Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY PRETREATMENT PROCESS AND BLEACHING COMPOSITIONS
Technical field
The present invention relates to bleaching compositions particularly suitable
to be used as a pretreater and to a process of pretreating fabrics.
Background
A great variety of cleaning compositions have been described in the art, that
are particularly suitable for pretreating fabrics.
For instance, EP-A-5g8 170 discloses a particular type of cleaning
compositions which are aqueous emulsions of a nonionic surfactant system
further comprising hydrogen peroxide or water-soluble source thereof and a
liquid bleach activator, or any other hydrophobic ingredient which needs to
be separated from said hydrogen peroxide.
European patent application number 95203330.6 discloses a particular type
of cleaning compositions which are aqueous microemulsions of a bleach
activator in a matrix comprising water, hydrogen peroxide and a hydrophilic
surfactant system.
However, a drawback associated with such emulsions or microemulsions
comprising a peroxygen bleach and a bleach activator, especially when used
in laundry pretreatment applications on different kinds of fabrics, e.g., cottonanu/or synthetic fabrics (e.g., polyester/polyamides), is that they do not
deliver effective performance which satisfactorily meet consumer's needs on
all types of stains including greasy stains, enzymatic stains, mud/clay stains
as well as bleachable stains. Indeed, there is still some room to further
improve the stain removal performance as well as the bleaching performance
of such bleach-containing compositions when pretreating a fabric therewith.
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It is thus an object of the present invention to provide improved stainremoval performance on a wide range of stains as well as improved
bleaching performance, especially under laundry pretreatment conditions,
i.e., when appiied neat onto at least a portion of a fabric before washing said
fabric.
Furthermore, another problem associated with such emulsions and/or
microemulsions especially with those containing relatively high
concentration of surfactants, e.g., about 8 % or above, is that important
viscosity tends to build up, which makes said emulsions/microemulsions
difficult to dispense, and thus unacceptable from a consumer viewpoint.
It is thus a further object of the present invention to provide liquid
emulsions or microemulsions comprising a peroxygen bieach and a
surfactant wherein the viscosity can be conveniently controlled while
maintaining adequate physical stability.
It has now been found that improved stain removal performance is
obtained, by using a liquid composition comprising a peroxygen bleach and
a soil dispersing agent selected from the group consisting of an ethoxylated
monoamine, an ethoxylated diamine, an ethoxyiated polyamine, an
ethoxylated amine polymer and mixture thereof, as described hereinafter, to
pretreat soiled fabrics. Indeed, the addition of such a soil dispersing agent,
in a liquid composition comprising a peroxygen bleach, and optionally a
bleach activator, delivers improved stain removal performance on various
types of stains including greasy stains, enzymatic stains, clay/mud stains,
and the like, under pretreatment conditions, as compared to the stain
removal performance delivered by the same composition without said soil
dispersing agent. Also, it has surprisingly been found that the liquid
compositions comprising both the peroxygen bleach and said soil dispersing
agent, when used to pretreat fabrics, provide improved bleaching efficacy,
as compared to the same compositions without said soil dispersing agent.
Thus, it has been found that the addition of a single compound, i.e., such a
soil dispersing agent, in a peroxygen bleach-containing composition, delivers
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both improved stain removal performance and improved bleaching
performance. Furthermore, it has been found that this improved stain
removal performance on various stains is maintained even for peroxygen
bleach-containing compositions having undergone long storage time. It is
thus speculated that the oxidized form of the soil suspeding agent that may
have formed in the presence of a peroxygen bleach under long storage time
and/or elevated temperature still provides improved stain removal
performance on various types of stains. Thus, in its broadest aspect, the
present invention encompasses a process for bleaching a fabric with a liquid
composition comprising from 0.01% to 15% by weight of the total
composition of a peroxygen bleach, and a soil dispersing agent, said
process comprising the steps of applying said liquid composition in its neat
form onto at least one portion of said fabric, optionally allowing said
composition to remain in contact with said fabric and then washing said
fabric.
Furthermore, it has been found that the addition of a soil dispersing agent
selected from the group consisting of an ethoxylated monoamine, an
ethoxylated diamine, an ethoxylated polyamine, an ethoxylated amine
polymer and mixture thereof, in a liquid composition formulated either as an
emulsion or microemulsion, comprising a peroxygen bleach and a
surfactant, reduces the viscosity of said composition, whatever the
viscosity was before the addition of said soil dispersing agent. Actually, an
advantage of the liquid compositions of the present invention formulated
either as an emulsion or a microemulsion, is that they deliver improved stain
removal performance and improved bleaching performance while delivering
acceptable viscosity, without the need to add viscosity control agents. In
other words, the present invention allows to formulate emulsions or
microemulsions with improved overall stain removal/bleaching performance
and desirable physical characteristics at reduced costs, i.e., without adding
any viscosity control agent that would raise the cost formula and bulk to
the compositions without contributing to the bleaching/cleaning
performance of said compositions.
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Another advantage of the present invention is that stable liquid emulsions or
microemulsions are provided that are suitable to be used in the most efficient
manner by the consumer over prolonged period of time.
Yet another advantage of the compositions according to the present
invention which are formulated as emulsions or microemulsions is that they
provide also excellent cleaning and/or bleaching performance when used in
applications other than laundry pretreaters, such as in other laundry
applications, as laundry detergents or laundry additives.
European patent application number 95870079.1 discloses laundry
compositions suitable for pretreating fabrics comprising polyamines and
peroxygen bleach. No ethoxylated amines, ethoxylated polyamines or
ethoxylated amine polymers are disclosed.
US application number 08/663501 discloses pretreater compositions with
particular chelants, a peroxygen bleach, and optional ingredients like bleach
activators, polymeric soil releasing agents like sulfonated poly-
ethoxy/propoxy end-capped ester oligomer. However, no ethoxylated
amines, ethoxylated polyamines, or ethoxylated amine polymers are
disclosed.
EP-A-27 1 3 12 discloses laundry compositions comprising a peroxyacid
bleach and a soil release agent like particular alkyl and hydroxyalkyl ethers ofcellulose, polymers comprising ethylene terephthalate and polyethylene oxide
terephthalate. No ethoxylated amines, ethoxylated polyamines or ethoxylated
amine polymers are disclosed.
W096/12004 discloses laundry compositions comprising a lipophilic enzyme
and a primary and/or tertiary amine. These compositions provide enhanced
cleaning of greasy/oily soils and stains, particularly when used in
pretreatment laundering process for cleaning fabrics stained with greasy
soils. The compositions exemplified comprise tetraethylenepentamine
ethoxylated ~1 5-1 8) but no bleach.
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EP-A- 1 12 593 discloses detergent compositions (pH= 6 to 8.5~ comprising
ethoxylated mono- or diamines, ethoxylated polyamines and/or ethoxylated
amine polymers as a clay soil removal/antiredeposition agent. Said
compositions may be used in laundry pretreatment application. No peroxygen
bleaches are disclosed.
Summarv of the invention
The present invention encompasses a process of bleaching a fabric with a
liquid composition comprising from 0.01% to 15% by weight of the total
composition of a peroxygen bleach, and a soil dispersing agent selected from
the group consisting of
~1 ) ethoxylated monoamines having the formula:
(X--L--)--N--(R2)2
(2) ethoxylated diamines having the formula:
R2 - N - Rl - N - R2 (R2)2 N - Rl - N - (R2)2
L L L
X X X
or
(X - L -)2- N - Rl - N - (R2)2
(3) ethoxylated polyamines having the formula:
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R3 - [(Al )q -(R4)t-N-L-XIp
(4) ethoxylated amine polymers having the general formula:
1 2
[(R2)2 -N-]w--[-Rl -N-]X--[-Rl -N-]y- -[-Rl -N-L-X]z
X
and (5) mixtures thereof,
O O O O O
wl~ Al is--NC--, NCO--, NCN--, CN--, OCN--
R R R R R R
O O 0 00
CO--, OCO--,--OC , CNC or O--,
R
R is H or C1 -C4 alkyl or hydroxyalkyl; R1 is C2-C1 2 alkylene,
hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene
moiety having from 2 to 20 oxyalkylene units provided that no O _ N bonds
are formed; each R2 js C1-C4 alkyl or hydroxyalkyl, the moiety _ L _ X, or
two R2 together form the moiety _ (CH2~r _ A2 _ ~CH2)S _, wherein A2
is _ O _or _ CH2 _, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is a
nonionic group, an anionic group or mixture thereof; R3 is substituted C3-
C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution
sites; R4 is C1-C1 2 alkylene, hydroxyalkylene, alkenylene, arylene or
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alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene
units provided that no 0 _ 0 or 0 _ N bonds are formed; L is a hydrophilic
chain which contains the polyoxyalkylene moiety _[(R50)mtCH2CH20)nl_,
wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers
~ such that the moiety _(CH2CH20)n--comprises at least 50% by weight of
said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is
at least 12; for said diamines, m is from 0 to 3, and n is at least 6 when R1
is C2-C3 alkylene hydroxyalkylene, or alkenylene, and at least 3 when R1 is
other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said
polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is
from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1
or 0; x + y + z is at least 2; and y + z is at least 2, said process
comprising the steps of applying said composition in its neat form onto at
least a portion of said fabric, before said fabric is washed.
The present invention encompasses a liquid composition suitable for
pretreating fabrics, comprising a peroxygen bleach, a surfactant and a soil
dispersing agent selected from the group consisting of an ethoxylated
monoamine, an ethoxylated diamine, an ethoxylated polyamine, an
ethoxylated amine polymers and mixture thereof as previously defined, said
composition being formulated either as an emulsion or a microemulsion.
.
Detailed descriDtion of the invention
The laundrY Dretreatment ~rocess
In its broadest embodiment, the present invention relates to a process of
pretreating a fabric with a liquid composition comprising a soil dispersing
agent, as defined herein, and from 0.01% to 15% by weight of the total
composition of a peroxygen bleach.
By "pretreating a fabric" it is to be understood that the liquid composition
herein is applied in its neat form onto at least a portion of a soiled fabric,
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optionally left to act onto said fabric typically for a period of time of 1
minute to several hours, before said fabric is washed, as described
hereinafter, in the process of bleaching fabrics according to the present
invention.
Indeed, the present invention is based on the finding that by adding a soil
dispersing agent, as described herein, in a liquid composition comprising a
peroxygen bleach, improved stain removal performance is obtained with said
composition when used to pretreat a soiled fabric before said fabric is
washed, as compared to the stain removal performance delivered with the
same composition without said soil dispersing agent.
By "stain removal performance" it is meant herein stain removal performance
on a variety of stains/soils such as greasy/oily stains, and/or enzymatic
stains and/or mud/clay stains as well as bleachable stains.
By "greasy/oily stains" it is meant herein any soil and stain of greasy nature
that can be found on a fabric like dirty motor oil, mineral oil, make-up,
lipstick vegetal oil, spaghetti sauce, mayonnaise and the like.
Examples of bleachable stains include tea, coffee, wine and the like.
Examples of enzymatic stains include grass, chocolate and blood.
The stain removal performance of a given composition on a soiled fabric
under pretreatment conditions, may be evaluated by the following test
method. A composition according to the present invention is first applied to
the stained portion of said fabric, left to act from about 1 to about-10
minutes, typically 5 minutes, and said pretreated fabric is then washed
according to common washing conditions with a conventional detergent
composition, at a temperature of from 30~C to 70~C for a period of time
sufficient to bleach said fabric. For example, typical soiled fabrics to be usedin this stain removal performance test method may be commercially available
from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA such as
clay, chocolate, spaghetti sauce, dirty motor oil, make-up, tea, coffee, blood
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on two different substrate/fabric, e.g., cotton (CW120) and polycotton
(PCW28).
The stain removal performance may then be evaluated by comparing side by
side the soiled fabric pretreated with the composition according to the
present invention with those pretreated with the reference, e.g., the same
composition without such a soil dispersing agent according to the present
invention. A visual grading scale may be used to assign differences in panel
score units (psu), in a range from 0 to 4.
Accordingly, the present invention encompasses a process of bleaching a
fabric with a liquid composition comprising from 0.01% to 15% by weight
of the total composition of a peroxygen bleach and a soil dispersing agent,
as defined herein, said process comprises the steps of applying said
composition in its neat form onto at least a portion of said fabric, optionally
allowing said composition to remain in contact with said fabric preferably
without leaving said composition to dry onto said fabric, before said fabric is
washed.
Said composition may remain in contact with said fabric, typically for a
period of 1 minute to several hours, preferably 1 minute to 1 hour, more
preferably 1 minute to 30 minutes, and most preferably 2 to 10 minutes.
Optionally, when the fabric is soiled with encrusted stains/soils which
otherwise would be relatively difficult to remove, said composition may be
rubbed and/or brushed more or less intensively, for example, by means of a
sponge or a brush or simply by rubbing two pieces of fabric each against the
other.
By "washing" it is to be understood herein to simply rinse the fabric with
water, or the fabric may be washed with a conventional composition
comprising at least one surface active agent, this by the means of a washing
machine or simply by hand.
By "in its neat form" it is to be understood that the liquid compositions are
applied directly onto the fabrics to be pre-treated without undergoing any
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dilution, e.g., the liquid compositions according to the present invention are
applied as described herein.
According to the process of pretreating soiled fabrics of the present
invention, the liquid compositions used in said process should preferably not
be left to dry onto the fabrics. Indeed, it has been found that water
evaporation contributes to increase the concentration of free radicals onto
the surface of the fabrics and, consequently, the rate of chain reaction. It is
also speculated that an auto-oxidation reaction occurs upon evaporation of
water when the liquid compositions are left to dry onto the fabrics. Said
reaction of auto-oxidation contributes to generate peroxy-radicals which may
cause color damage and/or fabric damage. Thus, not leaving the liquid
bleaching compositions used according to the present invention to dry onto
the fabrics, in the process of bleaching fabrics according to the present
invention would result in a safer pretreating operation with liquid bleaching
compositions.
As an essential element the compositions to be used according to thé
present invention comprise a peroxygen bleach or mixtures thereof.
The peroxygen bleach to be used herein is any peroxygen bleach, known to
those skilled in the art. Such peroxygen bleach includes hydrogen peroxide,
or a water-soluble source thereof, or mixtures thereof. Indeed, the presence
of the peroxygen bleach contributes to the excellent cleaning and bleaching
benefits of the compositions used according to the present invention. As
used herein a hydrogen peroxide source refers to any compound which
produces perhydroxyl ions when said compound is 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), magnesium
perphtalic acid, perlauric acid, perbenzoic and alkylperbenzoic acids,
hydroperoxides, diacyl peroxides and mixtures thereof. Plefer,ed peroxygen
bleaches used herein are hydrogen peroxide, hydroperoxide and/or aliphatic
diacyl peroxide.
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Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl
hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-
monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-
dihydroperoxide. Such hydroperoxides have the advantage to be particularly
safe to fabrics and color while delivering excellent bleaching performance.
Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide,
didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof. Such aliphatic
diacyl peroxides have the advantage to be particularly safe to fabrics and
color while delivering excellent bleaching performance.
The compositions used according to the present invention comprise from
0.01% to 15% by weight of the total composition of such a peroxygen
bleach or mixtures thereof, preferably from 0.1% to 12%, more preferably
from 0.5% to 10% and most preferably from 2% to 8%.
As an essential element the compositions to be used according to the
present invention comprise a soil dispersing agent selected from the group
consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated
polyamines, ethoxylated amine polymers, as previously defined and mixtures
thereof. Indeed, the presence of said soil dispersing agent contributes to the
excellent cleaning and bleaching benefits of the compositions used according
to the present invention.
In the preceding formulas of the soil dispersing agent used herein,
R1 can be branched
f H3
( e.g. - CH2 - CH -, - CH2 - CH - ), cyclic ( e.g. ~ ),
CH3
or most preferably linear
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12
I
( e.g. - CH2CH2 -, - CH2 - CH2 - CH2 -, - CH2 - CH - )
alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R 1 is
preferably C2-C6 alkylene for the ethoxylated diamines and amine polymers.
For the ethoxylated diamines, the minimum degree of ethoxylation required
for suitable soil removal/anti-redeposition properties decreases on going from
C2-C3 alkylene lethylene, propylene) to hexamethylene. However, for the
ethoxylated amine polymers, in particular the ethoxylated polyalkyleneamines
and polyalkyleneimines, especially at higher molecular weights, C2-C3
alkylene (ethylene, propylene) are preferred for R1 with ethylene being most
preferred. Each R2 is preferably the moiety _ L _ X.
In the preceding formulas, hydrophilic chain L usually COnSial~ entirely of the
polyoxyalkylene moiety _[(R50)m(CH2CH2 0)n]_. The moieties _(R50)m_
and _(CH2CH20)n_ of the polyoxyalkylene moiety can be mixed together or
prefe.dbly form blocks of _(R50)m_ and _(CH2CH20)r~ moieties. R5 is
~referal~ly C3H6 ~propylene). For the ethoxylated polyamines and amine
polymers, m is preferably from 0 to 5. For all ethoxylated amines of the presentinvention, m is most preferably 0, i.e. the polyoxyalkylene moiety consists
entirely of the moiety _(CH2CH20)n_. The moiety _(CH2CH20)n_
preferably co,--prises at least 85% by weight of the polyoxyalkylene moiety and
most preferably 100% by weight (m is 0).
In the preceding formula, X can be any compatible nonionic group, anionic
group or mixture thereof. Suitable nonionic groups include C1-C4 alkyl or
hydroxyalkyl ester or ether groups, preferably acetate or methyl ether,
respectively; hydrogen (H); or mixtures thereof. The particularly preferred
nonionic group is H. With regard to anionic groups, po3-2 and S03- are
suitable. The particularly preferred anionic group is S03-. It has been found
that the percentage of anionic groups relative to nonionic groups can be
important to the soil removal/anti-redeposition properties provided by the
ethoxylated amine. A mixture of from 0 to 30% anionic groups and from 70
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13
to 100% nonionic groups provides preferred properties. A mixture of from 5
to 10% anionic groups and from 90 to 95% nonionic groups provides the
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n is preferably at ieast 12, with a typical range of from 12 to 42; p is
preferably from 3 to 6. When R3 is a substituted aryl or alkaryl group, q is
preferably 1 and R4 is preferably C2-C3 alkylene. When R3 is an alkyl,
hydroxyalkyl, or alkenyl group, and when q is 0, R1 is preferably a C2-C3
oxyalkylene moiety; when q is 1, R4 is preferably C2-C3 alkylene.
These ethoxylated polyamines can be derived from polyamino amides such
as:
-CN~C3H6--~NH2
O O
HO CN t C3H6 t NH2 or ~ CN(C3H6 ~ NH2
O - 3
- CN ~-~ C3H6--t NH2
H
These ethoxylated polyamines can also be derived from polyaminopropylene-
oxide derivatives such as:
{~C3H6)c NH2
CH3 (0C3H6)C NH2
~oc3H6)c--NH2
wherein each c is a number from 2 to 20.
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Preferred ethoxylated amine polymers are the ethoxylated C2-C3
polyalkyleneamines and polyalkyleneimines Particularly preferred ethoxylated
polyalkyleneamines and polyalkyleneimines are the ethoxylated
polyethyleneamines (PEA's) and polyethyleneimines (PEl's). These preferred
compounds comprise units having the general formula:
[N] w- - [cH2cH2N]x--[cH2cH2N]-y -[cH2cH2N}~
[ ( CH2CH2~)n-X ] 2 (cH2cH2o)n - X [(CH2CH2~)n-X]2
wherein X, w, x, y, z and n are defined as before.
Prior to ethoxylation, the PEAs used in preparing compounds of the present
invention have the following general formula:
H2N]- - CH2CH2~ - - CH2cH2N - - CH2CH2NH2
w -- -- x -- -- y _ _ z
wherein x + y + z is from 2 to 9, y + z is from 2 to 9 and w is 0 or 1
~molecular weight of from 100 to 400). Each hydrogen atom attached to
each nitrogen atom represents an active site for subsequent ethoxyiation.
For preferred PEAs, y + z is from 3 to 7 tmolecular weight of from 140 to
310) and most prefarably from 3 to 4 (molecular weight of from 140 to
200). These PEA's can be obtained by reactions involving ammonia and
ethylene dichloride, followed by fractional distillation. The common PEAIs
c!~tained are triethylenetetramine ~TETA) and tetraethylenepenta",ine (TEPA).
Above the pentamines, i.e., the hexamines, heptamines, octamines and
possibly nonamines, the cogenerically derived mixture does not appear to
separate by distillation and can include other materials such as cyclic amines
and particularly piperazines. There can also be present cyclic amines with
side chains in which nitrogen atoms appear. See US Patent 2,792,372 to
Dickson, issued May 14, 1957, which describes the preparation of PEAs.
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16
~he minimum degree of ethoxylation required for preferred soil removal/anti-
redeposition performance can vary depending upon the number of units in
the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y
+ z is from 4 to 9, suitable benefits are achieved when n is at least 3. For
most preferred ethoxylated PEAs, n is at least 12, with a typical range of
from 12 to 42.
The PEls used in preparing the compounds of the present invention have a
molecular weight of at least 440 prior to ethoxylation, which represents at
least 10 units. Preferred PEls used in preparing these compounds have a
molecular weight of from 600 to 1800. The polymer backbone of these
PEls can be represented by the general formula:
H2N- -[ CH2CH2N ]X - - [ CH2cH2N ] -y - [ CH2CH2NH2 ] z
wherein the sum of x, y, and z represents a number of sufficient magnitude
to yield a polymer having the molecular weights previously specified.
Although linear polymer backbones are possible, branch chains can also
occur. The relative proportions of primary, secondary and tertiary amine
groups present in the polymer can vary, depending on the manner of
preparation. The distribution of amine groups is typically as follows:
- CH2CH2-NH2 30%
- CH2CH2-NH- 40%
- CH2CH2-N- 30%
I
Each hydrogen atom attached to each nitrogen atom of the PEI represents an
active site for subsequent ethoxylation. These PEls can be prepared, for
example, by polymerizing ethyleneimine in the presence of a catalyst such as
carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,
hydrochloric acid or acetic acid. Specific methods for preparing PEls are
disclosed in U.S. Patent 2,182,306 to Ulrich et al., issued December ~,
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1g39; U.S. Patent 3,033,746 to Mayle et al., issued May 8, 1962; US
Patent 2,208,095 to Esselmann et al., issued July 16, 1940; US Patent
2,806,839 to Crowther, issued Sept. 17, 1957; and US Patent. 2,553,696
to Wilson, issued May 21, 1951.
As defined in the preceding formulas, n is at least 3 for the ethoxylated PEls.
However, it should be noted that the minimum degree of ethoxylation
required for suitable soil removal/anti-redeposition performance can increase
as the molecular weight of the PEI increases, especially much beyond 1800.
Also, the degree of ethoxylation for preferred compounds increases as the
molecular weight of the PEI increases. For PEls having a molecular weight of
at least 600, n is preferably at least 12, with a typical range of from 12 to
42. For PEls having a molecular weight of at least 1800, n is preferably at
least 24, with a typical range of from 24 to 42.
Typically, the compositions used according to the present invention comprise
from 0.01 % to 20% by weight of the total composition of such a soil
dispersing agent or mixtures thereof, preferably from 0.1% to 10%, more
preferably 0.2% to 4% and most preferably from 0.5% to 2%.
The liquid compositions used according to the process of the present
invention are preferably aqueous compositions. The compositions used in the
process herein have a pH of from 0 to 6, preferably from 1 to 5, and more
preferably from 2 to 5 and most preferably from 3 to 5. Acidic compositions
are preferred herein for stability reasons.
The compositions used according to the present invention may comprise
optional ingredients like bleach activators, surfactants, perfumes,
brighteners, chelating agents, radical scavengers, stabilisers, soil suspenders,dye transfer agents, solvents, dyes, other amines, or mixtures thereof.
Preferred optional ingredients are further described in more details
hereinafter.
The comoositions
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lB
The present invention also encompasses a liquid composition suitable for
pretreating fabrics, comprising a peroxygen bleach, a soil dispersing agent
selected from the group consisting of an ethoxylated monoamine, an
ethoxylated diamine, an ethoxylated polyamine, an ethoxylated amine
polymer and mixture thereof, as defined hereinbefore, and a surfactant, said
composition being formulated either as an emulsion or a microemulsion.
It is by adding such a soil dispersing agent in a liquid composition comprising
a peroxygen bleach, a surfactant and being formulated either as an emulsion
or a microemulsion, that not only improved stain removal performance is
obtained especially under pretreatment conditions, on various stains
including greasy stains, enzymatic stains, clay/mud stains as well as
improved bleaching performance but also desirable viscosity is achieved.
It has now been found that the soil dispersing agents according to the
present invention are easily processed in a composition being formulated
either as an emulsion or a microemulsion, while providing the appropriate
viscosity, i.e., the viscosity of said composition is reduced, whatever the
viscosity was before the addition of said soil dispersing agents into said
composition comprising a peroxygen bleach and a surfactant.
Any surfactant or a mixture thereof known to those skilled in the art are
suitable to be used in the compositions of the present invention being
formulated either as an emulsion or a microemulsion including anionic,
nonionic, cationic, amphotheric, zwitternionic surfactants at a level of from
0.01% to 50% by weight of the total composition, preferably from 1% to
30%, and more preferably from 2% to 20%.
Preferably a surfactant system is used in the compositions according to the
present invention comprising at least one hydrophilic surfactant and at least
one hydrophobic surfactant. Said two surfactants in order to form emulsions
or microemulsions which are stable preferably have different HLB values
(hydrophilic lipophilic balance) and typically the difference in value of the
HLBs of said two surfactants is at least 1, preferably at least 2 and most
preferably at least 3.
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By "hydrophobic surfactant" it is meant herein a surfactant having an HLB
up to 10 or mixtures thereof, preferably below 10, more preferably below 9.
Indeed, the hydrophobic surfactants to be used herein have excellent grease
cutting properties, i.e., they have a solvent effect which contributes to
hydrophobic soil removal.
By "hydrophilic surfactant" it is meant herein a surfactant having an HLB
above 10 or mixtures thereof, preferably above 10.5, and more preferably
above 11.
Typically, the compositions according to the present invention formulated
either as an emulsion or a microemulsion comprise from 1 % to 50 % by
weight of the total composition of said hydrophilic and hydrophobic
surfactants, more preferably from 5 % to 40 % and most preferably from 8
% to 30 %. The preferred compositions according to the present invention
comprise at least from 0.01 % by weight of the total composition of said
hydrophobic surfactant, or mixtures thereof, preferably at least 2 % and
more preferably at least 4 % and at least from 0.01 % by weight of the total
composition of said hydrophilic surfactant, or mixtures thereof, preferably at
least 2%, and more preferaL,ly at least 4%.
Accordingly, particularly preferred surfactants to be used in the compositions
according to the present invention are nonionic surfactants. Indeed, 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 essenlially 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 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.
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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 compositions
according to the present invention are surfactants having an HLB up to 10
and being according to the formula RO-(C2H40)n~C3H60)mH, wherein R is
a C6 to C22 alkyl chain or a C6 to C28 alkyl benzene chain, and wherein
n+m is from 0.5 to 5 and n is from O to 5 and m is from O to 5 and
preferably n+m is from 0.5 to 4.5 and, n and m are from O to 4.5. The
preferred R chains for use herein are the C8 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
C1 5 alkyl chains, n is 3 and m is 0), or Tergitol R 25L3 (HLB= 7.7; R is in
the range of C12 to C1 5 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 su, ractal~s 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 in the compositions
according to the present invention are surfactants having an HLB above 10
and being sccording to the formula RO-(C2H40)n(C3H60)mH, wherein R is a
C6 to C22 alkyl chain or a C6 to C28 alkyl benzene chain, and wherein n +m
is from 5 to 1 1 and n is from O to 1 1 and m is from O to 1 1, preferably n + mis from 6 to 10 and, n and m are from O to 10. Throughout this description n
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21
and m refer to the average degree of the ethoxylation/propoxylation. The
preferred R chains for use herein are the C8 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 C1 2 to C1 5 alkyl chains, n
is 7 and m is 0), or Dobanol R 45 7 (HLB=11.6; R is a mixture of C14 and
C1s 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 aikyl chains, n is 5 and m is 0), or Dobanol R 91-6
(HLB= 12.5; R is a mixture of Cg to C1 1 alkyl chains, n is 6 and m is 0), or
Dobanol R 91-8 (HLB= 13.7; R is a mixture of Cg to C1 1 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 further be used in the compositions of the present invention such as
polyhydroxy fatty acid amide surfactants, 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 Cs 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 8 alkyl or alkenyl, more preferably a straight chain C11-
C1g 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 include glucose, fructose, maltose, lactose,
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22
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 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 formthe 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.
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Other suitable hydrophilic surfactants to be used in the compositions herein
include the anionic surfactants and mixtures thereof.
Suitable anionic surfactants to be used 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 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-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 C1 2-16 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 C10-C24
alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a
C1 2-C20 alkyl or hydroxyalkyl, more preferably C1 2-C18 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and
about 3, and M is H or a cation which can be, for example, a metal cation
(e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl
propoxylated sulfates are contemplated herein. Specific examples of
substituted ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium cations, such as tetramethyl-
ammonium, dimethyl piperdinium and cations derived from alkanolamines
such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate,
C1 2-C1 gE(1 .O)M), C1 2-C1 8 alkyl polyethoxylate (2.25) sulfate, C1 2-
C1 gE(2.25)M), C1 2-C1 8 alkyl polyethoxylate (3.0) sulfate C1 2-C1 8E(3-0),
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and C12-C1g alkyl polyethoxylate (4.0) sulfate C12-C1gE~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 taurates, alkyl
succinamates and sulfosuccinates, monoesters of sulfos~ccinate (especially
saturated and unsaturated C12-C1g monoesters) diesters of sulfosuccinate
(especially saturated and unsaturated C6-C 14 diesters), sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of the formula
RO(CH2CH20)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer
from O 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 ll 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 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:
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J~N ~,OM
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 1 1 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 their salt or in their acidic form as powder.
Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly andcompletely 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. C 14 acyl sarcosinate is
commercially available, for example, as Hamposyl M-30~) supplied by
Hampshire .
It has been observed that further improved stain removal performance isachieved with a surfactant system comprising a hydrophilic nonionic
surfactant and a hydrophobic nonionic surfactant as well as a further
hydrophilic surfactant like a polyhydroxy fatty acid amide surfactant and/or
an alkyl ethoxylated sulphate.
The bleaching compositions of the present invention may further comprise
an amine oxide surfactant according to the formula R1 R2R3N0, wherein
each of R1, R2 and R3 is independently a C1-C30, preferably a C1-C20,
most preferably a C 1 -C 1 6 hydrocarbon chain .
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26
In the embodiment of the present invention where the compositions are
formulated as emulsions said compositions are opaques. In centrifugation
examination, it was observed that said emulsions herein showed no phase
separation after 1~ 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 are
formulated as microemulsions said compositions are macroscopically
transparent in the absence of opacifiers and dyes. 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, preferably below 2 micron diameter.
In a preferred embodiment of the emulsions of the present invention wherein
the emulsions further comprise a non-water soluble ingredient to emulsify
like a bleach activator as described hereinafter, the emulsifying system
meets the equation:
weight%A weight%B
HLB(X) = x HLB(A) + _ x HLB(B) and weight %A+ weight%B =
1 00%;
100 100
where HLB (X) refers to the HLB of the ingredient to emulsify, if several
inyle~iellts are present to emulsify X refers to all of them (weighted average
based on % of each ingredient in the formula), HLB (A) refers to the HLB of
the hydrophilic surfactant, or mixtures thereof, and HLB (B) refers to the HLB
of the hydrophobic surfactant, or mixtures thereof.
In a particularly preferred embodiment of the emulsions of the present
invention, wherein the emulsions may further comprise a bleach activator
like acetyl triethyl citrate, an adequate 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
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27
HLB of 15, such as a Dobanol R 91-10. Other suitable nonionic surfactant
systems comprise for example a Dobanol R 23-6.5 (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).
The bleaching compositions of the present invention formulated in the form
of emulsions or microemulsions are chemically stable. By "chemically stable"
it is meant herein that said compositions of the present invention comprising
a peroxygen bleach do not undergo more than 10% available oxygen loss at
50~C in 2 weeks. The concentration of available oxygen can be measured
by chemical titration methods known in the art, such as the iodimetric
method, the permanganometric method and the cerimetric method. Said
methods and the criteria for the choice of the appropriate method are
described for example in "Hydrogen Peroxide", W. C. Schumb, C. N.
Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York,
1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science,
1970. Alternatively, the stability of said compositions may also be evaluated
by a bulging test method.
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.
The liquid compositions of the present invention formulated either as an
emulsion or microemulsion are typically aqueous and are formulated in the
acidic pH range up to 6, preferably at a pH of from 1 to 5, more preferably of
from 2 to 5 and most preferably from 3 to 5. Formulating the compositions
of the present invention in the acidic pH range contributes to the stability of
said compositions. The pH of the compositions of the present invention can
be adjusted by using organic or inorganic acids.
O~tionals
The compositions of the present invention may further comprise optionalingredients like bleach activators, stabilisers, chelating agents, radical
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28
scavengers, builders, soil suspenders, dye transfer agents, solvents,
brighteners, perfumes, foam suppressors or dyes or mixtures thereof.
As an optional but highly preferred ingredient, the compositions of thepresent 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. Paticularly 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. Typically, such hydrophobic
bleach activators have a secondary HLB (hydrophilic lipophilic balance) below
11, preferably below 10. Secondary HLB is known to those skilled in the art
and is defined for example in "Emulsions theory and practice" by P. Becher,
Reinhold, ~lew York, 1957, or in "Emulsion science" by P. Sherman,
Academic Press, London, 1969.
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 used herein are tetracetyl ethylene diamine
(TAED), sodium 3,5,6 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 n-
nonanoyloxybenzenesulphonate (NOBS). Also suitable are N-acyl
caprolaclams 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
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29
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 20% by weight of the total composition of said bleach activator,
or mixtures thereof, preferably from 1% to 10%, and more preferably from
3% to 7%.
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. 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 amino phosphonate chelating agents to be used
herein are diethylene triamine penta 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 isaminotri(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- P~3H2
N
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P03tl2-CH2 CH2-P03H2
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. Ethylenediamine
N,N'- disuccinic acids, especially the (S,S) isomer have been extensively
described in US patent 4, 704, 233, November 3, 1987, to Hartman and
Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance, commercially
available under the tradename ssEDDS@) from Palmer Research Laboratories.
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 I R.R3R~
~NH ~
OH COOH R5 R6 ~J
Rl R2R3R4
wherein R 1, R2, R3, and R4 are independently selected from the group
consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C~O)R', and -
SO2R"; 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 Rs, R6, R7, and R8 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 preferredis 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, and/or 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.
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32
The compositions of the present invention may further comprise up to 20%,
preferably from 2% to 10% by weight of the total composition of a solvent
or mixtures thereof. More particularly, it has been found that the addition of
a solvent system comprising at least one hydrophobic solvent and at least
one hydrophilic solvent, in a liquid composition according to the present
invention, further contributes to the benefits of said composition, i.e., further
improves the overail stain removal performance on various type of stains
including greasy stains, enzymatic stains as well as bleachable stains.
Suitable hydrophobic solvents to be used herein include terpenes like mono-
and bicyclic monoterpenes, especially those of the hydrocarbon class, which
include the terpinenes, terpinolenes, limonenes and pinenes and mixtures
thereof. Highly preferred materials of this type are d-limonene, dipentene,
alpha-pinene and/or beta-pinene. Other hydrophobic solvents include all type
of paraffins, both linear and not, containing from 2 to 20 carbons, preferably
from 4 to 10, more preferably from 6 to 8. Preferred herein is octane.
Another hydrophobic solvent suitable to be used herein is benzyl alcohol.
Particularly preferred hydrophobic solvents to be used herein include d-
limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol, or
mixtures thereof.
Suitable hydrophilic solvents to be used herein include alkoxylated aliphatic
alcohols like methoxy propanol, ethoxy propanol, propoxy propanol, buthoxy
propanol as well as alkoxylated glycols like ethoxy-ethoxy-ethanol, aliphatic
or aromatic alcohols like ethanol, propanol, as well as glycols like
propanediol or mixtures thereof.
Any polymeric soil release agent known to those skilled in the art can
optionally be employed in the compositions and processes of this invention.
Polymeric soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic 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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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 àt 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-C6 alkylene or oxy C4-C6 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 derivativesare amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether
and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester
synthetic fiber surfaces and retain a sufficient level of hydroxyls, once
adhered to such conventional synthetic fiber surface, to increase fiber
surface hydrophilicity, or a combination of (a) and (b).
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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-C6 alkylene hydrophobe segments include, but are not
limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-, where M is sodium and n is an integer from 4-6,
as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric
blocks of ethylene terephthalate or propylene terephthalate with polyethylene
oxide or polypropylene oxide terephthalate, and the like. Such agents are
commercially available and include hydroxyethers of cellulose such as
METHOCEL (Dow). Cellulosic soil release agents for use herein also include
those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl
cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
Soil reiease agents characterized by poly(vinyl ester) hydrophobe segments
include graft copolymers of poly(vinyl ester), e.g ., C 1 -C6 vinyl esters,
preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application O
219 048, published April 22, 1987 by Kud, et al. Commercially available
soil release agents of this kind include the SOKALAN type of material, e.g.,
SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having random blocks
of ~ethylene terephthalate and polyethylene oxide (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
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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 polyrner include
the commercially available material ZELCON 5126 (from Dupont) and
MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27,
1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties
covalently attached to the backbone. These soil release agents are
described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents
include the terephthalate polyesters of U.S. Patent 4,711,730, issued
December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580, issued 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, especi.qlly 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,
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and mixtures thereof. See U.S. Pat. No. 5,415,807, issued May 16, 1995,
to Gosselink et al.
If utilized, soil release agents will generally comprise from about 0.01% to
about 10.0%, by weight, of the detergent compositions herein, typically
from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
The compositions of the present invention may also include one or more
materials effective for inhibiting the transfer of dyes from one dyed surface
to another during the cleaning process. Generally, such dye transfer
inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. 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-0 group can be attached or the N-0 group
can form part of the polymerizable unit or the N-0 group can be attached to
both units; A is one of the following structures: -NC~0)-, -C(0)0-, -S-, -0-, -
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-0 group can be attached or the N-0 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-0 group can be represented by the following general structures:
O O
(Rl)X--N--(R2)y; N--(RI)x
(R3)z
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wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-0
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 copolymers where one monomer
type is an amine N-oxide and the other monomer type is an N-oxide. The
amine N-oxide polymers typically have a ratio of amine to the amine N-oxide
of 10:1 to 1 :1 ,000,000. However, the number of amine oxide groups
present in the polyamine oxide polymer can be varied by appropriate
copolymerization or by an appropriate degree of N-oxidation. The polyamine
oxides can be obtained in almost any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more
preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This
preferred class of materials can be referred to as "PVN0". The most
preferred polyamine N-oxide useful in the detergent compositions herein is
poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-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 Analvsis. Vol 1 13.
"Modern Methods of Polymer Characterization", the disclosures of which are
incorporated herein by reference.) The PVPVI copolymers typically have a
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1, more
preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These
copolymers can be either linear or branched.
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The present invention compositions 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 C1o-C16 alkanolamides can
be incorporated into the compositions, typically at 1%-10% levels. The
C1o-C14 monoethanol and diethanol amides illustrate a typical class of such
suds boosters. Use of such suds boosters with high sudsing adiunct
surfactants such as the amine oxides, betaines and sultaines noted above is
also advantageous. If desired, soluble magnesium salts such as MgCI2,
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 13rightening Agents", M.
Zahradnik, Published by John Wiley & Sons, New York (1982).
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Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon
on December 13, 1988. These brighteners include the PHORWHITE series
of brighteners from Verona. Other brighteners disclosed in this reference
include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-
Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[1,2-dltriazoles; 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
February 29, 1972 to Hamilton. Anionic brighteners are typically preferred
herein .
Although the preferred application of the compositions described herein is
laundry pretreatment as described hereinbefore, the compositions of the
present invention may also be used as a laundry detergent or as a laundry
detergent booster and as a household cleaner in the bathroom or in the
kitchen.
The compositions of the present invention suitable for pretreating fabrics can
be packaged in a variety of containers including conventional bottles, bottles
equipped with roll-on, sponge, brusher or sprayers.
The present invention will be further illustrated by the following examples.
ExamDles
The following compositions were made by mixing the listed ingredients in
the listed proportions (weight % unless otherwise specified).
.
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Compositions I ll lll IV V Vl
Dobanol(~) 45-7 6.4 6.4 6.4 1.5 12.0 6.0
Dobanol@) 23-3 8.6 8.6 8.6 - - 6.0
Dobanol(~ 23-6.5 - - - 1.5
C25-AE-2.5-S 4.0 4.0 4.0 1.5 12.0 6.0
Alkyl glucose amide 2.0 2.0 2.0
ATC* 3-5 3-5 3-5 ~ 3-5
H2~2 4.0 4.0 4.0 - 6.0 4.0
Dilauroyl peroxide 0.5 - - 1.0 - 2.0
Ethoxylated 15-18
tetraethylenepentamine 0.5 0.5 0.5 0.2 1.0 0.7
Limonene D(+) - - 0.5 0.1 0.5 1.0
Benzoyl alcohol - - 2.0 1.0
1-methoxy-2 propanol - - 5.0 - 2.0 3.0
ATMP** 0.2 0.1 - - 0.16
Water and minors up to 100",~-
H2S04 up to pH 4
* ATC is acetyl triethyl citrate.
Dobanol (~) 23-3 is a C12-C13 nonionic ethoxylated surfactant with HLB of
8.1 .
Dobanol ~ 23-6.5 is a C12-C13 nonionic ethoxylated surfactant with HLB of
11.9.
~obanol ~) 45-7 is a C14-C15 nonionic ethoxylated surfactant with HLB of
1 1 .6.
**ATMP is aminotri~methylene phosphonic acid).
Excellent stain removal performance is obtained on a variety of stains
including greasy/oily stains like clay, dirty motor oil, make-up, lipstick,
carotenoid-type stains like spaghetti sauce, bleachable stains like tea and
enzymatic stains like grass, blood, when pretreating soiled fabrics with any
of the compositions I to Vl, as described above, e.g., when leaving such a
composition to act onto the fabrics for a contact period of about 5 minutes,
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before rinsing said fabrics with water or washing with a conventional
detergent composition like Tide~) powder at a dilution level of, for example,
1 to 400.
