Note: Descriptions are shown in the official language in which they were submitted.
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BLEACHING COMPOSITIONS
Technical field
The present invention relates to a process for preparing a peroxycarboxylic
acid
raw material having average mean particle size of less than 100 microns.
Background of the invention
Commonly encountered liquid aqueous bleaching compositions suitable for the
bleaching of stains on fabrics and hard-surfaces are based on halogen
bleaches, especially hypochlorite bleaches. Halogen bleaches are extremely
effective bleaching agents, however they also present a number of drawbacks
which can sometimes dissuade a consumer from choosing the halogen-
containing product. For example halogen bleaches, especially chlorine
bleaches, emit a pungent odour during and after use (e.g., on consumer hands
and/or surfaces treated therewith) which some consumer find disagreeable.
Furthermore, it is known in the art halogen bleach-containing compositions
(typically hypochlorite) are relatively aggressive to fabrics and may cause
damage when used in relatively high concentration and/or repeated usage. In
particular the consumer may perceive damage to the fabric itself (e.g. loss of
tensile strength) or damage to the colour intensity of the fabric. While
colour
and fabric damage may be minimised by employing milder oxygen bleaches
such as hydrogen peroxide, the bleach performance characteristics of such
peroxygen bleaches are much less desirable than those of the halogen
bleaching agents. Therefore, liquid aqueous activated peroxygen bleach-
containing compositions have been developed containing activators, i.e.,
compounds which enhance peroxygen bleaching pertormance. However these
bleaches do not perform as well as hypohalogen bleaches in stain removal.
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It is thus an object of the present invention to provide a bleaching raw
material
and a bleaching composition which not only delivers effective bleaching
performance, when used in laundry applications and/or in any household
application (e.g. bleaching/disinfecting of hard-surfaces), but is also safe
to the
surfaces treated, e.g. to fabrics per se andlor colours of fabrics.
A particular problem encountered when formulating bleaching compositions, is
the tendency of the bleaching raw material to chemical instability upon
prolonged periods of storage. Thus it is thus a further object of the present
invention to provide a bleaching raw material and a bleaching composition
delivering effective bleaching performance and which are chemically stable
upon
prolonged periods of storage.
The raw material and compositions according to the present invention may be
useful in any laundry application, e.g., as a laundry detergent or a laundry
additive, and when used as a laundry pretreater. A particular advantage of the
compositions of the present invention is that they 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 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.
Another advantage of the bleaching compositions according to the present
invention is that they can be used 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 liquid aqueous compositions of the present invention 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 20mlIL 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
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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.
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.
Summary of the invention
According to the present invention there is provided a process for preparing
solid
pre-formed peroxycarboxylic acid raw material having mean average particle
size of less than 100 microns wherein the peroxycarboxylic acid is ground in
at
least two consecutive grinding steps; step (i) and step (ii).
The present invention further encompasses a bleaching composition comprising
the pre-formed peroxycarboxylic acid prepared.
Detailed description of the invention
Process
The present invention relates to a process for preparing a pre-formed
peroxycarboxylic acid (hereafter referred to as peracid) raw material having
mean average particle size of less than 100 microns. The process involves
grinding particles of peracid to achieve the mean average particle size as
required herein. Peracids are available in numerous forms. One of the most
useful forms available for use in bleaching compositions is a wet cake,
consisting of peracid and water formed into a particles of approximately 0.16
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mm to 1.4 mm. Whist it is possible to incorporate the wet cake into a
bleaching
composition, the Applicant has found that there are two problems generally
associated with the size of the peracid in this form. The first problem is the
appearance of the bleaching composition. Especially when the bleaching
composition is in liquid form, the wet cake is easily visible to the naked
eye. The
Applicant has found that consumers find the appearance of the bleaching
composition comprising the wet cake as unacceptable. The second problem
relates to performance. One of the benefits in using peracids as bleaching
agents is that they are generally less aggressive to fabrics than for example
hypochlorite bleaches. How ever, the Applicant has found that if the wet cake
is
used in bleaching compositions to clean fabrics, the large particles of the
wet
cake can sometimes deposit on the fabrics, potentially causing localised
colour
losslfading due to intense bleach action in that area.
The Applicant has found that by processing the peracid using the process of
the
present invention; relatively small particles can be achieved that are
consumer
acceptable and do not cause colour losslfading.
The process of the present invention involves grinding the peracid in two
consecutive steps. In the first step the peracid wet cake is ground using a
silverson rotar mill, a cobalt mill (for example a mill based on the corundum
stone) or mixtures thereof. At the end of this grinding step the peracid has
been
ground from a particle size of 0.16 to 1.4 mm to mean average particle size of
between 100 and 200 microns. In the second step, the product of the first step
is ground using a cobalt mill to the point where the peracid has a mean
average
particle size of less than 100 microns. In a preferred aspect the peracid has
mean average particle size of from 10 to 80 microns and most preferably from
20 to 50 microns.
The peracid may be any peracid known in the art suitable for use herein. In a
preferred embodiment of the present invention the peracid has the general
formula
X-R-C(O)OOH
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wherein R is a linear or branched alkyl chain having at least 1 carbon atom
and
X is hydrogen or a substituent group selected from the group consisting of
alkyl,
especially alkyl chains of from 1 to 24 carbon atoms, aryl, halogen, ester,
ether,
amine, amide, substituted phthalic amino, imide, hydroxide, sulphide,
sulphate,
sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, phosphonate,
phosphonic
or mixtures thereof.
More particularly the R group preferably comprises from 2 to 24 carbon atoms.
Alternatively, the R group may be a branched alkyl chain comprising one or
more side chains which comprise substituent groups selected from the group
consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic
amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic,
heterocyclic, nitrate, aldehyde, ketone or mixtures thereof.
In a preferred peracid the X group, according to the above general formula, is
a
phthalimido group. Thus, particularly preferred peracids are those having
general formula:
D O
II
C O
C ~ ~ ~N-(R)-COOH
g C
A O
where R is C1-20 alkyl group and where A, B, C and D are independently either
hydrogen or substituent groups individually selected from the group consisting
of
alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic,
sulphate,
sulphonate, aldehydes or mixtures thereof.
In a preferred aspect of the present invention R is an alkyl group having from
3
to 12 carbon atoms, more preferably from 5 to 9 carbon atoms. Preferred
substituent groups A, B, C and D are linear or branched alkyl groups having
from 1 to 5 carbon atoms, but more preferably hydrogen.
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Preferred peracids are selected from the group consisting of phthaloyl amido
peroxy hexanoic acid (also known as phthaloyl amido-peroxy caproic acid),
phthaloyl amido peroxy heptanoic acid, phthaloyl amido peroxy octanoic acid,
phthaloyl amido peroxy nonanoic acid, phthaloyl amido peroxy decanoic acid
and mixtures thereof.
Even more preferred peracids are any of having general formula:
0
0
c~
(R)" - COOH
C
O
wherein R is selected from C1-4 alkyl and n is an integer of from 1 to 5.
In a particularly preferred aspect of the present invention the peracid has
the
formula such that R is CH2 and n is 5 i.e. phthaloyl amido-peroxy caproic acid
or
PAP.
The peracid is preferably used as a substantially water-insoluble solid or
wetcake and is available from Ausimont under the trade name Euroco.
The bleaching composition
The present invention also relates to a bleaching compositions comprising the
peracid prepared according to the process described above. The composition of
the present invention are preferably liquid, as opposed to a solid or a gas.
As
used herein "liquid" includes "pasty" compositions. The liquid compositions
herein are preferably aqueous compositions, comprising water at a level of
preferably 10 to 99%, more preferably from 50% to 98% by weight of the
bleaching composition. The liquid compositions according to the present
invention have a pH below 7. Preferably, the pH of the compositions according
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to the present invention is from 0.1 to 6.5, more preferably from 0.5 to 5,
even
more preferably from 2 to 4. 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. The pH of the composition is
preferably below the pKa of the peracid used. It is believed that the acidic
pH
controlsllimits the formation of highly reactive species which are unstable in
acidic medium upon storage, and thus contributes to the stability of the
compositions for prolonged periods of storage.
The pH of the compositions may be adjusted by any acid or alkaline species
known to those skilled in the art. Examples of acidic species suitable for use
herein are organic acids, such as citric acid and inorganic acids, such as
sulphuric acid, suiphonic acid andlor metanesulphonic acid. Examples of
alkaline species are sodium hydroxide, potassium hydroxide andlor sodium
carbonate.
The bleaching performance of the present composition may be evaluated by the
following test methods on various type of bleachable stains.
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 is diluted with water typically at a dilution level of 1 to
100 mI/L,
preferably 20 mI/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 mI/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 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..
The bleaching performance is then evaluated by comparing side by side the
soiled fabrics treated with a composition of the present invention with those
treated with the reference, e.g., the same composition but comprising no
bleach
or a different bleach. A visual grading may be used to assign difference in
panel
units (psu) in a range from 0 to 4.
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An advantage of the compositions of the present invention is that they are
physically and chemically stable upon prolonged periods of storage.
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 peracid do not undergo
more than 15% Av0 loss, in one month at 25°C and preferably not more
than
10%.
The loss of available oxygen (Av0) of a peracid-containing composition over
time can be measured by titration with potassium permanganate after reduction
with a solution containing ammonium ferrous sulphate. This stability test
method is well known in the art and is reported, for example, on the technical
information sheet of CuroxR commercially available from Interox. Alternatively
peracid 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).
The peracid may be present in the composition at a level of from 0.1 % to 70%
more preferably 0.5% to 50% and most preferably 1 % to 30% by weight of the
bleaching composition.
Optional inaredients
The compositions herein may further comprise a variety of other optional
ingredients such as surfactants, chelating agents, radical scavengers,
antioxidants, stabilisers, builders, soil suspending polymer, polymeric soil
release agents, pH control agents, dye transfer inhibitor, solvents, suds
controlling agents, suds booster, brighteners, perfumes, pigments, dyes and
the
like.
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Surfactants
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, 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%.
Suitable anionic surfactants for use in the compositions herein include water-
soluble salts or acids of the formula ROS03M wherein R preferably is a C10-
C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C1 p-C20 alkyl
component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a
cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or
ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl
ammonium cations and quaternary ammonium cations, such as tetramethyl-
ammonium and dimethyl piperdinium cations and quaternary ammonium cations
derived from alkylamines such as ethylamine, diethylamine, triethylamine, and
mixtures thereof, and the like). Typically, alkyl chains of C12-16 are
preferred for
lower wash temperatures {e.g., below about 50°C} and C16-18 alkyl
chains are
preferred for higher wash temperatures (e.g., above about 50°C).
Other suitable anionic surfactants for use herein are water-soluble salts or
acids
of the formula RO(A}mS03M wherein R is an unsubstituted C1 p-C24 alkyl or
hydroxyalkyl group having a C1p-C24 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1g 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 ration. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein. Specific examples of substituted ammonium rations include methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium rations, such as
tetramethyl-ammonium, dimethyl piperdinium and rations derived from
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alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures
thereof,
and the like. Exemplary surfactants are C12-C1g alkyl polyethoxylate (1.0)
sulfate, C12-CIgE(1.0)M), C12-C1g alkyl polyethoxylate (2.25) sulfate, C12-
CIgE(2.25)M), C12-C1g alkyl polyethoxylate (3.0) sulfate C12-CIgE(3.0), and
C12-C1g alkyl polyethoxylate (4.0) sulfate C12-CIgE(4.0)M), wherein M is
conveniently selected from sodium and potassium.
Other particularly suitable anionic surfactants far use herein are alkyl
sulphonates including water-soluble salts or acids of the formula RSOgM
wherein R is a C6-C22 linear or branched, saturated or unsaturated alkyl
group,
preferably a C12-C1 g alkyl group and more preferably a C14-C16 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).
Suitable alkyl aryl sulphonates for use herein include water- soluble salts or
acids of the formula RS03M wherein R is an aryl, preferably a benzyl,
substituted by a Cg-C22 linear or branched saturated or unsaturated alkyl
group,
preferably a C12-C1g alkyl group and more preferably a C14-C16 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).
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 S03M or aryl-S03M
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).
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For example C14-C16 alkyl sulphonate salt is commercially available under the
name Hostapur O 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
suiphonates commercially available under trade name Nansa~ available from
Albright&W ilson.
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, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by
sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g.,
as
described in British patent specification No. 1,082,179, Cg-C24
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl
ester sulfonates such as C14-16 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 C12-C18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
Cg-C14 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(CH2CH20)kCH2C00-M+ wherein R is a C8-C22 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).
Other particularly suitable anionic surfactants for use herein are alkyl
carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in
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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(C2H40)10-CH2COONa, with R= C12-C14) commercially available under the
name Akyposoft~ 100NV from Kao Chemical Gbmh.
Suitable amphoteric surfactants for use herein include amine oxides having the
following formula R1 R2R3N0 wherein each of R1, R2 and R3 is independently a
saturated substituted or unsubstituted, linear or branched hydrocarbon chain
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
R1 R2R3N0 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.
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
R1-N+(R2)(R3)R4X_
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-Cg alkyl, hydroxy alkyl
or other substituted C1-Cg alkyl group; R3 is C1-Cg alkyl, hydroxy alkyl or
other
substituted C1-Cg alkyl group which can also be joined to R2 to form ring
structures with the N, or a C1-Cg carboxylic acid group or a C1-C6 sulfonate
group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic
group
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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.
Preferred hydrophobic groups R1 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 R1 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 R1 can also be an amido
radical of the formula Ra-C(O)-NH-(C(Rb)2)m, wherein Ra 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, Rb 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(Rb)2) moiety.
Preferred R2 is hydrogen, or a C1-C3 alkyl and more preferably methyl.
Preferred R3 is a C1-Cq. carboxylic acid group or C1-C4 sulfonate group, or a
C1-C3 alkyl and more preferably methyl. Preferred R4 is (CH2)n wherein n is an
integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
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.
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~.
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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".
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Poulenc under the trade name Mirataine H2C-HA ~.
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 persulfate
salt and are selected from the group of methyl sulfate, or methylsulfonate,
and
the like.
Particularly preferred for use in the compositions of the present invention
are
trimethyl quaternary ammonium compounds like myristyl trimethylsulfate, cetyl
trimethylsulfate andlor tallow trimethylsulfate. Such trimethyl quaternary
ammonium compounds are commercially available from Hoechst, or from
Albright & Wilson under the trade name EMPIGEN CMS.
Amongst the nonionic surfactants, alkoxylated nonionic surfactants and
especially ethoxylated nonionic surfactants are suitable for use herein.
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Particularly prefen-ed nonionic surfactants for use herein are the capped
alkoxylated nonionic surfactants.
Suitable capped alkoxylated nonionic surfactants for use herein are according
to
the formula:
R1 (O-CH2-CH2)n-(OR2)m-O-R3
wherein R1 is a Cg-C24 linear or branched alkyl or alkenyl group, aryl group,
alkaryl group, preferably R1 is a Cg-C1g alkyl or alkenyl group, more
preferably
a C10-C15 alkyl or alkenyl group, even more preferably a C10-C15 alkyl group;
wherein R2 is a C1-C10 linear or branched alkyl group, preferably a C2-C10
linear or branched alkyl group ;
wherein Rg is a C1-C10 alkyl or alkenyl group, preferably a C1-C5 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.
These surfactants are commercially available from BASF under the trade name
Plurafac~, from HOECHST under the trade name Genapol~ or from ICf 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.
Suspending agent
The composition of the present invention may preferably comprise a suspending
agent. A suspending agent is an ingredient which is specifically added to the
composition of the present invention to suspend a solid particulate ingredient
of
the composition. With regard to the present invention, a suspending agent is
particularly useful for suspending the PAP.
Suitable suspending agents are those known in the art. Examples of
suspending agents include polysaccharide polymers (e.g. xanthan gum),
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polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof
and
polycarboxylate polymers.
In a particularly preferred embodiment of the present invention, the
suspending
agent comprises a combination of at least two polymers. In this embodiment the
first polymer is a gum-type polymer and the second is a cross-linked
polycarboxylate polymer. The composition may additionally comprise further
polymers.
The gum-type polymer may be selected from the group consisting of
polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglucan gum,
Cellulose, derivatives of any of the above and mixtures thereof. In a
preferred
aspect of the present invention the gum-type polymer is a xanthan gum or
derivative thereof.
The gum-type polymer is preferably present at a level of from 0.01 % to 10%,
more preferably from 0.1 % to 3%.
The polycarobxylate polymer can be a homo or copolymer of monomer units
selected from acrylic acid, methacrylic acid, malefic acid, malic acid,
malefic
anhydride. Preferred polycarboxylate polymers are Carbopol from BF Goodrich.
Suitable polymers have molecular weight in the range of from
10 000 to 10 000 000, more preferably 100 000 to 10 000000.
The cross-linked polycarboxylate polymer is preferably present at a level of
from
0.01 % to 2%, more preferably from 0.01 % to 1 %, most preferably from 0.1 %
to
0.8%.
In an alternative embodiment the suspending agent comprises a combination of
at least 2 polymers. In this embodiment the first polymer is a gum-type
polymer
and the second is a cross-linked polycarboxylate polymer. The composition may
additionally comprise further polymers.
The ratio of gum-type poiymer to cross-linked polycarboxylate polymer is from
100:1 to 1:100, more preferably from 10:1 to 1:10.
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Chelating aaents
The compositions of the present invention may comprise a chelating agent as a
preferred optional ingredient. Suitable chelating agents may be any of those
known to those skilled in the art such a~ 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.
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.
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
yenta 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 yenta methylene phosphonate (DTPMP) and
ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents
are commercially available from Monsanto under the trade name DEQUEST~~
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.
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
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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.
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, ethanol-
diglycines, 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 yenta acetic acid, propylene diamine
tetracetic acid (PDTA} which is, for instance, commercially available from
BASF
under the trade name Triton FS~ and methyl glycine di-acetic acid (MGDA).
Further carboxylate chelating agents to be used herein include salicylic acid,
aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
Another chelating agent for use herein is of the formula:
R2R3R4
wherein R1, R2, R3, and R4 are independently selected from the group
consisting of -H, alkyl, alkoxy, aryl, aryloxy, -CI, -Br, -N02, -C(O)R', and -
S02R";
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 R5, Rg, R7, and Rg are independently selected from the group
consisting of -H and alkyl.
Particularly preferred chelating agents to be used herein are amino
aminotri(methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid,
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diethylene triamine penta methylene phosphonate, 1-hydroxy ethane
diphosphonate, ethylenediamine N, N'-disuccinic acid, and mixtures thereof.
Typically, the compositions according to the present invention comprise up to
5% by weight of the total composition of a ~helating agent, or mixtures
thereof,
preferably from 0.01 % to 1.5% by weight and more preferably from 0.01 % to
0.5%.
Radical scavengers
The compositions of the present invention may comprise a radical scavenger or
a
mixture thereof.
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
~.
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.
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
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
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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 a 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).
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.
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).
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.
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.
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
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chain length distribution such as palm kernel oil and babassu oil are included
with the term coconut oil.
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.
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.
Especially preferred silicone suds controlling agents are described in
Copending
European Patent application N°92201649.8. Said compositions can
comprise a
silicone/silica mixture in combination with fumed nonporous silica such as
AerosilR.
Especially preferred suds controlling agent are the suds controlling agent
system
comprising a mixture of silicone oils and the 2-alkyl-alcanols.
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%.
Stabilisers
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The compositions of the present invention may further comprise up to 10%,
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-C10 hydrocarbon chain and/or cycle. Preferred alcohol according to
that
formula is propanediol. Indeed, we have observed that these alcohols in
general
and propanediol in particular also improve the chemical stability of the
compositions.
Other stabilizers like inorganic stabilizers may be used herein. Examples of
inorganic stabilizers include sodium stannate and various alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate.
Soil suspending polymer
The compositions according to the present invention may further comprise a
soil
suspending polymer, for example a polyamine soil suspending polymer, as
optional ingredient. Any soil suspending polyamine polymer known to those
skilled in the art may be used herein. Particularly suitable polyamine
polymers
for use herein are polyalkoxylated polyamines. Such materials can conveniently
be represented as molecules of the empirical structures with repeating units
[N R] n Amine form
I
(alkoxy)y
and
R1
I
[N+ R] n nX- Quatemized form
I
(alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1-
C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is
2-30, most preferably from 10-20; n is an integer of at least 2, preferably
from 2-
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20, most preferably 3-5; and X- is an anion such as halide or methylsulfate,
resulting from the quaternization reaction.
The most highly preferred polyamines for use herein are the so-called
ethoxylated polyethylene amines, i.e., the polymerized reaction product of
ethylene oxide with ethyleneimine, having the general formula
(Et0) [N CH2 CH2~n N (Et0)y
(Et0)y (Et0)y
when y = 2-30. Particularly preferred for use herein is an ethoxylated
polyethylene amine, in particular ethoxylated tetraethylenepentamine, and
quaternized ethoxylated hexamethylene diamine.
Soil suspending polyamine polymers contribute to the benefits of the present
invention, i.e., that when added on top of said diacyl peroxide, further
improve
the stain removal performance of a composition comprising them, especially
under laundry pretreatment conditions, as described herein. Indeed, they allow
to improve the stain removal performance on a variety of stains including
greasy
stains, enzymatic stains, clay/mud stains as well as on bleachable stains.
Typically, the compositions comprise up to 10% by weight of the total
composition of such a soil suspending polyamine polymer or mixtures thereof,
preferably from 0.1 % to 5% and more preferably from 0.3% to 2%.
The compositions herein may also comprise other polymeric soil release agents
known to those skilled in the art. Such polymeric soil release agents are
characterised by having both hydrophilic segments, to hydrophilize the surface
of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments,
to deposit upon hydrophobic fibres 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.
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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) oxypropy~ene 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 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) Cg 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-Cg
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-C4
alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures
therein,
and such cellulose derivatives are amphiphilic, whereby they have a sufficient
level of C1-C4 alkyl ether andlor 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 about 1 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-Cg alkylene hydrophobe segments include, but are not limited to, end-
caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-, where
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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, co-polymeric
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 C1-C4 alkyl and C4 hydroxyalkyl
cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et
al.
Soil release agents characterised by polyvinyl ester) hydrophobe segments
include graft co-polymers of poly{vinyl ester), e.g., C1-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 co-polymer having random blocks
of ethylene terephthalate and polyethylene oxide (PEO) 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 which contains 10-15% by weight of ethylene
terephthalate units together with 90-80% by weight of polyoxyethylene
terephthalate units, derived from a polyoxyethylene 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
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terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are fully described 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;7.11,730, issued December 8, 1987 to
Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued 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 utilised, soil release agents will generally comprise from 0.01 % to 10.0%,
by
weight, of the detergent compositions herein, typically from 0.1 % to 5%,
preferably from 0.2% to 3.0%.
Dye transfer inhibitor
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
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agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, co-
polymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
typically comprise from 0.01 % to 10% by weight of the composition, preferably
from 0.01 % to 5%, and more preferably from 0.05% to 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-O 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
~t)X N-~2)y~ =NWRt)x
(R3)z
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, polyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof. These polymers
include random or block co-polymers where one monomer type is an amine N-
oxide and the other monomer type is an N-oxide. The amine N-oxide polymers
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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
r
polymer can be varied by appropriate co-polymerization 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.
Co-polymers of N-vinylpyrrolidone and N-vinylimidazole 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 20,000. (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 co-polymers 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 co-polymers can be either
linear or branched.
The present invention compositions may also employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from 5,000 to 400,000,
preferably from 5,000 to 200,000, and more preferably from 5,000 to 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 500 to 100,000, preferably from 1,000 to 10,000.
Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions
is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
Suds booster
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If high sudsing is desired, suds boosters such as C10-C16 alkanolamides can
be incorporated into the compositions, typically at 1 %-10% levels. The C10-
C14
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 (1982).
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, Tinopal PLC; available from
Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[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)thiophene; 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
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February 29, 1972, to Hamilton. Anionic brighteners are typically preferred
herein.
pH control agent
A variety of suitable means can be used for adjusting the pH of the
compositions, including organic or inorganic acids, alkanolamines and the
like. It
may be advantageous to use alkanolamines, in particular monoethanolamine,
inasmuch as they have an additional effect of regulating the viscosity of the
emulsion, without compromising on its physical stability.
Minor Ingredients
The composition described herein may also comprise minor ingredients such as
pigment or dyes and perfumes.
Processes of treating surfaces
In the present invention, the liquid aqueous composition of the present
invention
needs to be contacted with the surface to treat.
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.
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 peracid compound or a mixture thereof and optionally cleaning
as said compositions may comprise a surfactant or any other conventional
cleaning agents.
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31
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 is contacted with the fabrics to be
treated.
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.
The processes of bleaching surfaces according to the present invention,
especially fabrics, delivers effective whiteness performance as well as
effective
stain removal performance.
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.
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.
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, in its diluted form, then
allowing
said fabrics to remain in contact with said composition, for a period of time
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32
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 andlor after the step where said fabrics are
contacted with said bleaching composition and before the rinsing step and/or
after the rinsing step.
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, 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.
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.
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33
It is preferred to perform the bleaching processes herein after said fabrics
have
been washed with a conventional 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.
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, 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.
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.
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.
By "hard-surfaces", it is understood any hard-surfaces as mentioned herein
before as well as dishes.
Packaging form of the liguid compositions:
Depending on the end-use envisioned, the compositions herein can be
packaged in a variety of containers including conventional bottles, bottles
equipped with roll-on, sponge, brusher or sprayers.
In one embodiment of the present invention the composition is packaged in a
two compartment container, wherein the bleaching composition as described
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34
herein is packaged in one compartment and a second composition is packaged
in the second compartment. fn a particularly preferred aspect, the second
composition is a conventional heady duty liquid detergent composition,
preferably comprising ingredients, particularly bleach-sensitive ingredients
such
as surfactants, enzymes and perfumes. .
The invention is further illustrated by the following examples.
Examples
Following compositions were made by mixing the listed ingredients in the
listed
proportions (weight % unless otherwise specified).
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Compositions I II III IV V
(% weight)
Na alkylbenzene sulphonate- 1 - 1.5 -
Linear alkyl sulfonate - - 1 0.5 -
C12-15alkyl 7 ethoxylated- 1 ~~ - - -
Akyposoft 100 NV~ - - 2 -
PAP 3 2 4 1 20
Hydroxyethanediphosphonate0.1 0.05 0.16 0.1 0.1
Perfume - 0.2 0.2 0.3 -
brightener - 0.01 0.05 0.03 -
xanthan gum 0.3 0.2 0.3 - 0.5
carbopol ETD 2691 0.2 - 0.1 -
carbopol ETD 2623 - - - 0.3 -
carboxylmethoxycellulose - 1 0.5 1 -
Alkanizing / acidizing 2.5 3.5 4 4
agent up to pH 3.9
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
HEDP is ethane 1-hydroxy diphosphonate commercially available from Monsanto
under the serie Dequest~.
PAP is phthalimidoperoxyhexanoic acid available from Ausimont under the
tradename Euroco~
Carbopol~ETD 2623 and 2991 are polymers available from BFGoodrich
All the above 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.
These compositions are physically and chemically stable, i.e. they do not loos
more than 15% Av0 after a period of storage of one month at 25°C.
