, while such
current art catalysts are effective in lower temperature water conditions,
they can inactivate
certain enzymes. As most laundry and cleaning compositions are formulated with
enzymes,
formulating cleaning products with such catalysts can be problematic.
Accordingly, there is a need for an inexpensive cleaning composition
comprising an
organic catalyst that can provide the combined benefits of formulation
flexibility, low water
temperature bleaching performance and enzyme compatibility.
SUMMARY OF THE INVENTION
The present invention relates to cleaning compositions comprising organic
catalysts
having enhanced enzyme compatibility, and methods of making and using same.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
As used herein, the term "cleaning composition" includes, unless otherwise
indicated,
granular or powder-form all-purpose or "heavy-duty" washing agents, especially
laundry
detergents; liquid, gel or paste-form all-purpose washing agents, especially
the so-called heavy-
duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or
light duty
dishwashing agents, especially those of the high-foaming type; machine
dishwashing agents,
including the various tablet, granular, liquid and rinse-aid types for
household and institutional
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use; liquid cleaning and disinfecting agents, including antibacterial hand-
wash types, laundry
bars, mouthwashes, denture cleaners, car or carpet shampoos, bathroom
cleaners; hair shampoos
and hair-rinses; shower gels and foam baths and metal cleaners; as well as
cleaning auxiliaries
such as bleach additives and "stain-stick" or pre-treat types.
As used herein, the phrase "is independently selected from the group
consisting of ....."
means that moieties or elements that are selected from the referenced Markush
group can be the
same, can be different or any mixture of elements.
The test methods disclosed in the Test Methods Section of the present
application must be
used to determine the respective values of the parameters of Applicants'
inventions.
Unless otherwise noted, all component or composition levels are in reference
to the active
level of that component or composition, and are exclusive of impurities, for
example, residual
solvents or by-products, which may be present in commercially available
sources.
All percentages and ratios are calculated by weight unless otherwise
indicated. All
percentages and ratios are calculated based on the total composition unless
otherwise indicated.
It should be understood that every maximum numerical limitation given
throughout this
specification includes every lower numerical limitation, as if such lower
numerical limitations
were expressly written herein. Every minimum numerical limitation given
throughout this
specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader
numerical range, as if such narrower numerical ranges were all expressly
written herein.
The citation of any document is not to be construed as an admission that it is
prior art with
respect to the present invention.
Cleaning Compositions Comprising Organic Catalyst
Applicants have found that judicious selection of the R' moiety of the organic
catalyst of
the present invention results in improved enzyme compatibility. While not
being bound by
theory, Applicants believe this is due to favorable partitioning of the
catalyst in aqueous
environments as a result of the aforementioned judicious selection of the R'
moiety.
In one aspect of Applicants' invention, Applicants' cleaning compositions
comprise an
organic catalyst having an enzyme compatibility value of 70 or greater, or
even 80 or greater.
In one aspect of Applicants' invention, Applicants' cleaning compositions
comprise an
organic catalyst having Formula I or Formula 2 below or mixtures thereof.
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I1
O OS03
~NLO R
O R
Formula I
OSO~
~JOR1
O
Formula 2
wherein R1 is a branched alkyl group containing from 9 to 24 carbons or linear
alkyl group
containing from 11 to 24 carbons; a branched alkyl group containing from 9 to
18 carbons or
linear alkyl group containing from 1 I to 18 carbons; is selected from the
group consisting of 2-
propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-
tetradecyl, n-hexadecyl, n-
octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; or is
selected from the group
consisting of 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, iso-tridecyl and iso-
pentadecyl.
The balance of any aspects of the aforementioned cleaning compositions is made
up of
one or more adjunct materials.
Processes of Making Suitable Organic Catalysts
Suitable organic catalysts can be produced using a variety of reaction vessels
and processes
including batch, semi-batch and continuous processes.
In one aspect of Applicants invention, the process of making the
aforementioned catalyst
comprises the step of reacting 3,4-dihydroisoquinoline sulfur trioxide complex
with an epoxide to
form said organic catalyst.
In another aspect of Applicants' invention, the process of making the
aforementioned
catalyst comprises the steps of reacting 3,4-dihydroisoquinoline with a
material selected from the
group consisting of sulfur trioxide, a material that provides sulfur trioxide
and mixtures thereof,
to form a 3,4-dihydroisoquinoline sulfur trioxide complex, and reacting such
3,4-
dihydroisoquinoline sulfur trioxide complex with an epoxide to form said
organic catalyst.
In another aspect of Applicants' invention, the process of making the
aforementioned
catalyst comprises the step of reacting 3,4-dihydroisoquinoline with an
epoxide sulfur trioxide
complex to form said organic catalyst.
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In another aspect of Applicants' invention, the process of making the
aforementioned
catalyst comprises the steps of reacting an epoxide with a material selected
from the group
consisting of sulfur trioxide, a material that provides sulfur trioxide and
mixtures thereof, to form
an epoxide sulfur trioxide complex, and reacting such epoxide sulfur trioxide
complex with 3,4-
dihydroisoquinoline to form said organic catalyst.
The oxaziridinium ring containing version of the aforementioned catalyst may
be
produced by contacting an iminium ring containing version of said catalyst
with an oxygen
transfer agent such as a peroxycarboxylic acid or a peroxymonosulfuric acid,
for example, Oxone
. Such species can be formed in situ and used without purification.
While the skilled artisan who processes the teachings of this specification
can easily
determine the desired reaction conditions and reactant concentrations, typical
reaction parameters
for the aforementioned aspects of Applicants' invention include reaction
temperatures of from
about 0 C to about 150 C, or from about 0 C to about 125 C, reaction pressures
of from about
0.1 to about 100 atmospheres, from about 0.3 atmospheres to about 10
atmospheres or from about
1 atmosphere to about 10 atmospheres; reaction times of 0.1 hours to about 96
hours, from about
1 hour to about 72 hours, or from about 1 hour to about 24 hours. The reaction
may also be run
under an inert atmosphere or otherwise anhydrous conditions including, when a
solvent is
employed, the use of an anhydrous solvent.
Materials that are employed in practicing Applicants' process include 3,4-
dihydroisoquinoline; epoxides and mixtures thereof; sulfur trioxide, sources
of sulfur trioxide and
mixtures thereof; and solvents.
When 3,4-dihydroisoquinoline is employed, the initial reaction mixture
typically
comprises from about 0.5 weight % to about 70 weight %, from about 5 weight %
to about 70
weight %, or from about 10 weight % to about 50 weight % of such material. 3,4-
Dihydroisoquinoline can be made according to the protocol found in Example 1.
When epoxides are employed, the initial reaction mixture typically comprises
from about
0.5 weight % to about 70 weight %, from about 5 weight % to about 70 weight %,
or from about
10 weight % to about 50 weight % of such material. Suitable epoxides include
but are not
limited to epoxides such as 2-propylheptyl glycidyl ether; 2-butyloctyl
glycidyl ether; 2-
pentylnonyl glycidyl ether; 2-hexyldecyl glycidyl ether; n-dodecyl glycidyl
ether; n-tetradecyl
glycidyl ether; n-hexadecyl glycidyl ether; n-octadecyl glycidyl ether; iso-
nonyl glycidyl ether;
iso-decyl glycidyl ether; iso-tridecyl glycidyl ether, and mixtures thereof.
Such materials may
contain oligomeric forms of the glycidyl ether which may optionally be removed
prior to being
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employed as a reactant. 2-Propylheptyl glycidyl ether can be prepared as
described in Example 2
of this specification. All of the other aforementioned glycidyl ethers can be
prepared by
following the generic protocol of Example 2 by substituting the appropriate
alcohol in place of 2-
propylheptanol. Suitable alcohols include 2-propylheptanol, 2-butyloctanol, 2-
pentylnonanol, 2-
5 hexyldecanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, iso-
nonanol, iso-
decanol and iso-tridecanol.
When sulfur trioxide, sources of sulfur trioxide and mixtures thereof are
employed, the
initial reaction mixture typically comprises from about 0.5 weight % to about
70 weight %, from
about 5 weight % to about 70 weight %, or from about 10 weight % to about 50
weight % of such
material. Suitable materials include sulfur trioxide, and sulfur trioxide
complexes such as sulfur
trioxide trimethylamine, sulfur trioxide dioxane, sulfur trioxide pyridine,
sulfur trioxide N,N-
dimethylformamide, sulfur trioxide sulfolane, sulfur trioxide tetrahydrofuran,
sulfur trioxide
diethylether, sulfur trioxide 3,4-dyhydroisoquinoline and mixtures thereof.
The balance of any reaction mixture is typically solvent. When a solvent is
employed, the
initial reaction mixture typically comprises up to 99 weight % solvent, from
about 10 weight % to
about 90 weight % solvent, or from about 20 weight % to about 80 weight %
solvent. Suitable
solvents include aprotic, polar and apolar solvents such as acetonitile,
dioxane, tertbutyl
methylether, tetrahydrofuran, N,N-dimethylformamide, sulfolane, chlorobenzene,
toluene, 1,2 -
dichloroethane, methylene chloride, chloroform, diethyl ether, hexanes,
pentanes, benzene,
xylenes and mixtures thereof. Suitable solvents can be purchased from Aldrich,
P.O. Box 2060,
Milwaukee, WI 53201, USA.
Cleaning Compositions and Cleaning Composition Additives Comprising
Applicants' Organic
Catalysts
The cleaning composition of the present invention may be advantageously
employed for
example, in laundry applications, hard surface cleaning, automatic dishwashing
applications, as
well as cosmetic applications such as dentures, teeth, hair and skin. However,
due to the unique
advantages of both increased effectiveness in lower temperature solutions and
the superior
enzyme compatiblity, the organic catalysts of the present invention are
ideally suited for laundry
applications such as the bleaching of fabrics through the use of bleach
containing detergents or
laundry bleach additives. Furthermore, the organic catalysts of the present
invention may be
employed in both granular and liquid compositions.
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The organic catalysts of the present invention may also be employed in a
cleaning additive
product. A cleaning additive product including the organic catalysts of the
present invention is
ideally suited for inclusion in a wash process when additional bleaching
effectiveness is desired.
Such instances may include but, are not limited to, low temperature solution
cleaning application.
The additive product may be, in its simplest form, Applicants' organic
catalyst. Preferably, the
additive could be packaged in dosage form for addition to a cleaning process
where a source of
peroxygen is employed and increased bleaching effectiveness is desired. Such
single dosage
form may comprise a pill, tablet, gelcap or other single dosage unit such as
pre-measured
powders or liquids. A filler or carrier material may be included to increase
the volume of such
composition. Suitable filler or carrier materials include, but are not limited
to, various salts of
sulfate, carbonate and silicate as well as talc, clay and the like. Filler or
carrier materials for
liquid compositions may be water or low molecular weight primary and secondary
alcohols
including polyols and diols. Examples of such alcohols include, but are not
limited to, methanol,
ethanol, propanol and isopropanol. The compositions may contain from about 5%
to about 90%
of such materials. Acidic fillers can be used to reduce pH. Alternatively, the
cleaning additive
may include an activated peroxygen source defined below or the adjunct
ingredients as fully
defined below.
Applicants' cleaning compositions and cleaning additives require a
catalytically effective
amount of Applicants' organic catalyst. The required level of such catalyst
may be achieved by
the addition of one or more species of Applicants' organic catalyst. As a
practical matter, and not
by way of limitation, the compositions and cleaning processes herein can be
adjusted to provide
on the order of at least 0.001 ppm, from about 0.001 ppm to about 500 ppm,
from about 0.005
ppm to about 150 ppm, or even from about 0.05 ppm to about 50 ppm of
Applicants' organic
catalyst in the wash liquor. In order to obtain such levels in the wash
liquor, typical compositions
herein may comprise from about 0.0002% to about 5%, or even from about 0.001 %
to about
1.5%, of organic catalyst, by weight of the cleaning compositions.
When the Applicants' organic catalyst is employed in a granular composition,
it may be
desirable for the Applicants' organic catalyst to be in the form of an
encapsulated particle to
protect the Applicants' organic catalyst from moisture and/or other components
of the granular
composition during storage. In addition, encapsulation is also a means of
controlling the
availability of the Applicants' organic catalyst during the cleaning process
and may enhance the
bleaching performance of the Applicants' organic catalyst. In this regard, the
Applicants' organic
catalyst can be encapsulated with any encapsulating material known in the art.
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The encapsulating material typically encapsulates at least part, preferably
all, of the
Applicants' organic catalyst. Typically, the encapsulating material is water-
soluble and/or water-
dispersible. The encapsulating material may have a glass transition
temperature (Tg) of 0 C or
higher.
The encapsulating material is preferably selected from the group consisting of
carbohydrates, natural or synthetic gums, chitin and chitosan, cellulose and
cellulose derivatives,
silicates, phosphates, borates, polyvinyl alcohol, polyethylene glycol,
paraffin waxes and
combinations thereof. Preferably the encapsulating material is a carbohydrate,
typically selected
from the group consisting of monosaccharides, oligosaccharides,
polysaccharides, and
combinations thereof. Most preferably, the encapsulating material is a starch.
Preferred starches
are described in EP 0 922 499; U.S. 4,977,252; U.S. 5,354,559 and U.S.
5,935,826.
The encapsulating material may be a microsphere made from plastic such as
thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile,
polymethacrylonitrile and
mixtures thereof; commercially available microspheres that can be used are
those supplied by
Expancel of Stockviksverken, Sweden under the trademark Expancel , and those
supplied by PQ
Corp. of Valley Forge, Pennsylvania USA under the trademarks PM 6545, PM 6550,
PM 7220,
PM 7228, Extendospheres , Luxsil , Q-cel and Sphericel .
The cleaning compositions herein will preferably be formulated such that,
during use in
aqueous cleaning operations, the wash water will have a pH of between about
6.5 and about 11,
or even about 7.5 and 10.5. Liquid dishwashing product formulations may have a
pH between
about 6.8 and about 9Ø Laundry products typically have a pH of from about 9
to about 11.
Techniques for controlling pH at recommended usage levels include the use of
buffers, alkalis,
acids, etc., and are well known to those skilled in the art.
Adjunct Materials
While not essential for the purposes of the present invention, the non-
limiting list of
adjuncts illustrated hereinafter are suitable for use in the instant
compositions and may be
desirably incorporated in certain embodiments of the invention, for example to
assist or enhance
cleaning performance, for treatment of the substrate to be cleaned, or to
modify the aesthetics of
the cleaning composition as is the case with perfumes, colorants, dyes or the
like. 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. Suitable adjunct materials include, but are not limited to, surfactants,
builders, chelating
agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme
stabilizers, catalytic
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materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide,
preformed
peracids, polymeric dispersing agents, clay soil removal/anti-redeposition
agents, brighteners,
suds suppressors, dyes, perfumes, structure elasticizing agents, fabric
softeners, carriers,
hydrotropes, processing aids, solvents and/or pigments. In addition to the
disclosure below,
suitable examples of such other adjuncts and levels of use are found in U.S.
Patent Nos.
5,576,282, 6,306,812 B I and 6,326,348 B 1.
As stated, the adjunct ingredients are not essential to Applicants'
compositions. Thus,
certain embodiments of Applicants' compositions do not contain one or more of
the following
adjuncts materials: surfactants, builders, chelating agents, dye transfer
inhibiting agents,
dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach
activators, hydrogen
peroxide, sources of hydrogen peroxide, preformed peracids, polymeric
dispersing agents, clay
soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes,
perfumes, structure
elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids,
solvents and/or
pigments. However, when one or more adjuncts are present, such one or more
adjuncts may be
present as detailed below:
Bleaching Agents - The cleaning compositions of the present invention may
comprise one
or more bleaching agents. Suitable bleaching agents other than bleaching
catalysts include
photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen
peroxide, pre-formed
peracids and mixtures thereof. In general, when a bleaching agent is used, the
compositions of
the present invention may comprise from about 0.1% to about 50% or even from
about 0.1% to
about 25% bleaching agent by weight of the subject cleaning composition.
Examples of suitable
bleaching agents include:
(1) photobleaches for example sulfonated zinc phthalocyanine;
(2) preformed peracids: Suitable preformed peracids include, but are not
limited to,
compounds selected from the group consisting of percarboxylic acids and salts,
percarbonic acids
and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for
example, Oxzone ,
and mixtures thereof. Suitable percarboxylic acids include hydrophobic and
hydrophilic peracids
having the formula R-(C=O)O-O-M wherein R is an alkyl group, optionally
branched, having,
when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12
carbon atoms and,
when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4
carbon atoms; and
M is a counterion, for example, sodium, potassium or hydrogen;
(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts,
including alkali
metal salts such as sodium salts of perborate (usually mono- or tetra-
hydrate), percarbonate,
persulphate, perphosphate, persilicate salts and mixtures thereof. In one
aspect of the invention
the inorganic perhydrate salts are selected from the group consisting of
sodium salts of perborate,
percarbonate and mixtures thereof. When employed, inorganic perhydrate salts
are typically
present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall
composition and are
typically incorporated into such compositions as a crystalline solid that may
be coated. Suitable
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coatings include, inorganic salts such as alkali metal silicate, carbonate or
borate salts or mixtures
thereof, or organic materials such as water-soluble or dispersible polymers,
waxes, oils or fatty
soaps; and
(4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally
branched,
having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms,
or from 8 to 12
carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon
atoms or even less
than 4 carbon atoms; and L is leaving group. Examples of suitable leaving
groups are benzoic
acid and derivatives thereof - especially benzene sulphonate. Suitable bleach
activators include
dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl
oxybenzoic acid
or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl
ethylene diamine
(TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators
are also
disclosed in WO 98/17767. While any suitable bleach activator may be employed,
in one aspect
of the invention the subject cleaning composition may comprise NOBS, TAED or
mixtures
thereof.
When present, the peracid and/or bleach activator is generally present in the
composition
in an amount of from about 0.1 to about 60 wt%, from about 0.5 to about 40 wt
% or even from
about 0.6 to about 10 wt% based on the composition. One or more hydrophobic
peracids or
precursors thereof may be used in combination with one or more hydrophilic
peracid or precursor
thereof.
The amounts of hydrogen peroxide source and peracid or bleach activator may be
selected
such that the molar ratio of available oxygen (from the peroxide source) to
peracid is from 1:1 to
35:1, or even 2:1 to 10:1.
Surfactants - The cleaning compositions according to the present invention may
comprise
a surfactant or surfactant system wherein the surfactant can be selected from
nonionic surfactants,
anionic surfactants, cationic surfactants, ampholytic surfactants,
zwitterionic surfactants, semi-
polar nonionic surfactants and mixtures thereof. When present, surfactant is
typically present at a
level of from about 0.1% to about 60%, from about 1% to about 50% or even from
about 5% to
about 40% by weight of the subject composition.
Builders - The cleaning compositions of the present invention may comprise one
or more
detergent builders or builder systems. When a builder is used, the subject
composition will
typically comprise at least about 1%, from about 5% to about 60% or even from
about 10% to
about 40% builder by weight of the subject composition.
Builders include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline
earth and alkali metal
carbonates, aluminosilicate builders and polycarboxylate compounds, ether
hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl
methyl ether, 1,
3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid, the various
alkali metal, ammonium and substituted ammonium salts of polyacetic acids such
as
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ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such as
mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Chelating Agents - The cleaning compositions herein may contain a chelating
agent.
5 Suitable chelating agents include copper, iron and/or manganese chelating
agents and mixtures
thereof. When a chelating agent is used, the subject composition may comprise
from about
0.005% to about 15% or even from about 3.0% to about 10% chelating agent by
weight of the
subject composition.
Dye Transfer Inhibiting Agents - The cleaning compositions of the present
invention may
10 also include one or more dye transfer inhibiting agents. Suitable polymeric
dye transfer
inhibiting agents include, but are not limited to, polyvinylpyrrolidone
polymers, polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyloxazolidones
and polyvinylimidazoles or mixtures thereof. When present in a subject
composition, the dye
transfer inhibiting agents may be present at levels from about 0.0001% to
about 10%, from about
0.01 % to about 5% or even from about 0.1 % to about 3% by weight of the
composition.
Brighteners - The cleaning compositions of the present invention can also
contain
additional components that may tint articles being cleaned, such as
fluorescent brighteners.
Suitable fluorescent brightener levels include lower levels of from about
0.01, from about 0.05,
from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75
wt %.
Dispersants - The compositions of the present invention can also contain
dispersants.
Suitable water-soluble organic materials include the homo- or co-polymeric
acids or their salts, in
which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other
by not more than two carbon atoms.
Enzymes - The cleaning compositions can comprise one or more enzymes which
provide
cleaning performance and/or fabric care benefits. Examples of suitable enzymes
include, but are
not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases,
phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases,
keratinases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases,
pentosanases, malanases, f3-glucanases, arabinosidases, hyaluronidase,
chondroitinase, laccase,
and amylases, or mixtures thereof. A typical combination is an enzyme cocktail
that may
comprise, for example, a protease and lipase in conjunction with amylase. When
present in a
cleaning composition, the aforementioned enzymes may be present at levels from
about
0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001%
to about
0.5% enzyme protein by weight of the composition.
Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by
various
techniques. The enzymes employed herein can be stabilized by the presence of
water-soluble
sources of calcium and/or magnesium ions in the finished compositions that
provide such ions to
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the enzymes. In case of aqueous compositions comprising protease, a reversible
protease
inhibitor, such as a boron compound, can be added to further improve
stability.
Catalytic Metal Complexes - Applicants' cleaning compositions may include
catalytic
metal complexes. One type of metal-containing bleach catalyst is a catalyst
system comprising a
transition metal cation of defined bleach catalytic activity, such as copper,
iron, titanium,
ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal
cation having little
or no bleach catalytic activity, such as zinc or aluminum cations, and a
sequestrate having defined
stability constants for the catalytic and auxiliary metal cations,
particularly
ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic
acid) and water-
soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese
compound.
Such compounds and levels of use are well known in the art and include, for
example, the
manganese-based catalysts disclosed in U.S. 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for
example, in U.S.
5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known
procedures, such
as taught for example in U.S. 5,597,936, and U.S. 5,595,967.
Compositions herein may also suitably include a transition metal complex of
ligands such
as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands -
abbreviated as
"MRLs". As a practical matter, and not by way of limitation, the compositions
and processes
herein can be adjusted to provide on the order of at least one part per
hundred million of the
active MRL species in the aqueous washing medium, and will typically provide
from about 0.005
ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about
0.1 ppm to
about 5 ppm, of the MRL in the wash liquor.
Suitable transition-metals in the instant transition-metal bleach catalyst
include, for
example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-
1,5,8,12-
tetraazabicyclo[6.6.2]hexadecane.
Suitable transition metal MRLs are readily prepared by known procedures, such
as taught
for example in WO 00/3260 1, and U.S. 6,225,464.
Solvents - Suitable solvents include water and other solvents such as
lipophilic fluids.
Examples of suitable lipophilic fluids include siloxanes, other silicones,
hydrocarbons, glycol
ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines,
perfluorinated and
hydrofluoroether solvents, low-volatility nonfluorinated organic solvents,
diol solvents, other
environmentally-friendly solvents and mixtures thereof.
Processes of Makin Cleaning and/or Treatment Compositions
The cleaning compositions of the present invention can be formulated into any
suitable
form and prepared by any process chosen by the formulator, non-limiting
examples of which are
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described in Applicants' examples and in U.S. 5,879,584; U.S. 5,691,297; U.S.
5,574,005;
U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S.
5,486,303.
Method of Use
The present invention includes a method for cleaning a situs inter alia a
surface or fabric.
Such method includes the steps of contacting an embodiment of Applicants'
cleaning
composition, in neat form or diluted in a wash liquor, with at least a portion
of a surface or fabric
then optionally rinsing and optionally drying such surface or fabric. The
surface or fabric may be
subjected to a washing step prior to the aforementioned rinsing step. For
purposes of the present
invention, washing includes but is not limited to, scrubbing, and mechanical
agitation. Drying of
such surfaces or fabrics may be accomplished by any one of the common means
employed either
in domestic or industrial settings. Such means include but are not limited to
forced air or still air
drying at ambient or elevated temperatures at pressures between 5 and 0.01
atmospheres in the
presence or absence of electromagnetic radiation, including sunlight,
infrared, ultraviolet and
microwave irradiation. In one aspect, said drying may be accomplished at
temperatures above
ambient by employing an iron wherein, for example, said fabric may be in
direct contact with said
iron for relatively short or even extended periods of time and wherein
pressure may be exerted
beyond that otherwise normally present due to gravitational force. In another
aspect, said drying
may be accomplished at temperatures above ambient by employing a dryer.
Apparatus for drying
fabric is well known and it is frequently referred to as a clothes dryer. In
addition to clothes such
appliances are used to dry many other items including towels, sheets,
pillowcases, diapers and so
forth and such equipment has been accepted as a standard convenience in many
nations of the
world substantially replacing the use of clothes lines for drying of fabric.
Most dryers in use today
use heated air which is passed over and or through the fabric as it is tumbled
within the dryer.
The air may be heated, for example, either electronically, via gas flame, or
even with microwave
radiation. Such air may be heated from about 15 C to about 400 C, from about
25 C to about
200 C, from about 35 C to about 100 C, or even from about 40 C to about 85 C
and used in the
dryer to dry a surface and/or a fabric. Without being bound by theory, it is
believed that additional
bleaching may be obtained from organic catalyst remaining on the surface or
fabric during and/or
after drying thus it may be advantageous to dry said surface or fabric. As
will be appreciated by
one skilled in the art, the cleaning compositions of the present invention are
ideally suited for use
in laundry applications. Accordingly, the present invention includes a method
for laundering a
fabric. The method comprises the steps of contacting a fabric to be laundered
with a said
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cleaning laundry solution comprising at least one embodiment of Applicants'
cleaning
composition, cleaning additive or mixture thereof. The fabric may comprise
most any fabric
capable of being laundered in normal consumer use conditions. The solution
preferably has a pH
of from about 8 to about 10.5. The compositions may be employed at
concentrations of from
about 500 ppm to about 15,000 ppm in solution. The water temperatures
typically range from
about 5 C to about 90 T. The water to fabric ratio is typically from about
1:1 to about 30:1.
Organic Catalyst/Enzyme Compatibility Test
The test described below uses an alpha amylase activity assay to measure the
impact of organic
catalysts on the enzyme.
Equipment. UVNis spectrophotometer capable of measuring @ 415 nm, heated
magnetic stirrer capable of 40 C, 5 mL Luer lock syringe and filters
(AcrodiscTM 0.45 m), pH
meter, and balance (4-place analytical).
Reagents. MerckTM Amylase Kit (Merck Eurolab, Cat. No. 1.19718.0001); Trizma
Base
(Sigma Cat # T-1503, or equivalent); Calcium Chloride Dihydrate (Sigma Cat # C-
5080, or
equivalent); Sodium Thiosulfate Pentahydrate (Sigma Cat # S-6672 or
equivalent); Hydrochloric
Acid (VWR Cat # JT9535-0, or equivalent); Hardness solution (CTC Group, 3.00
gr/cc or
equivalent); Sodium Percarbonate; Peracetic Acid (Aldrich, Cat.# 26933-6 or
equivalent);
Amylase enzymes: TermamylTM, NatalaseTM, and DuramylTM (Novozymes, Denmark);
Granular
detergent matrix containing no enzyme, organic catalyst or bleaching agents.
1.) Solution Preparation: prepare the following:
a.) TRIS Assay Buffer. Prepare 1 liter of 0.1M TRIS buffer, 0.5% sodium
thiosulphate
(WN), 0.11% calcium chloride (w/v) at pH 8.3.
b.) Blank Detergent Solution. Prepare one liter of 0.5% enzyme and bleach free
granular
detergent product in deionized water (WN) that is 250 ppm H202 (0.77 gm
percarbonate) and 10 gpg hardness (880 Ul of hardness).
c.) Termamyl, Duramyl and Natalase Stock. Make 100 mL solutions each of a
0.1633
mg active Termamyl per mL TRIS Buffer, a 0.1159 mg active Natalase per mL TRIS
Buffer, and a 0.1596 mg active Duramyl per mL TRIS Buffer.
d.) Organic catalyst stocks. Make a 500 ppm in methanol solution of gm.
e.) Peracetic acid stock. Make a 3955 ppm peracetic acid solution in deionized
water.
f.) Amylase reagent. Follow Merck kit instructions for preparing flacons
(containers) 1
and 2 using flacon 3 and subsequent mixing of flacons 1 and 2 to produce the
final
reagent used in the amylase activity analysis.
2.) Sample Analysis
a.) Analysis of sample with enzyme only: Add 100 mL of blank detergent
solution to a
150 mL beaker. Place beaker on heated stir plate and bring temperature to 40 C
with
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stirring. Add Y L of enzyme stock to the beaker where Y= 612 L for Duramyl,
306
L for Termamyl, or 918 L for Natalase. Spike only enzyme of interest. Stir
sample
for 1 minute. Start timer. At 7 minutes 45 seconds, pull a sample and filter
it using a
0.45 m syringe filter (5 mL syringe). Mix 6 gL of filtered sample with 250 L
of
amylase reagent in a cuvette and place the cuvette in a UV/VIS
spectrophotometer and
monitor change in absorbance at 415 nm. Determine length of time (tE) to the
nearest
second required to obtain an absorbance reading of 1.0 for each enzyme. Use
each
enzyme's tE in Steps 2.)b.) and 2.)c.) below.
b.) Analysis of sample with enzyme and peracetic acid only. Follow Step 2.)a.)
except
after enzyme addition, allow solution to stir for 1 minute then add 127 L of
peracetic
acid stock and start timer. Pull sample at 7 minutes 45 seconds as in Step
2.)a.).
Once sample and reagent are mixed, record the absorbance at tE for the
respective
enzyme. Designate such absorbance Ab.
c.) Analysis of sample with enzyme, peracetic acid, and organic catalyst.
Follow Step
2.)a.) except after enzyme addition, allow solution to stir for 1 minute then
add 127
L of peracetic acid stock and 100 gL of organic catalyst stock and start
timer. Pull
sample at 7 minutes 45 seconds as in Step 2.)a.). Once sample and reagent are
mixed,
record the absorbance at tE for the respective enzyme. Designate such
absorbance A,.
3.) Calculate Enzyme Compatibility Value (ECV)
a.) Calculate the ECV for each specific enzyme: Termamyl (ECVter), Duramyl
(ECVdur)
and Natalase (ECVõat). The ECV for any specific enzyme is (A JAb) x 100 where
Ab
and Ac are the values determined in Steps 2.)b.) and 2.)c.), respectively, for
that
enzyme.
b.) The ECV for a given organic catalyst is the average of the individual ECV
values for
the three enzymes. Thus, ECV = (ECVter + ECVdur + ECVõat)/3.
EXAMPLES
Unless otherwise indicated, materials can be obtained from Aldrich, P.O. Box
2060, Milwaukee,
WI 53201, USA. In Examples 1-12, the solvent acetonitrile may be replaced with
other
solvents, including but not limited to, 1,2-dichloroethane.
Example 1: Preparation of Sulfuric acid mono-(2-(3,4-dihydro-isoquinolin-2-yl)-
1-(2-
propylheptyloxymethyl -ethyl] ester, internal salt
Preparation of 2-propylheptyl glycidyl ether: To a flame dried, 500 mL round
bottomed flask
equipped with an addition funnel charged with epichlorohydrin (15.62 gm., 0.17
moles), is added
2-propylheptanol (Pfaltz & Bauer, Inc., 172 E. Aurora Street, Waterbury CT,
06708, USA) (20
gm., 0.127 moles) and stannic chloride (0.20 gm., 0.00 1 moles). The reaction
is kept under an
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argon atmosphere and warmed to 90 C using an oil bath. Epichlorohydrin is
dripped into the
stirring solution over 60 minutes followed by stirring at 90 C for 18 hours.
The reaction is fitted
with a vacuum distillation head and 1-chloro-3-(2-propyl-heptyloxy)-propan-2-
ol is distilled at a
temperature range of 90 C->95 C under 0.2mm Hg. Wt.=22.1 gm. The 1-chloro-3-
(2-propyl-
5 heptyloxy)-propan-2-ol (5.0 gm., 0.020 moles) is dissolved in
tetrahydrofuran (50 mL) and stirred
at RT under an argon atmosphere. To the stirring solution is added potassium
tert-butoxide (2.52
gm., 0.022 moles) and the suspension is stirred at RT for 18 hours. The
reaction is then
evaporated to dryness, residue dissolved in hexanes and washed with water (100
mL). The
hexanes phase is separated, dried with Na2SO4, filtered and evaporated to
dryness to yield the
10 crude 2-propylheptyl glycidyl ether, which can be further purified by
vacuum distillation.
Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)- 1 -(2-
propylheptyloxymethyl)-ethyl] ester, internal salt: To a flame dried 250 mL
three neck round
bottomed flask, equipped with a condenser, dry argon inlet, magnetic stir bar,
thermometer, and
15 heating bath is added 3,4-dihydroisoquinoline (0.38 mol.; prepared as
described in Example I of
U.S. 5,576,282), 2-propylheptyl glycidyl ether (0.38 mol, prepared as
described above), SO3-
DMF complex (0.38 mol), and acetonitrile (500 mL). The reaction is warmed to
80 C and
stirred at temperature for 72 hours. The reaction is cooled to room
temperature, evaporated to
dryness and the residue recrystallized from ethyl acetate and/or ethanol to
yield the desired
product.
Example 2: Preparation of Sulfuric acid mono-[2-(3 4-dihydro-isoquinolin-2-yl)-
1-(2-butyl-
octyloxy ethyl)-ethyl] ester, internal salt
The desired product is prepared according to Example 1, substituting 2-
butyloctanol for 2-
propylheptanol.
Example 3: Preparation of Sulfuric acid mono-[2-(3 4-dihydro-isoguinolin-2-
]y)-1-(2-pentyl-
nonyloxymethyl-ethyllester, internal salt
The desired product is prepared according to Example 1, substituting 2-
pentylnonanol (obtained
from Pfaltz & Bauer, Inc., Wayerbury, CT 06708) for 2-propylheptanol.
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Example 4: Preparation of Sulfuric acid mono-I2-(3,4-dihydro-isoquinolin-2-yl)-
1-(2-hexyl-
decyloxymethyl)-ethyl] ester, internal salt
The desired product is prepared according to Example 1, substituting 2-
hexyldecanol for 2-
propylheptanol.
Example 5: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-
I-(
dodecyloxymethyl)-ethyl] ester, internal salt
The desired product is prepared according to Example 1, substituting n-
dodecanol for 2-
propylheptanol.
Example 6: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-
1-
(tetradec ymethyl)-ethyll ester, internal salt
The desired product is prepared according to Example 1, substituting n-
tetradecanol for 2-
propylheptanol.
Example 7: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-vl)-
1-
(hexadecyloxmethyl)-ethyll ester, internal salt
The desired product is prepared according to Example 1, substituting n-
hexadecanol for 2-
propylheptanol.
Example 8: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-
1-
ctadecyloxymethyl -ethyl] ester, internal salt
The desired product is prepared according to Example 1, substituting n-
octadecanol for 2-
propyiheptanol.
Example 9: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2 yl)-
1-(iso-
nonylox methyl -ethyl ester, internal salt
The desired product is prepared according to Example 1, substituting iso-
nonanol
(ExxaITM 9 obtained from ExxonMobil Chemical, Houston, Texas USA) for 2-
propylheptanol.
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Example 10.: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-
yl)-1-(iso-
decyloxymethyl)-ethyll ester, internal salt
The desired product is prepared according to Example 1, substituting iso-
decanol (obtained from
City Chemicals LLC, West Haven, Connecticut USA) for 2-propylheptanol.
Example 11: Preparation of Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-
yi)-1-(iso-
tridecyloxymethyl-ethyll ester, internal salt
The desired product is prepared according to Example 1, substituting iso-
tridecanol (obtained
from BASF Corporation, Mount Olive, New Jersey USA) for 2-propylheptanol.
Example 12: Simultanoeous Preparation of Sulfuric acid mono-[2-(3,4-dihydro-
isoquinolin-2-yl)-
1-(iso-tridecyloxymethyi -ethyll ester, internal salt and Sulfuric acid mono-
[2-(3,4-dihydro-
isoguinolin-2-l)-1-(iso-pentadecyloxymethyl)-ethyll ester, internal salt
The desired products are prepared according to Example 1, substituting a
mixture of isomeric
tridecanols to pentadecanols (obtained from BASF Corporation, Mount Olive, New
Jersey USA)
for 2-propylheptanol.
Example 13
Bleaching detergent compositions having the form of granular laundry
detergents are exemplified
by the following formulations.
A B C D E F
Linear alkylbenzenesulfonate 20 22 20 15 20 20
C12 Dimethylhydroxyethyl
ammonium chloride 0.7 1 1 0.6 0.0 0.7
AE3S 0.9 0.0 0.9 0.0 0.0 0.9
AE7 0.0 0.5 0.0 1 3 1
sodium tripolyphosphate 23 30 23 17 12 23
Zeolite A 0.0 0.0 0.0 0.0 10 0.0
1.6R Silicate 7 7 7 7 7 7
Sodium Carbonate 15 14 15 18 15 15
Polyacrylate MW 4500 1 0.0 1 1 1.5 1
Carboxy Methyl Cellulose I 1 1 1 1 1
Savinase 32.89mg/g 0.1 0.07 0.1 0.1 0.1 0.1
Natalase 8.65mg/g 0.1 0.1 0.1 0.0 0.1 0.1
Brightener 15 0.06 0.0 0.06 0.18 0.06 0.06
Brightener 49 0.1 0.06 0.1 0.0 0.1 0.1
Diethylenetriamine
pentacetic acid 0.6 0.3 0.6 0.25 0.6 0.6
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MgSO4 1 1 1 0.5 1 1
Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0 0.0
Photobleach 0.0030 0.0015 0.0015 0.0020 0.0045 0.0010
Sodium Perborate
Monohydrate 4.4 0.0 3.85 2.09 0.78 3.63
NOBS 1.9 0.0 1.66 1.77 0.33 0.75
TAED 0.58 1.2 0.51 0.0 0.015 0.28
Organic Catalyst * 0.0185 0.0185 0.0162 0.0162 0.0111 0.0074
Balance Balance to Balance to Balance Balance Balance
Sulfate/Moisture to 100% 100% 100% to 100% to 100% to 100%
* Organic catalyst prepared according to Examples I through 12, or mixtures
thereof.
Any of the above compositions is used to launder fabrics at a concentration of
3500 ppm in
water, 25 C, and a 25:1 water:cloth ratio. The typical pH is about 10 but can
be can be adjusted
by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate.
Example 14
Bleaching detergent compositions having the form of granular laundry
detergents are exemplified
by the following formulations.
A B C D
Linear alkylbenzenesulfonate 8 7.1 7 6.5
AE3S 0 4.8 0 5.2
Alkylsulfate 1 0 1 0
AE7 2.2 0 3.2 0.1
CIO-12 Dimethyl
hydroxyethylammonium chloride 0.75 0.94 0.98 0.98
Crystalline layered silicate (S-
Na2Si205) 4.1 0 4.8 0
Zeolite A 20 0 17 0
Citric Acid 3 5 3 4
Sodium Carbonate 15 20 14 20
Silicate 2R (Si02:Na2O at ratio 2:1) 0.08 0 0.11 0
Soil release agent 0.75 0.72 0.71 0.72
Acrylic Acid/Maleic Acid Copolymer 1.1 3.7 1.0 3.7
Carboxymethylcellulose 0.15 1.4 0.2 1.4
Protease (56.00mg active/g) 0.37 0.4 0.4 0.4
Amylase (21.55mg active/g) 0.3 0.3 0.3 0.3
Lipase (11.00mg active/g) 0 0.7 0 0.7
Tetraacetyl ethylene diamine (TAED) 3.6 4.0 3.6 4.0
Percarbonate 13 13.2 13 13.2
Organic Catalyst* 0.04 0.02 0.01 0.06
Na salt of Ethylenediamine-N,N'-
disuccinic acid, (S,S) isomer (EDDS) 0.2 0.2 0.2 0.2
Hydroxyethane di phosphonate
(HEDP) 0.2 0.2 0.2 0.2
MgSO4 0.42 0.42 0.42 0.42
Perfume 0.5 0.6 0.5 0.6
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Suds suppressor agglomerate 0.05 0.1 0.05 0.1
Soap 0.45 0.45 0.45 0.45
Sodium sulfate 22 33 24 30
Sulphonated zinc phthalocyanine 0.07 0.12 0.07 0.12
Photobleach 0.0014 0.002 0.0014 0.001
Speckles 0.03 0.05 0.03 0.05
Balance Balance Balance Balance
to 100% to 100% to to
Water & Miscellaneous 100% 100%
* Organic catalyst prepared according to Examples I through 12, or mixtures
thereof.
Any of the above compositions is used to launder fabrics at a concentration of
10,000 ppm
in water, 20-90 C, and a 5:1 water:cloth ratio. The typical pH is about 10
but can be can be
adjusted by altering the proportion of acid to Na-salt form of
alkylbenzenesulfonate.
Example 15
Bleaching detergent compositions having the form of granular laundry
detergents are
exemplified by the following formulations.
A B C D E F
Linear Alkylbenzenesulfonate 19.0 15.0 20.0 19.0 18.0 17.5
Alkylsulfate 1.1 1.0 0.8 1.0 1.1 1.2
AE3S 0.3 0.2 0.0 0.1 0.3 0.5
Polyacrylic Acid, partially 6.0 5.5 7.5 7.0 5.8 6.0
neutralized
Sodium Xylene Sulfonate* 1.5 1.9 2.0 1.7 1.5 1.0
PEG 4000 0.3 0.25 0.35 0.15 0.2 0.10
Brightener 49 0 0 0.32 0.04 0.04 0.16
Brightener 15 0 0 0.68 0.08 0.08 0.32
Moisture 2.50 2.00 2.90 2.20 2.40 1.80
Sodium carbonate 20.0 17.5 21.0 20.2 19.0 18.0
Sodium Sulfate 0.20 0.30 0.50 0.30 0.45 0.10
Sodium Silicate 0.25 0.25 0.55 0.30 0.25 0.10
Layered Silicate Builder 2.7 3.0 2.2 3.7 1.5 1.0
Zeolite A 11.0 11.0 12.5 10.2 9.5 8.0
Protease 0.20 0.50 1.0 0.15 0.40 0.0
Silicone Suds Suppressor 0.40 0.35 1.00 0.60 0.50 0.00
Coarse Sulfate 21.5 23.0 21.0 21.0 20.0 18.5
Amine Reaction Product 0.40 0.25 0.10 0.35 0.60 0.00
comprising 8-Damascone* * * *
Perfume 0.10 0.30 0.20 0.20 0.40 0.50
Sodium Percarbonate 2.8 4.5 2.00 4.7 7.4 10.0
Conventional Activator (NOBS) 2.10 3.7 1.00 3.0 5.0 10.0
Organic Catalyst** 0.005 0.10 1.00 0.25 0.05 0.05
Bluing agent*** 0.50 0.20 1.00 0.30 0.10 0.00
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Balance Balance Balance Balance Balance Balance
to to to to to to
Filler 100% 100% 100% 100% 100% 100%
* Other hydrotropes, such as sodium toluenesulfonate, may also be used.
** Organic catalyst prepared according to Examples 1 through 12, or mixtures
thereof.
*** Such as Ultramarine Blue or Azo-CM-Cellulose (Megazyme, Bray, Co. Wicklow,
Ireland)
* * * * Prepared according to WO 00/02991.
5 Any of the above compositions is used to launder fabrics at a concentration
of 500 - 1500
ppm in water, 5-25 C, and a 15:1 - 25:1 water:cloth ratio. The typical pH is
about 9.5-10 but can
be can be adjusted by altering the proportion of acid to Na- salt form of
alkylbenzenesulfonate.
Example 16
10 The organic catalysts listed below are tested according to Applicants'
Organic Catalyst/Enzyme
Compatibility Test using [Peracetic Acid] = 5.0 ppm; [organic catalyst] = 0.5
ppm and the
following results are obtained.
Enzyme Compatibility Values
Entry* Catalyst Moiety ECVter ECVdur ECVnat ECV
R1
I tert-butyl 51 86 58 65
2 2-ethylhexyl 54 90 57 67
3 2- ro the l 98 101 99 99
4 2-but loct l 101 101 102 101
5 n-C 12114 102 100 100 101
6 iso-nonyl 86 96 88 90
7 iso-decyl 98 97 96 97
8 iso-tridecyl 99 100 101 100
* Entries 1 and 2 are respectively C4 and C8 branched alkyl moieties which are
not encompassed
15 by Applicants' Formula 1.
Example 17
A fabric requiring cleaning is contacted at ambient temperature for 12 minutes
at a 25:1
water:cloth ratio with an aqueous solution of 500 ppm of bleaching detergent
composition
20 formulation E described in Example 15. The fabric is removed from the wash
water, rinsed in
ambient temperature water, and subsequently tumble dried in a domestic clothes
dryer at a
temperature between 35 and 100 C. Additional bleaching is obtained during
drying and after the
fabric has been dried.
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While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
