Note: Descriptions are shown in the official language in which they were submitted.
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THE USE OF AN ALIPHATIC-AROMATIC DIACYL PEROXIDE IN A
BLEACHING COMPOSITION
10
Technical field
The present invention relates to the use of an aliphatic-aromatic diacyl
peroxide
in a bleaching composition.
Background
Peroxygen bleach-containing compositions typically based on hydrogen peroxide
have been extensively described in laundry applications as laundry detergents,
laundry additives or laundry pretreaters.
An example of such a bleaching agent is a diacyl peroxide. Diacyl peroxides
and
compositions containing such compounds, including dialiphatic, diaromatic and
aliphatic-aromatic diacyl peroxides have been described in the prior art.
JP1009601 (KAO) describes a composition comprising hydrogen peroxide, a
diacyl peroxide and a surfactant. The diacyl peroxide can be dialiphatic,
diaromatic or aliphatic-aromatic. The composition is described to have good
storage stability.
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W098111189 (Procter & Gamble) describes a process for bleaching a fabric with
a liquid composition comprising a dialiphatic peroxide. This document does not
describe aliphatic-aromatic diacyl peroxides.
It has been found that although diaromatic peroxides provide good stain
removal,
they are aggressive bleaching agents that cause fabric damage, resulting in
poor
fabric colour safety.
It is believed that a radical decomposition of hydrogen peroxide occurs on the
surface of the fabric, generating free radicals. It is further speculated that
this
generation of free radicals may provide an aggressive decomposition of certain
dyes present in the fabrics, resulting in chemical damage of dye molecules
visible as discoloration and/or loss of colour intensity. Thus, bleaching
performance and fabric colour safety are somewhat conflicting requirements,
but
both are desirable in a single bleaching composition.
It is therefore an aspect of the present invention to provide a bleaching
composition that provides good stain removal and good fabric colour safety.
European patent number EP-A-742 279 and EP-A-752 469 disclose laundry
bleaching compositions containing chefating agents, radical scavengers and
polyamines, and which are safe to colors and fabrics. The peroxygen bleaches
disclosed therein include peroxy acids such as diperoxydodecandioic acid but
do
no describe aliphatic-aromatic diacyl peroxides.
It has now been found that the above aspects can be met by using an
aliphatic-aromatic diacyl peroxide to treat soiled fabrics. Indeed, it has
been
found that the mixed aliphatic-aromatic diacyl peroxide, especially in an
aqueous
bleaching composition, delivers good stain removal performance on fabrics,
when compared to the use of the same composition either without an aliphatic-
aromatic diacyl peroxide or comprising a dialiphatic diacyl peroxide. Also, it
has
been found that the mixed aliphatic-aromatic diacyl peroxide, especially in an
aqueous bleaching composition, reduces the colour damage of colored fabrics
(i.e. improves colour safety), when compared to the colour damage observed
with the same composition but comprising a different peroxygen bleach, for
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example a diaromatic diacyl peroxide, instead of said aliphatic-aromatic
diacyl
peroxide.
An advantage of the present invention is that the improved stain removal
performance obtained is consumer noticeable on a variety of stains/soils,
including enzymatic stains like blood, grass, and especially carotenoid-type
stains like tomato sauce.
Thus, the applicant has found that the diacyl peroxides of the present
invention
provide not only good stain removal but also provide good fabric colour
safety.
Summary of the invention
According to the present invention there is provided the use of a diacyl
peroxide
having the general formula:
O O
II I~
/ 1 / 1
R~ O _______O R2
wherein R1, is an aliphatic group and R2 is an aromatic group to provide stain
removal and improved fabric colour safety.
Detailed description of the invention
Diac~peroxide
The diacyl peroxide of the present invention has general formula
O O
II II
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C C
/1 /1
R, O ___-__--_-O R2
wherein R1 is an aliphatic group and R2 is an aromatic group. In a preferred
aspect of the present invention R1 has from 1 to 30, more preferably 4 to 20
carbon atoms. R1 may be linear, branched, cyclic, saturated, unsaturated,
substituted, unsubstituted or mixtures thereof. Preferably R1 is linear and
comprises from 8 to 16 carbon atoms. Where R1 is substituted, the carbon atom
is preferably substituted with a halide or sulpate-containing or nitrogen-
conatining
functionality such as S03-, S04-, N02, NR3+ where R = H or alkyl chain.
R2 may be mono or polycyclic aromatic ring, homo or heteroatomic aromatic
ring,
substituted or unsubstituted and mixtures thereof. Where R2 is substituted,
the
carbon atom is preferably substituted with a halide, sulphur-containing
functionality, nitrogen-containing or an alkyl chain wherein the number of
carbon
atoms ranges from 1 to 20, most preferably from 4 to 10. Suitable sulphur-
containing or nitrogen-containing substituents include S03-, S04-, N02, NR3+
where R=H or an alkyl chain. Preferably R2 is benzene. In a preferred
embodiment of the present invention the diacyl peroxide is preferably benzoyl
alkanoyl peroxide wherein the alkanoyl group has from 8 to 18 carbon atoms.
More preferably the diacyl peroxide is selected from the group consisting of
benzoyl lauroyl peroxide, benzoyl decanoyl peroxide, benzoyl cetoyl peroxide,
para-alkyl benzoyl lauroyl peroxide, para-alkyl benzoyl decanoyl peroxide,
para-
alkyl benzoyl cetoyl peroxide and mixtures thereof. In a particularly
preferred
embodiment the diacyl peroxide is benzoyl lauroyl peroxide.
The diacyl peroxides described herein are easily synthesized by persons
skilled
in the art, see for example Organic Peroxides Vol. 1; page 65, edited by
Daniel
Swern of Wiley Interscience.
The present invention also relates to the use of a bleaching composition
comprising the diacyl peroxides described herein. Where the present invention
relates to a bleaching composition, the diacyl peroxide is typically present
in the
range of from 0.01 % to 10% preferably 0.1 % to 3%, more preferably from 0.3%
to 2% and most preferably from 0.5% to 1 % by weight of the composition.
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The compositions used according to the present invention may further comprise
another peroxygen bleach in addition to said aliphatic diacyl peroxide,
hereinafter
called the "second" peroxygen bleach. Additional optional ingredients may be
5 added in said compositions, for example bleach activators, surfactants,
brighteners, chelating agents, radical scavengers, stabilisers, soil
suspending
polymers, soil release agents, dye transfer inhibiting agents, solvents,
colourants,
rheology modifiers, sud suppressors catalysts, perfumes, or mixtures thereof.
Preferred optional ingredients are described in more detail hereinafter.
In a preferred embodiment of the present invention, it has been found that the
use of preferably aqueous bleaching compositions comprising a diacyl peroxide
as describe herein, and a second peroxygen bleach, provide improved stain
removal performance and bleaching performance whilst still ensuring good
fabric
colour safety, as compared to the same compositions but without said diacyl
peroxide described herein. Thus, the present invention also encompasses the
use of a bleaching composition preferably comprising from 0.05% to 10% by
weight of the total composition of the diacyl peroxide described herein and
from
0.01 % to 10% by weight of a second peroxygen bleach. Furthermore, in another
preferred embodiment of the present invention the composition also comprises a
bleach activator. Such compositions deliver even more effective bleaching
performance, especially at ambient temperature.
The second peroxygen bleach to be used herein can be any peroxygen bleach
known in the art, with the exception of the diacyl peroxide described herein.
Such
peroxygen bleaches include hydrogen peroxide, a water-soluble source thereof,
or mixtures thereof. Hydrogen peroxide is most preferred for use in the
compositions according to the present invention. Moreover, the presence of the
second peroxygen bleach, preferably hydrogen peroxide, contributes to the
excellent cleaning and bleaching benefits of the compositions. As used herein
a
hydrogen peroxide source refers to any compound which produces perhydroxyl
ions when in contact with water.
Suitable water-soluble sources of hydrogen peroxide for use herein include
percarbonates, persilicate, persulphate such as monopersulfate, perborates,
peroxyacids such as diperoxydodecandioic acid (DPDA), phthaloyl amino
peroxycaproic acid (PAP), magnesium perphtalic acid, perlauric acid,
perbenzoic
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and alkylperbenzoic acids, hydroperoxide like t-butyl hydroperoxide and
mixtures
thereof.
The compositions according to the present invention comprise from 0.01 % to
10%, preferably from 0.5% to 8%, more preferably from 2% to 8%, and most
preferably from 4% to 7% by weight of the composition of a second peroxygen
bleach.
In a particularly preferred aspect of the present invention, the bleaching
composition comprises a diacyl peroxide as described herein and a surfactant.
The surfactant may be a surfactant system comprising more than one surfactant.
The compositions of the present invention are preferably aqueous liquid
compositions. Said aqueous compositions are most preferably formulated to
have pH from 2 to 5. The pH of the compositions of the present invention can
be
adjusted by using organic or inorganic acids known to those skilled in the
art.
Particularly suitable organic acids to be used herein are aryl and/or alkyl
sulfonate, such as methane sulfonic acid or naphtalene disulfonic acid, citric
acid,
succinic acid, tartaric acid, sulphamic acid, glutaric acid, adipic acid and
the like.
Particularly suitable inorganic acids are sulfuric acid, phosphoric acid,
nitric acid.
The compositions used according to the process of the present invention are
preferably aqueous compositions. The compositions used herein have a pH of
from 0 to 12. Preferably the composition has pH of from 0 to 10, more
preferably
from 1 to 7, most preferably from 2 to 4.
By the term "improve colour safety" it is meant that the damage to dyes
present
on a fabric caused by the diacyl peroxide of the present invention is reduced
when compared with damage cause by other bleaching agents, especially
diaromatic peroxides, for example dibenzoyl peroxide i.e. improved fabric
colour
safety is equated to reduced fabric colour damage. The damage caused to the
dyes is seen as a loss of colour intensity. Furthermore, this reduction in
colour
damage is seen even when the diacyl peroxide of the present invention is left
in
contact with the fabric, and thus the fabric dye, for prolonged periods at
time
before subsequent washing or rinsing of the fabric, e.g. 24 hours.
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It is speculated that colour safety is achieved due to the lower reactivity of
the
diacyl peroxide of the present invention versus other bleaching agents,
especially
diaromatic diacyl peroxide which are known to cause fabric colour damage.
The stain removal performance and fabric colour safety of the diacyl peroxide
may
be evaluated by the following test method. A diacyl peroxide according to the
present invention, but preferably a composition comprising the diacyl
peroxide, is
first applied onto a fabric, preferably on the stained portion of said fabric,
it is left to
act thereon for 1 minute to 24 hours, preferably 5 to 10 minutes, after which
the
fabric is washed according to common washing conditions, at a temperature of
from 30°C to 70°C for a period of time sufficient to bleach said
fabric.
The stain removal performance may be evaluated by comparing side by side the
soiled coloured fabric pre-treated with the diacyl peroxide composition or
product,
according to the present invention with those pre-treated with the reference
containing it, e.g., the same compositions but without the diacyl peroxide of
the
present invention. For example, typical stains to be used in such a stain
removal
test method are commercially available from WFK (Krefeld, Germany) or from
EMC {Empirical Manufacturing Company) Cincinnati, Ohio, USA, such as grass,
coffee, tomato sauce, dirty motor oil, cosmetics, barbecue sauce, blood on
different substrate/fabric, e.g., cotton (CW120) or polycotton (PCW28). A
visual
grading scale may be used to assign differences in panel score units (psu), in
a
range from 0 to 4 for the stain removal performance.
Colour safety may be evaluated by determination of the colour damage by side-
by-side comparison of the soiled coloured fabric treated with the diacyl
peroxide
according to the present invention with those treated with the reference
product,
e.g., the same composition but without the diacyl peroxide of the present
invention
or a different bleaching agent, for example a diaromatic peroxide. Technical
coloured swatcheslfabrics suitable to be used in the colour damage test method
herein, are commercially available from Tecnotessile (Prato, Italy) or EMC
(Empirical Manufacturing Company) Cincinnati, Ohio, US. Typical colored
fabrics/swatches used are for example the most sensitive to bleach like: C83
Reactive BIueO, C102 Reactive BIueO, C65 Reactive Violet ~t , C73 Direct
BIueO,
C105 Direct Brown~, C111 Direct Redo, C40 Sulphur GreenO. A visual grading
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and/or instrumental methods with the "Hunterlab Tristimulus MINISCAN" may be
used for the colour damage evaluation.
It is envisaged that the diacyl peroxide or a composition comprising it may be
used as a pre-treatment, as an additive or a component of a detergent
composition. Where the diacyl peroxide is used as a pre-treatment, it is
preferred that the fabric to which the diacyl peroxide has been added is
subsequently washed. By "washing" it is to be understood herein to simply
rinse
the fabrics with water, or the fabrics may be washed with a conventional
detergent composition comprising at least one surface active agent, by means
of
a washing machine or simply by hand.
Where the diacyl peroxide is a component of a composition, the composition may
be used in neat or dilute form. By "neat form" it is understood that the
compositions is applied directly onto the fabric without undergoing any
dilution.
Optionals
Where the present invention relates to the use of a composition comprising the
diacyl peroxide, the composition may further comprise optional ingredients
like
bleach activators, surfactants, brighteners, chelating agents, radical
scavengers,
stabilisers, soil suspending polymers, soil release agents, dye transfer
inhibiting
agents, solvents, colourants, rheology modifiers, sud suppressors, catalysts,
perfumes, or mixtures thereof.
As an optional but highly preferred ingredient, the compositions of the
present
invention comprise a bleach activator or mixtures thereof. By "bleach
activator",
it is meant herein a compound which reacts with hydrogen peroxide to form a
peracid. The peracid thus formed constitutes the activated bleach.
Particularly
suitable bleach activators to be used herein are hydrophobic bleach
activators,
i.e., a bleach activator which is not substantially and stably miscible with
water.
Suitable bleach activators to be used herein include those belonging to the
class
of esters, amides, imides, or anhydrides. Examples of suitable compounds of
this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a
method for their formation into a prilled form is described in European
Published
Patent Application EP-A-62 523. Suitable examples of such compounds to be
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used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl
hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for
instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for
instance in US 4 259 201 and alkyl-benzene sulphonates such as n-
nonanoyloxybenzenesulphonate (NOES). Also suitable are N-acyl caprolactams
selected from the group consisting of substituted or unsubstituted benzoyl
caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl
caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam
pentanoyl caprolactam or mixtures thereof. A particular family of bleach
activators of interest was disclosed in EP 624 154, and particularly preferred
in
that family is acetyl triethyl citrate (ATC). Acetyl triethyl citrate has the
advantage
that it is environmental-friendly as it eventually degrades into citric acid
and
alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical
stability in the
product upon storage and it is an efficient bleach activator. Finally, it
provides
good building capacity to the composition.
The compositions according to the present invention may comprise from 0.01
to 30% by weight of the total composition of a bleach activator, or mixtures
thereof, preferably from 0.5% to 10%, and more preferably from 3% to 7%.
The compositions according to the present invention may comprise a surfactant
or mixtures thereof. Any surfactant known to those skilled in the art may be
used
herein including anionic surfactants, nonionic surfactants, zwitterionic
surfactants,
amphoteric surfactants and/or cationic surfactants up to a level of 50% by
weight
of the total composition.
The compositions according to the present invention may be formulated as
solutions, emulsions, microemulsions, suspensions, pastes or powders.
For stability reasons, the compositions according to the present invention
that
may typically comprise a bleach activator, as described hereinbefore, are
preferably formulated either as aqueous emulsions of said bleach activator in
a
matrix comprising water, the aliphatic diacyl peroxide, the second peroxygen
bleach and an emulsifying surfactant system, or as microemulsions of said
bleach activator in a matrix comprising water, the aliphatic diacyl peroxide,
the
second peroxygen bleach and a hydrophilic surfactant system.
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Preferred peroxygen bleach-containing compositions herein comprise an
emulsifying surfactant system of at least two different surfactants, i.e., at
least a
hydrophobic surfactant having an HLB up to 9.5 or mixtures thereof, and at
least
5 a hydrophilic surfactant having an HLB above 10, or mixtures thereof, in
order to
emulsify the hydrophobic bleach activator where present. Preferred herein,
said
two different surfactants should have different HLB values (hydrophilic /
lipophilic
balance) in order to form stable compositions, and preferably the difference
in
value of the HLBs of said two surfactants is at least 1, preferably at least
2.
10 Indeed, by appropriately combining at least two of said surfactants with
different
HLBs in water, emulsions will be formed which do not substantially separate
into
distinct layers, upon standing for at least two weeks at 40°C.
The preferred compositions according to the present invention comprise from
0.1
% to 50 %, more preferably from 1 % to 20 % and most preferably from 2 % to 10
%, by weight of surfactant. The surfactant may be hydrophilic or hydrophobic.
The preferred compositions according to the present invention comprise at
least
from 0.01 %, preferably at least 2 % and more preferably at least 4 % of a
hydrophobic surfactant and at least from 0.01 %, preferably at least 2%, and
more preferably at least 4% of a hydrophilic surtactant.
The hydrophilic surfactant have an HLB above 10. Preferably hydrophilic
nonionic surfactants having an HLB above 10 and more preferably above 10.5.
Preferred hydrophobic surfactants are the hydrophobic nonionic surfactants.
Said hydrophobic nonionic surfactants have an HLB of up to 9.5, preferably
below 9.5, more preferably below 9. The hydrophobic nonionic surfactants to be
used herein have excellent grease cutting properties, i.e., they have a
solvent
effect which contributes to hydrophobic soils removal.
Suitable nonionic surfactants for use herein include alkoxylated fatty
alcohols
preferably, fatty alcohol ethoxylates and/or propoxylates. Indeed, a great
variety
of such alkoxylated fatty alcohols are commercially available which have very
different HLB values (hydrophilic / lipophilic balance). The HLB values of
such
alkoxylated nonionic surfactants depend essentially on the chain length of the
fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation.
Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation
and a
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short chain fatty alcohol, while hydrophobic surfactants tend to have a low
degree of alkoxylation and a long chain fatty alcohol. Surfactant catalogs are
available which list a number of surfactants including nonionics, together
with
their respective HLB values.
Suitable chemical processes for preparing the nonionic surfactants for use
herein include condensation of corresponding alcohols with alkylene oxide, in
the desired proportions. Such processes are well-known to the man skilled in
the art and have been extensively described in the art. As an alternative, a
great variety of alkoxylated alcohols suitable for use herein is commercially
available from various suppliers.
Preferred hydrophobic nonionic surfactants to be used in the present invention
are surfactants having an HLB up to 9 and being according to the formula RO-
(C2H40)n(C3Hg0)mH, wherein R is a Cg to C22 alkyl chain or a Cg to C2g
alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and
m is from 0 to 5 and preferably n+m is from 0.5 to 4.5 and, n and m are from 0
to 4.5. The preferred R chains for use herein are the Cg to C22 alkyl chains.
Accordingly, suitable hydrophobic nonionic surfactants for use herein are
Dobanol R 91-2.5 (HLB= 8.1; R is a mixture of Cg and C11 alkyl chains, n is
2.5
and m is 0), or Lutensol R T03 (HLB=8; R is a mixture of C13 and C15 alkyl
chains, n is 3 and m is 0), or Tergitol R 25L3 (HLB= 7.7; R is in the range of
C12
to C15 alkyl chain length, n is 3 and m is 0), or Dobanol R 23-3 (HLB=8.1; R
is a
mixture of C12 and C13 alkyl chains, n is 3 and m is 0), or Dobanol R 23-2
(HLB= 6.2; R is a mixture of C12 and C13 alkyl chains, n is 2 and m is 0), or
mixtures thereof. Preferred herein are Dobanol R 23-3, or Dobanol R 23-2,
Lutensol R T03, or mixtures thereof. These Dobanol R surfactants are
commercially available from SHELL. These Lutensol R surfactants are
commercially available from BASF and these Tergitol R surfactants are
commercially available from UNION CARBIDE. Other suitable hydrophobic
nonionic surfactants to be used herein are non alkoxylated surfactants. An
example is Dobanol R 23 (HLB<3).
Preferred hydrophilic nonionic surfactants to be used herein are surfactants
having
an HLB above 10 and being according to the formula RO-(C2Hq.0)n(C3Hg0)mH,
wherein R is a Cg to C22 alkyl chain or a C6 to C2g alkyl benzene chain, and
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wherein n+m is from 5 to 11 and n is from 0 to 11 and m is from 0 to 11,
preferably
n+m is from 6 to 10 and, n and m are from 0 to 10. Throughout this description
n
and m refer to the average degree of the ethoxylation/propoxylation. The
preferred R chains for use herein are the Cg to C22 alkyl chains. Accordingly,
suitable hydrophilic nonionic surfactants for use herein are Dobanol R 23-6.5
(HLB=11.9 ; R is a mixture of C12 and C13 alkyl chains, n is 6.5 and m is 0),
or
Dobanol R 25-7 (HLB=12 ; R is a mixture of C12 to C15 alkyl chains, n is 7 and
m
is 0), or Dobanol R 45-7 (HLB=11.6 ; R is a mixture of C14 and C15 alkyl
chains, n
is 7 and m is 0), or Dobanol R 91-5 (HLB=11.6 ; R is a mixture of Cg to C11
alkyl
chains, n is 5 and m is 0), or Dobanol R 91-6 (HLB=12.5 ; R is a mixture of Cg
to
C11 alkyl chains, n is 6 and m is 0), or Dobanol R 91-8 (HLB=13.7; R is a
mixture
of Cg to C11 alkyl chains, n is 8 and m is 0), or Dobanol R 91-10 (HLB= 14.2 ;
R is
a mixture of Cg to C11 alkyl chains, n is 10 and m is 0), or mixtures thereof.
Preferred herein are Dobanol R 91-10, or Dobanol R 45-7, Dobanol R 23-6.5, or
mixtures thereof. These Dobanol R surfactants are commercially available from
SHELL.
Apart from the hydrophilic nonionic surfactants, other hydrophilic surfactants
may
also be used in the compositions of the present invention such as anionic
surfactants described hereinafter andlor polyhydroxy fatty acid amide
surfactant,
or mixtures thereof, according to the formula
R2 - C(O) - N(R1 ) - Z,
wherein R1 is H, or C1_C4 alkyl, C1_C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5_C31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof.
Preferably, R1 is C1_C4 alkyl, more preferably C1 or C2 alkyl and most
preferably
methyl, R2 is a straight chain C7_C1g alkyl or alkenyl, preferably a straight
chain
Cg_C1 g alkyl or alkenyl, more preferably a straight chain C11 _C1 g alkyl or
alkenyl, and most preferably a straight chain C11_C14 alkyl or alkenyl, or
mixtures thereof. Z preferably will be derived from a reducing sugar in a
reductive
amination reaction; more preferably Z is a glycityl. Suitable reducing sugars
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include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As
raw materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn syrup can be utilised as well as the individual sugars listed
above.
These corn syrups may yield a mix of sugar components for Z. It should be
understood that it is by no means intended to exclude other suitable raw
materials. Z preferably will be selected from the group consisting of -CH2-
(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n-1-CH20H, -CH2-(CHOH)2-
(CHOR')(CHOH)-CH20H, where n is an integer from 3 to 5, inclusive, and R' is H
or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof.
Most
preferred are glycityls wherein n is 4, particularly CH2-(CHOH)4-CH20H.
In the formula R2 - C(O) - N(R1 ) - Z, R1 can be, for example, N-methyl, N-
ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R2 -
C(O) - N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide and the like. Z can be 1-
deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-
deoxygalactityl,
1-deoxymannityl, 1-deoxymaltotriotityl and the like.
Suitable polyhydroxy fatty acid amide surfactants to be used herein may be
commercially available under the trade name HOE~ from Hoechst.
Methods for making polyhydroxy fatty acid amide surfactants are known in the
art. In general, they can be made by reacting an alkyl amine with a reducing
sugar in a reductive amination reaction to form a corresponding N-alkyl
polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty
aliphatic ester or triglyceride in a condensation/amidation step to form the N-
alkyl,
N-polyhydroxy fatty acid amide product. Processes for making compositions
containing polyhydroxy fatty acid amides are disclosed for example in GB
patent
specification 809,060, published February 18, 1959, by Thomas Hedley & Co.,
Ltd., US patent 2,965,576, issued December 20, 1960 to E.R. Wilson, US patent
2,703,798, Anthony M. Schwartz, issued March 8, 1955, US patent 1,985,424,
issued December 25, 1934 to Piggott and W092/06070, each of which is
incorporated herein by reference.
In a particularly preferred embodiment of the present invention, wherein the
compositions comprise acetyl triethyl citrate as the bleach activator, an
adequate
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surfactant system, would comprise a hydrophobic nonionic surfactant with for
instance an HLB of 6, such as a Dobanol R 23-2 and a hydrophilic nonionic
surfactant with for instance an HLB of 15, such as a Dobanol R 91-10. Other
suitable nonionic surfactant systems comprise for example a Dobanol R 23-8.5
(HLB about 12) and a Dobanol R 23 (HLB below 6) or a Dobanol R 45-7
(HLB=11.6) and a Dobanol 23-3 (HLB=8.1 ).
In the embodiment of the present invention where the compositions are
formulated as emulsions said compositions are opaque. In centrifugation
examination, it was observed that said emulsions herein showed no phase
separation after 15 minutes at 6000 rpm. Under microscopic examination, said
emulsions appeared as a dispersion of droplets in a matrix.
In the embodiment of the present invention where the compositions of the
present invention are formulated as microemulsions, said bleaching
microemulsions according to the present invention comprise a hydrophilic
surfactant system comprising at least two different surfactants like a
nonionic
surfactant and an anionic surfactant.
Suitable hydrophilic surfactants to be used herein are those hydrophilic
surfactants mentioned herein. A key factor in order to stably incorporate for
example the bleach activator in said microemulsions is that at least one of
said
surfactants of the hydrophilic surfactant system must have a different HLB
value
to that of the bleach activator. Indeed, if all said surfactants had the same
HLB
value as that of the activator, a continuous single phase might be formed,
thus
lowering the chemical stability of the bleach/bleach activator system.
Preferably,
at least one of said surfactants has an HLB value which differs by at least
1.0
HLB unit, preferably 2.0 to that of said bleach activator.
Suitable anionic surfactants to be used herein include water-soluble salts or
acids
of the formula ROS03M or RS03M wherein R preferably is a C10-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-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-
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ammonium and dimethyl piperdiniurn 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
5 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 C10-C24 alkyl or
hydroxyalkyl group having a C1p-C24 alkyl component, preferably a C12-C20
10 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 cation. Alkyl
15 ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated
herein. Specific examples of substituted ammonium cations include methyl-,
dirnethyl-, 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 C12-C1 g alkyl polyethoxylate (1.0)
sulfate, C12-C18E(1.0)M), C12-C1g alkyl polyethoxylate (2.25) sulfate, C12-
C18E(2.25)M), C12-C1 g alkyl polyethoxylate (3.0) sulfate C12-C18E(3.0), and
C12-C1g alkyl polyethoxylate (4.0) sulfate C12-C18E(4.0)M), wherein M is
conveniently selected from sodium and potassium.
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-C20 linear alkylbenzenesulfonates, Cg-C22 primary or secondary
alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids
prepared by sulfonation of the pyrolyzed product of alkaline earth metal
citrates,
e.g., as described in British patent specification No. 1,082,179, Cg-C24
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl
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
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16
taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate
(especially saturated and unsaturated C12-C1g 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. 1 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)..
Particularly preferred anionic surfactants for use in the compositions
described
herein are alkali or alkaline earth metal, preferably sodium, paraffin
sulphonates
(e.g. NaPS available from for example Hoescht or Huls).
Other suitable anionic surfactants to be used herein also include acyl
sarcosinate
or mixtures thereof, in its acid and/or salt form, preferably long chain acyl
sarcosinates having the following formula:
O
OM
R
I
CH3 O
wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of
from
11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms. Preferred M
are
hydrogen and alkali metal salts, especially sodium and potassium. Said acyl
sarcosinate surfactants are derived from natural fatty acids and the amino-
acid
sarcosine (N-methyl glycine). They are suitable to be used as aqueous solution
of
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17
their salt or in their acidic form as powder. Being derivatives of natural
fatty acids,
said acyl sarcosinates are rapidly and completely biodegradable and have good
skin compatibility.
Accordingly, particularly preferred long chain acyl sarcosinates to be used
herein
include C12 acyl sarcosinate (i.e. an acyl sarcosinate according to the above
formula wherein M is hydrogen and R is an alkyl group of 11 carbon atoms) and
C14 acyl sarcosinate (i.e. an acyl sarcosinate according to the above formula
wherein M is hydrogen and R is an alkyl group of 13 carbon atoms). C12 acyl
sarcosinate is commercially available, for example, as Hamposyl L-30~ supplied
by Hampshire. C14 acyl sarcosinate is commercially available, for example, as
Hamposyl M-30~ supplied by Hampshire.
Suitable other hydrophilic nonionic surfactants for use in the microemulsions
herein include the hydrophilic nonionic surfactants as defined herei~nbefore
for
the emulsions.
The preferred making of the microemulsions of the present invention includes
premixing the surfactants with water and subsequently adding the other
ingredients including the aliphatic diacyl peroxide, the second peroxygen
bleach,
e.g., hydrogen peroxide, and other ingredients like a bleach activator if
present.
Irrespective of this preferred order of addition, it is important that during
the
mixing of the ingredients, the microemulsions be constantly kept under
stirring
under relatively high stirring energies, preferably 30 minutes at 750 rpm,
most
preferably 30 minutes at 1000 rpm.
In the embodiment of the present invention where the compositions are
formulated as microemulsions said compositions are macroscopically
transparent in the absence of opacifiers and colourants: In centrifugation
examination, it was observed that said microemulsions herein showed no phase
separation after 15 minutes at 6000 rpm. Under microscopic examination, said
microemulsions appeared as a dispersion of droplets in a matrix. We have
observed that the particles had a size which is typically around or below 3
micron diameter.
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18
Accordingly, said bleaching compositions of the present invention may be
packaged in a given deformable container/bottle without compromising the
stability of said containerlbottle comprising it upon standing, for long
periods of
time.
Suitable chelating agents to be used herein include chelating agents selected
from
the group of phosphonate chelating agents, amino carboxylate chelating agents,
polyfunctionally-substituted aromatic chelating agents, and further chelating
agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic
acid, or
mixtures thereof. Chelating agents when used, are typically present herein in
amounts ranging from 0.001 % to 5% by weight of the total composition and
preferably from 0.05% to 2% by weight.
Suitable phosphonate chelating agents to be used herein may include ethydronic
acid as well as amino phosphonate compounds, including amino alkylene poly
(alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo
trimethylene phosphonates, ethylene diamine tetra methylene phosphonates,
and diethylene triamine penta methylene phosphonates. In a preferred
embodiment, the phosphonate chelant is alkali metal ethane 1-hydroxy
diphosphonates (HEDP). 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 phosphonates. Such phosphonate chelating
agents are commercially available from Monsanto under the trade name
DEQUEST~~
The most preferred phosphonate chelating agent to be used herein is
aminotri(methylene phosphonic acid), herein referred to as ATMP. Indeed, it
has
been found that the addition of ATMP, i.e. the compound of formula
CH2-P03H2
N
/1
P03H2-CH2 CH2-P03H2
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in a liquid composition of the present invention considerably reduces the
damage
otherwise associated with the pretreatment of fabrics with peroxygen bleach-
containing compositions, especially those fabrics which contain metal ions,
such
as copper, iron, chromium, and manganese.
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. Ethyienediamine 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.
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 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).
Another preferred chelating agent for use herein is of the formula:
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R~
RZR3R4
wherein R1, R2, R3, and R4 are independently selected from the group
5 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 ATMP, diethylene
triamine methylene phosphonate, ethylene N,N'-disuccinic acid, diethylene
triamine pantaacetate, glycine, salicylic acid, aspartic acid, glutamic acid,
malonic
acid or mixtures thereof and highly preferred is ATMP.
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. Radical scavengers when used, are typically present herein in
amounts ranging from 0.001 % to 2% by weight of the total composition and
preferably from 0.001 % to 0.5% by weight.
The presence of chelating agents, especially ATMP, andlor radical scavengers
allows to contribute to the safety profile of the compositions of the present
invention suitable for pretreating a soiled colored fabric upon prolonged
contact
times before washing said fabric.
Other stabilizers like inorganic stabilizers may be used herein. Examples of
inorganic stabilizers include sodium stannate and various alkali metal
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21
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate.
The compositions according to the present invention may further comprise a
foam suppressor such as 2-alkyl alkanol, or mixtures thereof, as an 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 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). Typically,
the
compositions of the present invention comprise up to 2 % by weight of the
total
composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.05 %
to
1.5 % and more preferably from 0.1 % to 0.8 %.
The compositions according to the present invention may further comprise a
soil
suspending polymer or mixtures thereof, as optional ingredient. Any soil
suspending polymer known to those skilled in the art may also be used herein.
Particularly suitable are polyamine polymers such as polyalkoxylated
polyamines.
Such materials can conveniently be represented as molecules of the empirical
structures with repeating units
[N R] n Amine form
(alkoxy)y
and
R1
I
[N+ R] n nX- Quaternized form
(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-
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22
30, most preferably from 10-20; n is an integer of at least 2, preferably from
2-20,
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.
It has surprisingly been found that said soil suspending polyamine polymers
contribute to the benefits of the present invention, i.e., that when added on
top of
said aliphatic diacyl peroxide, they 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
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23
segments. This can enable stains occurring subsequent to treatment with the
soil release agent to be more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil
release agents having: (a) one or more nonionic hydrophile components
consisting essentially of (i) polyoxyethylene segments with a degree of
polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene
segments
with a degree of polymerization of from 2 to 10, wherein said hydrophile
segment
does not encompass any oxypropylene unit unless it is bonded to adjacent
moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene
units
comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said
mixture contains a sufficient amount of oxyethylene units such that the
hydrophile
component has hydrophilicity great enough to increase the hydrophilicity of
conventional polyester synthetic fiber surfaces upon deposit of the soil
release
agent on such surface, said hydrophile segments preferably comprising at least
about 25% oxyethylene units and more preferably, especially for such
components having about 20 to 30 oxypropylene units, at least about 50%
oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3
oxyalkylene terephthalate segments, wherein, if said hydrophobe components
also comprise oxyethylene terephthalate, the ratio of oxyethylene
terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii)
C4-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 and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fiber surfaces and retain a sufficient level
of
hydroxyls, once adhered to such conventional synthetic fiber surface, to
increase
fiber surtace 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-
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24
caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-, where
M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent
4,721,580,
issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers, 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 polyvinyl 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.
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Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of
terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are fully described in
U.S.
5 Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P.
Gosselink.
Other suitable polymeric soil release agents include the terephthalate
polyesters
of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the
anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January
26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S.
10 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 about 0.01 % to
about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
The compositions of the present invention may also include one or more
materials effective for inhibiting the transfer of dyes from one dyed surface
to
another during the cleaning process. Generally, such dye transfer inhibiting
agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, co-
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26
polymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and mixtures thereof. If used, these agents typically comprise
from
about 0.01 % to about 10% by weight of the composition, preferably from about
0.01 % to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form part of the polymerizable unit or the N-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
I I
~Rt )x- i .'yR2)y~ =N-(R~ )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
typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
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However, the number of amine oxide groups present in the polyamine oxide
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-vinylpyrroiidone 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 about 5,000 to about
400,000; preferably from about 5,000 to about 200,000, and more preferably
from
about 5,000 to about 50,000. PVP's are known to persons skilled in the
detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated
herein by reference. Compositions containing PVP can also contain polyethylene
glycol ("PEG") having an average molecular weight from about 500 to about
100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of
PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to
about 50:1, and more preferably from about 3:1 to about 10:1.
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
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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.
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; 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-dJtriazoles; 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-dJoxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-dJtriazole. See also
U.S.
Patent 3,646,015, issued February 29, 1972, to Hamilton. Anionic brighteners
are typically preferred herein.
If desired, compositions herein may additionally incorporate a catalyst or
accelerator to further improve bleaching or soil removal. Any suitable bleach
catalyst can be used. For detergent compositions used at a total level of from
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about 1,000 to about 5,000 ppm in water, the composition will typically
deliver a
concentration of from about 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to about 50 ppm, or less, of the catalyst species in the wash
liquor.
Bleach catalysts may also be used herein. Typical bleach catalysts comprise a
transition-metal complex, for example one wherein the metal co-ordinating
ligands are quite resistant to labilization and which does not deposit metal
oxides
or hydroxides to any appreciable extent under the typically alkaline
conditions of
washing. Such catalysts include manganese-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S. 5,114,606; and EP Nos.
549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; preferred examples of
these catalysts include MnIV2(~,-O)3(TACN)2-(PF6)2, Mnlll2(~,-O)1 (~,-
OAc)2(TACN)2(CI04)2~ MnIV4(~-O)6(TACN)4(CI04)4, MnIIIMnIV4_(~_O)1(w-
OAc)2-(TACN)2-(C104)3, MnIV-(TACN)-(OCH3)3(PF6), and mixtures thereof
wherein TACN is trimethyl-1,4,7-triazacyclononane or an equivalent macrocycle;
though alternate metal-co-ordinating ligands as well as mononuclear complexes
are also possible and monometallic as well as di- and polymetallic complexes
and complexes of alternate metals such as iron or ruthenium are all within the
present scope. Other metal-based bleach catalysts include those disclosed in
U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with
various complex ligands to enhance bleaching is also reported in the following
United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153,161; and 5,227,084.
Transition metals may be precomplexed or complexed in-sifu with suitable donor
ligands selected in function of the choice of metal, its oxidation state and
the
denticity of the ligands. Other complexes which may be included herein are
those of U.S. Application Ser. No. 08/210,186, filed March 17, 1994.
The present invention will be further illustrated by the following examples.
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Examples
The following compositions were prepared in accordance with the present
invention. All amounts are described in weight % of the total composition.
5
Composition 1
Dobanol 45-7 5%
NaPS
10 Benzoyl Lauroyl Peroxide 0,5%
H202 g.g%
Water and minors to balance
pH 4
15 Comiaosition 2
Dobanol 45-7 5%
NaPS
Isopar M 1.5%
20 Benzvyl Lauroyl Peroxide 2%
Water and minors to balance
PH 4
Composition 3
Dobanol 45-7 3%
NaPS 3%
Isopar M 1.5%
Benzoyl Lauroyl Peroxide 0.5%
H202 6.g%
Water and minors to balance
pH 4
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Composition 4
Dobanol 45-7 5%
NaPS 1 %
Isopar M 1.5%
Benzoyl Lauroyl Peroxide 0.5%
HEDP 0.16%
H202 6,g%
Water and minors to balance
PH 5
Composition 5
Dobanol45-7 5%
NaPS 1 %
Isopar M 1.5%
p-Pentyl-Benzoyl Lauroyl Peroxide0.5%
H202 6.8%
Water and minors to balance
pH 4
Composition 6
NaAS 2.7%
Dobanol 23-3 2.5%
Dobanol 91-10 2.6%
Isopar M 1.5%
Benzoyl Lauroyl Peroxide 0.5%
H202 6.8%
Water and minors to balance
pH 4
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Composition 7
Dobanol23-6.5 7,p%
Dobanol 23-3 1.5%
Dobanol 91-10 1,g%
NaAS 1.7%
Isopar M 1.5%
Benzoyl Lauroyl Peroxide 0.5%
H202 g,g%
Water and minors to balance
pH
