Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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LIQUID AQUEOUS BLEACHING COMPOSITIONS
AND PRETREATMENT PROCESS
15
Technical field
The present invention relates to liquid acidic aqueous bleaching
compositions particularly suitable to be used as a pretreater and to a
process of pretreating fabrics.
Background
A great variety of liquid aqueous cleaning compositions have been described
in the art, that are particularly suitable for pretreating fabrics.
A problem associated with common liquid aqueous cleaning compositions,
especially those containing a peroxygen bleach, when used to pretreat
different kinds of fabrics, including cotton and synthetic fabrics such as
polyesters, polyamides and the like, is that they do not deliver an effective
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2
performance satisfactorily meeting consumer's needs, on afi types of stains
including greasy stains, enzymatic stains, mudlclay stains and the like. Also
it has been found that a problem with such liquid peroxygen bleach-
containing compositions is that despite the tendency of the peroxygen
bleach to migrate to the fabric surface, it does not necessarily interact
fully
with the bleachabfe stain or soil components. It has been found that the
peroxygen bleaches can be prevented from migration onto bleachable
stains/soils (such as peat stains) by deposition on the fabric of other active
ingredients that may be present in such a liquid peroxygen bleach-containing
1 o composition such as clay-soil particulates on the fabric. Thereby, their
bleaching performance can be diminished. This results in a lessening of the
bleachable/ dingy soil cleaning performance of the peroxygen bleach.
It is thus an object of the present invention to provide improved stain
~ 5 removal performance on a wide range of stains as well as excellent
bleaching performance, especially under laundry pretreatment conditions,
i.e., when applying a liquid aqueous composition neat onto at least a portion
of a soiled fabric before washing said fabric.
2o Also suitable ingredients to be used in a liquid aqueous peroxygen bleach-
containing composition must be selected such that they are suitable for
imparting the desirable stain removal performance to such a composition.
However, the use of such ingredients must not lead to an unacceptable
degree of chemical stability.
Given the foregoing, there is clearly a continuing need to identify and
provide liquid aqueous peroxygen bleach-containing compositions, suitable
for pretreating fabrics, that have a commercially acceptable chemical
stability along with an excellent overall stain removal performance and
3o bleaching performance.
It has now been found that improved stain removal performance is
obtained, by using an aqueous composition being formulated in the acidic
pH range at a pH below 6, and comprising a peroxygen bleach and a soil
suspending agent selected from the group consisting of an ethoxylated
cationic diamine, an ethoxylated cationic polyamine, an ethoxylated cationic
amine polymer and mixture thereof, as described hereinafter, to pretreat
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soiled fabrics, while maintaining adequate chemical stability. Indeed, it has
now been found that the soil suspending agents, as defined herein, are
easily processed in the acidic aqueous compositions according to the
present invention comprising a peroxygen bleach with a reduced impact on
the chemical stability properties of said compositions. In other words, the
specific soil suspending agents, as defined herein, are fully compatible with
peroxygen bleaches in acidic medium.
Indeed, the acidic aqueous compositions of the present invention comprising
a peroxygen bleach and a soil suspending agent, as defined herein, deliver
improved stain removal performance on various types of stains including
greasy stains, enzymatic stains, clay/mud stains, and the like, under laundry
pretreatment conditions, as compared to the stain removal performance
delivered by the same compositions without said soil suspending agent.
Also, it has surprisingly been found that the acidic aqueous compositions
comprising both the peroxygen bleach and said soil suspending agent, when
used to pretreat fabrics, provide improved bleaching efficacy, as compared
to the same compositions without said soil suspending agent. Thus, it has
been found that the addition of a single compound, i.e., such a soil
2o suspending agent, in an acidic aqueous peroxygen bleach-containing
composition, delivers both improved stain removal performance and
improved bleaching performance. Furthermore, it has been found that this
improved stain removal performance on various stains and improved
bleaching performance is maintained even for acidic aqueous peroxygen
25 bleach-containing compositions having undergone long storage periods.
An advantage of the present invention is that chemically and physically
stable acidic aqueous compositions are provided that are suitable to be used
in the most efficient manner by the consumer over prolonged period of time.
Furthermore, it has been found that in a preferred embodiment of the
present invention, the acidic aqueous compositions herein may be
formulated either as an emulsion or microemulsion, without the need for
modifying the Theology of the compositions. Indeed, it has been found that
said soil suspending agent reduces the viscosity of an acidic aqueous
composition herein comprising a peroxygen bleach, whatever the viscosity
was before the addition. of said soil suspending agent.
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4
Background art
EP-A-271 312 discloses laundry compositions comprising a peroxyacid
bleach and a soil release agent tike particular alkyl and hydroxyalkyl ethers
of cellulose, polymers comprising ethylene terephthalate and polyethylene
oxide terephthaiate. No ethoxylated cationic diamines, ethoxylated cationic
polyamines, ethoxylated cationic polymers are disclosed.
US 4 659 802 discloses detergent compositions comprising ethoxylated
cationic diamines, ethoxylated cationic polyamines and/or ethoxylated
cationic polymers as a clay soil removal/antiredeposition agent. No
peroxygen bleaches are disclosed.
~ 5 EP-A-1 1 1 965 discloses detergent compositions (pH = 6 to 8.5) comprising
ethoxylated cationic mono- or diamines, ethoxylated cationic polyamines
and/or ethoxylated cationic polymers as a clay soil removal/antiredeposition
agent. No peroxygen bleaches are disclosed.
20 Summary of the invention
The present invention encompasses a liquid aqueous composition suitable
for pretreating fabrics, having a ph below 6 and comprising a peroxygen
bleach, and a soil suspending agent selected from the group consisting of:
25 1 ) ethoxylated cationic diamines having the formula:
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~R3 )d R3 ~R3 )d R3
X-L-M1-R1 ~N+-L~ X or R3-M1- Rl ~N+-R or
i / ~
L L L L L
i
X X X X X
~R3~d
L-~Z-M2-RI-M2- R2
R2
wherein M ~ is an N + or N group; each M2 is an N + or N group, and
at least one M2 is an N + group;
5
2) ethoxylated cationic polyamines having the formula:
(R3)d
R4 UAl)q (RS)t-M2.-L-~P
i2
R
3) ethoxylated cationic polymers which comprises a polymer backbone,
at least 2M groups and at least one L-X group, wherein M is a cationic
group attached to or integral with the backbone; X is a nonionic group
selected from the group consisting of H, C ~ -C4 alkyl or hydroxyalkyl
ester or ether groups, and mixtures thereof; and L is a hydrophilic chain
~ 5 connecting groups M and X or connecting X to the polymer backbone,
41 mixtures thereof;
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O O O O O
;. ;,
wherein A1 is-NC-, NCO-, NCN-, CN-, OCN-,
R R R R R R
O O O O O
i~ ~~ ;, ,
CO-, OCO-, OC-, CNC or O-,
R
R is H or C 1-Cq. alkyl or hydroxyalkyl, R 1 is C2-C 12 alkylene,
hydroxyalkylene, alkenylene, aryfene or alkaryiene, or a C2-Cg
oxyalkylene moiety having from 2 to about 20 oxyalkytene units
provided that no O-N bonds are formed; each R2 is C 1-C4 alkyl or
hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -
(CH2)r-A2-(CH2)S-, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2
and r + s is 3 or 4; each R3 is G1-Cg alkyl or hydroxyalkyl, benzyl, the
1 o moiety L-X, or two R3 or one R2 and one R3 together form the moiety
(CH2)r-A2-(CH2)S-; R4 is a substituted Cg-C12 alkyl) hydroxyalkyl,
' alkenyl, aryl or alkaryl group having p substitution sites; R5 is C 1-C 12
alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-Cg
oxyalkyiene moiety having from 2 to about 20 oxyalkylene units
~ 5 provided that no O-0 or O-N bonds are formed; X is a nonionic group
selected from the group consisting of H, C 1-C,q, alkyl or ~hydroxyalkyl
ester or ether groups, and mixtures thereof; L is a hydrophilic chain
which contains the polyoxyalkyiene moiety -I(R60),y~(CH2CH20)n~-%
wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are
20 numbers such that the moiety -(CH2CH20)~- comprises at least about
50~yb by weight of said polyoxyalkylene moiety; d is 1 when M2 is N +
and is 0 when M2 is N; n is at least 6 for said cationic diamines and is
at least 3 for said cationic poiyamines and cationic polymers; 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
The present invention also encompasses a process of bleaching a soiled
fabric with a liquid acidic aqueous composition as defined herein before,
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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.
Detailed description of the invention
The COmpOSItIOnS
The present invention encompasses a liquid acidic aqueous composition
suitable for pretreating fabrics, comprising a peroxygen bleach, and a soil
suspending agent selected from the group consisting of an ethoxylated
cationic diamine, an ethoxylated cationic polyamine, an ethoxylated cationic
amine polymer and mixture thereof, as defined hereinbefore.
The addition of such a soil suspending agent in a liquid acidic aqueous
~ 5 composition comprising a peroxygen bleach, provides improved stain
removal performance especially under laundry pretreatment conditions, on
various stains including greasy stains, enzymatic stains, clay/mud stains as
well as improved bleaching performance while maintaining adequate
chemical stability.
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 (particulate 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 enzymatic stains
include grass, chocolate and blood.
Three mechanisms ace believed to be responsible for the unexpected
3o benefits, i.e., improved stain removal and bleaching performance. Firstly,
the peroxygen bleach is surface active, especially on organic material
containing surfaces, and will thus migrate to the fabric surface. It will then
be capable of removing organic bleachable material from the surface.
Secondly, the soil suspending agent can interact with the negatively
charged soils on the fabric surface, thereby neutralising the fabric surface.
This will facilitate the migration of the peroxygen bleaches to the fabric
surface. Thirdly, the soil suspending agent is capable of removing and
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suspending soils like greasy soil, particulate soil (mud/clay? and/or
enzymatic soil deposited on the fabric surface, thereby facilitating the
partition of the peroxygen bleaches into bleachable stains/soils on the
fabric.
The soil suspending agents herein are fully compatible with peroxygen
bleaches. Without wishing to be bound by theory, the bleach-compatibility
of the soil suspending agents herein can be explained as follows. The
quaternization of the nitrogen groups of these molecules is believed to have
0 a dual purpose. It provides a cationic charge on the molecule, improving
adsorption onto stains/particles like clay on the fabric surface, and it
removes the oxidisable lone pair on the nitrogen groups from attack by
bleaching species, thus making the molecule stable in an aqueous
peroxygen bleach containing composition. Also, the soil suspending agents
~ 5 herein are fully compatible with acidic medium.
The aqueous bleaching compositions of the present invention 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
20 than 20% 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.
25 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.
3o The bleaching compositions of the present invention are physically stable.
By "physically stable" it is meant herein that the compositions of the
present invention do not split in two or more phases when exposed in
stressed conditions, e.g., at a temperature of 40 ~C during 2 weeks.
35 The compositions according to the present invention are aqueous, thus they
comprise from 50% to 98% by weight of the total composition of water,
preferably from 50% to 95% and more preferably from 55% to 90%.
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9
As an essential element the compositions according to the 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 thereaf. 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.
~o
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,
~ 5 hydroperoxides, diacyl peroxides and mixtures thereof. Preferred peroxygen
bleaches used herein are hydrogen peroxide, hydroperoxide and/or aliphatic
diacyl peroxide.
Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl
2o hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-
monohydroperoxide, tent-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.
25 Suitable aliphatic diacyl peroxides for use herein ace dilauroyi 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 according to the present invention comprise from 0.01
3o 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 according to the present invention
comprise a soil suspending agent selected from the group consisting of
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ethoxylated cationic diamines, ethoxylated cationic polyamines, ethoxylated
cationic amine polymers, as previously defined and mixtures thereof.
in the preceding formulas for the cationic amines, R1 can be branched
5 (e. g.
CH3
-CH2-CH , CH2-CH-);
C3
cyclic (e.g. ),
or must preferably linear
(e, g. - CH2CH2 - , - CH2CH2 - CH2 - )
alkytene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R 1 is
preferably C2-Cg alkylene for the ethoxylated cationic diamines. Each R2 is
preferably methyl or the moiety -L-X; each R3 is preferably C ~ -Cq, alkyl or
hydroxyatkyl, and most preferably methyl.
The positive charge of the N + groups is offset by the appropriate number
of counter anions. Suitable counter anions include C1-, Br-, S03-2, P04-2.
MeOS03- and the tike. Particularly preferred counter anions ace C1- and Br-
X can be a nonionic group selected from hydrogen (H), C 1-C4 alkyl or
hydroxyalkyl ester or ether groups, or mixtures thereof. Preferred esters or
ethers are the acetate ester and methyl ether, respectively. The particularly
preferred nonionic groups are H and the methyl ether.
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In the preceding formulas, hydrophilic chain L usually consists entirely of
the
polyoxyalkylene moiety -[(R60),n(CHZCH2_0~)-1. The moieties -(R60)m- and -
(CH2CH20)n- of the polyoxyalkylene moiety can be mixed together or
preferably form blocks of -(R60),~.~- and -(CH2CH201~- moieties. R6 is
preferably C3Hg (propylene); m is preferably from 0 to about 5 and is most
preferably 0, i.e. the poiyoxyalkylene moiety consists entirely of the moiety -
(CH2CH20)~-. The moiety -(CH2CH201~- preferably comprises at least about
85~~ by weight of the polyoxyalkylene moiety and most preferably 100% by
weight (m is 0).
In the preceding formulas, M 1 and each M2 are preferably an N + group for
the cationic diamines and polyamines.
~ 5 Preferred ethoxylated cationic diamines have the formula:
CH3 CH3
X-(-OCH CH N+-CH -CH CH N+-CH CH O-3-X
2 2~n I 2 2 ~ 2~a b 2 2
(CH2CH20 ~ X (CHZCH20 ~ X
wherein X and n are defined as before, a is from 0 to 4 (e.g. ethylene,
2o propylene, hexamethylene) b is 1. For preferred cationic diamines, n is at
least about 12 with a typical range of from about 12 to about 42.
In the preceding formula for the ethoxylated cationic polyamines, R4 (linear,
branched, or cyclic) is preferably a substituted Cg-Cg alkyl, hydroxyalkyl or
aryl group; A 1 is preferably
O
CN-;
I
25 H
n is preferably at least about 12, with a typical range of from about 12 to
about 42; p is preferably from 3 to 6. When R4 is a substituted aryl or
aikaryl group, q is preferably 1 and R5 is preferably C2-Cg alkylene. When
R4 is a substituted alkyl, hydroxyalkyl, or alkenyl group, and when q is 0,
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R5 is preferably a C2-C3 oxyaikylene moiety; when q is 1, R5 is preferably
C2-C3 alkylene.
These ethoxyiated cationic polyamines can be derived from polyamino
amides such as:
O
CN-f-C3H6-j-NH2
i H
~o o
HO ;-CN--f-C3H6~--NH2 or ~ CN(C3H6--~--NH2
H H
'O 3
~- CN --~ C H --~- NH
3 6 2
H
These ethoxylated cationic polyamines can also be derived from
polyaminopropyleneoxide derivatives such as:
~OC3H6}c ~2
CH3 ~ (OC3H6)c -NH2
~ o '~OC3H6)c - NH2
wherein each c is a number from 2 to about 20.
The water soluble cationic polymers of the present invention comprises a
polymer backbone, at least 2M groups and at least one L-X group, wherein
~ 5 M is a cationic group attached to or integral with the backbone; X is a
nonionic group selected from the group consisting of H, C 1 -C4 alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a
hydrophilic chain connecting groups M and X or connecting X to the
polymer bac kbone.
2o
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As used herein, the term "polymer backbone" refers to the polymeric moiety
to which groups M and L-X are attached or are integral with. Included
within this term are oligomer backbones (2 to 4 units), and true polymer
backbones ~5 or more units).
As used herein, the term "attached to " means that the group is pendent
from the polymer backbone, examples of such attachment being
represented by the following general structures A and B:
a
M M L
i f
L X
X
A B
io
As used herein, the term "integral with" means that the group forms part of
the polymer backbone, examples of which are represented by the following
general structures C and D:
M - M --T-
L L
X X
C D
Any polymer backbone can be used as long as the cationic polymer formed '
is water-soluble and has soil removai/anti-redeposition properties. Suitable
polymer backbones can be derived from the polyurethanes, the polyesters,
the polyethers, the polyamides, the polyimides and the tike, the
2o polyacrylates, the polyacrylamides, the polyvinylethers, the polyethylenes,
the polypropylenes and like polyaikylenes, the polystyrenes and like
polyalkarylenes, the polyalkyleneamines, the polyalkyleneimines, the
polyvinylamines, the polyalylamines, the polydiallylamines, the
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polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the
aminopolyureylenes, and mixtures thereof.
M can be any compatible cationic group which comprises an N +
(quarternary), positively charged center. The quarternary positively charged
center can be represented by the following general structures E and F:
+I ~ +
N N
E F
o Particularly preferred M groups are those containing a quarternary center
represented by general structure E. The cationic group is preferably
positioned close to or integral with the polymer backbone.
The positive charge of the N + centres is offset by the appropriate number
~5 of counter anions. Suitable counter anions include C1-, Br-, S032-, S042-,
P042-, MeOS03- and the like. Particularly preferred counter anions are C1-
and Br-)
X can be a nonionic group selected from hydrogen f H), C 1-C4 alkyl or
2o hydroxyalkyi ester or ether groups, and mixtures thereof. The preferred
ester or ether groups are the acetate ester and methyl ether, respectively;
The particularly preferred nonionic groups are H and the methyl ether,
The cationic polymers suitable for use in compositions in accord with the
25 present inventions normally have a ratio of cationic groups M to nonionic
groups X of from about 1:1 to about 1:2. However, for example, by
appropriate copolymerization of cationic, nonionic (i.e. containing the group
L-X), and mixed cationiclnonionic monomers, the ratio of cationic groups M
to nonionic groups X can be varied. The ratio of groups M to groups X can
3o usually range from about 2:1 to about 1:10. in preferred cationic polymers,
the ratio is from about 1:1 to about 1:5. The polymers formed from such
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copolymerization are typically random, i.e. the cationic, nonionic and mixed
cationc/nonionic monomers copolymerize in a nonrepeating sequence.
The units which contain groups M and groups L-X can comprise 100% of
5 the cationic polymers of the present invention. However, inclusion of other
units (preferably nonionic) in the polymers is also permissible. Examples of
other units include acryiamides, vinyl ethers and those containing
unquaternized tertiary amine groups (M 1 ) containing an N centre. These
other units can comprise from 0% to about 90% of the polymer (from
about 10% to 100% of the polymer being units containing M and L-X
groups, including M 1-L-X groups). Normally, these other units comprise
from 0% to about 50% of the polymer (from about 50% to 100% of the
polymer being units containing M and L-X groups).
~ 5 The number of groups M and L-X each usually ranges from about 2 to about
200. Typically the number of groups M and L-X are each from about 3 to
about 100. Preferably, the number of groups M and L-X are each from
about 3 to about 40.
2o Other than moieties for connecting groups M and X, or for attachment to
. the polymer backbone, hydrophilic chain L usually consists entirely of the
polyoxyalkylene moiety -((R'O),n(CH2CH20)~]-. The moieties -(R'O),n- and
-(CH2CH20)~- of the polyoxyalkylene moiety can be mixed together, or
preferably form blocks of -(R'O),n- and -(CH2CH20)~- moieties. R' is
preferably C3Hg (propylene); m is preferably from 0 to 5, and most
preferably 0; i.e. the polyoxyalkylene moiety consists entirely of the moiety-
(CH2CH20)~-. The moiety -(CH2CH20)~- preferably comprises at least
about 85% by weight of the polyoxyalkylene moiety, and most preferably
100% by weight (m is 0). For the moiety -(CH2CH20)n-, n is usually from
3 to 100. Preferably, n is from 12 to 42.
A plurality (2 or more) of moieties -L-X can also be hooked together and
attached to group M or to the polymer backbone, examples of which are
represented by the following general structures G and H:
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M
I
i
i
L L
i I L L
X x
X X
G H
Structures such as G and H can be formed, for example, by reacting
giycidoi with group M or with the polymer backbone) and ethoxylating the
subsequently formed hydroxy groups.
Representative classes of cationic polymers of the present invention are as
follows:
o A. Polyurethane, Polyester, Polyether, Polyamide or like Polymers.
One class of suitable cationic polymers are derived from polyurethanes,
polyesters, polyethers, polyamides and the like. These polymers comprise
units selected from those having formulas I, II and III;
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R4 I
~A1 ~R1-A1~ -R2~N+.-R3
x
x
(RS)k [(C3H60)m(CH2CI-I20)n] - X
( ~R62~k
I_~A1-Rl-AI~X-R2-N+-R3 II
L
Y
R~ III
~A1-R1-A1~ -R2-C R3
x
(RS)k [(C3H60)m(CH2CH20)nJ - X
wherein A 1 is
O O O O O
~~ t
NC-,-CN-,-CO-,-OC or C ;
R R
X is 0 or 1; R is H or C 1-Cq, alkyl or hydroxyalkyl; R ~ is C2-C 12 alkylene,
hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-
C3 oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided
that no O-0 or O-N bonds are formed with A 1; when x is 1 ( R2 is -R5-
except when A 1 is
O
C ,
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or is -(OR8)Y or -OR5- provided that no O-O or N-O bonds are formed with
A 1, and R3 is -R5- except when A 1 is
O
C
or is -(R80)-y or -R50- provided that no 0-O or O-N bonds are formed with
A1; when x is 0, R2 is
(ORg) OR I I OR i ~ O I ~ RS ., ~ - O i RS~
I
O O O
I IRS-,- i ioRS-,-iI~S-, or ocrrRS ,
RO RO OR OI R
io
and R3 is -R5-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R5)k-
[(C3Hg0),n(CH2CH201~1-X; R5 is C1-C12 alkylene, hydroxyalkylene,
.alkenylene, arylene, or alkarylene; each R6 is C 1 _C4 alkyl or hydroxyalkyl,
or the moiety -(CH2)~AZ-(CH2)s-, wherein A2 is -O- or -CH2-; R~ is H or
t 5 R4; R8 is C2-C3 alkylene or hydroxyalkylene; X is H)
O
CR9,
20 -R9 or a mixture thereof, wherein R9 is C 1-C4 alkyl or hydoxyalkyl; k is 0
or 1; m and n are numbers such that the moiety -(CH2CH20)~- comprises
at least about 85~r6 by weight of the moiety -[(C3Hg0),n(CH2CH20)~)-; m
is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r +
s
is 3 or 4; y is from 2 to about 20; the number of u, v and w are such that
25 there are at least 2 N + centers and at least 2 X groups.
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In the above formulas, A1 is preferably
O O
I~
NC or CN ;
R R
A2 is preferably -O-; x is preferably 1; and R is preferably H. R1 can be
linear (e.g. -CH2-CH2-CH2-,
CH3
CH2 CH - ) or branched (e. g. - CH2 - CH - , CH2 CH - )
I
CH3 I
alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or
oxyalkylene; when R1 is a C2-C3 oxyalkylene moiety, the number of
oxyalkylene units is preferably from about 2 to about 12; R 1 is preferably
C2-Cg alkylene or phenylene, and most preferably C2-Cg alkylene (e.g.
ethylene, propylene, hexamethylene). R2 is preferably -OR5- or -(OR8)r;
~ 5 R3 is preferably -R50- or -(OR8)y-; R4 and Rs are preferably methyl. Like
R1 ( R5 can be linear or branched) and is preferably C2-C3 alkylene; R~ is
preferably H or C1-C3 alkyl; Rg is preferably ethylene; R9 is preferably
methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0, r
and s are each preferably 2; y is preferably from 2 to about 12.
In the above formulas, n is preferably at least about 6 when the number of
N + centers and X groups is 2 or 3; n is most preferably at least about 12,
with a typical range of about 12 to about 42 for all ranges of a + v + w.
For homopolymers (v and w are 0), a is .preferably from about 3 to about
20. For random copolymers (u is at least 1 or preferably 0), v and w are
each preferably from about 3 to about 40.
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B. Polyacrylate, Polyacrylamide, Polyvinylether or like Polymers
Another class of suitable cationic polymers are derived from polyacrylates,
polyacrylamides, polyvinylethers and the like. These polymers comprise
5 units selected from those having formulas IV, V and VI.
~R1
(AI).1
(R2).1
(R3)2 - ~ - (R2)k - UC3H60)m(CH2CH20)n] - X
IV
R1 -~ 1
(A1)v L R
J
I ~A1 ).1
(R2)kUC3H60)~(CH2CH20)n] - X (R2)~\
(R )3
V VI
0 0 00 0
II ;l il ai II
wherein Al is-O-,-NC-,-NCO-,-CNC-,-CN-,
R R R R
O O O O O
II II ~I I~ II
OCN OC-,-OCO-,-CO-,or i CN-;
R R R
R is H or C ~ -C4 alkyl or hydroxyalkyl; R I is substituted C2-C ~ 2 alkylene,
hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene;
each R2 is C 3 -C ~ 2 alkylene, hydroxyalkylene, alkenylene, arylene or
alkarylene; each R3 is C ~ -C4 alkyl or hydroxyalkyl, the moiety -(R2)k-
I(C3Hg0)m/CH2CH201~]-X, or together form the moiety -(CH21rA2_
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21
tCH2)S-, wherein A2 is -O- or -CH2-; each R4 is C1-Cq, alkyl or
hydroxyalkyl, or two R4 together form the moiety -ICH2),-A2-tCH2)S-; X is
H,
O
CRS,
-R5 or mixture thereof, wherein R5 is C 1-Cq. alkyl or hydroxalkyl; j is 1 or
0; k is 1 or 0; m and n are numbers such that the moiety -(CH2CH201~-
comprises at least about 85% by weight of the moiety
itC3Hg0),~.~tCHZCH201~)-; m is from 0 to about 5; n is at least about 3; r
is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number of u, v and w are such
that there are at least 2N + centres and at least 2 X groups.
In the above formulas, A 1 is preferably
O O
CN , CO or O-;
R
A2 is preferably -O-; R is preferably H. R1 can be linear
(e.g.-CHZ-CH-CH2-,-CH2CH-) or
CH3
branched (e. g. - CH2 - C - , - CH2 i H - ,
CH3
CH
CH2 i -, - CH2 i - )
~ CH2
I
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22
substituted alkylene, hydroxyalkylene, alkenylene, aikarylene or oxyalkylene;
R~ is preferably substituted C2-Cg alkylene or substituted C2-C3
oxyalkylene) and most preferably
CH3
CH2CH-or-CH2-C
r
Each R2 is preferably C2-C3 atkylene, each R3 and R4 are preferably
methyl; R5 is preferably methyl; X is preferably H or methyl; j is preferably
1; k is preferably 0; m is preferably 0; r and s are each preferably 2.
0
In the above formulas, n, u, v and w can be varied according to the n, u, v
and w for the polyurethane and like polymers.
C. Polyalkyleneamine, Polyalkyleneimine or like polymers.
Another class of suitable cationic polymers are derived from
polyalkyleneamines, polyalkyleneimines and the like. These polymers
comprise units selected from those having formulas VII and V111 and IX.
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23
(RZ)d
{R1-M
x
{R2)d
{R1 V M,
Y
{R3)k [(C3H60)m(CH2CH20)n)-X
{R2)d
(R1-M,
z
{R3~ [(C3H60)m(CH2CH20)nJ-X
wherein R 1 is C2-C 12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene,
arylene or alkarylene, or a C2-Cg oxyalkylene moiety having from 2 to about
20 oxyalkyiene units provided that no O-N bonds are formed; each R2 is
C 1-C4 alkyl or hydroxyalkyl, or the moiety -tR3)k-[(C3Hg0),r,tCH2CH20)~)-
X; R3 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or
alkarylene; M' is an N + or N centre; X is H,
CR4,
O
-R4 or mixture thereof, wherein R4 is C 1-C4 alkyl or hydroxyalkyl; d is 1
when M' is N + and is 0 when M' is N; a is 2 when M' is N + and is 1
when M' is N; k is 1 or 0; m and n are numbers such that the moiety
-(CH2CH20)~- comprises at least about 85% by weight of the moiety
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24
-[(C3HgOl,n(CH2CH201~]-; m is from 0 to about 5; n is at least about 3;
the number of x, y and z are such that there are at least 2M' groups, at
least 2N + centres and at least 2 X groups.
In the above formulas, R 1 can be varied like R 1 of the polyurethane and like
polymers; each R2 is preferably methyl or the moiety -(R3)k-
[(C3H60),~.r(CH2CH20)~)-X; R3 is preferably C2-C3 alkylene; R4 is
preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
In the above formulas, n is preferably at least about 6 when the number of
M' and X groups is 2 or 3; n is most preferably at least about 12, with a
typical range of from about 12 to about 42 for all ranges of x + y + z.
Typically, x + y + z is from 2 to about 40 and preferably from 2 to about
20. For short chain length polymers, x + y + z can range from 2 to 9 with
from 2 to 9 N + centres and from 2 to 1 1 X groups. For long chain length
polymers, x + y + z is at least 10, with a preferred range of from 10 to
about 42. For the short and long chain length polymers, the M' groups are
typically a mixture of from about 50 to 100% N + centres and from 0 to
about 50% N centres.
Preferred cationic polymers within this class are derived from the C2-C3
poiyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x +
y + z is at least 10, preferably from 10 to about 42). Particularly preferred
cationic polyalkyleneamines and polyalkyleneimines are the cationic
polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred
cationic polymers comprise units having the general formula:
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(R2)d ~2)d
[M~]a [CH2 - CHUM']x_
[(CH2CHZ0 ']n- X]2
(R2)d (R2)d
I I
[CHZCH2M']y [CH2CH2M']Z
(CH2CH20)n- X [(CH2CH20)n- X]2
wherein R2 (preferably methyl), M', X, d, x, y, z and n are defined as
before; a is 1 or 0.
5
Prior to ethoxylation, the PEAs used in preparing cationic polymers of the
present invention have the following genera) formula:
[H2N]a [CH2CH2N]X [CH2CH2N]y ---~CH2CH2NH2)Z
H
io
wherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from
about 100 to about 400). Each hydrogen atom attached to each nitrogen
atom represents an active site for subsequent ethoxylation. For preferred
PEAs, x + y + z is from about 3 to about 7 (molecular weight is from
~ 5 about 140 to about 310). These PEA's can be obtained by reactions
involving ammonia and ethylene dichloride, followed by fractional
distillation. The common PEA's obtained are triethylenetetramine (TETA)
and tetraethylenepentamine (TEPA). Above the pentamines, i,e., the
hexamines, heptamines, octamines and possibly nonamines, the
2o 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 Pat. No. 2,792,372 to Dickson,
issues May 14, 1957, which describes the preparation of PEAs.
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2f
The 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 feast about 6. Where y
+ z is from 4 to 9, suitable benefits are achieved when n is at least about
3. For preferred cationic PEAs, n is at least about 12, with a typical range
of about 12 to about 42.
The PEIs used in preparing the polymers of the present invention have a
molecular weight of at feast about 440 prior to ethoxylation, which
represents at least about 10 units. Preferred PEIs used in preparing these
polymers have a molecular weight of from about 600 to about 1800. The
polymer backbone of these PEIs can be represented by the general formula:
H
H2N --~ CH2CH2N ~ -~- CH2CH2N --~- --f- 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%
Each hydrogen atom attached to each nitrogen atom of the PEi represents
an active site for subsequent ethoxylation. These PEIs can be prepared, for
example, by polymerizing ethyleneimine in the presence of a catalyst such
as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,
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27
hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are
disclosed in US Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939;
US Pat No. 3,033,746 to Mayle et al., issued May 8, 1962; US Pat. No.
2,208,095 to Esselmann et al., issued July 16, 1940; US Pat. No.
2,806,839 to Crowther, issued Sept. 17, 1957; and US Pat. No.
2,533,696 to Wilson, issued May 21, 1951 (all herein incorporated by
reference).
As defined in the preceding formulas, n is at least about 3 for the cationic
1 o PEIs. However, it should be noted that the minimum degree of ethoxylation
required for suitable soil rernoval/anti-redeposition performance can increase
as the molecular weight of the PE1 increases, especially much beyond about
1800. Also, the degree of ethoxyaiation for preferred polymers increases
as the molecular weight of the PEI increases. For PEIs having a molecular
~ 5 weight of at least about 600, n is preferably at least about 12, with a
typical range of from about 12 to about 42. For PEIs having a molecular
weight of at least 1800, n is preferably at least about 24, with a typical
range of from about 24 to about 42.
20 D. Diallylamine Polymers
Another class of suitable cationic polymers are those derived from the
diallylamines. These polymers comprise units selected from those having
formulas X and XI:
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28
(CH2) (CH
2
(CH2)x ,
i
a
R1 (R2)k j(C3H60)m(CH2CH20)n) X
xi
( (cH2
\ Y
~R3~2
wherein R ~ is C 1-C4 alkyl or hydroxyalkyl, or the moiety -(R2)k-
f(C3Hg0),n(CH2CH20)~l-X; R2 is C1-C12 alkylene, hydroxyalkylene,
alkylene, arylene or alkarylene; each R3 is C 1-C4 alkyl or hydroxyalkyl, or
together form the moiety -(CH2)rA-tCH2)S-, wherein A is -O- or -CH2-; X
is H,
CR4,
O
-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or
0; m and n are numbers such that the moiety -(CH2CH20)~- comprises at
least about 85~r6 by weight of the moiety -[(CgHgO),n(CH2CH20)~]-; m is
from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s
is 3 or 4; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1; the number of
~ 5 a and v are such that there are at least 2N + centres and at least 2 X
groups.
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29
In the above formulas, A is preferably -O-; R 1 is preferably methyl; each
R2 is preferably C2-C3 alkylene; each R3 is preferably methyl; R4 is
preferably methyl; X is preferably H; k is preferably 0; m is preferably 0; r
and s are each preferably 2.
In the above formulas, n is preferably at least about 6 when the number of
N + centres and X groups are each 2 or 3, n is preferably at least 12, with a
typical range of from about 12 to about 42 for all range of a + v.
Typically, v is 0, and a is from 2 to about 40, and preferably from 2 to
about 20.
The compositions according to the present invention comprise from 0.01
to 10% by weight of the total composition of such a soil suspending agent
or mixtures thereof, preferably from 0.05 % to 5 %, more preferably 0.1 % to
4% and most preferably from 0.2% to 2%.
~ 5 The aqueous compositions according to the present invention are
formulated in the acidic pH range. Indeed acidity herein contributes to the
stain removal/bleaching benefit of the compositions of the present
invention. Indeed, the compositions herein have a pH below 6, more
preferably below 5, even more preferably from 1 to 4.5 and most preferably
2o from 2 to 4.5.
The compositions according to the present invention may comprise optional
ingredients like surfactants, bleach activators, stabilisers, chelating
agents,
radical scavengers, builders, soil suspenders, dye transfer agents, solvents,
25 brighteners, perfumes, foam suppressors, dyes or mixtures thereof.
Preferred optional ingredients are further described in more details
hereinafter.
The laundry pretreatment process
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fn its broadest embodiment, the present invention relates to a process of
pretreating a fabric with a liquid acidic aqueous composition as described
herein before.
By "pretreating a fabric" it is to be understood that the liquid aqueous
5 composition herein is applied in its neat form onto at least a portion of a
soiled fabric, 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.
Accordingly, the present invention encompasses a process of bleaching a
fabric with a liquid aqueous composition, as defined herein before, 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
2o 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 aqueous
compositions are applied directly onto the fabrics to be pre-treated without
undergoing any dilution, e.g., the liquid aqueous compositions according to
the present invention are applied as described herein.
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31
According to the process of pretreating soiled fabrics of the present
invention, the liquid aqueous 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 aqueous 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 aqueous bleaching compositions.
Optional ingredients
The compositions of the present invention may further comprise optional
ingredients Pike surfactants, bleach activators, stabilisers, chelating
agents,
radical scavengers, builders, soil suspenders, dye transfer agents, solvents,
2o brighteners, perfumes, foam suppressors, or dyes or mixtures thereof.
Accordingly, the liquid aqueous compositions of the present invention
preferably comprise a surfactant or mixtures thereof. Any surfactant known
to those skilled in the art may be suitable herein including nonionic,
anionic,
cationic, zwitterionic, and/or amphoteric surfactants up to 50% by weight
of the total composition. Surfactants allow to further improve the stain
removal properties of the compositions according to the present invention.
Nonionic surfactants are highly preferred herein for performance reasons.
3o The liquid compositions herein may comprise up to 50% of a nonionic
surfactant or mixtures thereof, preferably from 0.3% to 30% and more
preferably from 0.4% to 25%. Suitable nonionic surfactants to be used
herein are fatty alcohol ethoxylates and/or propoxyiates which are
commercially available with a variety of fatty alcohol chain lengths and a
variety of ethoxylation degrees. Indeed, 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.
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32
Surfactant catalogues 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.
1 o Particularly suitable to be used herein as nonionic surfactants are
hydrophobic nonionic surfactants having an HLB (hydrophilic-lipophilic
balance) below 16, preferably below 15, more preferably below 12) and
most preferably below 10. Those hydrophobic nonionic surfactants have
been found to provide good grease cutting properties.
Preferred hydrophobic nonionic surfactants to be used in the compositions
according to the present invention are surfactants having an HLB below 16
and being according to the formula RO-(C2H40)n(C3H60)mH, wherein R is
a C6 to C22 alkyl chain or a C6 to C2g alkyl benzene chain, and wherein
n + m is from 0 to 20 and n is from 0 to 15 and m is from O to 20,
preferably n + m is from 1 to 15 and, n and m are from 0.5 to 15, more
preferably n + m is from 1 to 10 and, n and m are from 0 to 10. 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 C9 and C 1 1 alkyl chains, n
is 2.5 and m is 0), or Lutensol R T03 (HLB = 8; R is a C 13 alkyl chains, n is
3 and m is 0), or Lutensol R A03 (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 C 12 and C 13 alkyl
chains, n is 2 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) 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 and C15 alkyl chains, n is 7 and m
is 01, or Dobanol R 91-5 (HLB=11.6; R is a mixture of Cg and C11 alkyl
chains, n is 5 and m is 0), or Dobanol R 91-6 (HLB=12.5 ; R is a mixture of
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33
Cg and C11 alkyl chains, n is 6 and m is 0), or Dobanol R 91-8 (HLB=13.7
R is a mixture of Cg and C1 1 alkyl chains, n is 8 and m is 0), Dobanol R
91-10 (HLB=14.2 ; R is a mixture of Cg to C11 alkyl chains, n is 10 and m
is 01, or mixtures thereof. Preferred herein are Dobanol R 91-2.5 , or
Lutensol R T03, or Lutensol R A03, or Tergitol R 25L3, or Dobanol R 23-3,
or Dobanol R 23-2, or mixtures thereof. These DobanolR surfactants are
commercially available from SHELL. These LutensolR surfactants are
commercially available from BASF and these Tergitol R surfactants are
commercially available from UNION CARBIDE.
'10
Other suitable nonionic surfactants for use herein include polyhydroxy fatty
acid amide surfactants, or mixtures thereof, according to the formula
R2-C10)-N(R1)-Z,
wherein R 1 is H, or C 1 _C4 alkyl, C 1 _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
2o thereof.
Preferably, R1 is C1_C4 alkyl, more preferably C1 or C2 alkyl and most
preferably methyl, R2 is a straight chain C7_C 1 g alkyl or alkenyl,
preferably
a straight chain Cg_C 1 g alkyl or alkenyl, more preferably a straight chain
C 1 1 _C 1 g alkyl or alkenyl, and most preferably a straight chain C 11 _C 14
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, galactose, mannose and xylose. As raw materials, high dextrose
3o 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)-(CHOHIn_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
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34
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~ frorn Hoechst.
Z 5 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
2o to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for
making compositioris 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.
25 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.
The liquid aqueous compositions according to the present invention may
3o further comprise other surfactants like an anionic surfactant, or mixtures
thereof on top of nonionic surfactants. Anionic surfactants are preferred
herein as optional ingredient as they act as wetting agent) i.e., in a laundry
application I they wet the stains on the fabrics, especially on hydrophilic
fabrics, and thus help the peroxygen bleach perform i s bleaching action
35 thereby contributing to improved laundry performance on bleachable stains.
Furthermore, anionic surfactants allow to obtain clear compositions even
when said compositions comprise hydrophobic ingredients such as
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hydrophobic surfactants. The compositions herein may comprise from 0.1
to 20 % by weight of the total composition of said anionic surfactant, or
mixtures thereof, preferably from 0.2 % to 15 % and more preferably from
0.5 % to 13 % .
5
Particularly suitable for use herein are sulfonate and sulfate surfactants.
The like anionic surfactants are well-known in the art and have found wide
application in commercial detergents. These anionic surfactants include the
C8-C22 alkyl benzene sulfonates (LAS), the C8-C22 alkyl sulfates (AS),
unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy
sulfates (A8S) and the C 10-C 18 alkyl alkoxy carboxylates. The neutralising
canon for the anionic synthetic sulfonates and/or sulfates is represented by
conventional cations which are widely used in detergent technology such as
sodium, potassium or alkanolammonium. Preferred herein are the alkyl
~ 5 sulphate, especially coconut alkyl sulphate having from 6 to 18 carbon
atoms in the alkyl chain, preferably from 8 to 15, or mixtures thereof.
Other anionic surfactants useful for detersive purposes can also be used
herein. These can include salts (including, for example, sodium, potassium,
2o ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, 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,
25 Cg-C24 alkylpolygiycoiethersulfates (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
3o sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated C 12-C ~ g monoesters) diesters of sulfosuccinate (especially
saturated and unsaturated Cg-C ~ 4 diestersl, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described below). Resin acids and
35 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
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36
Detergents" (Voi. 1 and Il by Schwactz, 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 acyi sarcosinates having the following formula:
O
OM
R
I
CH3 O
15
2o
wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group
of from 1 1 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
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 C 14 acyl sarcosinate (i.e. an acyl sarcosinate according
25 to the above formula wherein M is hydrogen and R is an alkyl group of 13
carbon atoms). C 12 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.
The liquid aqueous compositions according to the present invention may
further comprise other surfactants known to those skilled in the art like an
amine oxide surfactant according to the formula R1 R2R3N0, wherein each
of R 1, R2 and R3 is independently a C 1-C30, preferably a C 1-C20, most
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37
preferably a C 1-C 1 g hydrocarbon chain. Amine oxides may be present in
amounts up to 10 % by weight of the total composition, more preferably
from 1 % to 3%.
As an optional but highly preferred ingredient, the compositions of the
present invention comprise a bleach activator or mixtures thereof. The
compositions herein that further comprise a bleach activator or mixtures
thereof deliver more effective bleaching performance, especially at ambient
temperature at which the pretreatment operation is performed. 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
~ 5 bleach activators have a secondary HLB (hydrophilic iipophilic balance?
below 1 1, 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, New York, 1957, or in "Emulsion science" by P.
Sherman, Academic Press, London, 1969.
2o 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
25 examples of such compounds to be used herein are tetracetyl ethylene
diamine f 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 n-nonanoyloxybenzenesulphonate (NOBS). Also suitable are N-acyl
3o caprolactams selected from the group consisting of substituted or
unsubstituted benzoyl caprofactam, octanoyl caprolactam, nonanoyl
caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl
caproiactam, formyl caprolactam, acetyl caprolactam, propanoyl
caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures
35 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
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38
IATC). 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 20% by weight of the total composition of said bleach activator,
or mixtures thereof, preferably from 1 % to 10%, and more preferably from
2% to 7%.
The aqueous compositions herein may be formulated as solutions,
emulsions or microemulsions depending on the respective ingredients
present and respective levels thereof. The compositions according to the
present invention that 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 peroxygen bleach, the soil
suspending agent and an emulsifying surfactant system, or as
microemulsions of said bleach activator in a matrix comprising water, the
peroxygen bleach, the soil suspending agent and a hydrophilic surfactant
system.
Preferred peroxygen bleach-containing emulsions herein comprise an
emulsifying surfactant system of at least two different surfactants.
Preferred herein, said two different surfactants should have different HLB
values (hydrophilic / lipophilic balance) in order to form stable emulsions,
and preferably the difference in value of the HLBs of said two surfactants is
at least 1, preferably at least 2. 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
3o standing for at least two weeks at 40~C.
The emulsions according to the present invention may further comprise
other surfactants on top of said emulsifying surfactant system, which
should however not significantly alter the weighted average HLB value of
the overall emulsion.
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In a preferred embodiment of the emulsions of the present invention
wherein the emulsions 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 =
100%;
100 100
where HLB (X) refers to the HLB of the ingredient to emulsify, if several
ingredients 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
~ 5 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 comprise acetyl triethyl citrate as the
2o bleach activator, 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
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
25 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
3o 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
35 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
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nonionic surfactant and an anionic surfactant. Suitable hydrophilic
surfactants to be used herein are those hydrophilic surfactants mentioned
herein. In the embodiment wherein the microemulsions herein comprise a
peroxygen bleach and a bleach activator, a key factor in order to stably
5 incorporate 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.
in the embodiment of the present invention where the compositions are
formulated as microemulsions said compositions are macroscopically
~ 5 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
2o around or below 3 micron diameter.
Suitable chelating agents to be used herein include chelating agents
selected from the group of phosphonate chelating agents, amino
carboxylate chelating agents, poiyfunctionally-substituted aromatic chelating
agents, and further chelating agents like glycine, salicylic acid, aspartic
acid,
25 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.
3o 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 yenta methylene
35 phosphonates. The phosphonate compounds may be present either in their
acid form or as salts of different rations on some or all of their acid
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41
functionalities. Preferred amino phosphonate chelating agents to be used
herein are diethylene triamine penta methylene phosphonate (DTPMP), 1-
hydroxy ethane diphosphonate (HEDP) and amino-tri-(methylene phosphonic
acid) (ATMP). Such phosphonate chelating agents are commercially
available from Monsanto under the trade name DEQUEST~~
Polyfunctionally-substituted aromatic chelating agents may also be useful in
the compositions herein. See U.S. patent 3,812,044, issued May 21,
1974, to Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable cheiating 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
~5 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 Paimer
Research Laboratories.
Suitable amino carboxyfates to be used herein include ethylene diamine tetra
acetates, diethylene triamine pentaacetates, diethylene triamine
pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-
acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-
acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and
methyl glycine di-acetic acid (MGDA), both in their acid form, or in their
alkali metal, ammonium, and substituted ammonium salt forms. Particularly
suitable amino carboxylates to be used herein are diethylene triamine yenta
acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance,
commercially available from BASF under the trade name Triton FS~ and
methyl glycine di-acetic acid (MGDA).
Another preferred chelating agent for use herein is of the formula:
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42
RiR2R3R4
Rg COOH OH
R1
NH
NH
OH COOH RS ~
R~RZR3R4
wherein R1, R2, R3, and R4 are independently selected from the group
consisting of -H) alkyl, alkoxy, aryl, aryloxy, -CI, -Br, -N02, -C(O)R', .and -
S02R"; wherein R' is selected from the group consisting of -H, -OH, alkyl,
alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl,
alkoxy, aryl, and aryloxy; and R5, Rg, R7, and Rg are independently
selected from the group consisting of -H and alkyl.
Particularly preferred chelating agents to be used herein are 1-hydroxy
1 o ethane diphosphonate (HEDP) and amino-tri-(methylene phosphonic acid)
(ATMP), diethylene triamine methylene phosphonate (DTPMP), ethylene
N, N'-disuccinic acid, diethylene triamine pantaacetate, glycine, salicylic
acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof.
Suitable radical scavengers for use herein include the well-known
substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl
carboxylates and mixtures thereof. Preferred such radical scavengers for
use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-
butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy
2o anysole, benzoic acid, toluic acid, catechol, t-butyl catechoi,
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, 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
3o before washing said fabric.
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The compositions according to the present invention may also comprises a
soil suspending polyamine polymer or mixtures thereof. Any soil suspending
polyamine polymer known to those skilled in the art may also be used
herein. Particularly suitable polyamine polymers for use herein are
polyalkoxylated polyamines. Such materials can conveniently be
represented as molecules of the empirical structures with repeating units
[N R] n Amine form
(alkoxyly
and
R1
~ 5 fN + R] n nX' Quaternized form
(alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R 1 may be a
2o C1-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like,
and y is 2-30, most preferably from 10-20; n is an integer of at least 2,
preferably from 2-20, most preferably 3-5; and X- is an anion such as halide
or methylsulfate, resulting from the quaternization reaction.
25 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
30 (Et0) (N CH2 CH2 ] n N (Et0)y
(Eto)y (Eto)y
when y - 2-30. Particularly preferred for use herein is an ethoxylated
35 polyethylene amine, in particular ethoxylated tetraethylenepentamine, and
quaternized ethoxylated hexamethylene diamine.
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Typically, the compositions of the present invention comprise from 0.01
to 15% 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 0.2% to 3% .
The compositions of the present invention may further comprise 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 overall stain removal performance on various type
of stains including greasy stains, enzymatic stains as well as bleachable
stains. Typically, the liquid aqueous compositions herein may comprise up
to 10% from by weight of the total composition of a hydrophobic solvent or
mixtures thereof, preferably from 0. 7 % to 5 % and more preferably from
0.2% to 2%, and up to 20% by weight of the total composition of a
hydrophilic solvent or mixtures thereof, preferably from 0.5% to 15% and
more preferably from 1 % to 10%.
2o 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 andlor beta-pinene. Other hydrophobic solvents
iriciude 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
3o alcohol, or mixtures thereof.
Suitable hydrophilic solvents to be used herein include alkoxylated aliphatic
alcohols like methoxy propanol, ethoxy propanol, propoxy propanoi, buthoxy
propanol as well as alkoxylated glycols like ethoxy-ethoxy-ethanol, aliphatic
alcohols like ethanol, propanol, as well as glycols like propanedioi or
mixtures thereof.
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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
5 polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibres and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic
segments. This can enable stains occurring subsequent to treatment with
the soil release agent to be more easily cleaned in later washing procedures.
1o
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
~ 5 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
20 oxyethylene units such that the hydrophiie 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
25 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 2:7
30 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 C 1-C4 alkyl ether or C4 hydroxyalkyl
35 ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C 1-C4
alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional
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46
polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls,
once adhered to such conventional synthetic fiber surface, to increase fiber
surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a) (i) will have a degree of
polymerization of from about 1 to about 200, although higher levels can be
used, preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C4-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
~ 5 cellulosic derivatives such as hydroxyether cellulosic polymers,
copofymeric
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
2o 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 characterized by polyvinyl ester) hydrophobe segments
25 include graft copolymers of polyvinyl ester), e.g., C 1-Cg vinyl esters,
preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0
219 048, published April 22, 1987 by Kud, et al. Commercially available
soil release agents of this kind include the SOKALAN type of material, e.g.,
3o 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
35 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.
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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
polyoxyethyiene terephthalate units, derived from a polyoxyethylene glycol
of average molecular weight 300-5,000. Examples of this polymer include
the commercially available material ZELCON 512fi (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 oxyalkylenevxy repeat units and terminal
moieties covalently attached to the backbone. These soil release agents are
described fully in U.S. Patent 4,9fi8,451, 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 4,71 1,730, 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,
2o and the block polyester oligomeric compounds of U.S. Patent 4,702,857,
issued October 27, 1987 to Gosselink.
Preferred polymeric soil relea$e agents also include the soil release agents
of
U.S. Patent 4,877,89fi, issued October 31, 1989 to Maldonado et al,
25 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-
30 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-
35 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
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48
group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate,
and mixtures thereof. See U.S. Pat. No. 5,415,807, issued May 16, 1995,
to Gosselink et al.
If utilized, soil release agents will generally comprise from about 0.01 % to
about 10.0%, by weight, of the detergent compositions herein, typically
from about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
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-vinyipyrrolidone and N-vinylimidazole,
manganese phthaiocyanine, peroxidases, and mixtures thereof. if used,
~ 5 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
2o 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 polymerizabie unit or the N-O group can be attached to
both units; A is one of the following structures: -NC(OI-, -C(O)O-, -S-, -O-, -
N =; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
25 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-0 group can be represented by the following general structures:
O O
I
~t~c- i -~2~~ =NWRuc
(R3)z
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wherein R 1, R2, R3 are aliphatic, aromatic, heterocyclic or aiicyclic 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 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 50O to 1,000,000;
more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This
2o preferred class of materials can be referred to as "PVNO". The most
preferred poiyamine 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 poiyrners (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
3o scattering as described in Barth, et al., Chemical Analysis, Vol 113.
"Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) The PVPVI copolymers typically have
a molar ratio of N-vinylimidazole to N-vinylpyrroiidone 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
5 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 C 10-C 16 alkanolamides
can be incorporated into the compositions, typically at 1 %-10% levels. The
~ 5 C 10-C 14 monoethanol and diethanol amides illustrate a typical class of
such suds boosters. Use of such suds boosters with high sudsing adjunct
surfactants such as the amine oxides, betaines and sultaines noted above is
also advantageous. If desired, soluble magnesium salts such as MgCl2,
MgS04, and the like, can be added at levels of, for example, 0.1 %-2%, to
2o 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
25 levels typicatty from about 0.05~lo to about 1.2%, by weight, of the
detergent compositions herein. Commercial optical brighteners which may
be usefu) in the present invention can be classified into subgroups, which
include, but are not necessarily limited to, derivatives of stilbene,
pyrazoiine,
coumarin, carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxide,
3o 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).
35 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
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series of brighteners from Verona. Other brighteners disclosed in this
reference include: Tinopal UNPA, Tinopal CBS and Tinopal SBM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, available from
Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[ 1,2-
d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-
bislstyryl)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-dloxazole; 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.
The compositions of the present invention suitable for pretreating fabrics
can be packaged in a variety of containers including conventional bottles,
~ 5 bottles equipped with roll-on, sponge, brusher or sprayers. Also as the
aqueous compositions herein are chemically stable, they may be packaged
in a given deformable container/bottle without compromising the stability of
said container/bottle comprising it upon standing, for long periods of time.
20 Stain removal performance/bleachinq_performance test method
The stain removal and/or bleaching performance of a given composition on a
soiled fabric under pretreatment conditions, may be evaluated by the
following test method. An aqueous composition according to the present
25 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
3o soiled fabrics to be used in this 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 on two different substrate/fabric, e.g., cotton (CW 120) and
polycotton (PCW28). The stain removal/bleaching performance may then be
35 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 suspending
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52
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.
The present invention will be further illustrated by the following examples.
Examples
The following compositions were made by mixing the listed ingredients in
the listed proportions (weight % unless otherwise specified).
Compositions I II III IV V VI VII VIII
Dobanol~ 45-7 6.4 6.4 6.4 1.5 12.0 6.0 - 1.5
Dobanol~ 23-3 8.6 8.6 8.6 - - 6.0 1.5 1.5
Dobanol~ 23-6.5 - - - 1.5 - - - -
Dobanol~ 91-10 - - - - - - 1.5 -
C25-AE-2.5-S 4.0 4.0 4.0 1.5 12.0 6.0 - -
C10 Alkyl Sulphate- - - - - - 1.7 1.7
Alkyl glucose 2.0 2.0 2.0 - - - - -
amide
ATC * 3. 3. 3.5 - 3. - - -
5 5 5
H202 4.0 4.0 4.0 - 6.0 4.0 7.0 7.0
Dilauroyl peroxide0.5 - - 1.0 - 2.0 - -
EHDQ* * 0.5 0.5 0.5 0.2 1.0 0.7 0.5 0.5
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 - - -
HEDP**** - - - - - - - 0.16
DTPMP***** - - - - - - 0.18 -
Water and minors __-______________-_____________up 100%-
_______________________
to
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.
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Dobanol ~ 45-7 is a C14-C15 nonionic ethoxylated surfactant with HLB of
11.6.
Dobanol ~ 91-10 is a C9-C11 nonionic ethoxylated surfactant with HLB of
14.7.
ATMP~* ~ ~" is aminotri(methylene phosphonic acid).
DTPMP~* ~'* ~" ~" is diethylene triamine yenta methylene phosphonate.
HEDP~ *' *' ~ is 1-Hydroxy Ethane Diphosponate.
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EHDQ'~ ~" *' is 24-Ethoxyfated Hexamethylene Diamine Quaternized methyl
chloride
Me Me
(E~~24~ ~+
N +~ ~(E~~24
N
~E~~24~ ~ (EO)
24
EHDQ
Excellent stain removal performance is obtained on a variety of stains
including greasy/oily stains tike 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 VIII, as described above, e.g., when leaving such a
composition to act onto the fabrics for a contact period of about 5 minutes.,
before rinsing said fabrics with water or washing according to standard US
or European washing conditions.
