Technical field
[0001] The present invention relates to liquid aqueous stable monopersulfate-containing
compositions packaged in a UV resistant container.
Background of the invention
[0002] Liquid aqueous bleaching compositions suitable for example laundry applications are
well known in the art. It is also known that bleaching compositions relying on hypochlorite
as the bleaching agent can be preferred over oxygen beaches like hydrogen peroxide,
mainly for performance reasons, especially at lower temperatures.
[0003] However, there are some limitations to the convenience of hypochlorite bleaches.
In particular, it is well known from consumers that hypochlorite bleaching may cause
yellowing and/or damage of the fabrics which are being bleached. This holds particularly
true for synthetic fabrics and indeed there is a standing prejudice against using
hypochlorite beaches on synthetic fibers, as evidenced by warnings on labels of commercially
available hypochlorite bleaches. Also, a variety of fabrics made of or containing
synthetic fibers are labelled by their manufacturers as non-bleachable. Also another
drawback associated to hypochlorite based bleaching compositions is that undesirable
typical chlorine odor may be perceived by the consumer during and after use, e.g.,
on the hands of the user or fabrics that have been bleached with such compositions.
[0004] Colour and fabric damage can be minimised by using milder oxygen bleaches such as
monopersulfate salts. Advantageously, such monopersulfate salts are also odor free.
However, a drawback associated when formulating liquid aqueous monopersulfate salt
containing compositions that are desirable for convenience of use versus solid monopersulfate
containing compositions is that upon ageing of the compositions (i.e. upon prolonged
periods of storage), their bleaching and stain removal performance when typically
used in any laundry application diminish. It has now surprisingly been found that
light and especially UV light promotes the monopersulfate salt decomposition upon
ageing of the composition. In other words, it has been observed that monopersulfate
salts in a liquid aqueous composition tend to be photosensitive upon prolonged periods
of storage in for example sunlight.
[0005] It is therefore an object of the present invention to address the issues mentioned
above, namely those of providing effective overall stain removal performance on a
wide range of stains as well as effective bleaching performance when bleaching fabrics
upon ageing of the composition, i.e. after prolonged periods of storage (typically
up to 12 months at room temperature (20°C)). It is another object of the present invention
to provide a liquid aqueous bleaching composition delivering effective bleaching performance,
when used in laundry applications and/or in any household application (e.g. bleaching/disinfecting
of hard-surfaces), while being safe to the surfaces treated, e.g. to fabrics perse
and/or colours.
[0006] It has now been found that these objects can be efficiently met by formulating a
liquid aqueous composition having a pH from 0.6 to 7 and comprising a monopersulfate
salt and optionally a bleach activator being an aldehyde and/or ketone and/or halide
activator compound, said composition being packaged in a UV light resistant container.
More particularly, it has now been found that improved bleaching performance is provided
with the compositions according to the present invention being packaged in a UV light
resistant container upon ageing of the composition, when used in various applications,
e.g. in a laundry operation at a conventional dilution level of for example 100 ml/L
to 1 ml/L (composition:water), as compared to the bleaching performance delivered
by the same composition not packaged in a UV light resistant container.
[0007] The present invention delivers a liquid aqueous bleaching composition which exhibits
a great flexibility in the surfaces and soils it may bleach. Indeed, the compositions
according to the present invention are particularly suitable in any laundry application,
e.g., as a laundry detergent or a laundry additive, and when used as a laundry pretreater
or in other household applications like in hard surface cleaning applications.
[0008] An advantage of the compositions of the present invention is that these bleaching
compositions are suitable for the bleaching of different types of fabrics including
natural fabrics, (e.g., fabrics made of cotton, and linen), synthetic fabrics such
as those made of polymeric fibres of synthetic origin (e.g., polyamide-elasthane)
as well as those made of both natural and synthetic fibres. For example, the bleaching
compositions of the present invention based on monopersulfate salt and optionally
the activator compound described herein may be used on synthetic fabrics despite a
standing prejudice against using bleaches on synthetic fabrics, as evidenced by warnings
on labels of clothes and commercially available bleaching compositions like hypochlorite-containing
compositions.
[0009] Another advantage of the bleaching compositions according to the present invention
is that they are able to perform in a variety of conditions, i.e., in hard and soft
water as well as when used neat or diluted. More particularly, it has been found that
the preferred liquid aqueous compositions of the present invention comprising a monopersulfate
salt and a bleach activator as described herein, find a preferred application when
used in their diluted form in any application and especially in any conventional laundry
application. Indeed, upon dilution (typically at a dilution level of 20ml/L or more
(composition:water)) the compositions of the present invention become less acidic,
e.g., from a pH of about 1.5 to about 6.5 or more. The compositions according to the
present invention although delivering effective bleaching performance in their neat
form surprisingly exhibit further enhanced bleaching performance in their diluted
form. Actually, this

pH jump

effect allows to formulate acidic liquid aqueous compositions (i.e. pH below 7, preferably
below 3 and more preferably below 2) which are physically and chemically stable upon
prolonged periods of storage and which deliver outstanding bleaching performance under
diluted usage conditions.
[0010] Yet another advantage of the compositions of the present invention is that they exhibit
also effective stain removal performance on various stains including enzymatic stains
and/or greasy stains. Furthermore, when used in any hard-surface application these
compositions have been found to deliver excellent limescale removal performance and
to leave less streaking/filming on the surface treated as compared for example to
hypochlorite based compositions. Thus, an advantage of the compositions herein is
that it may not be necessary to rinse the surface with water after having treated
it with a composition of the present invention, this especially when used in its diluted
form.
Summary of the invention
[0011] The present invention encompasses a liquid aqueous composition having a pH from 0.6
to 7 and comprising a monopersulfate salt and optionally a bleach activator selected
from the group consisting of an aldehyde activator compound, a ketone activator compound,
a halide activator compound and a mixture thereof, said composition being packaged
in a UV light resistant container.
[0012] The present invention further encompasses processes of treating a surface, e.g. a
fabric or a hard-surface, starting from a liquid composition as defined herein packaged
in a UV light resistant container. For example, the processes of treating, especially
bleaching fabrics, include the steps of contacting said fabrics with the liquid composition
according to the present invention packaged in a UV light resistant container, in
its neat or diluted form, allowing said fabrics to remain in contact with said bleaching
composition for a period of time sufficient to bleach said fabrics, and subsequently
rinsing said fabrics with water. The processes of treating hard-surfaces herein include
the steps of applying the compositions herein, packaged in a UV light resistant container
to said hard-surfaces in their neat or diluted form, and optionally rinsing said hard-surfaces.
Detailed description of the invention
The liquid bleaching composition
[0013] The compositions according to the present invention are liquid compositions as opposed
to a solid or a gas. As used herein "liquid" includes "pasty" compositions. The liquid
compositions herein are aqueous compositions. The liquid compositions according to
the present invention have a pH from 0.6 to 7. Preferably, the pH of the compositions
herein is from 0.6 to 6, more preferably from 0.8 to 4, even more preferably from
1 to 3 and most preferably from 1 to 2. Formulating the compositions according to
the present invention in the acidic pH range is critical to the chemical stability
of the compositions according to the present invention. Typically, in the preferred
embodiment of the present invention where a bleach activator as described herein is
present, the acidic pH controls/limits the formation of highly reactive species which
are unstable in acidic medium like dioxirane upon storage, and thus contributes to
the stability of the compositions for prolonged periods of storage. Indeed, dioxirane
may result from the reaction between the monopersulphate salt and the activator (aldehyde
and/or ketone activator compound as described herein after).
[0014] The pH of the compositions may be adjusted by any acidifying or alkalinizing agents
known to those skilled in the art. Examples of acidifying agents are organic acids
such as citric acid and inorganic acids such as sulphuric acid, sulphonic acid and/or
metanesulphonic acid. Examples of alkalinizing agents are sodium hydroxide, potassium
hydroxide and/or sodium carbonate.
[0015] As a first essential element, the compositions according to the present invention
comprise a monopersulfate salt or a mixture thereof.
[0016] Suitable monopersulfate salts include any alkali metal monopersulfate salt including
sodium monopersulfate salts and/or potassium monopersulfate salts. Examples of monomonopersulfate
salts commercially available are those commercialised by Interox under the trade name
Curox®, by Degussa under the trade name Caroat® or by DuPont under the trade name
Oxone®. It is to understand herein that when the commercially available Curox®, Caroat®
and/or Oxone® are used, the % weights of monopersulfate salts mentioned herein, refer
to the total weight of said Curox®, Caroat® and/or Oxone®. The active concentration
is approximately 1/2 of the total weight.
[0017] Typically, the compositions herein comprise from 0.01% to 50% by weight of the total
composition of said monopersulfate salt or mixtures thereof, preferably from 0.5%
to 20%, more preferably from 1% to 15% and most preferably from 2% to 10%.
[0018] An advantage of the compositions of the present invention is that they are physically
and chemically stable upon prolonged periods of storage.
[0019] Chemical stability of the compositions herein may be evaluated by measuring the concentration
of available oxygen at given storage time after having manufactured the compositions.
By "chemically stable" it is meant herein that the compositions of the present invention
comprising a monopersulfate salt or mixtures thereof and optionally the activator
compound do not undergo more than 15% AvO loss, in one month at 25°C and preferably
not more than 10%.
[0020] Available oxygen (AvO) loss of a monopersulfate containing composition can be measured
by titration with potassium permanganate after reduction with a solution containing
ammonium ferrous sulphate. Said stability test method is well known in the art and
is reported, for example, on the technical information sheet of Curox
R commercially available from Interox. Alternatively monopersulfate concentration can
also be measured using a chromatography method described in the literature for peracids
(F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids,
Analyst, Vol 113, May 1988, p 793-795).
[0021] By "physically stable", it is meant herein that no phase separation occurs in the
compositions according to the present invention for a period of 7 days at 50°C.
The UV light resistant container
[0022] The compositions of the present invention are packaged in a UV light resistant container.
[0023] By

UV light resistant container

, it is meant any container that has a transmittance of UV-light (i.e., for the wavelengths
from 400 nm to 200 nm) of less than 50%, preferably less than 30%, more preferably
less than 10%, even more preferably less than 5% and most preferably of 0%. In a preferred
embodiment, this container also has a transmittance of less than 70%, preferably less
than 50%, more preferably less than 20% in the visible light (i.e., with wavelength
from 700 nm to 401 nm). Transmittance can be measured by any spectrophotometric common
test method.
[0024] The UV light resistant containers for use herein can be made of any material known
to those in the art provided it comprises a UV stabilizer (also called

UV absorber

). The containers can be made of thermoplastic resins. The container may be made from
a single material but also from a blend, a co-extruded or from a laminated material.
It may be more or less rigid or may have parts which are more rigid than others, by
modifying the thickness of the material used for example. Such resins may be made
using various methods, including Ziegler Natta or Metallocene catalysis.
[0025] Suitable thermoplastic resins for use herein include polyolefin resins preferably
polyethylene and/or polypropylene. For example low density polyethylene (high pressure
branched homopolyethylene, LDPE), linear low density polyethylene (low pressure or
modified high pressure ethylene- a- olefin copolymer, L-LDPE), high density polyethylene,
HDPE), ethylene-vinyl acetate copolymer (EVA), polypropylene (homo, random, block,
PP), polyethylene terephthalate (polyester, PET), polyamide (PA), polyvinyl chloride
(PVC), vinylidene chloride-vinyl chloride copolymer (PVDC), ethylene-vinyl alcohol
copolymer (EVOH), polyvinyl alcohol (PVA), polystyrene (PS) and the like or mixture
thereof.
[0026] Typically, the UV light resistant container herein contains more than 50% by weight
of a thermoplastic resin or a mixture thereof, preferably more than 85% and more preferably
more than 90%.
[0027] The UV light resistant container herein comprises as an essential material a UV stabilizer
or a mixture thereof. All the UV stabilizers currently used in the packaging field
are suitable herein. Suitable UV stabilizers include oxides like silica, diatomaceous
earth, aluminia, titanium dioxide, iron oxide, zinc oxide, magnesium oxide, antimony
oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon,
alumina fiber and the like, hydroxides like aluminium hydroxides, magnesium hydroxides,
basic magnesium carbonate and the like, carbonates like calcium carbonate, magnesium
carbonate, dolomite, sulphate, sulphites like calcium sulphate, barium sulphate, ammonium
sulphate, calcium sulphite, silicates like talc, clay mica, asbestos, glass fiber,
glass balloon, glass bead, calcium silicare, montmorillonite, bentonite, carbons like
carbon black, graphite, carbon fiber, carbon hollow bead, as well as nickel chelates,
benzotriazoles, benzophenones, hindered amine light stabilizers (HALS) like derivatives
of 2,2,6,6-tetramethyl piperidine, or mixtures thereof.
[0028] Typically the UV light resistant container herein comprises from 0.01% to 30% by
weight of the total container of a UV stabilizer or mixture thereof, preferably from
0.1% to 15% more preferably from 0.5% to 10%.
[0029] The containers herein essential those made of thermoplastic resins may also include
additional materials that do not affect its essential character, for instance stabilizers,
pigments, processing aids such as waxes, deodorizing agents, anti-static agents, anti-blocking
agents, plasticizers and the like.
[0030] Alternatively glass material modified with UV stabilizers may also be used.
[0031] Depending on the end-use envisioned, these containers include conventional bottles,
bottles equipped with roll-on, sponge, brusher or sprayer, pouches, bags, gusset bags
or plastified carboards (e.g. tetrapack®). Preferred containers for use herein are
bottles made of thermoplastic resins comprising a UV stabiliser. Such bottles may
be made by conventional manufacturing methods include blow moulding, extrusion and
injection.
[0032] Advantageously, the compositions of the present invention being packaged in a UV
light resistant container deliver effective stain removal performance and bleaching
performance when used to bleach a surface, preferably in any laundry application,
even upon ageing of the compositions, i.e. after prolonged periods of storage (typically
up to 12 months at room temperature (about 20°C)). Indeed, packing the compositions
herein in such UV light resistant containers maintains the properties associated to
these compositions upon prolonged periods of time after their manufacturing.
[0033] It has also been found that the liquid aqueous compositions of the present invention
are particularly safe to both the fabrics bleached therewith and colours in a typical
laundry soaking operation, as compared to a soaking operation with solid (granular)
monopersulfate salt-containing compositions.
Optional ingredients
[0034] As a highly preferred optional ingredient, the compositions according to the present
invention may comprise an aldehyde activator compound, a ketone activator compound,
a halide activator compound or a mixture thereof.
[0035] By

aldehyde

, it is meant herein any compound which contains at least one carbonyl group and has
two hydrogen atoms or carbon atom and a hydrogen atom attached directly to at least
one of the carbonyl carbon atoms.
[0036] By

ketone

, it is meant herein any compound which contains at least one carbonyl group and has
two carbon atoms attached directly to at least one of the carbonyl carbon atoms.
[0037] These compounds can be aliphatic or aromatic substituted or unsubstituted, saturated
or unsaturated, or acyclic, carbocyclic or heterocyclic.
[0038] By

halide

, it is meant chloride, bromide and/or iodide.
[0039] By

activator

, it is meant herein ketone, aldehyde and halide compounds and mixtures thereof that
react with monopersulfate salt to form an activated bleaching specie, i.e. a dioxirane
(when the activator compound is ketone or aldehyde) or a hypohalogenite (when the
activator compound is a halide). These activation mechanisms are known in the art
and are for example described in US 3822114.
[0040] It is the activated species, i.e. dioxirane and hypohalogenite, which are thought
to greatly enhance the bleaching in the present invention over monopersulfate alone
or over other activated bleaching system, e.g. hydrogen peroxide and acetyl triethyl
citrate. These activation mechanisms mainly occur upon dilution of the compositions
herein with water and are emphased with the pH jump in the neutral to alkaline pH
range (i.e. around 6 and higher) associated to this dilution. It is at those pHs that
more dioxiranes and/or hypohalogenites are generated thereby outstandingly improving
the bleaching performance of the compositions of the present invention.
[0041] Suitable aldehyde activator compounds for use herein include chloral-hydrate, acetaldehyde,
butyraldehyde, benzaldehyde, and/or 4-trimethylammonio benzaldehyde methyl sulfate.
Particularly preferred aldehyde activator compounds for use herein are acetaldehyde,
butyraldehyde and/or, benzaldehyde and most preferred is acetaldehyde. Aldehyde activator
compounds are in general less preferred than the ketone activators compounds as they
may be oxidised during prolonged storage periods.
[0042] For example acetaldehyde may be commercially available from Aldrich.
[0043] Suitable aliphatic ketone activator compounds for use herein include acetacetone,
2,3-hexanedione, trimethylammonio acetone nitrate, 5-diethylbenzylammonio 2-pentanone
nitrate, 5-diethylmethylammonio 2-pentanone nitrate, methyl pyruvate, diethyl keto
malonate, 3-hydroxy-2-butanone, acetol, hexachloracetone, 2,5-hexanedione, phenylacetone,
ethyl levulinate, 3-hydroxy-2-pentanone, acetone, 3-penten-2-one, methyl ethyl ketone,
4-hydroxy-3-methyl-2-butanone, 3-pentanone, and/or 2-heptanone.
[0044] For example acetacetone may be commercially available from Aldrich under its chemical
name.
[0045] Suitable aromatic ketone activator compounds for use herein include hydroxyquinoline,
4-acetyl-1-methylpyridinium nitrate, di-2-pyridyl ketone N-oxide, 2-acetylquinoxaline,
2-acetyl-3-methylquinoxaline oxaline, di-2- pyridyl ketone, 6-acetyl-1,2,4-trimethyl
quinolinium nitrate, 8-hydroxyquinoline N-oxide, methyl phenyl glyoxalate, N-methyl-p-morpholinio
acetophenone methyl sulfate, 3-acetyl pyridine N-oxide, p-nitroacetophenone, m-nitroacetophenone,
sodium p-acetyl benzene sulfonate, p-acetylbenzonitrile, 3,5-dinitroacetophenone,
4-trimethylammonioacetophenone nitrate, 4-methoxy-3-nitroacetophenone, p-chloroacetophenone,
p-diacetylbenzene, N-methyl-p-morpholinio acetophenone nitrate, phenacyltriphenylphosphonium
nitrate, 2-acetyl pyridine, 2-acetyl pyridine N-oxide, 3-acetyl pyridine, 4-acetyl
pyridine, 4-acetyl pyridine N-oxide, 2,6- diacetyl pyridine, 3-acetyl pyridine N-oxide,
and/or triacetylbenzene.
[0046] Suitable cyclic ketone activator compounds for use herein include cyclohexanone,
2-methylcyclohexanone, 2,6-dimethyl cyclohexanone, 3-methyl cyclohexanone, 4-ethyl
cyclohexanone, 4-t-butyl cyclohexanone, 4,4-dimethyl cyclohexanone, methyl 4-oxo-cyclohexanone
carboxylate, sodium 4-oxo-cyclohexanone carboxylate, 2-trimethylammoniocyclohexanone
nitrate, 4-trimethylammonio cyclohexanone nitrate, 3 oxo-cyclohexyl acetic acid, cycloheptanone,
1,4-cyclohexadione, dehydrochloric acid, tropinone methonitrate, N-methyl-3-oxoquinuclidinium
nitrate, cyclooctanone and/or cyclopentanone.
[0047] For example cyclohexanone may be commercially available from Aldrich under its chemical
name.
[0048] Suitable heterocyclic ketone activator compounds for use herein include, 2,2,6,6-tetramethyl-4-piperidone
hydrate, 1-methyl-4-piperidone N-oxide, N-carbethoxy 4-piperidone, tetrahydrothiopyran-4-one
methonitrate, tetrahydrothiopyran-4-one S,S- dioxide, tetrahydrothiopyran-3-one,S,S,-dioxide,
and/or 4-oxacyclohexanone.
[0049] All of the above-described aldehyde and ketone examples are all either commercially
available or can obviously be synthesized by the skilled artisan having before him
the teaching of the prior art Gardini et al.,
J. Chem. Soc.(C), (1970) page 929 and Lyle et al.,
J. Org. Chem., Vol. 24 (March, 1959), page 342 are examples of such art and are hereby incorporated herein
by reference. Also a method for the synthesis of oxopiperidinium compounds is described
in "S.E. Denmark, D.C. Forbes, D.S. Hays, J.S. De Pue and R.G. Wilde, J.Org. Chem.
1995, 60, 1391-1407".
[0050] Particularly preferred bleach activators for use herein are the ketone activator
compounds and highly preferred are the ketones activator compounds bearing a positive
charge.
[0051] Particularly suitable ketone activator compounds bearing a positive charge are for
example oxopiperidinium salts having the following formula:

wherein the carbonyl group >C=O, can be either at the 2, 3 or at the 4 position of
the oxopiperidinium; R1 and R2 are each independently a substituted or unsubstituted
hydrocarbon chain having from 1 to 20 carbon atoms, preferably a substituted or unsubstituted
alkyl or alkenyl or alkinyl group containing from 1 to 20 carbon atoms, preferably
from 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group containing
from 6 to 10 atoms, or a C1-C20 alkyl aryl group wherein the aryl group contains from
6 to 10 carbon atoms; X
- can be any negative ion, e.g., triflate, tosilate, mesilate, nitrate, more preferred
is triflate, mesilate, tosilate and most preferred is triflate and the oxopiperidinium
ring can be mono or polysubstituted at the 2,3,5, or 6 positions by one or more substituents
as defined for R1 or R2 above or a halogen atom.
[0052] Examples of oxopiperidinium salts particularly suitable for use herein include 1,1-dimethyl-3-oxopiperidinium
nitrate, 1,1-dimethyl-4-oxopiperidinium triflate, 1,1-dimethyl-3-oxopiperidinium triflate,
1,1-dimethyl-4-oxopiperidinium nitrate, 1-benzyl-4-piperidone methonitrate, 1-t-butyl-1-methyl-4-oxopiperidinium
nitrate, 1-(4-dodecylbenzyl) 1-methyl-4 oxopiperidinium chloride, 3-(N-methyl-4 oxopiperidinium)-propane
sulfonate, 1-allyl-1-methyl-4- oxopiperidinium chloride, 1-methyl-1-(1-naphthyl-methyl)-4-
oxopiperidinium chloride, 1-methyl-1-pentamethylbenzyl- 4-oxopiperidinium chloride,
N,N'-dimethyl-N,N'-phenylene dimethylene -bis(4- oxopiperidinium nitrate), 1-benzyl-1-methyl-4-oxopiperidinium
triflate, 1-benzyl-1-methyl-3-oxopiperidinium triflate, 1-benzyl-1-methyl-4-oxopiperidinium
nitrate, 1-dodecyl-1-methyl-4-oxopiperidinium nitrate, 1-octyl-1-methyl-4-oxopiperidinium
nitrate, 1-nonyl-1-methyl-4-oxopiperidinium nitrate or a mixture thereof.
[0053] Other suitable ketone activator compounds bearing a positive charge suitable for
use herein are for example the ammonium acetophenone salts according to the following
formula:

wherein the ammonium group can be either at the 2 , at the 3 position or at the 4
position ; R1, R2 and R3 are each independently a substituted or unsubstituted hydrocarbon
group having from 1 to 20 carbon atoms, preferably a substituted or unsubstituted
alkyl, or alkenyl or alkinyl group containing from 1 to 20 carbon atoms, preferably
from 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group containing
from 6 to 10 atoms or a C1-C20 alkyl aryl group wherein the aryl group contains from
6 to 10 carbon atoms; R4 is a substituted or nonsubstituted halogenate alkyl group
having from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms and more preferably
is methyl, or trifluoromethyl or trichloromethyl or tribromomethyl, ;X
- can be any negative ion, e.g., triflate, tosilate, mesilate, or nitrate and the benzenic
ring can be substituted at the 2, 3 and/or 4 positions by one or more substituents
as defined for R1, R2 or R3 as described above or a halogen atom.
[0054] Examples of such ammonium acetophenone salts for use herein include 4-trimethylammonium
acetophenone nitrate, 2-trimethylammoniumacetophenone nitrate, 4-triethylammoniumacetophenone
mesilate, 3-trimethylammoniumacetophenone mesilate, trihalogenatedmethylphenyl ketone
like trifluoromethylphenylketone, trichloromethylphenylketone, tribromomethylphenylketone
or a mixture thereof.
[0055] Suitable halide activator compounds for use herein include chloride, bromide, iodide
and mixtures thereof. Particularly preferred halide activator compounds for use herein
is an alkali metal of chloride. For example sodium chloride may be commercially available
from Aldrich under its chemical name.
[0056] Typically, the compositions herein may comprise from 0.01% to 10% by weight of the
total composition of said ketone, aldehyde and/or halide activator compound, preferably
from 0.05% to 5%, more preferably from 0.1% to 2% and most preferably from 0.2% to
1.5%.
[0057] Indeed, this activated bleaching system provides effective bleaching performance
on a variety of soils, from hydrophobic to hydrophilic soils under any household application
and especially laundry application on both hydrophilic and hydrophobic fabrics.
[0058] Advantageously the present invention provides not only effective bleaching performance
but also good stain removal performance of various types of stains including greasy
stains (e.g., lipstick, tomato, make-up) and/or enzymatic stains (e.g. blood, choco
pudding), as compared to the same formulation without said activator compounds as
described herein.
[0059] The bleaching performance may be evaluated by the following test methods on various
type of bleachable stains.
[0060] A suitable test method for evaluating the bleaching performance on a soiled fabric
under diluted conditions is the following: A composition according to the present
invention packaged in a UV light resistant container, is diluted after for example
6 months storage time at 20°C, with water typically at a dilution level of 1 to 100
ml/L, preferably 20 ml/L (composition :water), then the soiled fabrics are soaked
in it for 20 minutes to 6 hours and then rinsed. Alternatively the bleaching composition
can be used in a washing machine at a dilution level of typically at a dilution level
of 1 to 100 ml/L (composition :water). In the washing machine the soiled fabrics are
washed at a temperature of from 30° to 70°C for 10 to 100 minutes and then rinsed.
The reference composition (i.e., same composition at same storage time but not packaged
in an UV light resistant container) in this comparative test undergoes the same treatment.
Soiled fabrics/swatches with for example tea, coffee and the like may be commercially
available from E.M.C. Co. Inc..
[0061] The bleaching performance is then evaluated by comparing side by side the soiled
fabrics treated with the composition of the present invention with those treated with
the reference. A visual grading may be used to assign difference in panel units (psu)
in a range from 0 to 4.
[0062] The compositions herein may further comprise a variety of other optional ingredients
such as surfactants, chelating agents, radical scavengers, antioxidants, other stabilisers,
builders, soil suspenders, polymeric soil release agents, catalysts, dye transfer
agents, solvents, suds controlling agents, brighteners, perfumes, pigments, dyes and
the like.
Surfactants:
[0063] The compositions of the present invention may comprise a surfactant or a mixture
thereof including nonionic surfactants, anionic surfactants, cationic surfactants,
zwitterionic surfactants and/or amphoteric surfactants. Typically these surfactants
do not contain functional groups that can be oxidised by the monopersulphate salt,
or that can substantially hydrolize at a low pH.
[0064] Typically, the compositions according to the present invention may comprise from
0.01% to 50% by weight of the total composition of a surfactant or a mixture thereof,
preferably from 0.1% to 30 % and more preferably from 0.2% to 10%.
[0065] Suitable anionic surfactants for use in the compositions herein include water-soluble
salts or acids of the formula ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C
10-C
20 alkyl component, more preferably a C
12-C
18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C
12-
16 are preferred for lower wash temperatures (e.g., below about 50°C) and C
16-
18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C).
[0066] Other suitable anionic surfactants for use herein are water-soluble salts or acids
of the formula RO(A)
mSO
3M wherein R is an unsubstituted C
10-C
24 alkyl or hydroxyalkyl group having a C
10-C
24 alkyl component, preferably a C
12-C
20 alkyl or hydroxyalkyl, more preferably C
12-C
18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and about 3, and
M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium
and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine,
mixtures thereof, and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate, C
12-C
18E(1.0)M), C
12-C
18 alkyl polyethoxylate (2.25) sulfate, C
12-C
18E(2.25)M), C
12-C
18 alkyl polyethoxylate (3.0) sulfate C
12-C
18E(3.0), and C
12-C
18 alkyl polyethoxylate (4.0) sulfate C
12-C
18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
[0067] Other particularly suitable anionic surfactants for use herein are alkyl sulphonates
including water-soluble salts or acids of the formula RSO
3M wherein R is a C
6-C
22 linear or branched, saturated or unsaturated alkyl group, preferably a C
12-C
18 alkyl group and more preferably a C
14-C
16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
[0068] Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids
of the formula RSO
3M wherein R is an aryl, preferably a benzyl, substituted by a C
6-C
22 linear or branched saturated or unsaturated alkyl group, preferably a C
12-C
18 alkyl group and more preferably a C
14-C
16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g.,
methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations,
such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium
cations derived from alkylamines such as ethylamine, diethylamine, triethylamine,
and mixtures thereof, and the like).
[0069] The alkylsulfonates and alkyl aryl sulphonates for use herein include primary and
secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates. By "secondary
C6-C22 alkyl or C6-C22 alkyl aryl sulphonates", it is meant herein that in the formula
as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl
chain being placed between two other carbons of the said alkyl chain (secondary carbon
atom).
[0070] For example C14-C16 alkyl sulphonate salt is commercially available under the name
Hostapur ® SAS from Hoechst and C8-alkylsulphonate sodium salt is commercially available
under the name Witconate NAS 8® from Witco SA. An example of commercially available
alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma. Particularly preferred
alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under
trade name Nansa® available from Albright&Wilson.
[0071] Other anionic surfactants useful for detersive purposes can also be used herein.
These can include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap,
C
8-C
24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in British
patent specification No. 1,082,179, C
8-C
24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl
ester sulfonates such as C
14-
16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated
C
12-C
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C
6-C
14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH
2CH
2O)
kCH
2COO-M
+ wherein R is a C
8-C
22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin
acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin, and resin acids and hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
[0072] Other particularly suitable anionic surfactants for use herein are alkyl carboxylates
and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain,
preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy
and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20,
preferably from 5 to 15. Preferred alkylalkoxycarboxylate for use herein is sodium
laureth 11 carboxylate (i.e., RO(C
2H
4O)
10-CH
2COONa, with R= C12-C14) commercially available under the name Akyposoft® 100NV from
Kao Chemical Gbmh.
[0073] Suitable amphoteric surfactants for use herein include amine oxides having the following
formula R
1R
2R
3NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted,
linear or branched hydrocarbon chains of from 1 to 30 carbon atoms. Preferred amine
oxide surfactants to be used according to the present invention are amine oxides having
the following formula R
1R
2R
3NO wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably
from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein
R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon
chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and
more preferably are methyl groups. R1 may be a saturated substituted or unsubstituted
linear or branched hydrocarbon chain. Suitable amine oxides for use herein are for
instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially
available from Hoechst.
[0074] Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic
group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same
molecule at a relatively wide range of pH's. The typical anionic hydrophilic groups
are carboxylates and sulfonates, although other groups like sulfates, phosphonates,
and the like can be used. A generic formula for the zwitterionic surfactants to be
used herein is:
R
1-N
+(R
2)(R
3)R
4X
-
wherein R
1 is a hydrophobic group; R
2 is hydrogen, C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group; R
3 is C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group which can also be joined to R
2 to form ring structures with the N, or a C
1-C
6 carboxylic acid group or a C
1-C
6 sulfonate group; R
4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically
an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon
atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group.
[0075] Preferred hydrophobic groups R
1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chains that can contain linking groups such as amido groups, ester groups.
More preferred R
1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18,
and more preferably from 10 to 16. These simple alkyl groups are preferred for cost
and stability reasons. However, the hydrophobic group R
1 can also be an amido radical of the formula R
a-C(O)-NH-(C(R
b)
2)
m, wherein R
a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms,
preferably up to 18, more preferably up to 16, R
b is selected from the group consisting of hydrogen and hydroxy groups, and m is from
1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group
in any (C(R
b)
2) moiety.
[0076] Preferred R
2 is hydrogen, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
3 is a C
1-C
4 carboxylic acid group or C1-C4 sulfonate group, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
4 is (CH2)
n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is
from 1 to 3.
[0077] Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275,
2,702,279 and 2,255,082, incorporated herein by reference.
[0078] Examples of particularly suitable alkyldimethyl betaines include coconut-dimethyl
betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate,
2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl
betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. For example Coconut dimethyl
betaine is commercially available from Seppic under the trade name of Amonyl 265®.
Lauryl betaine is commercially available from Albright & Wilson under the trade name
Empigen BB/L®.
[0079] Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine
or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine. For example C10-C14
fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from
Sherex Company under the trade name "Varion CAS® sulfobetaine".
[0080] A further example of betaine is Lauryl-immino-dipropionate commercially available
from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
[0081] Suitable cationic surfactants for use herein include derivatives of quaternary ammonium,
phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants for
use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon
groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to
30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to
20 carbon atoms, and wherein the other hydrocarbon groups (i.e. three when one hydrocarbon
group is a long chain hydrocarbon group as mentioned hereinbefore or two when two
hydrocarbon groups are long chain hydrocarbon groups as mentioned hereinbefore) linked
to the nitrogen are independently substituted or unsubstituted, linear or branched,
alkyl chain of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and
more preferably are methyl groups. Preferred quaternary ammonium compounds suitable
for use herein are non-chloride/non halogen quaternary ammonium compounds. The counterion
used in said quaternary ammonium compounds are compatible with any monopersulfate
salt and are selected from the group of methyl sulfate, or methylsulfonate, and the
like.
[0082] Particularly preferred for use in the compositions of the present invention are trimethyl
quaternary ammonium compounds like myristyl trimethylsulfate, cetyl trimethylsulfate
and/or tailow trimethylsulfate. Such trimethyl quaternary ammonium compounds are commercially
available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN CM®.
[0083] Amongst the nonionic surfactants alkoxylated nonionic surfactants and especially
ethoxylated nonionic surfactants are suitable for use herein. Capped alkoxylated nonionic
surfactants are particularly suitable for use herein as they have improved stability
to the monopersulfate salts.
[0084] Suitable capped alkoxylated nonionic surfactants for use herein are according to
the formula:
R
1(O-CH
2-CH
2)
n-(OR
2)
m-O-R
3
wherein R
1 is a C
8-C
24 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably
R
1 is a C
8-C
18 alkyl or alkenyl group, more preferably a C
10-C
15 alkyl or alkenyl group, even more preferably a C
10-C
15 alkyl group;
wherein R
2 is a C
1-C
10 linear or branched alkyl group, preferably a C
2-C
10 linear or branched alkyl group;
wherein R
3 is a C
1-C
10 alkyl or alkenyl group, preferably a C
1-C
5 alkyl group, more preferably methyl;
and wherein n and m are integers independently ranging in the range of from 1 to 20,
preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
[0085] These surfactants are commercially available from BASF under the trade name Plurafac®,
from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
Preferred capped nonionic alkoxylated surfactants of the above formula are those commercially
available under the tradename Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
Chelating agents:
[0086] The compositions of the present invention may comprise a cheating agent as a preferred
optional ingredient. Suitable chelating agents may be any of those known to those
skilled in the art such as the ones selected from the group comprising phosphonate
chelating agents, amino carboxylate chelating agents, other carboxylate chelating
agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'-
disuccinic acids, or mixtures thereof.
[0087] The presence of chelating agents contribute to further enhance the chemical stability
of the compositions. A chelating agent may be also desired in the compositions of
the present invention as it allows to increase the ionic strength of the compositions
herein and thus their stain removal and bleaching performance on various surfaces.
[0088] Suitable phosphonate chelating agents for use herein may include alkali metal ethane
1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as
amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP),
nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates,
and diethylene triamine penta methylene phosphonates (DTPMP). The phosphonate compounds
may be present either in their acid form or as salts of different cations on some
or all of their acid functionalities. Preferred phosphonate chelating agents to be
used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane
1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially
available from Monsanto under the trade name DEQUEST®.
[0089] Polyfunctionally-substituted aromatic chelating agents may also be 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.
[0090] A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-
disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium
salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially
the (S,S) isomer have been extensively described in US patent 4, 704, 233, November
3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance,
commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
[0091] Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates,
diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine
triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates,
ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic
acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted
ammonium salt forms. Particularly suitable amino carboxylates to be used herein are
diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which
is, for instance, commercially available from BASF under the trade name Trilon FS®
and methyl glycine di-acetic acid (MGDA).
[0092] Further carboxylate chelating agents to be used herein include salicylic acid, aspartic
acid, glutamic acid, glycine, malonic acid or mixtures thereof.
[0093] Another chelating agent for use herein is of the formula:

wherein R
1, R
2, R
3, and R
4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl,
aryloxy, -Cl, -Br, -NO
2, -C(O)R', and - SO
2R''; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl,
and aryloxy; R'' is selected from the group consisting of alkyl, alkoxy, aryl, and
aryloxy; and R
5, R
6, R
7, and R
8 are independently selected from the group consisting of -H and alkyl.
[0094] Particularly preferred chelating agents to be used herein are amino aminotri(methylene
phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta
methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic
acid, and mixtures thereof.
[0095] Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a chelating agent, or mixtures thereof, preferably
from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.
Radical scavengers:
[0096] The compositions of the present invention may comprise a radical scavenger or a mixture
thereof.
[0097] Suitable radical scavengers for use herein include the well-known substituted mono
and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures
thereof. Preferred such radical scavengers for use herein include di-tert-butyl hydroxy
toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,
tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol,
benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate
or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene. Such radical
scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories
under the trade name Nipanox S1 ®.
[0098] Radical scavengers when used, are typically present herein in amounts up to 10% by
weight of the total composition and preferably from 0.001% to 0.5% by weight.
[0099] The presence of radical scavengers may contribute to the chemical stability of the
bleaching compositions of the present invention as well as to the safety profile of
the compositions of the present invention.
Suds controlling agents:
[0100] The compositions according to the present invention may further comprise a suds controlling
agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
Particularly suitable to be used in the present invention are the 2-alkyl alkanols
having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12
and a terminal hydroxy group, said alkyl chain being substituted in the α position
by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and
more preferably 3 to 6. Such suitable compounds are commercially available, for instance,
in the Isofol® series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl
decanol).
[0101] Other suds controlling agents may include alkali metal (e.g., sodium or potassium)
fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from
about 10 to about 20 carbon atoms.
[0102] The fatty acids including those used in making the soaps can be obtained from natural
sources such as, for instance, plant or animal-derived glycerides (e.g., palm oil,
coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow,
grease, lard and mixtures thereof). The fatty acids can also be synthetically prepared
(e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process).
[0103] Alkali metal soaps can be made by direct saponification of fats and oils or by the
neutralization of the free fatty acids which are prepared in a separate manufacturing
process. Particularly useful are the sodium and potassium salts of the mixtures of
fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow
and coconut soaps.
[0104] The term "tallow" is used herein in connection with fatty acid mixtures which typically
have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18,
2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are
saturated). Other mixtures with similar distribution, such as the fatty acids derived
from various animal tallows and lard, are also included within the term tallow. The
tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated
fatty acid moieties to saturated fatty acid moieties.
[0105] When the term "coconut" is used herein it refers to fatty acid mixtures which typically
have an approximate carbon chain length distribution of about 8% C8, 7% C10, 48% C12,
17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed
being saturated). Other sources having similar carbon chain length distribution such
as palm kernel oil and babassu oil are included with the term coconut oil.
[0106] Other suitable suds controlling agents are exemplified by silicones, and silica-silicone
mixtures. Silicones can be generally represented by alkylated polysiloxane materials
while silica is normally used in finely divided forms exemplified by silica aerogels
and xerogels and hydrophobic silicas of various types. These materials can be incorporated
as particulates in which the suds controlling agent is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds controlling agent can be dissolved or
dispersed in a liquid carrier and applied by spraying on to one or more of the other
components.
[0107] A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S.
Patent 3 933 672. Other particularly useful suds controlling agents are the self-emulsifying
silicone suds controlling agents, described in German Patent Application DTOS 2 646
126 published April 28, 1977. An example of such a compound is DC-544, commercially
available from Dow Corning, which is a siloxane-glycol copolymer.
[0108] Especially preferred silicone suds controlling agents are described in Copending
European Patent application N°92201649.8. Said compositions can comprise a silicone/silica
mixture in combination with fumed nonporous silica such as Aerosil
R.
[0109] Especially preferred suds controlling agent are the suds controlling agent system
comprising a mixture of silicone oils and the 2-alkyl-alcanols.
[0110] Typically, the compositions herein may comprise up to 4% by weight of the total composition
of a suds controlling agent, or mixtures thereof, preferably from 0.1% to 1.5% and
most preferably from 0.1% to 0.8%.
Processes of treating surfaces
[0111] In the present invention, the liquid aqueous composition of the present invention,
packaged in a UV light resistant container needs to be contacted with the surface
to treat.
[0112] By "surfaces", it is meant herein any inanimate surface. These inanimate surfaces
include, but are not limited to, hard-surfaces typically found in houses like kitchens,
bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth
vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary
fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as
well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table
cloths, sleeping bags, tents, upholstered furniture and the like, and carpets. Inanimate
surfaces also include household appliances including, but not limited to, refrigerators,
freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers
and so on.
[0113] By

treating a surface

, it is meant herein bleaching and/or disinfecting said surfaces as the compositions
of the present invention comprise a bleaching system based of monopersulfate salt
and optionally a ketone, aldehyde or halide activator compound or a mixture thereof
and optionally cleaning as said compositions may comprise a surfactant or any other
conventional cleaning agents.
[0114] Thus, the present invention also encompasses a process of treating, especially bleaching
a fabric, as the inanimate surface. In such a process a composition according to the
present invention, packaged in a UV light resistant container, is contacted with the
fabrics to be treated.
[0115] This can be done either in a so-called "pretreatment mode", where a liquid bleaching
composition, as defined herein, is applied neat onto said fabrics before the fabrics
are rinsed, or washed then rinsed, or in a "soaking mode" where a liquid bleaching
composition, as defined herein, is first diluted in an aqueous bath and the fabrics
are immersed and soaked in the bath, before they are rinsed, or in a "through the
wash mode", where a liquid bleaching composition, as defined herein, is added on top
of a wash liquor formed by dissolution or dispersion of a typical laundry detergent.
It is also essential in both cases, that the fabrics be rinsed after they have been
contacted with said composition, before said composition has completely dried off.
[0116] The processes of bleaching surfaces according to the present invention, especially
fabrics, delivers effective whiteness performance as well as effective stain removal
performance.
[0117] The compositions according to the present invention are preferably contacted to fabrics
in a liquid form. Indeed, by "in a liquid form", it is meant herein the liquid compositions
according to the present invention per se in neat or in their diluted form.
[0118] The compositions according to the present invention are typically used in diluted
form in a laundry operation. By "in diluted form", it is meant herein that the compositions
for the bleaching of fabrics according to the present invention may be diluted by
the user, preferably with water. Such dilution may occur for instance in hand laundry
applications as well as by other means such as in a washing machine. Said compositions
can be diluted up to 500 times, preferably from 5 to 200 times and more preferably
from 10 to 80 times.
[0119] More specifically, the process of bleaching fabrics according to the present invention
comprises the steps of first contacting said fabrics with a bleaching composition
according to the present invention, packaged in a UV light resistant container, in
its diluted form, then allowing said fabrics to remain in contact with said composition,
for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes,
preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics
are to be washed, i.e., with a conventional composition comprising at least one surface
active agent, said washing may be conducted together with the bleaching of said fabrics
by contacting said fabrics at the same time with a bleaching composition according
to the present invention and said detergent composition, or said washing may be conducted
before or after that said fabrics have been bleached. Accordingly, said process according
to the present invention allows to bleach fabrics and optionally to wash fabrics with
a detergent composition comprising at least one surface active agent before the step
of contacting said fabrics with said bleaching composition and/or in the step where
said fabrics are contacted with said bleaching composition and/or after the step where
said fabrics are contacted with said bleaching composition and before the rinsing
step and/or after the rinsing step.
[0120] In another embodiment of the present invention the process of bleaching fabrics comprises
the step of contacting fabrics with a liquid bleaching composition according to the
present invention, packaged in a UV light resistant container, in its neat form, of
allowing said fabrics to remain in contact with said bleaching composition for a period
of time sufficient to bleach said fabrics, typically 5 seconds to 30 minutes, preferably
1 minute to 10 minutes and then rinsing said fabrics with water. If said fabrics are
to be washed, i.e., with a conventional composition comprising at least one surface
active agent, said washing may be conducted before or after that said fabrics have
been bleached. Advantageously, the present invention provides liquid bleaching compositions
that may be applied neat onto a fabric to bleach, despite a standing prejudice against
using bleach-containing compositions neat on fabrics while being safe to colors and
fabrics perse.
[0121] Alternatively instead of following the neat bleaching method as described herein
above (pretreater application) by a rinsing step with water and/or a conventional
washing step with a liquid or powder conventional detergent, the bleaching pre-treatment
operation may also be followed by the diluted bleaching process as described herein
before either in bucket (hand operation) or in a washing machine.
[0122] It is preferred to perform the bleaching processes herein after said fabrics have
been washed with a convention laundry detergent composition. Indeed, it has been observed
that bleaching said fabrics with the compositions according to the present invention
(typically diluted bleaching methods) after to washing them with a detergent composition
provides superior whiteness and stain removal with less energy and detergent than
if said fabrics are bleached first then washed.
[0123] In another embodiment the present invention also encompasses a process of treating
a hard-surface, as the inanimate surface. In such a process a composition, as defined
herein, packaged in a UV light resistant container, is contacted with the hard-surfaces
to be treated. Thus, the present invention also encompasses a process of treating
a hard-surface with a composition, as defined herein, wherein said process comprises
the step of applying said composition to said hard-surface, preferably only soiled
portions thereof, and optionally rinsing said hard-surface.
[0124] In the process of treating hard-surfaces according to the present invention the composition,
as defined herein, may be applied to the surface to be treated in its neat form or
in its diluted form typically up to 200 times their weight of water, preferably into
80 to 2 times their weight of water, and more preferably 60 to 2 times.
[0125] When used as hard surfaces bleaching/disinfecting compositions the compositions of
the present invention are easy to rinse and provide good shine characteristics on
the treated surfaces..
[0126] By

hard-surfaces

it is understood any hard-surfaces as mentioned herein before as well as dishes.
[0127] The invention is further illustrated by the following examples.
Examples
[0128] Following compositions were made by mixing the listed ingredients in the listed proportions
(weight % unless otherwise specified).
Compositions (% weight) |
I |
II |
III |
IV |
V |
Akyposoft 100 NV® |
0.5 |
0.5 |
- |
0.3 |
0.4 |
Curox® |
6 |
4 |
4 |
4.3 |
10 |
Trifluoromethylphenylketone |
0.5 |
- |
- |
0.3 |
- |
Acetoacetone |
- |
0.4 |
- |
- |
0.4 |
HEDP |
0.1 |
0.05 |
0.16 |
0.1 |
- |
BHT |
0.05 |
- |
- |
- |
0.1 |
Propyl gallate |
- |
0.1 |
- |
0.05 |
- |
NaCl |
- |
- |
0.1 |
0.5 |
- |
NaBr |
- |
- |
- |
- |
1.0 |
Water and minors |
up to 100% |
Alkanizing agent up to pH |
2 |
2.5 |
4 |
4 |
1.5 |
Compositions (% weight) |
VI |
VII |
VIII |
IX |
X |
XI |
Akyposoft 100 NV® |
0.5 |
0.5 |
0.5 |
0.2 |
0.2 |
- |
Curox® |
5 |
7 |
10 |
10 |
6 |
9.5 |
Acetylacetone |
0.5 |
0.5 |
0.5 |
- |
- |
- |
N,N dymethyl-4 -oxopiperidinium nitrate |
- |
- |
- |
0.5 |
0.5 |
- |
Propyl gallate |
0.05 |
0.05 |
0.1 |
0.1 |
0.05 |
- |
Water and minors |
up to 100% |
pH |
2 |
1.8 |
1.5 |
1.5 |
2 |
2 |
Compositions (% weight) |
XII |
XIII |
XIV |
XV |
XVI |
XVII |
Akyposoff 100 NV® |
0.5 |
0.5 |
0.5 |
0.2 |
0.2 |
0.2 |
Curox® |
5 |
7 |
10 |
10 |
6 |
9.5 |
Cyclohexanone |
0.5 |
- |
0.5 |
0.5 |
- |
- |
N,N dymethyl-3 -oxopiperidinium nitrate |
- |
0.5 |
- |
- |
0.5 |
- |
Propyl gallate |
0.05 |
0.05 |
0.1 |
0.1 |
0.05 |
0.1 |
Water and minors |
up to 100% |
pH |
2 |
1.8 |
1.5 |
1.5 |
2 |
2 |
Compositions (% weight) |
XVIII |
XIX |
XX |
XXI |
XXII |
XXIII |
Witconate NAS 8 |
|
|
|
|
|
|
(40% active)® |
5 |
5 |
5 |
5 |
5 |
- |
Curox® |
9.5 |
9.5 |
9.5 |
9.5 |
9.5 |
9.5 |
N,N dymethyl-4 -oxopiperidinium triflate |
0.5 |
1 |
0.1 |
0.5 |
0.5 |
- |
HEDP |
0.1 |
0.2 |
0.1 |
- |
- |
0.1 |
BHT |
0.05 |
0.05 |
0.1 |
0.1 |
0.05 |
0.05 |
Water and minors |
up to 100% |
pH |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
Compositions (% weight) |
XXIV |
XXV |
Witconate NAS 8 (40% active)® |
5 |
5 |
Curox® |
9.5 |
9.5 |
Cycloheptanone |
0.5 |
0.5 |
HEDP |
- |
0.1 |
BHT |
- |
0.05 |
Water and minors |
up to 100% |
pH |
1.5 |
1.5 |
Akyposoft 100 NV® is a C12-C14 alkyl (ethoxy) 10 carboxylate commercially available
from Kao Chemicala Gmbh.
Witkonate NAS 8® is an alkylsulphonate available from Witco AS BHT is di-tert butyl
hydroxy toluene.
HEDP is ethane 1-hydroxy diphosphonate commercially available from Monsanto under
the serie Dequest®.
Cycloheptanone is commercially available from Aldrich.
Curox® is a triple salt of potassium monomonopersulfate, potassium sulphate and potassium
bisulphate commercially available from Interox.
[0129] All the above compositions were packaged in a UV light resistant container, e.g.,
a white opaque thermoplastic bottle, like the package of Ace Candeggina® commercially
available for instance in Italy. These compositions exhibit excellent bleaching performance
as well as good stain removal performance when used to bleach fabrics or to treat
a hard-surface, this both under neat and especially diluted conditions, even upon
ageing of the composition, e.g. when used after 12 months storage at 20°C.
1. A liquid aqueous composition having a pH from 0.6 to 7 and comprising a monopersulfate
salt and optionally a bleach activator selected from the group consisting of an aldehyde
activator compound, a ketone activator compound, a halide activator compound and a
mixture thereof, said composition being packaged in a UV light resistant container.
2. A composition according to claim 1 wherein said composition comprises from 0.01% to
50% by weight of the total composition of said monopersulfate salt or mixtures thereof,
preferably from 0.5% to 20%, more preferably from 1% to 15% and most preferably from
2% to 10%.
3. A composition according to any of the preceding claims wherein said monopersulfate
salt is sodium monomonopersulfate and/or potassium monomonopersulfate.
4. A composition according to any of the preceding claims wherein said composition comprises
from 0.01% to 10% by weight of the total composition of said ketone, aldehyde and/or
halide activator compound, preferably from 0.05% to 5%, more preferably from 0.1%
to 2% and most preferably from 0.2% to 1.5%.
5. A composition according to any of the preceding claims wherein said bleach activator
is an oxopiperidinium salt, an ammonium acetophenone salt, acetacetone, 2,3-hexanedione,
trimethylammonio acetone nitrate, 5-diethylbenzylammonio 2-pentanone nitrate, 5-diethylmethylammonio
2-pentanone nitrate, methyl pyruvate, diethyl keto malonate, 3-hydroxy-2-butanone,
acetol, hexachloracetone, 2,5- hexanedione, phenylacetone, ethyl levulinate, 3-hydroxy-2-pentanone,
acetone, 3-penten-2-one, methyl ethyl ketone, 4-hydroxy-3-methyl-2-butanone, 3-pentanone,
2-heptanone, hydroxyquinoline, 4-acetyl-1-methylpyridinium nitrate, di-2-pyridyl ketone
N-oxide, 2-acetylquinoxaline, 2-acetyl-3-methylquinoxaline oxaline, di-2-pyridyl ketone,
6-acetyl-1,2,4-trimethyl quinolinium nitrate, 8-hydroxyquinoline N-oxide, methyl phenyl
glyoxalate, N-methyl-p-morpholinio acetophenone methyl sulfate, 3-acetyl pyridine
N-oxide, p-nitroacetophenone, m-nitroacetophenone, sodium p-acetyl benzene sulfonate,
p-acetylbenzonitrile, 3,5-dinitroacetophenone, 4-trimethylammonioacetophenone nitrate,
4-methoxy-3-nitroacetophenone, p-chloroacetophenone, p-diacetylbenzene, N-methyl-p-morpholinio
acetophenone nitrate, phenacyltriphenylphosphonium nitrate, 2-acetyl pyridine, 2-acetyl
pyridine N-oxide, 3-acetyl pyridine, 4-acetyl pyridine, 4-acetyl pyridine N-oxide,
2,6- diacetyl pyridine, 3-acetyl pyridine N-oxide, triacetylbenzene, cyclohexanone,
2-methylcyclohexanone, 2,6-dimethyl cyclohexanone, 3-methyl cyclohexanone, 4-ethyl
cyclohexanone, 4-t-butyl cyclohexanone, 4,4-dimethyl cyclohexanone, methyl 4-oxo-cyclohexanone
carboxylate, sodium 4-oxo-cyclohexanone carboxylate, 2-trimethylammoniocyclohexanone
nitrate, 4-trimethylammonio cyclohexanone nitrate, 3 oxo-cyclohexyl acetic acid, cycloheptanone,
1,4-cyclohexadione, dehydrochloric acid, tropinone methonitrate, N-methyl-3-oxoquinuclidinium
nitrate, cyclooctanone, cyclopentanone, 2,2,6,6-tetramethyl-4-piperidone hydrate,
1-methyl-4-piperidone N-oxide, N-carbethoxy 4-piperidone, tetrahydrothiopyran-4-one
methonitrate, tetrahydrothiopyran-4-one S,S- dioxide, tetrahydrothiopyran-3-one,S,S,-dioxide,
4-oxacyclohexanone, or a mixture thereof.
6. A composition according to any of the preceding claims wherein said bleach activator
is an oxopiperidinium salt having the following formula:

wherein the carbonyl group >C=O, can be either at the 2, 3 or at the 4 position of
the oxopiperidinium; R1 and R2 are each independently a substituted or unsubstituted
hydrocarbon chain having from 1 to 20 carbon atoms, preferably a substituted or unsubstituted
alkyl or alkenyl or alkinyl group containing from 1 to 20 carbon atoms, preferably
from 1 to 12, or a substituted or unsubstituted aryl group containing from 6 to 10
atoms, or a C1-C20 alkyl aryl group wherein the aryl group contains from 6 to 10 carbon
atoms; X
- can be any negative ion, e.g., triflate, tosilate, mesiltae, nitrate, more preferred
is triflate, mesilate, tosilate and most preferred is triflate and the oxopiperidinium
ring can be mono or polysubstituted at the 2,3,5, or 6 positions by one or more substituents
as defined for R1 or R2 or a halogen atom and/or an ammonium acetophenone salt according
to the following formula:

wherein the ammonium group can be either at the 2, at the 3 position or at the 4
position ; R1, R2 and R3 are each independently a substituted or unsubstituted hydrocarbon
group having from 1 to 20 carbon atoms, preferably a substituted or unsubstituted
alkyl, or alkenyl or alkinyl group containing from 1 to 20 carbon atoms, preferably
from 1 to 12, or a substituted or unsubstituted aryl group containing from 6 to 10
atoms or a C1-C20 alkyl aryl group wherein the aryl group contains from 6 to 10 carbon
atoms; R4 is an alkyl group having from 1 to
20 carbon atoms, preferably from 1 to 12 and more preferably is methyl, or trifluoromethyl,
trichloromethyl or tribromomethyl; X
- can be any negative ion, e.g., triflate, tosilate, mesilate, or nitrate and the benzenic
ring can be substituted at the 2, 3 and/or 4 positions by one or more substituents
as defined for R1, R2 or R3 as described above or a halogen atom.
7. A composition according to any of the preceding claims wherein said bleach activator
is 1,1-dimethyl-3-oxopiperidinium nitrate, 1,1-dimethyl-4-oxopiperidinium triflate,
1,1-dimethyl-3-oxopiperidinium triflate, 1,1-dimethyl-4-oxopiperidinium nitrate, 1-benzyl-4-piperidone
methonitrate, 1-t-butyl-1-methyl-4-oxopiperidinium nitrate, 1-(4-dodecylbenzyl) 1-methyl-4
oxopiperidinium chloride, 3-(N-methyl-4 oxopiperidinium)-propane sulfonate, 1-allyl-1-methyl-4-
oxopiperidinium chloride, 1-methyl-1-(1-naphthyl-methyl)-4- oxopiperidinium chloride,
1-methyl-1-pentamethylbenzyl- 4-oxopiperidinium chloride, N,N'-dimethyl-N,N'-phenylene
dimethylene -bis(4- oxopiperidinlum nitrate), 1-benzyl-1-methyl-4-oxopiperidinium
triflate, 1-benzyl-1-methyl-3-oxopiperidinium triflate, 1-benzyl-1-methyl-4-oxopiperidinium
nitrate, 1-dodecyl-1-methyl-4-oxopiperidinium nitrate, 1-octyl-1-methyl-4-oxopiperidinium
nitrate, 1-nonyl-1-methyl-4-oxopiperidinium nitrate, 4-trimethylammonium acetophenone
nitrate, 2-trimethylammoniumacetophenone nitrate, 4-triethylammoniumacetophenone mesilate,
3-trimethylammoniumacetophenone mesilate, trihalogenatedmethylphenyl ketone or a mixture
thereof.
8. A composition according to any of the preceding claims wherein said composition has
a pH in the range from 0.6 to 6, more preferably from 0.8 to 4, even more preferably
from 1 to 3 and most preferably from 1 to 2.
9. A composition according to any of the preceding claims wherein said composition further
comprises a chelating agent or a mixture thereof typically up to 5% by weight of the
total composition, preferably from 0.01% to 1.5%.
10. A composition according to claim 9 wherein said chelating agent is a phosphonate chelating
agent, an amino carboxylate chelating agent, another carboxylate cheating agent, a
polyfunctionally-substituted aromatic cheating agent, ethylenediamine N, N'-disuccinic
acid or mixtures thereof, and more preferably amino aminotri(methylene phosphonic
acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene
phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid
or mixtures thereof.
11. A composition according to any of the preceding claims wherein said composition further
comprises a radical scavenger or a mixture thereof up to 10% by weight of the total
composition, preferably from 0.001% to 0.5% by weight, said radical scavenger being
preferably di-tert-butyl hydroxy toluene, hydroquinone, di-tert-butyl hydroquinone,
mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid,
catechol, t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)
butane, and/or n-propyl-gallate.
12. A composition according to any of the preceding claims wherein said composition further
comprises at least an optional ingredient selected from the group consisting of builders,
surfactants, antioxidants, stabilisers, soil suspenders, polymeric soil release agents,
catalysts, dye transfer agents, solvents, suds controlling agents, brighteners, perfumes,
dyes, pigments and mixtures thereof.
13. A composition according to any of the preceding claims wherein said container has
a transmittance of UV-light (wavelength from 400 nm to 200 nm) of less than 50%, preferably
less than 30%, more preferably less than 10%, even more preferably less than 5% and
most preferably of 0% and preferably a transmittance of less than 70%, preferably
less than 50%, more preferably less than 20% in the visible light (wavelength from
700 nm to 401 nm).
14. A composition according to any of the preceding claims wherein said container is a
bottle made of thermoplastic resin comprising a UV stabilizer or mixture thereof typically
at a level of from 0.01% to 30% by weight of the container, preferably 0.1% to 15%.
15. A process of bleaching fabrics which comprises the steps of:
- contacting said fabrics with a bleaching composition according to any of the preceding
claims packaged in a UV light resistant container, in its diluted form or neat form,
- allowing said fabrics to remain in contact with said bleaching composition for a
period of time sufficient to bleach said fabrics,
- and then rinsing said fabrics with water.
16. A process according to claim 15 wherein the compositions is diluted with water at
a dilution level up to 500 times its weight, preferably from 5 to 200 times and more
preferably from 10 to 80 times.
17. A process according to any of the claims 15 or 16 wherein said fabrics are washed
with a detergent composition comprising at least one surface active agent before the
step of contacting said fabrics with said bleaching composition and/or in the step
where said fabrics are contacted with said bleaching composition in its diluted form
and/or after the step where said fabrics are contacted with the bleaching composition
and before the rinsing step and/or after the rinsing step.
18. A process of treating a hard-surface with a composition according to any of the claims
1 to 14, wherein said process comprises the step of applying said composition to said
hard-surface, in its neat or diluted form, and optionally rinsing said hard-surface.