Note: Descriptions are shown in the official language in which they were submitted.
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PEROXYGEN BLEACHING COMPOSITIONS COMPRISING
PEROXYGEN BLEACH AND ATMP, SUITABLE FOR
USE AS A PRETREATER FOR FABRICS
Technical Field
The present invention relates to bleach-containing compositions
suitable for use as pretreater and to a pretreatment process whereby
fabric safety and/or color safety is improved. The liquid compositions of
the invention are also very stable, and the preferred bleaching
compositions herein are acidic.
Background of the Invention
Bleaching compositions have been extensively described in laundry
applications as laundry detergents, laundry additives or even laundry
pretreaters.
Indeed, it is known to use such bleach-containing compositions in
laundry pretreatment applications to boost the removal of encrusted
stains/soils and "problem" stains, such as grease, coffee, tea, grass,
mud/clay-containing soils, which are otherwise particularly difficult to
remove by typical machine washing. However, a drawback associated
with such bleach-containing compositions is that said compositions may
damage fabrics, resulting in dye damage and/or loss of tensile strength
of the fabric fibers, especially when used in pretreatment applications
under stressed conditions, e.g. when applied directly onto the fabric and
left to act onto said fabric for prolonged periods of time before washing
said fabrics, especially when the fabric to be treated is contains metal
ions such as copper, iron, manganese, or chromium. Without being
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limited by theory, it is believed that peroxygen bleach can be responsible
for the dye and fabric damage associated with these bleaching
compositions. It is furthered believed that these metal ions on the
surface of the fabrics, especially on cellulosic fabrics, catalyze the
decomposition of peroxygen bleaches like hydrogen peroxide. Thus, the
decomposition of the peroxygen bleach can result in fabric and/or dye
damage.
When said compositions are applied directly to fabrics, the
different components in said compositions diffuse or migrate, possibly at
different rates, through the fabric fibers. This is also true for the
peroxygen bleach component of bleaching compositions designed for the
pretreatment of fabrics.
Now a solution to the damage resulting from pretreating fabrics
with bleaching compositions comprising peroxygen bleach is provided by
adding a certain fabric protection agent which acts to reduce fabric
andlor dye damage. This fabric protection agent, aminotri(methylene
phosphonic acid) - hereinafter ATMP - has been found to considerably
reduce the damage associated with the treatment of fabrics with
peroxygen bleach-containing compositions, especially those fabrics
which are contaminated with metal ions.
Accordingly, the present invention solves the long-standing need
for an effective, bleaching composition suitable for use as a pretreater
which does not promote damage to fabrics. Moreover, the compositions
of the present invention provide excellent performance when used in
other applications apart from laundry pretreater application, such as in
other laundry applications, as a laundry detergent or laundry additive, or
even in hard surface cleaning applications or in carpet cleaning
applications.
In the preferred compositions of the invention, which are liquid
compositions, ATMP further provides the benefit of exceptional chemical
stability for the peroxygen bleach.
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Background Art
Peroxygen bleach-containing compositions have been extensively
described in the art. For example EP-629,691 A discloses emulsions of
nonionic surfactants comprising a silicone compound, and as optional
ingredients, hydrogen peroxide, or a water soluble source thereof. EP-
629,690A discloses emulsions of nonionic surfactants comprising a
terephthalate-based polymer, and as optional ingredients, hydrogen
peroxide, or a water soluble source thereof. EP-209,228B discloses
compositions comprising a peroxide source Pike hydrogen peroxide. EP-
209,228B discloses that the hydrogen peroxide-containing compositions
may be used as pre-spotters. See also U.S. Pat. No. 4,891,147, issued
Jan. 2, 1990, and U.S. Pat. No. 5,019,289, issued May 28, 1991.
Compositions comprising ATMP in a laundry context have been disclosed
in EP 517 605, DD 280 783 and DD 280 784, however the
compositions herein do not comprise a peroxygen bleach.
Summary of the Invention
The present invention encompasses a composition comprising a
peroxygen bleach, such as hydrogen peroxide or a source thereof, and
ATMP. Preferred compositions are liquid aqueous compositions which
have a pH of from greater than 0 to about 6 and a viscosity of 1 cps or
greater, preferably from about 50 to about 2000 cps, at 20°C when
measured with a Brookfield viscometer at 50 rpm with a spindle no. 3.
The present invention further encompasses a process of
pretreating soiled fabrics with a liquid, aqueous .composition comprising
a peroxygen bleach and ATMP, preferably in .its neat form, onto the
fabric and allowing said composition to remain in contact with said
fabric, preferably without leaving said composition to dry on the fabric,
before said fabric is washed.
By "pretreat soiled fabrics" it is to be understood that the aqueous
composition is applied in its neat form onto the soiled fabric and left to
act onto said fabric before said fabric is washed. Alternatively, the
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aqueous composition may be applied to the fabric substrate along with
enough water to wet the fabric.
All percentages, ratios, and proportions herein are by weight of
total liquid composition, unless otherwise specified.
Detailed Description of the Invention
The present invention encompasses a composition comprising a
peroxygen bleach, and ATMP. ATMP has been found to considerably
reduce the damage associated with the treatment of fabrics with
peroxygen bleach-containing compositions, especially those fabrics
which contain metal ions, such as copper, iron, chromium, and
manganese.
Fabric Protection Agient
As the fabric protection agent, the compositions herein comprise
ATMP, i.e. the compound of formula
CHZ - P03H2
N
POgH2-CH2 CH2-P03H2
Preferably, the compositions herein will comprise from about
0.00596 to about 5.0%, more preferably from about 0.0196 to about
1.096, by weight of the total bleaching composition of ATMP.
The preferred compositions according to the present invention are
aqueous liquid cleaning compositions. Said aqueous compositions
should be formulated in the acidic pH, preferably at a pH of from greater
than 0 to about fi and more preferably at a pH of from 3 to 5.
Formulating the compositions of the present invention in the acidic pH
range contributes to the stability of said compositions. The pH of the
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compositions of the present invention can be adjusted by using organic
or inorganic acids or bases.
Tensile strength test method - By "fabric damage" herein is meant
the degree of tensile strength loss of a fabric. The tensile strength loss of
fabrics can be determined by the following: Krefeld cotton ribbons
(dimension 12.5 x 5 cm2) having a copper(2+) concentration of 30 ppm
per gram of cotton are treated with 2 ml of the test composition
according to Example I. The test composition is left in contact with the
ribbons for 24 hours. The ribbons are then rinsed with water, and the
tensile strength loss measured with an INSTRON, model no. 4411.
Damage on the cotton ribbons is evaluated by stretching said ribbons until
they break. The force necessary to break the ribbons, i.e. the Ultimate
Tensile Stress, is measured while the ribbons are wet with a INSTRON,
model 441 1. The lower the force needed to break the cotton ribbons, the
more serious is the damage caused on the fabrics. A good confidence
(standard deviation = 2-4 Kg) in the results is obtained using five replicates
for each test.
Peroxvaen Bleach - An essential element of the compositions of
the present invention is peroxygen bleach. A preferred peroxygen bleach
herein is hydrogen peroxide or a water soluble source thereof or mixtures
thereof. Hydrogen peroxide is most preferred. Indeed, the presence of
peroxygen bleach, preferably hydrogen peroxide, provides strong
cleaning benefits which are particularly noticeable in laundry
applications. As used herein, a hydrogen peroxide source refers to any
compound which produces hydrogen peroxide when said compound is in
contact with water.
Suitable water-soluble sources of hydrogen peroxide for use herein
include sodium carbonate peroxyhydrate or equivalent percarbonate
salts, persilicate, perborates, e.g., sodium perborate (any hydrate but
preferably the mono- or tetra-hydrate), sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, sodium peroxide, and mixtures
thereof. Alternative peroxygen sources include persulfates such as
monopersulfate, peroxyacids such as diperoxydodecandioic acid (DPDA),
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magnesium perphthalatic acid, perbenzoic and alkylperbenzoic acids, and
mixtures thereof.
An "effective amount" of a peroxygen bleach is any amount
capable of measurably improving soil/stain removal from the soiled fabric
substrate compared to a peroxygen bleach-free composition when the
soiled substrate is washed by the consumer in the presence of alkali.
Typically, the compositions of the present invention comprise from 0.5%
to 20% by weight of the total composition of said peroxygen bleach,
preferably from 1 % to 15% and most preferably from 2% to 6%.
Optional Bleach Activators - The peroxygen-containing compositions
herein may optionally, but preferably, further comprise a bleach
activator. By bleach activator, it is meant herein a compound which
reacts with hydrogen peroxide to form a peracid. The peracid thus
formed constitutes the activated bleach. Particularly preferred is acetyl
triethyl citrate. Said bleach activators, if present, will typically comprise
from about 0.5% to about 20%, preferably from 2% to 10%, most
preferably from 3% to 7%, by weight of the total composition.
Bleach activators suitable herein are any known activators typified
by NOBS (nonanoyl oxybenzenesulfonate), TAED
(tetraacetylethylenediamine), or ATC (acetyl triethyl citrate). Numerous
other bleach activators are known. See for example activators
referenced in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et
al, and U.S. Patent 4,412,934. See also U.S. 4,634,551 f_or other
typical conventional bleach activators. Also known are amido-derived
bleach activators of the formulae: R1 N(R5~C(01R2C(O)L or
R1 C(O)N(R5)R2C(O)L wherein R1 is an alkyl group containing from
about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1
to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing
from about 1 to about 10 carbon atoms, and L is any suitable leaving
group. Further illustration of bleach activators of the above formulae
include (6-oct-anamidocaproyl)-oxybenzenesulfonate, (6-
nonanamidocaproyl)oxybenzenesulfonate, (6-
decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as
described in U.S. Patent 4,634,551. Another class of bleach activators
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comprises the benzoxazin-type activators disclosed by Hodge et al in
U.S. Patent 4,966,723, issued October 30, 1990. Still another class of
bleach activators includes acyl lactam activators such as substituted and
unsubstituted benzoyl caprolactam, t-butyl-benzoylcaprolactam, n-
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam, t-butyl-
benzoyivaierolactam and mixtures thereof.
Preferred bleach activators useful herein include those selected
from the group consisting of acetyl triethyl citrate, n-octanoyl
caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, n-octanoyl vaierolactam, 3,5,5-
trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl
valerolactam, nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and
mixtures thereof. Particularly preferred are the bleach activators which
are liquid or oil at room temperature. Examples of liquid bleach
activators are acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, and mixtures thereof. The present compositions can
optionally comprise aryl benzoates, such as phenyl benzoate.
Pretreatment Process - Although preferred application of the
compasitions described herein is laundry pretreatment, the compositions
according to the present invention may also be used as a laundry
detergent or as a laundry detergent booster and as a household cleaner
in the bathroom or in the kitchen, for the cleaning of dishes or carpets.
Said liquid composition may remain in contact with the fabric,
typically for a period of 1 minute to 24 hours, preferably 1 minute to 1
hour, and more preferably 5 minutes to 30 minutes, or so as to avoid
drying of the liquid composition on the fabric. Optionally, when the
fabric is soiled with encrusted stains/soils which otherwise would be
relatively difficult to remove, the liquid compositions according to the
present invention may be rubbed and/or brushed, for example, by means
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of a sponge or a brush or simply by rubbing two pieces of fabric each
against the other.
By "washing" it is to be understood herein to simply rinse the
fabrics with water, or the fabrics may be washed with conventional
compositions comprising at least one surface active agent, this by the
means of a washing machine or simply by hand.
By "in its neat form" it is to be understood that the liquid
compositions described herein are applied onto the fabrics to be pre-
treated without undergoing any dilution, i.e. they are applied as
described herein.
Other Conventional Ingredients for Cleaning Compositions - The
bleaching compositions herein typically will also comprise other optional
conventional ingredients to improve or modify performance. Typical,
non-limiting examples of such ingredients are disclosed hereinafter for
the convenience of the formulator.
Organic Stabilizers - The compositions herein may also optionally
contain organic stabilizers for improving the chemical stability of the
composition, provided that such materials are compatible or suitably
formulated. Organic stabilizers can be selected from the following group:
monophenols such as 2,6-di-tert-butylphenol or 2,6-di-tert-butyl-4-
methylphenol; diphenols such as 2,2'-methylenebis(4-methyl-6-tert-
butyiphenol) or 4,4'-methylenebis(2,6-di-tert-butylphenoll; polyphenois
such as 1, 3, 5-trimethyl-2;4, 6-tris(3', 5'-di-tert-butyl-4-
hydroxybenzyl)benzene; hydroquinones such as 2,5-di-tert-
amylhydroquinone or tert-butylhydroquinone; aromatic amines such as N
phenyl-N'-( 1,3-dimethylbutyl)-p-phenylenediamirre or N phenyl-a-
napthylamine; dihydroquinolines such as 2,2,4-trimethyl-1,2-dihydro-
quinoline; ethane-1-hydroxy-1,1-diphosphonate and other known
phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148 and 3,422,137), and mixtures thereof.
Organic stabilizers are typically used in the present compositions at
levels from 0.01 % to 5.0%, more preferably from 0.05% to 0.5%.
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The peroxygen bleach-containing compositions according to the
present invention may further comprise from 0.5% to 5%, preferably from
2% to 4% by weight of the total composition of an alcohol according to
the formula HO - CR'R" - OH, wherein R' and R" are independently H or a
C2-C 10 hydrocarbon ,chain and/or cycle. Preferred alcohol according to
that formula is propanediol.
Inorganic Stabilizers - Examples on inorganic stabilizers include
sodium stannate and various alkali metal phosphates such as the well-
known sodium tripolyphosphates, sodium pyrophosphate and sodium
orthophosphate.
Detersive Surfactants --Surfactants are useful herein for their usual
cleaning power and may be included in preferred embodiments of the
instant compositions at the usual detergent-useful levels. Generally,
surfactants will comprise from about 0.1 % to about 50%, preferably
from about 1 % to about 30%, more preferably from about 5% to about
25%, by weight of the bleaching compositions herein.
Nonlimiting examples , of surfactants useful herein include the
conventional C 1 1 _C 1 g alkylbenzene sulfonates ("LAS") and primary,
branched-chain and random C10-C2p alkyl sulfates ("AS"1; the C10-C1 g
secondary alkyl sulfates of the formula CH3(CH2)x(CHOS03 M + )CH3
and CH3(CH2)y(CHOS03 M + )CH2CH3 where x and (y + 1 ) are
integers of at least about 7, preferably at least about 9, and M is a
water-solubilizing cation, especially sodium; unsaturated sulfates such as
oleyl sulfate; the C10-C1 g alkyl alkoxy sulfates ("AEXS") especially
those wherein x is from 1 to about 7; C10-C1 g alkyl alkoxy carboxylates
(especially the EO 1-5 ethoxycartioxylates); the C 10-C 1 g glycerol ethers;
the C 10-C 1 g alkyl polyglycosides and their corresponding sulfated
polyglycosides; and C12-C1 g alpha-sulfonated fatty acid esters.
Detersive surfactants may be mixed in varying proportions for improved
surfactancy as is well-known in the art. Also optionally included in the
compositions are conventional nonionic and amphoteric surfactants such
as the C12-C1 g alkyl ethoxylates ("AE") including the so-called narrow
peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially
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ethoxylates and mixed ethoxylate/ propoxylates), C 12-C 1 g betaines and
sulfobetaines ("sultaines"), C 1 p-C 1 g amine oxides, and the like, can also
be included in the cleaning compositions, The C 10-C 1 g N-alkyl
polyhydroxy fatty acid amides can also be used. Typical examples
include the 012-C1g N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as 010-C1 g N-(3-methoxypropyl) glucamide. The N-propyl
through N-hexyl C 12-C 1 g glucamides can be used for low sudsing.
C 10-020 conventional soaps may also be employed. If high sudsing is
desired, the branched-chain C 10-C 16 soaps may be used. Mixtures of
anionic and nonionic surfactants are especially useful.
Builders - Detergent builders can optionally be included in the
compositions herein to assist in controlling mineral hardness. Inorganic
as well as organic builders can be used. Builders are typically used_in
fabric laundering compositions to assist in the removal of particulate
soils.
The level of builder can vary widely depending upon the end use of
the composition and its desired physical form. When present, the
compositions will typically comprise at least about 0.1 % builder.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate compounds. As used herein, "polycarboxylate" refers to
compounds having a plurality of carboxylate groups, preferably at least 3
carboxylates. Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt or "overbased". When utilized in salt form, alkali metals,
such as sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
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January 18, 1972. See also "TMS/TDS" builders of U.S. Patent
4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarboxylates also include cyclic compounds, particularly alicyclic
compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene
or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid,
and carboxymethyloxysuccinic acid, the various alkali metal, ammonium
and substituted ammonium salts of polyacetic acids such as
nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts
thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of particular
importance due to their availability from renewable resources and their
biodegradability. Oxydisuccinates are also especially useful in such
compositions and combinations.
Also suitable in the detergent compositions of the present' invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related
compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the C5-C2p alkyl and
alkenyl succinic acids and salts thereof. Specific examples of succinate
builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred, 2-pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are
described in European Patent Application 86200690.5/0,200,263,
published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also U.S. Patent
3,723,322.
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Fatty acids, e.g., C12-C1 g monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will generally
result in a diminution of sudsing in laundry compositions, which may
need to be be taken into account by the formulator.
Where phosphorus-based builders can be used, and especially in
hand-laundering operations, the various alkali metal phosphates such as
the well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as
ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used though such materials are
more commonly used in a low-level mode as chelants or stabilizers.
Inorganic or P-containing detergent builders include, but are not
limited to, the alkali metal, ammonium and aikanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates,
and glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulfates, and aluminosilicates.
Chelating Agents in addition to ATMP - The compositions herein
may also optionally contain a transition-metal selective sequestrants or
"chelating agents", e.g., iron and/or copper and/or manganese chelating
agents, provided that such materials are compatible or suitably
formulated. Chelating agents suitable for use herein can be selected
from the group consisting of aminocarboxylates, phosphonates
(especially the aminophosphonatesl, polyfunctionally-substituted
aromatic chelating agents, and mixtures thereof. Without intending to
be bound by theory, it is believed that the benefit of these materials is
due in part to their exceptional ability to remove iron, copper and
manganese ions from washing solutions by formation of soluble
chelates; other benefits include inorganic film prevention or scale
inhibition. Commercial chelating agents for use herein include the
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DEQUEST~ series, and chelants from Monsanto, DuPont, and Nalco,
Inc.
Aminocarboxylates useful as optional chelating agents are further
illustrated by ethylenediaminetetracetates, N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and substituted ammonium salts thereof. In general, chelant
mixtures may be used for a combination of functions, such as multiple
transition-metal control, long-term product stabilization, and/or control of
precipitated transition metal oxides. and/or hydroxides.
Polyfunctionally-substituted aromatic chelating agents are also
useful in the compositions herein. See U.S. Patent 3,812,044, issued
May 21, 1974, to Connor et al. Preferred compounds of this type in
acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene.
A highly preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially (but not limited tot the
ES,S) isomer as described in U.S. Patent 4,704,233, November 3, 1987,
to Hartman and Perkins. The trisodium salt is preferred though other
forms, such as magnesium salts, may also be useful.
Another preferred chelator for use herein is of the formula:
R~RzR~
R8 COOH OH
R~
/ NH
NH
OH COOH RS ~
RtR2RsR4
wherein R 1, R2, R3, and R4 are independently selected from the group
consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -N02, -C(O)R', and
-S02R"; wherein R' is selected from the group consisting of -H, -OH,
alkyl, alkoxy, aryl, and aryfoxy; R" is selected from the group consisting
of alkyl, alkoxy, aryl, and aryloxy; and R5, Rg, R7, and Rg are
independently selected from the group consisting of -H and alkyl.
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Aminophosphonates are also suitable for use as chelating agents in
the compositions of the invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include the
ethylenediaminetetrakis (methylenephosphonates) and the
diethylenetriaminepentakis (methylenephosphonatesl. Preferably, these
aminophosphonates do not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
If utilized, chelating agents or transition-metal-selective
sequestrants will preferably comprise from about 0.001 % to about 10%,
more preferably from about 0.05% to about 1 % by weight of the
compositions herein.
Polymeric Soil Release Agent - Any polymeric soil release agent
known to those skilled in the art can optionally be employed in the
compositions and processes of this invention. Polymeric soil release
agents are characterized by having both hydrophilic segments, to
hydrophilize the surface of hydrophobic fibers, such as polyester and
nylon, and hydrophobic segments, to deposit upon hydrophobic fibers
and remain adhered thereto through completion of washing and rinsing
cycles and, thus, serve as an anchor for the hydrophilic segments. This
can enable stains occurring subsequent to treatment with the soil release
agent to be more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include
those soil release agents having: (a) one or more nonionic hydrophile
components consisting essentially of (i) polyoxyethylene segments with
a degree 'of polymerization of at least 2, or (ii) oxypropylene or
polyoxypropylene segments with ~a degree of polymerization of from 2 to
10, wherein said hydrophile segment does not encompass any
oxypropylene unit unless it is bonded to adjacent moieties at each end
by ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to about 30 oxypropylene units wherein said
mixture contains a sufficient amount of oxyethylene units such that the
hydrophile component has hydrophilicity great enough to increase the
hydrophilicity of conventional polyester synthetic fiber surfaces upon
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deposit of the soil release agent on such surface, said hydrophile
segments preferably comprising at least about 25% oxyethylene units
and more preferably, especially for such components having about 20 to
30 oxypropylene units, at least about 50% oxyethylene units; or (b) one
or more hydrophobe components comprising (i) C3 oxyalkylene
terephthalate segments, wherein, if said hydrophobe components also
comprise oxyethylene terephthalate, the ratio of oxyethylene
terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower,
(ii) C4-C6 alkylene or oxy C4-Cg alkylene segments, or mixtures therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a
degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4
hydroxyalkyl ether substituents, or mixtures therein, wherein said
substituents are present in the form of C1-Cq. alkyl ether or Cq.
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such
cellulose derivatives are amphiphilic, whereby they have a sufficient level
of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fiber surfaces and retain a sufficient
level of hydroxyls, once adhered to such conventional synthetic fiber
surface, to increase fiber surface hydrophilicity, or a combination of (a)
and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree
of polymerization of from about1 to about 200, although higher levels
can be used, preferably from 3 to about 150, more preferably from 6 to
about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include,
but are not limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-, where M is sodium and n is an integer from
4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink.
Polymeric soil release agents useful in the present invention also
include cellulosic derivatives such as hydroxyether cellulosic polymers,
copolymeric blocks of ethylene terephthalate or propylene terephthalate
with polyethylene oxide or polypropylene oxide terephthalate, and the
like. Such agents are commercially available and include hydroxyethers
of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for
use herein also include those selected from the group consisting of C 1-
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C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093,
issued December 28, 1976 to Nicol, et at.
Soil release agents characterized by polyvinyl ester) hydrophobe
segments include graft copolymers of polyvinyl ester), e.g., C 1-Cg vinyl
esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones. See European Patent
Application 0 219 048, published April 22, 1987 by Kud, et al.
Commercially available soil release agents of this kind include the
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(West Germany).
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethylene oxide (PE01
terephthalate. The molecular weight of this polymeric soil release agent
is in the range of from about 25,000 to about 55,000. See U.S. Patent
3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to
Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with
repeat units of ethylene terephthalate units contains 10-15% by weight
of ethylene terephthalate units together with 90-80% by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethyiene
glycol of average molecular weight 300-5,000. Examples of this
polymer include the commercially available material ZELCON 5126 (from
Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857,
issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated
product of a substantially linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat
units and terminal moieties covalentiy attached to the backbone. These
soil release agents are described fully in U.S. Patent 4,968,451, issued
November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable
polymeric soil release agents include the terephthalate polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the
anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued
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January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Preferred polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, issued October 31, 1989 to
Maldonado et al, which discloses anionic, especially sulfoaroyl, end-
capped terephthalate esters.
Still another preferred soil release agent is an oligomer with repeat
units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy
and oxy-1,2-propylene units. The repeat units form the backbone of the
oligomer and are preferably terminated with modified isethionate end-
caps. A particularly preferred soil release agent of this type comprises
about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about
1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-
ethanesulfonate. Said soil release agent also comprises from about
0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing
stabilizer, preferably selected from the group consisting of xylene
sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
See U.S. Pat. No. 5,415,807, issued May 16, 1995, to Gosselink et al.
If utilized, soil release agents will generally comprise from about
0.01 % to about 10.0%, by weight, of the detergent compositions
herein, typically from about 0.1 % to about 5%, preferably from about
0.2% to about 3.0%.
Other Ingredients - Detersive ingredients or adjuncts optionally
included in the instant compositions can include one or more materials
for assisting or enhancing cleaning performance, treatment of the
substrate to be cleaned, or designed to improve the aesthetics of the
compositions. Such materials are further illustrated in U.S. Pat. No.
3,936,537, Baskerville et al. Adjuncts which can also be included in
compositions of the present invention, in their conventional art-
established levels for use (generally from 0% to about 20% of the
detergent ingredients, preferably from about 0.5% to about 10%),
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include other active ingredients such as dispersant polymers from BASF
Corp, or Rohm & Haas; anti-tarnish and/or anti-corrosion agents, dyes,
fillers, optical brighteners, germicides, hydrotropes, enzyme stabilizing
agents, perfumes, solubilizing agents, clay soil removal/anti-redeposition
agents, carriers, processing aids, pigments, solvents, fabric softeners,
static control agents, etc.
Dye Transfer Inhibitingi Ac e~ nts - The compositions of the present
invention may also include one or more materials effective for inhibiting
the transfer of dyes from one dyed surface to another during the cleaning
process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and mixtures thereof. It used, these agents typically
comprise from about 0.01 % to about 10% by weight of the
composition, preferably from about 0.01 % to about 5%, and more
preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for
use herein contain units having the following structural formula: R-Ax-P;
wherein P is a polymerizable unit to which an N-O group can be attached
or the N-O group can form part of the polymerizable unit or the N-0
group can be attached to both units; A is one of the following structures:
-NC(O)-, -C(O)O-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination thereof to which the nitrogen of the N-O group can be
attached or the N-O group is part of these groups. Preferred polyamine
N-oxides are those wherein R is a heterocyclic group such as pyridine,
pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general
structures:
O O
I I
~ t hc- i W2)y~ =N WRnc
(R3)z
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wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of
the N-O group can be attached or form part of any of the aforementioned
groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10,
preferably pKa < 7, more preferred pKa < 6.
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,
poiyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mixtures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically
have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine
oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree of N-oxidation. The polyamine oxides can be
obtained in almost any degree of polymerization. Typically, the average
molecular weight is within the range of 500 to 1,000,000; more
preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This
preferred class of materials can be referred to as "PVNO". The most
preferred polyamine N-oxide useful in the detergent compositions herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of
about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinyfimidazole polymers
(referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the PVPVI has an average molecular weight range from 5,000
to 1,000,000, more preferably from 5,000 to 200,000, and most
preferably from 10,000 to 20,OOb. (The average molecular weight range
is determined by light scattering as described in Barth, et al., Chemical
Analysis, Vol 113. "Modern Methods of Polymer Characterization", the
disclosures of which are incorporated herein by reference.) The PVPVI
copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1,
most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or branched.
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The present invention compositions also may employ a
polyvinylpyrrolidone ("PVP") having an average molecular weight of from
about 5,000 to about 400,000, preferably from about 5,000 to about
200,000, and more preferably from about 5,000 to about 50,000.
PVP's are known to persons skilled in the detergent field; see, for
example, EP-A-262,897 and EP-A-256,696, incorporated herein by
reference. Compositions containing PVP can also contain polyethylene
glycol ("PEG") having an average molecular weight from about 500 to
about 100,000, preferably from about 1,000 to about 10,000.
Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions is from about 2:1 to about 50:1, and more preferably from
about 3:1 to about 10:1.
Suds Boosters - If high sudsing is desired, suds boosters such as
C10-C16 alkanolamides can be incorporated into the compositions,
typically at 1 %-10% levels. The C 10-C 14 monoethanol and diethanol
amides illustrate a typical class of such suds boosters. Use of such suds
boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and sultaines noted above is also advantageous. If
desired, soluble magnesium salts such as MgCl2, MgS04, and the like,
can be added at levels of, for example, 0.1 %-2%, to provide additional
suds and to enhance grease removal performance.
Brightener - Any optical brighteners, fluorescent whitening agents
or other brightening or whitening agents known in the art can be
incorporated in the instant compositions when they are designed for
fabric treatment or laundering, at levels typically from about 0.05% to
about 1.2%, by weight, of the detergent compositions herein.
Commercial optical brighteners which may be useful in the present
invention can be classified into subgroups, which include, but are not
necessarily limited to, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,
5- and 6-membered-ring heterocyclic brighteners, this list being
illustrative and non-limiting. Examples of such brighteners are disclosed
in "The Production and Application of Fluorescent Brightening Agents",
M. Zahradnik, Published by John Wiley & Sons, New York (19821.
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Specific examples of optical brighteners which are useful in the
present compositions are those identified in U.S. Patent 4,790,856,
issued to Wixon on December 13, 1988. These brighteners include the
PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and
Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White
CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-
phenyl)-2H-naphthoi(1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil-
benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific
examples of these brighteners include 4-methyl-7-diethyl- amino
coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 2,5-bis(benzoxazol-2-
yl)thiaphene; 2-styryl-napth-(1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-
naphtho- (1,2-d]triazole. See also U.S. Patent 3,646,015, issued
February 29, 1972 to Hamilton. Anionic brighteners are typically
preferred herein.
Bleach catalysts - If desired, compositions herein may additionally
incorporate a catalyst or accelerator to further improve bleaching or soil
removal. Any suitable bleach catalyst can be used. For detergent
compositions used at a total level of from about 1,000 to about 5,000
ppm in water, the composition will typically deliver a concentration of
from about 0.1 ppm to about 700 ppm, more preferably from about 1
ppm to about 50 ppm, or less, of the catalyst species in the wash liquor.
Typical bleach catalysts comprise a transition-metal complex, for
example one wherein the metal co-ordinating ligands are quite resistant
to labilization and which does not deposit metal oxides or hydroxides to
any appreciable extent under the typically alkaline conditions of washing.
Such catalysts include manganese-based catalysts disclosed in U.S. Pat.
5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S. 5,114,606; and EP
Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1;
preferred examples of these catalysts include MnIV2lp-0)3(TACN)2-
(PF6)2, Mnlll2(~_O) 1 (~_pAcl2(TACN)2(C104)2, MnIV4(p_
0)6(TACN)4(C104)4, MnIIIMnIV4_(~_O)1 (p_OAc)2-(TACN)2-(C104)3,
MnIV-(TACN)-(OCH3)3(PF6), and mixtures thereof wherein TACN is
trimethyl-1,4,7-triazacyclononane or an equivalent macrocycle; though
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22
alternate metal-co-ordinating ligands as well as mononuclear complexes
are also possible and monometallic as well as di- and polymetallic
complexes and complexes of alternate metals such as iron or ruthenium
are all within the present scope. Other metal-based bleach catalysts
include those disclosed ~~in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of manganese with various complex ligands to
enhance bleaching is also reported in the following United States
Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153,161; and 5,227,084.
Transition matals may be precomplexed or complexed in-situ with
suitable donor ligands selected in function of the choice of metal, its
oxidation state and the denticity of the ligands. Other complexes which
may be included herein are those of WO 95/25159 published
September 21, 1995.
Pretreater Formulation - The preferred compositions of the present
invention are liquid, they have a viscosity 1 cps or greater at 20°C
when
measured with a Brookfield viscometer at 50 rpm with a spindle n°3,
more preferably of from about 50 to about 2000 cps, and still more
preferably of from about 200 to about 1500 cps. Any surfactant system
or polymeric thickener known in the art to increase the viscosity of a
composition can be used to achieve the preferred viscosity. Thus the
surfactants suitable to be used herein may be thickening surfactants such
as nonionic, anionic, cationic, zwitterionic and/or amphotheric surfactants.
The liquid bleaching composition herein comprise water in any
amount up to about 98°i6 by weight of the total composition.
Preferably,
the compositions herein will comprise from about 5°Xo to about 98%,
more preferably from about 10% to about 95%, by weight of the
bleaching composition, of water.
When the liquid peroxygen bleach-containing compositions
according to the present invention further comprise an optional bleach
activator, it is highly desired herein to formulate said compositions either
as a microemulsion or as a stable emulsion.
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When formulated as a microemulsion, the composition comprises
the bleach activator in a matrix of water, the peroxygen bleach, and
hydrophilic anionic and nonionic surfactants. Suitable anionic
surfactants herein include the alkyl benzene sulfonates, alkyl sulfates,
alkyl alkoxylated sulfates, and mixtures thereof. Suitable nonionic
surfactants for use in the microemulsions herein include the hydrophilic
nonionic surfactants as defined hereinafter for the emulsions according
to the present invention.
When formulated as an emulsion, the composition comprises at
least a hydrophilic surfactant having an HLB (hydrophilic-lipophilic
balance) above 10 and at least a hydrophobic surfactant having an HLB
up to 9, wherein said bleach activator is emulsified by said surfactants.
The two different surfactants in order to form emulsions which are
stable must have different HLB values, and preferably the difference in
value of the HLBs of said two surfactants is at least 1, preferably at
least 3. In other words, by appropriately combining at least two of said
surfactants with different HLBs in water, stable emulsions will be
formed, i.e. emulsions which do not substantially separate into distinct
layers, upon standing for at least two weeks at 40 °C, preferably 50
°C. The emulsions comprise from about 2 % to about 50%, by weight
of the total composition, of said hydrophilic and hydrophobic
surfactants, preferably from about 5% to about 40%, and more
preferably from about 8% to about 30%. The emulsions comprise at
least about 0.1 %, preferably at least 3%, more preferably at least 5%,
by weight of the total emulsion, of one or more hydrophobic surfactant
and at least about 0.1 %, preferably at least 3%, more preferably at least
5%, by weight of the total emulsion, of one or more hydrophilic
surfactant. Preferred to be used herein are the hydrophobic nonionic
surfactants and hydrophilic nonionic surfactants. Said hydrophobic
nonionic surfactants to be used herein have an HLB up to 9, preferably
below 9, more preferably below 8 and said hydrophilic surfactants have
an HLB above 10, preferably above 1 1, more preferably above 12.
Suitable nonionic surfactants for use herein include alkoxylated fatty
alcohols, preferably fatty alcohol ethoxylates and/or propoxylates. A
variety of alkoxyiated fatty alcohols are commercially available which
have very different HLB values. For further discussion of HLB theory and
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surfactants and hydrophilic nonionic surfactants. Said hydrophobic
nonionic surfactants to be used herein have an HLB up to 9, preferably
below 9, more preferably below 8 and said hydrophilic surfactants have
an HLB above 10, preferably above 11, more preferably above 12.
Suitable nonionic surfactants for use herein include alkoxylated fatty
alcohols, preferably fatty alcohol ethoxylates and/or propoxylates. A
variety of alkoxylated fatty alcohols are commercially available which
have very different HLB values. For further discussion of HLB theory
and its application to the formation of emulsions, please see the:
Encyclopedia of Emulsion Technology; Becher, P., Ed.; Marcel Dekker,
Inc.: New York, 1985; Volumes 1 and 2, and references cited therein.
In a particularly preferred embodiment of the emulsion, if present,
wherein the emulsions comprise acetyl triethyl citrate as the bleach
activator, an adequate nonionic surfactant system would comprise a
hydrophobic nonionic surfactant with, for instance, an HLB of 6, such
as a DobanolR 23-2 and a hydrophilic nonionic surfactant with, for
instance, an HLB of 15, such as a DobanolR 91-10. Other suitable
nonionic surfactant systems comprise for example a DobanolR 23-6.5
(HLB about 12) and a DobanolR 23 (HLB below 6) or a DobanolR 45-7
(HLB=11.6) and LutensolR t03 (HLB=8). DobanolR are commercially
available nonionic surfactants available from Shell Corp. LutensolR are
commercially available nonionic surfactants available from BASF Corp.
The peroxygen bleach-containing compositions according to the
present invention may further comprise an amine oxide surfactant
according to the formula R1R2R3N0, viiherein each of R1, R2 and R3 is
independently a C6-C30, preferably a C10-C30, most preferably a C12-
C16 hydrocarbon chain. It ilas been further observed that in a
pretreatment process, the presence of said amine oxide further
improves the cleaning performance on particulate and/or greasy stains.
It is believed that this improvement in cleaning performance is matrix
independent. To obtain either of these benefits, amine oxides, if
present, should be present in amounts ranging from 0.1 % to 10 % by
weight of the total composition, preferably from 1.5% to 3%.
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The following examples illustrate the compositions of this
invention, but are not intended to be limiting thereof. All materials in
the Examples satisfy the functional limitations herein.
Formulation I
Na Alkylsulphate 2.0
Dobanol ~ 45-7 6.5
Dobanol ~ 23-3 8.5
ATC 3.5
H202 ~ 4.0
BHT 0.05
ATMP 0.15
H2S04 up to pH 4
water balance to 100%
Formulation II
Na Alkylsulphate 12.0
Dobanol ~ 45-7 6.0
Dobanol ~ 23-6.5 6.0
ATC 3.5
H202 6.0
BHT 0.05
ATMP 0.15
Propaned iol 3.0
H2S04 up to pH 4
water balance to 100%
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Formulation III
Na Alkylsulphate 1.5
Dobanol ~ 45-7 1.5
Dobanol ~ 91-10 1.5
H202 7.0
BHT 0.02
ATMP 0.02
Citric Acid 0.02
H2S04 up to pH 4
water balance to 100%
