Note: Descriptions are shown in the official language in which they were submitted.
CA 02252855 2003-05-02
LAUNDRY DETERGENT COMPOSITIONS COMPRISING CATIONIC
SURFACTANTS AND MODIFIED POLYAMINE SOIL DISPERSANTS
FIELD OF THE INVENTION
The present invention relates to laundry detergent compositions comprising C
12-
C 14 dimethyl hydroxyethyl quaternary ammonium cationic surfactants in
combination
with certain modified polyamines which provide increased fabric cleaning
benefits. The
compositions also provide increased cotton soil release benefits. The present
invention
also relates to methods for laundering fabrics with the disclosed
compositions.
BACKGROUND OF THE INVENTION
Detergent formulators are faced with the task of devising products to remove a
broad spectrum of soils and stains from fabrics. Chemically and physico-
chemically. the
varieties of soils and stains ranges the spectrum from polar soils, such as
proteinaceous,
clay, and inorganic soils, to non-polar soils, such as soot, carbon-black, by-
products of
incomplete hydrocarbon combustion, and organic soils. Detergent compositions
have
become more complex as formulators attempt to provide products which handle
all types
concurrently.
Formulators have been highly successful in developing traditional dispersants
which are particularly useful in suspending polar, highly charged ,
hydrophilic particles
such as clay. As yet, however, dispersants designed to disperse and suspend
non-polar,
hydrophobic-type soils and particles have been more difficult to develop.
Surprizingly, it
has recently been discovered that the modified polyamines of the present
invention are
capable of mediating the re-depositon of non-polar soils
In addition, a wide variety of soil release agents for use in domestic and
industrial
fabric treatment processes such as laundering, fabric drying in hot air
clothes dryers, and
the like are known in the art. Various soil release agents have been
commercialized and
are currently used in detergent compositions and fabric softener/antistatic
articles and
compositions. Such soil release polymers typically comprise an oligomeric or
polymeric
ester "backbone".
Soil release polymers are generally very effective on polyester or other
synthetic
fabrics where the grease, oil or similar hydrophobic stains spread out and
form a attached
film and thereby are not easily removed in an aqueous laundering process. Many
soil
release polymers have a less dramatic effect on "blended" fabrics, that is on
fabrics that
comprise a mixture of cotton and synthetic material, and have little or no
effect on cotton
articles. The reason for the affinity of many soil release agents for
synthetic fabric is that
CA 02252855 2003-05-02
2
the backbone of a polyester soil release polymer typically comprises a mixture
of
terephthalate residues and ethyleneoxy or propyleneoxy polymeric units; the
same
materials that comprise the polyester fibers of synthetic fabric. This similar
structure of
soil release agents and synthetic fabric produce an intrinsic affinity between
these
compounds.
It has now been surprisingly discovered that in addition to the ability to
mediate
hydrophobic soil redeposition, certain polyamines act in cancert with selected
cationic
surfactants to provide increase fabric soil removal, especially from cotton
fabrics. This
increased soil removal benefit has been found to be independent of the type of
soil
present on the cotton fabric.
The modified polyamine/cationic surfactant combinations of the present
invention have the increased benefit of being compatible with hypochlorite and
oxygen
"peracid" bleaching agents. This is especially important in the area of
surface active
agents that are effective on non-colored cotton fabric. The hydrophilic
cellulosic
composition of cotton fabric presents a surface that is not compatible with
the traditional
polyester terephthalate-based soil release agents. Indeed, the polyamines of
the present
invention themselves exhibit a propensity for attachment to the surface of the
cotton
fabric.
The C 12-C 14 dimethyl hydroxyethyl quaternary ammonium salts which serve as
cationic surfactants for the purposes of the present invention, combine with
the modified
polyamine surface agent/dispersants to remove soils from fabric surfaces. This
combination of materials also acts to prevent redeposition of soil by holding
the soil
suspended in the laundry liquor which ~is removed prior to rinsing.
It is a purpose of the present invention to provide laundry detergent
compositions
which combine C 12-C I 4 dimethyl hydroxyethyl quaternary ammonium cationic
surfactants with modified polyamine dispersants.
It is a further object of the present invention to combine the C12-C14
dimethyl
hydroxyethyl quaternary ammonium cationic surfactant and polyamine dispersants
with
non-cotton soil release agents. This combination of ingredients provides a
soil release
benefit to all laundered fabric as well as the increase in cleaning capacity.
It is yet a fivther purpose of the present invention to provide a bleach
stable
cationic surfaetant/polyamine dispersant composition.
A further purpose of the present invention is to provide a method for
laundering
soiled fabric which comprises the step of contacting the soiled fabric,
especially cotton,
with a laundry detergent composition containing C 12-C 14 dimethyl
hydroxyethyl
quaternary ammonium cationic surfactants and the disclosed polyarnines.
CA 02252855 2004-06-09
BACKGROU,T1D ART
The following disclose various soil release polymers or modified polyamines;
U.S. Patent 4,548,744, Connor, issued October 22, 1985; U.S. Patent 4,597,898,
Pander
Meer, issued July 1, 1986; U.S. Patent 4,877,896, Maldonado, et al., issued
October 31,
1989; U.S. Patent 4,891,160, Vander Meer, issued January 2, 1990;.U.S. Patent
4,9?6.879, Maldonado, et al., issued December 11, 1990; U.S. Patent 5,415,807,
Gosselink, issued May 16,1995; U.S. Patent 4,235,733, Marco, et al., issued
November
25, 1980; WO 95/32272, published November 30, 1995; U.K. Patent 1,537,288,
published December 29, 1978; U.K. Patent 1,498,520, published January 18,
1978;
German Patent DE 28 29 022, issued January 10, 1980; Japanese Kokai JP
06313271,
published April 27, 1994.
The following relates to ethoxylated cationic surfactants in laundry detergent
compositions; U.S. Patent 5,441,541, Mchreteab et al., issued August 15, 1995;
U.K.
2,040,990, Murphy et al., issued September 3, 1980.
SUMMARY OF THE 1NVENT10N
The present invention relates to laundry compositions comprising:
a) at least 0.01 % by weight, of a cationic surfactant having the formula
CH3
R-N-CH2CH20H X
CH3
wherein R is Cl2-C14 alkyl and X is a water soluble anion;
b) at least 0.01 % by weight, of a water-soluble or dispersible, modified
polyamine soil
dispersing agent having a modified linear polyamine formula V(n+1)WmynZ:
wherein the
linear polyamine backbone prior to modification corresponds to the formula:
H
f~lzN'RJn+1-[N-R]m fN'R)ri NH2
or a modified cyclic polyamine soil dispersing agent having a modified
polyamine formula
V(n-k+1 )Wm~'n~' kZ: wherein the cyclic polyamine backbone prior to
modification
corresponds to the formula:
fH2N'RJrrk+1-(~'1'RJrri ~N'RJn-(N'RJkvNH2
wherein k is less than or equal to n, said polyamine backbone prior to
modification has a
molecular weight greater than Z00 daltons,
or a modified complete ring cyclic polyamine soil dispersing agent having a
modified
polyamine formula Vn.kWmYn~'~k> wherein the complete ring cyclic polyamine
backbone
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4
prior to modification corresponds to the formula:
H I
~2N-R~ri ~-R~tri ~-R~ri
wherein
i) V units are terminal units having the formula:
E O
X
E-N-R- or E-N~ R- or E-N-R-
I I I
E E E
ii) W units are backbone units having the formula:
E O
N -R- or X or
-N R- -N-R
I I I
E E E
iii) Y units are branching units having the formula:
E O
X
-N-R- or -N~ R- or -N-R-
iv) Y' units, when present, have the formula
I
R
-L1'~ _Rl-
wherein every Y' unit has a corresponding Y unit having the formula
I
-h'~ _ R~-
forming a ring to the cyclic polyamine backbone or cyclic polyamine branch;
and
v) Z units are terminal units having the formula:
E X_
O
-N-E or -N~ E or -N-E
I I I
E E E
wherein backbone linking R units are selected from the group consisting of C2-
C12
alkylene, Cq-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-
alkylene, Cg-C12 dialkylarylene, -(R10)XRl-, -(Rl0)XRS(ORl)x',
-(CH2CH(OR2)CH20)Z (R10)yRl(OCHZCH(OR2)CNZ)N; , -C(O)(R4)rC(O)-,
CA 02252855 2004-10-20
-CH2CH(OR2)CH2-, or mixtures thereof, wherein R1 is C2-C6 alkylene; R2 is
hydrogen, -(R10)xB, or mixtwes thereof; R4 is C1-C12 alkylene, C4-C12
aikenylene, Cg-C12 arylalkylene, C6-C10 ary(ene, or mixtures thereof; RS is
Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12
dialkylarylene, -C(O)-, -C(O)NHR6-NHC(O)-, -Rl(ORl)-, -C(O)(R4)rC(O)-,
-CH2CH(OH)CH2-, -CH2CH(OH)CH2O-(R10)yR10CH2CH(OH)CH2-, or
mixtwes thereof; R6 is C2-C12 alkylene or C6-Cl2 arylene; E wets are selected
from the group consisting of hydrogen, Cl-C22 alkyl, C3-C22 alkenyl, C~-C22
arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)qS03M,
-CH(CH2C02M)C02M, -(CH2)pP03M, -(R10)xB, -C(O)R3, or mixtwes thereof;
providedthat when any E unit of a nitrogen is a hydrogen, said nitrogen is not
also
an N-oxide; R3 is C1-Clg alkyl, C~-C12 arylalkyl, C~-C12 alkyl substituted
aryl,
C6-C12 aryl, or mixtures thereof; B is hydrogen, C1-C6 alkyl, -(CH2)qSOgM, -
(CH2)p-COZM, -(CH2)q (CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2-S03M, -
(CH2)pP03M, -P03M, or mixtwes thereof, provided at least one backbone nitrogen
is quaterdized or oxidized; M is hydrogen or a water soluble cation in
suffcient
amount to satisfy charge balance; X is a water soluble anion; m has the value
from 4
to 400; n has the value from 1 to 200; p has the value from 1 to 6, q has the
value
from 0 to 6; r has the value of 0 or 1; w has the value 0 or 1; x has the
value from 1
to 100; y has the value from 0 to 100; z has the value 0 or 1; and
c) the balance carrier and adjunct ingredients.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. Atl temperatures are in degrees Celsius (o C) unless otherwise
specified.
DETAILED DESCRIPTION OF THE INVENTION
The laundry detergent compositions of the present invention comprise:
a) at least 0.01% by weight, of a cationic surfactant having the formula
CH3 +
R-N-CH2CH20H X
CH3
wherein R is C 12-C 14 alkyl and X is a water soluble anion;
b) at least about 0.01% by weight, of a water-soluble or dispersible, modified
poiyamine soil dispersing agent according to the present invention; and
c) the balance carriers and adjunct ingredients.
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6
More preferably the detergent compositions of the present invention comprise:
a) at least 0.01 % by weight, of a cationic surfactant having the formula
CH3 +
R-N-CHZCH20H X
CH3
wherein R is C 12-C 14 alkyl and X is a water soluble anion;
b} at least about 0.01 % by weight, of a water-soluble or dispersible,
modified
polyamine soil dispersing agent according to the present invention;
c) at least about 0.01 % by weight, of a soil release agent; and
d) the balance carriers and adjunct ingredients.
More preferably the laundry detergent compositions of the present invention
comprise:
a) at least O.OI% by weight, of a cationic surfactant having the formula
CH3 +
R-N-CH2CH20H X
CH3
wherein R is C 12-C 14 alkyl and X is a wate: soluble anion;
b) at least about 0.01 % by weight, of a water-soluble or dispersible,
modified
polyamine soil dispersing agent according to the present invention;
c) at least about 0.01 % by weight, of a soil release agent;
d) from about 0% to about 30% by weight, of a bleach; and
e) the balance carriers and adjunct ingredients.
Cationic Surfactant
The laundry deteregent compositions of the present invention comprise at least
0.01% by weight, of a cationic surfactant having the formula
CH3 +
R-N-CH2CH~OH X
CH3
wherein R is C 12-C 14 alkyl and X is a water soluble anion;. X is a water
soluble anion
providing suitable charge balance to the quaternary ammonium cation. X is
preferably
CA 02252855 2003-05-02
7
chloride, bromide, iodide, sulfonate, sulfate, more preferably chloride and
bromide, most
preferably chloride anion.
The R moiety may be a mixture of C 12-C 14 alkyl moieties or the R moiety may
comprise pure C 12, C 13, or C 14 alkyl moieties or any mixtures thereof. For
the
purposes of the present invention no single alkyl moiety or combination of
alkyl moieties
is preferred.
The C 12-C 14 alkyl dimethyl hydroxyethyl quaternary ammonium cationic
surfactant comprises at least 0.01%, preferably from about 0.05°.~o to
about 5%, more
preferably from about 0.1 % to about 3% by weight, of the composition. The
ratio of the
the C 12-C 14 alkyl dimethyl hydroxyethyl quaternary ammonium cationic
surfactant to
the modified polyamine is from about 0.1:1 to about 10:1. Other suitable
cationic
materials including fabric conditioning agents may be combined with the C12-
C14 alkyl
dimethyl hydroxyethyl quaternary ammonium cationic surfactant of the present
invention.
Polyamine Dispersants
The soil dispersant agents of the present invention are water-soluble or
dispersible, modified polyamines. These polyamines comprise backbones that can
be
either linear or cyclic. The polyamine backbones can also comprise polyamine
branching chains to a greater or lesser degree. In general, the polyamine
backbones
described herein are modified in such a manner that each nitrogen of the
polyamine chain
is thereafter described in terms of a unit that is substituted, quaternized,
oxidized, or
combinations thereof.
For the purposes of the present invention the term "modification" is defined
as
replacing a backbone -NH hydrogen atom by an E unit (substitution),
quatemizing a
backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-
oxide
(oxidized). The terms "modification" and "substitution" are used
interchangeably when
referring to the process of replacing a hydrogen atom attached to a backbone
nitrogen
with an E unit. Quaternization or oxidation may take place in some
circumstances
without substitution, but substitution must be accompanied by oxidation or
quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil
release agents of the present invention have the general formula:
~ZN'Rln+1-II'I'RJm ~'RJri NH2
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8
said backbones prior to subsequent modification, comprise primary, secondary
and
tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine
backbones comprising the cotton soil release agents of the present invention
have the
general formula:
~zN-R]n k+r-[N-R]m ~'R]n'-~-R)k-NHz
said backbones prior to subsequent modification, comprise primary, secondary
and
tertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising
the
backbone or branching chain once modified are defined as V or Z "terminal"
units. For
example, when a primary amine moiety, located at the end of the main polyamine
backbone or branching chain having the structure
H2N-R]-
is modified according to the present invention, it is thereafter defined as a
V "terminal"
unit, or simply a V unit. However, for the purposes of the present invention,
some or all
of the primary amine moieties can remain unmodified subject to the
restrictions further
described herein below. These unmodified primary amine moieties by virtue of
their
position in the backbone chain remain "terminal" units. Likewise, when a
primary amine
moiety, located at the end of the main polyamine backbone having the structure
-NH2
is modified according to the present invention, it is thereafter defined as a
Z "terminal"
unit, or simply a Z unit. This unit can remain unmodif ed subject to the
restrictions
further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or
branching chain once modified are defined as W "backbone" units. For example,
when a
secondary amine moiety, the major constituent of the backbones and branching
chains of
the present invention, having the structure
H
-IN _ R]-
is modified according to the present invention, it is thereafter defined as a
W "backbone"
unit, or simply a W unit. However, for the purposes of the present invention,
some or all
of the secondary amine moieties can remain unmodified. These unmodified
secondary
amine moieties by virtue of their position in the backbone chain remain
"backbone"
units.
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WO 97/42292 PCT/US97/07057
9
In a further similar manner, tertiary amine nitrogens comprising the backbone
or
branching chain once modified are further referred to as Y "branching" units.
For
example, when a tertiary amine moiety, which is a chain branch point of either
the
polyamine backbone or other branching chains or rings, having the structure
-fN _ RJ-
is modified according to the present invention, it is thereafter defined as a
Y "branching"
unit, or simply a Y unit. However, for the purposes of the present invention,
some or all
or the tertiary amine moieties can remain unmodified. These unmodified
tertiary amine
moieties by virtue of their position in the backbone chain remain "branching"
units. The
R units associated with the V, W and Y unit nitrogens which serve to connect
the
polyamine nitrogens, are described herein below.
The final modified structure of the polyamines of the present invention can be
therefore represented by the general formula
V(n+1 )WmYnZ
for linear polyamine cotton soil release polymers and by the general formula
V(n-k+1 )WmYnY~kZ
for cyclic polyamine cotton soil release polymers. For the case of polyamines
comprising rings, a Y' unit of the formula
R
-h'1 _RJ-
serves as a branch point for a backbone or branch ring. For every Y' unit
there is a Y unit
having the formula
-fN _RJ-
that will form the connection point of the ring to the main polymer chain or
branch. In
the unique case where the backbone is a complete ring, the polyamine backbone
has the
formula
H
fI-I2N'RJri (N'RJrri fN'RJri
therefore comprising no Z terminal unit and having the formula
Vn-kWm1'n1'~k
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WO 97/42292 PCT/US97/07057
wherein k is the number of ring forming branching units. Preferably the
polyamine
backbones of the present invention comprise no rings.
In the case of non-cyclic polyamines, the ratio of the index n to the index m
relates to the relative degree of branching. A fully non-branched linear
modified
polyamine according to the present invention has the formula
V WmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m
to n), the
greater the degree of branching in the molecule. Typically the value for m
ranges from a
minimum value of 4 to about 400, however larger values of m, especially when
the value
of the index n is very low or nearly 0, are also preferred.
Each polyamine nitrogen whether primary, secondary or tertiary, once modified
according to the present invention, is further defined as being a member of
one of three
general classes; simple substituted, quaternized or oxidized. Those polyamine
nitrogen
units not modified are classed into V, W, Y, or Z units depending on whether
they are
primary, secondary or tertiary nitrogens. That is unmodified primary amine
nitrogens are
V or Z units, unmodified secondary amine nitrogens are W units and unmodified
tertiary
amine nitrogens are Y units for the purposes of the present invention.
Modified primary amine moieties are defined as V "terminal" units having one
of
three forms:
a) simple substituted units having the structure:
E-N-R-
i
E
b) quaternized units having the structure:
E
X-
E-N~ R-
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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11
O
E-N-R-
I
- E
Modified secondary amine moieties are defined as W "backbone" units having
one of three forms:
a) simple substituted units having the structure:
-N-R-
E
b) quaternized units having the structure:
E X_
-N~ R-
I
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N -R-
I
E
Modified tertiary amine moieties are defined as Y "branching" units having one
of three forms:
a) unmodified units having the structure:
-N-R-
b) quaternized units having the structure:
E
_ N+ R
,
_ wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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12
O
-N-R-
Certain modified primary amine moieties are defined as Z "terminal" units
having
one of three forms:
a) simple substituted units having the structure:
-N-E
E
b) quaternized units having the structure:
E
N E
I
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-E
I
E
When any position on a nitrogen is unsubstituted of unmodified, it is
understood
that hydrogen will substitute for E. For example, a primary amine unit
comprising one E
unit in the form of a hydroxyethyl moiety is a V terminal unit having the
formula
(HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain
terminating
units, the V and Z units. The Z "terminal" unit derives from a terminal
primary amino
moiety of the structure -NH2. Non-cyclic polyamine backbones according to the
present
invention comprise only one Z unit whereas cyclic polyamines can comprise no Z
units.
The Z "terminal" unit can be substituted with any of the E units described
further herein
below, except when the Z unit is modified to form an N-oxide. In the case
where the Z
unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and
therefore E
cannot be a hydrogen.
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The polyamines of the present invention comprise backbone R "linking" units
that serve to connect the nitrogen atoms of the backbone. R units comprise
units that for
the purposes of the present invention are referred to as "hydrocarbyl R" units
and "oxy
R" units. The "hydrocarbyl" R units are C2-C 12 alkylene, C4-C 12 alkenylene,
C3-C 12
hydroxyalkylene wherein the hydroxyl moiety may take any position on the R
unit chain
except the carbon atoms directly connected to the polyamine backbone
nitrogens; C4-
C 12 dihydroxyalkyIene wherein the hydroxyl moieties may occupy any two of the
carbon atoms of the R unit chain except those carbon atoms directly connected
to the
polyamine backbone nitrogens; Cg-C 12 dialkylarylene which for the purpose of
the
present invention are arylene moieties having two alkyl substituent groups as
part of the
linking chain. For example, a dialkylarylene unit has the formula
-(CH2)2 / ~ CH2- -(CH2)a / \ (CH2~-
or
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3
substituted C2-
C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more
preferably
ethylene. The "oxy" R units comprise -(R10)xR5(OR1)x-, -
CH2CH(OR2)CH20)Z(R10)yRl(OCH2CH(OR2)CH2)~,~,-, -CH2CH(OR2)CH2-, -
(R10)xRl-, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(R10)xRl-, -
CH2CH(OR2)CH2-, -(CH2CH(OH)CH20)Z(R10)yRl(OCH2CH-(OH)CH2)~, -
(R10)xR5(OR1)x-, more preferred R units are C2-C12 alkylene, C3-C12 hydroxy-
alkylene, C4-C12 dihydroxyalkylene, -(R10)xRl-, -(R10)xR5(OR1)x-, -
(CH2CH(OH)CH20)Z(R10)yRl(OCH2CH-(OH)CH2)~,-, and mixtures thereof, even
more preferred R units are C2-C 12 alkylene, C3 hydroxyalkylene, and mixtures
thereof,
most preferred are C2-C6 alkylene. The most preferred backbones of the present
invention comprise at least SO% R units that are ethylene.
R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is
hydrogen, and -(R10)xB, preferably hydrogen.
R3 is C 1-C 1 g alkyl, C~-C 12 arylaikylene, C~-C 12 alkyl substituted aryl,
C6-C 12
aryl, and mixtures thereof , preferably C I -C 12 alkyl, C~-C 12 arylalkylene,
more
preferably C 1-C 12 alkyl, most preferably methyl. R3 units serve as part of E
units
described herein below.
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14
R4 is C 1-C 12 alkylene, C4-C 12 alkenylene, Cg-C 12 arylalkylene, C6-C 10
arylene, preferably C 1-C 10 alkylene, Cg-C 12 arylalkylene, more preferably
C2-Cg
alkylene, most preferably ethylene or butylene.
RS is C 1-C 12 alkylene, C3-C 12 hydroxyalkylene, C4-C 12 dihydroxyalkylene,
Cg-C 12 dialkylarylene, -C(O}-, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-,
-R1(OR1)-, -CH2CH(OH)CH20(R10)yR10CH2CH(OH)CH2-, -C(O)(R4)rC(O)-,
-CH2CH(OH)CH2-, RS is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
-R1(OR1)-, -CH2CH(OH)CH2-, -CH2CH(OH)CH20{R10)yR10CH2CH-(OH)CH2-,
more preferably -CH2CH(OH)CH2-.
R6 is C2-C 12 alkylene or C6-C 12 arylene.
The preferred "oxy" R units are further defined in terms of the R1, R2, and RS
units. Preferred "oxy" R units comprise the preferred Rl, R2, and RS units.
The
preferred cotton soil release agents of the present invention comprise at
least 50% R1
units that are ethylene. Preferred R1, R2, and RS units are combined with the
"oxy" R
units to yield the preferred "oxy" R units in the following manner.
i) Substituting more preferred RS into -(CH2CH20)xRS(OCH2CH2)x-
yields -(CH2CH20)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH20)Z-
(R10)yRIO(CH2CH(OR2)CH2)~ yields -(CH2CH(OH)CH20)Z-
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)~,-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields
-CH2CH(OH)CH2-.
E units are selected from the group consisting of hydrogen, C 1-C22 alkyl, C3-
C22 alkenyl, C~-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)gS03M, -
CH(CH2C02M)COZM, -(CH2)pP03M, -(R10)mB, -C(O)R3, preferably hydrogen, C2-
C~ hydroxyalkylene, benzyl, C1-C22 alkylene, -(R10)mB, -C(O)R3, -(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)C02M, more preferably C1-C22 alkylene, -(R10)xB,
-C(O)R3, -(CH2)pC02M, -{CH2)qS03M, -CH(CH2C02M)COZM, most
preferably C1-C22 alkylene, -(R10)xB, and -C(O)R3. When no
modification or substitution is made on a nitrogen then hydrogen atom will
remain as the
moiety representing E.
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WO 97!42292 PCT/US97/07057
E units do not comprise hydrogen atom when the V, W or Z units are oxidized,
that is the nitrogens are N-oxides. For example, the backbone chain or
branching chains
do not comprise units of the following structure:
-N-R or H-N-R or -N-H
H H H
Additionally, E units do not comprise carbonyl moieties directly bonded to a
nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens
are N-oxides.
According to the present invention, the E unit -C(O)R3 moiety is not bonded to
an N-
oxide modified nitrogen, that is, there are no N-oxide amides having the
structure
O '~ '~ O
-N-R or R3-C-N-R or -N-C-R3
C=O E E
R3
or combinations thereof.
B is hydrogen, C1-C6 alkyl, -(CH2)qS03M, -(CH2)pCO2M, -(CH2)q-
(CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2S03M, -(CH2)pP03M, -P03M,
preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M, -(CH2)q-
(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
M is hydrogen or a water soluble cation in suff cient amount to satisfy charge
balance. For example, a sodium cation equally satisfies -(CH2)pC02M, and -
(CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -(CH2)qS03Na moieties.
More than one monovalent cation, (sodium, potassium, etc.) can be combined to
satisfy
the required chemical charge balance. However, more than one anionic group may
be
charge balanced by a divalent cation, or more than one mono-valent cation may
be
necessary to satisfy the charge requirements of a poly-anionic radical. For
example, a -
(CH2)pP03M moiety substituted with sodium atoms has the formula -(CH2)pP03Na3.
Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted
for or
combined with other suitable mono-valent water soluble cations. Preferred
cations are
sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (Cl-), bromine (Br-) and iodine
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WO 97/42292 PCT/US97/07057
16
(I-) or X can be any negatively charged radical such as sulfate (S042-) and
methosulfate
(CH3S03-).
The formula indices have the following values: p has the value from 1 to 6, q
has
the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x has
the value from
1 to 100; y has the value from 0 to 100; z has the value 0 or 1; k is less
than or equal to
the value of n; m has the value from 4 to about 400, n has the value from 0 to
about 200;
m + n has the value of at least 5.
The preferred cotton soil release agents of the present invention comprise
polyamine backbones wherein less than about 50% of the R groups comprise "oxy"
R
units, preferably less than about 20% , more preferably less than 5%, most
preferably the
R units comprise no "oxy" R units.
The most preferred cotton soil release agents which comprise no "oxy" R units
comprise polyamine backbones wherein less than 50% of the R groups comprise
more
than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene
comprise
3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is
when
backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most
preferred is
ethylene.
The cotton soil release agents of the present invention comprise modified
homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of
the
-NH units are modified. For the purpose of the present invention the term
"homogeneous
polyamine backbone" is defined as a polyamine backbone having R units that are
the
same (i.e., all ethylene). However, this sameness definition does not exclude
polyamines
that comprise other extraneous units comprising the polymer backbone which are
present
due to an artifact of the chosen method of chemical synthesis. For example, it
is known
to those skilled in the art that ethanolamine may be used as an "initiator" in
the synthesis
of polyethyleneimines, therefore a sample of polyethyleneimine that comprises
one
hydroxyethyl moiety resulting from the polymerization "initiator" would be
considered
to comprise a homogeneous polyamine backbone for the purposes of the present
invention. A polyamine backbone comprising all ethylene R units wherein no
branching
Y units are present is a homogeneous backbone. A polyamine backbone comprising
all
ethylene R units is a homogeneous backbone regardless of the degree of
branching or the
number of cyclic branches present.
For the purposes of the present invention the term "non-homogeneous polymer
backbone" refers to polyamine backbones that are a composite of various R unit
lengths
and R unit types. For example, a non-homogeneous backbone comprises R units
that are
a mixture of ethylene and 1,2-propylene units. For the purposes of the present
invention
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17
a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-
homogeneous backbone. The proper manipulation of these "R unit chain lengths"
provides the formulator with the ability to modify the solubility and fabric
substantivity
of the cotton soil release agents of the present invention.
Preferred cotton soil release polymers of the present invention comprise
homogeneous polyamine backbones that are totally or partially substituted by
polyethyleneoxy moieties, totally or partially quatemized amines, nitrogens
totally or
partially oxidized to N-oxides, and mixtures thereof. However, not all
backbone amine
nitrogens must be modified in the same manner, the choice of modification
being left to
the specific needs of the formulator. The degree of ethoxylation is also
determined by
the specific requirements of the formulator.
The preferred polyamines that comprise the backbone of the compounds of the
present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines
(PAI's),
preferably polyethyleneamine (PEA'S), polyethyleneimines (PEI's), or PEA's or
PEI's
connected by moieties having longer R units than the parent PAA's, PAI's,
PEA's or
PEI's. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are
obtained by reactions involving ammonia and ethylene dichloride, followed by
fractional
distillation. The common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,
heptamines,
octamines and possibly nonamines, the cogenerically derived mixture does not
appear to
separate by distillation and can include other materials such as cyclic amines
and
particularly piperazines. There can also be present cyclic amines with side
chains in
which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May
14,
1957, which describes the preparation of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's
have at least
moderate branching, that is the ratio of m to n is less than 4:1, however
PEI's having a
ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to
modification have the general formula:
H
~2NCH2CH2~ri ~CH2CHZ~iri ~CH2CH2)ri NH2
wherein m and n are the same as defined herein above. Preferred PEI's, prior
to
modification, will have a molecular weight greater than about 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the
polyamine backbone, especially in the case of PEI's, will vary, depending on
the manner
CA 02252855 2003-05-02
I8
of preparation. Each hydrogen atom attached to each nitrogen atom of the
polyamine
backbone chain represents a potential site for subsequent substitution,
quatemization or
oxidation.
These poiyamines can be prepared, for example, by polymerizing ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulFite,
sulfiuic acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing
these poiyamine backbones are disclosed in U.S. Patent 2,182,30ti, Ulrich et
al., issued
December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Patent
2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839,
Crowther,
issued September 1?, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21,
1951.
Examples of modified cotton soil release polymers of the present invention
comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a cotton soil release polymer comprising a PEI backbone
wherein all substitutable nitrogens are modified by replacement of hydrogen
with a
polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula
tHcoc~~~hN~. ~M(c,-i,cH?ohHh
N ~~~~.N~Ntl~~hoh~'ilz
(~x~t~hH ~ (CHzCliiOy,H
[H(OC1-IzCH=hI:N~N~~~N~~N~, N~ N~., ~N[(CFh_CHzOy,HJi
(GiiiCli=Oy,H (CNZCIiiO~H ~ (C3ixCH:o~rH
~N~
[H(OCt~~CHzhIZN Jr N~,N[(~~:~hHlx
~N[(~~hoh~
Formula 1
This is an example of a cotton soil release polymer that is fully modified by
one type of
moiety.
Formula II depicts a cotton soil release polymer comprising a PEI backbone
wherein all substitutable primary amine nitrogens are modified by replacement
of
hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)?H, the molecule is then
modified by subsequent oxidation of all oxidizable primary and secondary
nitrogens to
N-oxides, said cotton soil release agent having the formula
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
19
0 0
[H(OCH,CHzhlzN NI(CHzCHzphHlz aCH CH.,O)6H
O
N O~ ~~NUCHz~zOhM2
H(OCH CHz)e ~O O(CHzCHzO)6H 1 f O(CHzCH O) H
O ~ \I I/ O O z
O
IH(OCH,CH ],N~N~N~N~~ ~N~ ~ ~N~~ ~N[(Cf-IzC
_ zh _
O(CHzCH,O) H ~ CO(CHZCH O) H
N 2 6
O 1 O
j ~N~NI(CHz~zOhl-Ilz
li-t(~z~zhhN O'~ ~ ~ f(Cf-lzC1-tzohH)z
0
Formula II
Formula III depicts a cotton soil release polymer comprising a PEI backbone
wherein all backbone hydrogen atoms are substituted and some backbone amine
units are
quaternized. The substituents are polyoxyalkyleneoxy units, -(CH2CH20)~H, or
methyl
groups. The modified PEI cotton soil release polymer has the formula
fH(~z~zhlzN N(~z~zChH CH3
I- ~3. ~ _N~c~
~3 ~ ~3 ~3. ~3
f H(OCH2CHzhlz~N~~N~~N~1~N~N~N(~3h
I I I
CI' ~3 ~3 ~ CI' CHs
CI'
IH(~z~zh
Formula III
Cl'
N(~3h
Formula IV depicts a cotton soil release polymer comprising a PEI backbone
wherein the backbone nitrogens are modified by substitution (i.e. by -
(CH2CH20)~H or
methyl), quaternized, oxidized to N-oxides or combinations thereof. The
resulting cotton
soil release polymer has the formula
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
~3
lH(OCHz~zh)zN N(CHzCH20)~,H
O CH3
~NJ CI CH3,N~N(CHz~zO~H
CI~
O
CH3 ~ CH3 O ~ CH3 ~ CH3, . CH3
IH(OCHzCHzh)zN~N~_ ~~ i ~N~N~N~N~N~N(~3)Z
CI ~3 O
Formula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of
the
secondary amine nitrogens ethoxylated while having other secondary amine
nitrogens
oxidized to N-oxides. This also applies to the primary amine nitrogens, in
that the
formulator may choose to modify all or a portion of the primary amine
nitrogens with
one or more substituents prior to oxidation or quaternization. Any possible
combination
of E groups can be substituted on the primary and secondary amine nitrogens,
except for
the restrictions described herein above.
Preferred Soil Release A ent
In addition to the polyamine dispersent, suitable soil release agents are
preferably
combined with the cationic surfactant. For the purposes of the present
invention the
preferred soil release polymer is described herein below.
The preferred non-cotton soil release agent according to the present invention
comprises:
A) at least about 10% by weight of a substantially linear sulfonated poly-
ethoxy/propoxy end-capped ester having molecular weight ranging from
about 500 to about 8,000; said ester consisting essentially of on a molar
basis:
i) from about 1 to about 2 moles of sulfonated poly ethoxy/propoxy
end-capping units of the formula:
(MS03)(CH2)m(CH2CH20)(RO)n-
wherein M is a salt-forming cation such as sodium of
tertraa)kylammonium, m is 0 or 1, R is ethylene, propylene, and
mixtures thereof; and n is fro 0 to 2; and mixtures thereof;
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WO 97/42292 PCT/US97/07057
21
ii) from about 0.5 to about 66 moles of units selected from the group
consisting of:
a) oxyethyleneoxy units;
b) a mixture of oxyethyleneoxy and oxy-1,2,-propyleneoxy
units wherein said oxyethyleneoxy units are present in an
oxyethyleneoxy of oxy-1,2-propyleneoxy mole ratio
ranging from 0.5 :1 to about 10:1; and
c) a mixture of a) or b) with poly(oxyethylene)oxy units have
a degree of polymerization of from 2 to 4; provided that
when said poly(oxyethylene)oxy units have a degree of
polymerization of 2, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units ranges
fro 0:1 to 0.33:1; and when said poly(oxyethylene)oxy
units have a degree of polymerization of 3; the mole ration
of poly(oxyethylene)oxy units to total group ii) units
ranges from 0:1 to about 0.22:1; and when said
poly(oxyethylene)oxy units have a degree of
polymerization equal to 4, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units ranges
from 0:1 to about 0.14:1;
iii) from about 1.5 to about 40 moles of terephthaloyl units; and
iv) from 0 to about 26 moles of 5-sulphophthaloyl units of the
formula:
-(~)C(C6H3)(S03M)C(~)_
wherein M is a salt forming cation; and
B) from about 0.5% to about 20% by weight of ester, of one or more
crystallization-reducing stabilizers.
Stabilizers useful in this invention should be water soluble or water
dispersible.
The stabilizing agents that are useful herein include sulfonate-type
hydrotropes, linear or
branched alkylbenzenesulfonates, paraffin a]sulfonates, and other thermally-
stable alkyl
sulfonate variations with from about 4 to about 20 carbon atoms. Preferred
agents
include sodium dodecylbenzenesulfonate, sodium cumenesulfonate, sodium
toluenesulfonate, sodium xylenesulfonate, and mixtures thereof. When higher
levels of
stabilizers are used, mixtures of hydrotropes and/or other stabilizers are
preferred over
pure components to insure full. integration into the oligomer and to reduce
the possibility
of crystallization of the stabilizer.
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22
In general, the level of such agents should be kept as low as possible while
providing the primary benefit, i.e., the reduction in the amount of
crystallization that the
soil release agent undergoes during manufacture, storage and when introduced
to the
wash liquor. the composition may comprise from about 0.5% to about 20%
stabilizer.
Most preferably, these ester compositions comprise an amount sufficient to
reduce the
crystallization of the oligomer during manufacture and when introduced to the
wash
liquor, i.e., at least 3% by weight.
The above described soil release agent is disclosed in U.S. 5,415,807,
Gosselink
et al., issued May 16, 1995.
The compositions herein can optionally include one or more other detergent
adjunct materials or other materials for assisting or enhancing cleaning
performance,
treatment of the substrate to be cleaned, or to modify the aesthetics of the
detergent
composition (e.g., perfumes, colorants, dyes, etc.). The following are
illustrative
examples of such adjunct materials.
Detersive Surfactants - Nonlimiting examples of surfactants useful herein
typically at levels from about 1% to about 55%, by weight, include the
conventional
C 11-C 1 g alkyl benzene sulfonates ("LAS") and primary, branched-chain and
random
C l 0-C20 alkyl sulfates ("AS"), the C 1 p-C 1 g secondary (2,3) alkyl
sulfates of the
formula CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y{CHOS03-M+) CH2CH3
where x and (y + 1 ) are integers of at least about 7, preferably at least
about 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl sulfate,
the C 1 p-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
sulfates),
C l 0-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-
1 g glycerol ethers, the C 1 p-C 1 g alkyl polyglycosides and their
corresponding sulfated
polyglycosides, and C 12-C 1 g alpha-sulfonated fatty acid esters. If desired,
the
conventional nonionic and amphoteric surfactants such as the C 12-C 1 g alkyl
ethoxylates
("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12
alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12-C 1 g
betaines and
sulfobetaines ("sultaines"), C l 0-C 1 g amine oxides, and the like, can also
be included in
the overall compositions. The C l 0-C 1 g N-alkyl polyhydroxy fatty acid
amides can also
be used. Typical examples include the C 12-C 1 g N-methylglucamides. See WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid
amides, such as C l 0-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl
through N-
hexyl C 12-C 1 g glucamides can be used for low sudsing. C l 0-C20
conventional soaps
may also be used. If high sudsing is desired, the branched-chain C 1 p-C 16
soaps may be
CA 02252855 1998-10-29
WO 97!42292 PCT/L1S97107057
23
used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful surfactants are listed in standard texts.
Other Ingredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments,
solvents for liquid
formulations, solid fillers for bar compositions, etc. If high sudsing is
desired, suds
boosters such as the C 10-C 16 alkanolamides can be incorporated into the
compositions,
typically at 1 %-10% levels. The 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, typically, 0. i %-2%, to provide additional suds
and to enhance
grease removal performance.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing said ingredients onto a porous
hydrophobic
substrate, then coating said substrate with a hydrophobic coating. Preferably,
the
detersive ingredient is admixed with a surfactant before being absorbed into
the porous
substrate. In use, the detersive ingredient is released from the substrate
into the aqueous
washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark
SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme solution
containing
3%-5% of C 13-15 e~oxylated alcohol (EO 7) nonionic surfactant. Typically, the
enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder
is
dispersed with stirring in silicone oil (various silicone oil viscosities in
the range of 500-
12,500 can be used). The resulting silicone oil dispersion is emulsified or
otherwise
added to the final detergent matrix. By this means, ingredients such as the
aforementioned enzymes, bleaches, bleach activators, bleach catalysts,
photoactivators,
dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be
"protected" for
use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from 2 to about
6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol,
glycerin, and 1,2-propanediol) can also be used. The compositions may contain
from 5%
to 90%, typically 10% to 50% of such Garners.
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WO 97/42292 PCT/US97/07057
24
The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
about 6.5
and about 11, preferably between about 7.5 and 10.5. Laundry products are
typically at
pH 9-11. Techniques for controlling pH at recommended usage levels include the
use of
buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Enzymes - Enzymes can be included in the present detergent compositions for a
variety of purposes, including removal of protein-based, carbohydrate-based,
or
triglyceride-based stains from surfaces such as textiles, for the prevention
of refugee dye
transfer, for example in laundering, and for fabric restoration. Suitable
enzymes include
proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of
any suitable
origin, such as vegetable, animal, bacterial, fungal and yeast origin.
Preferred selections
are influenced by factors such as pH-activity and/or stability optima,
thermostability, and
stability to active detergents, builders and the like. In this respect
bacterial or fungal
enzymes are preferred, such as bacterial amylases and proteases, and fungal
cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in a laundry, hard surface cleaning or
personal
care detergent composition. Preferred detersive enzymes are hydrolases such as
proteases, amylases and lipases. Preferred enzymes for laundry purposes
include, but are
not limited to, proteases, cellulases, lipases and peroxidases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on
substrates such as fabrics. In practical terms for current commercial
preparations, typical
amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of
active
enzyme per gram of the detergent composition. Stated otherwise, the
compositions
herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by
weight of a
commercial enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005 to 0.1
Arson units
(AU) of activity per gram of composition. For certain detergents it may be
desirable ~o
increase the active enzyme content of the commercial preparation in order to
minim:
the total amount of non-catalytically active materials and thereby improve
spotting/filming or other end-results. Higher active levels may also be
desirable in
highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease
is obtained
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WO 97/42292 PCT/US97107057
from a strain of Bacillus, having maximum activity throughout the pH range of
8-I2,
developed and sold as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter
"Novo". The preparation of this enzyme and analogous enzymes is described in
GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The
Netherlands;
as well as Protease A as disclosed in EP /30,756 A, January 9, 1985 and
Protease B as
disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.
See also
a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to
Novo. Enzymatic detergents comprising protease, one or more other enzymes, and
a
reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred
proteases include those of WO 9510591 A to Procter & Gamble . When desired, a
protease having decreased adsorption and increased hydrolysis is available as
described
in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D"
is a
carbonyl hydrolase variant having an amino acid sequence not found in nature,
which is
derived from a precursor carbonyl hydrolase by substituting a different amino
acid for a
plurality of amino acid residues at a position in said carbonyl hydrolase
equivalent to
position +76, preferably also in combination with one or more amino acid
residue
positions equivalent to those selected from the group consisting of +99, +101,
+103,
+104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197,
+204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
numbering of Bacillus amyloliguefaciens subtilisin, as described in WO
95/10615
published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO 95/30010 published
Novenber 9, 1995 by The Procter & Gamble Company; WO 95/30011 published
Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published
Novenber 9, 1995 by The Procter & Gamble Company.
Amylases suitable herein include, for example, a-amylases described in GB
1,296,839 to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and
TERMAMYL~, Novo. FUNGAMYL~ from Novo is especially useful. Engineering of
enzymes for improved stability, e.g., oxidative stability, is known. See, for
example J.
Biological Chem., Vol. 260, No. I 1, June 1985, pp 6518-6521. Certain
preferred
embodiments of the present compositions can make use of amylases having
improved
stability in detergents, especially improved oxidative stability as measured
against a
reference-point of TERMAMYL~ in commercial use in 1993. These preferred
amylases
CA 02252855 2003-05-02
26
herein share the characteristic of being "stability-enhanced" amylases,
characterized, at a
minimum, by a measurable improvement in one or more of: oxidative stability,
e.g., to
hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-
10; thermal
stability, e.g., at common wash temperatures such as about 60oC; or alkaline
stability,
e.g., at a pH from about 8 to about I 1, measured versus the above-identified
reference-
point amylase. Stability can be measured using any of the art-disclosed
technical tests.
See, for example, references disclosed in WO 9402597. Stability-enhanced
amylases can
be obtained from Novo or from Genencor International. One class of highly
preferred
amylases herein have the commonality of being derived using site-directed
mutagenesis
from one or more of the Baccillus amylases, especialy the Bacillus a-amylases,
regardless of whether one, two or multiple amylase strains are the immediate
precursors.
Oxidative stability-enhanced amylases vs. the above-identified reference
amylase are
preferred for use, especially in bleaching, more preferably oxygen bleaching,
as distinct
from chlorine bleaching, detergent compositions herein. Such preferred
amylases include
(a) an amylase according to the hereinbefore noted WO 9402597, Novo, Feb. 3,
1994, as further illustrated by a mutant in which substitution is made, using
alanine or
threonine, preferably threonine, of the methionine residue located in position
197 of the
B.lichenijormis alpha-amylase, known as TERMAMYL~, or the homologous position
variation of a similar parent amylase, such as B. amyloliquejaciens~,
B.subtilis, or
B.stearothermophilus; (b) stability-enhanced amylases as described by Genencor
lntemational in a paper entitled "Oxidatively Resistant alpha-Amylases"
presented at the
207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing
detergents
inactivate alpha-amylases but that improved oxidative stability amylases have
been made
by Genencor from B.lichenijormis NCIB8061. Methionine (Met) was identified as
the
most likely residue to be modified. Met was substituted, one at a time, in
positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly important
being
M 197L and M 197T with the M 197T variant being the most stable expressed
variant.
Stability was measured in CASCADE~ and SUNLIGHT~; (c) particularly preferred
amylases herein include amylase variants having additional modification in the
immediate parent as described in WO 9510603 A and are available from the
assignee,
Novo, as DURAMYL~. Other particularly preferred oxidative stability enhanced
amylase include those described in WO 9418314 to Genencor International and WO
9402597 to Novo. Any other oxidative stability-enhanced amylase can be used,
for
example as derived by site-directed mutagenesis from known chimeric, hybrid or
simple
CA 02252855 2003-05-02
27
mutant parent forms of available amylases. Other preferred enzyme
modifications are
accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably
having
a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6,
1984,
discloses suitable fungal cellulases from Humicola insolens or Humicola strain
DSMI800 or a cellutase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275
and DE-OS-2.247.832. CAREZYME~ (Novo) is especially useful. See also WO
9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent
Application
53,20487, laid open Feb. 24, 1978. This lipase is available from Amano
Pharmaceutical
Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano," or "Amano-P."
Other
suitable commercial lipases include Amano-CES, lipases ex Chromobacter
viscosum,
e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata,
Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and
Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. L1POLASE~
enzyme derived from Humicola lanuginosa and commercially available from Novo,
see
also EP 341,947, is a preferred lipase for use herein. Lipase and amylase
variants
stabilized against peroxidase enzymes are described in WO 9414951 A to Novo.
See
also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention
of transfer of dyes or pigments removed from substrates during the wash to
other
substrates present in the wash solution. Known peroxidases include horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO 89099813 A,
October
19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18,
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
28
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful
for
liquid detergent formulations, and their incorporation into such formulations,
are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed
and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405
and EP
200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases
and cellulases, is described in WO 9401532 A to Novo.
Enzyme Stabilizing System - Enzyme-containing, including but not limited to,
liquid
compositions, herein may comprise from about 0.001 % to about 10%, preferably
from
about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by
weight of
an enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing
system which is compatible with the detersive enzyme. Such a system may be
inherently
provided by other formulation actives, or be added separately, e.g., by the
formulator or
by a manufacturer of detergent-ready enzymes. Such stabilizing systems can,
for
example, comprise calcium ion, boric acid, propylene glycol, short chain
carboxylic
acids, boronic acids, and mixtures thereof, and are designed to address
different
stabilization problems depending on the type and physical form of the
detergent
composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
magnesium ions in the finished compositions which provide such ions to the
enzymes.
Calcium ions are generally more effective than magnesium ions and are
preferred herein
if only one type of cation is being used. Typical detergent compositions,
especially
liquids, will comprise from about 1 to about 30, preferably from about 2 to
about 20,
more preferably from about 8 to about 12 millimoles of calcium ion per liter
of finished
detergent composition, though variation is possible depending on factors
including the
multiplicity, type and levels of enzymes incorporated. Preferably water-
soluble calcium
or magnesium salts are employed, including for example calcium chloride,
calcium
hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide
and
calcium acetate; more generally, calcium sulfate or magnesium salts
corresponding to the
exemplified calcium salts may be used. Further increased levels of Calcium
and/or
Magnesium may of course be useful, for example for promoting the grease-
cutting action
of certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or
more of the
composition though more typically, levels of up to about 3% by weight of boric
acid or
CA 02252855 1998-10-29
WO 97/42292 PCTlUS97/07057
29
other borate compounds such as borax or orthoborate are suitable for liquid
detergent
use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-
bromophenylboronic acid or the like can be used in place of boric acid and
reduced
levels of total boron in detergent compositions may be possible though the use
of such
substituted boron derivatives.
Stabilizing systems of certain cleaning compositions may further comprise from
0
to about 10%, preferably from about 0.01 % to about 6% by weight, of chlorine
bleach
scavengers, added to prevent chlorine bleach species present in many water
supplies
from attacking and inactivating the enzymes, especially under alkaline
conditions. While
chlorine levels in water may be small, typically in the range from about 0.5
ppm to about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact with
the enzyme, for example during fabric-washing, can be relatively large;
accordingly,
enzyme stability to chlorine in-use is sometimes problematic. Since perborate
or
percarbonate, which have the ability to react with chlorine bleach, may
present in certain
of the instant compositions in amounts accounted for separately from the
stabilizing
system, the use of additional stabilizers against chlorine, may, most
generally, not be
essential, though improved results may be obtainable from their use. Suitable
chlorine
scavenger anions are widely known and readily available, and, if used, can be
salts
containing ammonium cations with sulfite, bisuifite, thiosulfite, thiosuIfate,
iodide, etc.
Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine
(MEA), and mixtures thereof can likewise be used. Likewise, special enzyme
inhibition
systems can be incorporated such that different enzymes have maximum
compatibility.
Other conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate
and
sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate,
citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures
thereof can be used
if desired. In general, since the chlorine scavenger function can be performed
by
ingredients separately listed under better recognized functions, (e.g.,
hydrogen peroxide
sources), there is no absolute requirement to add a separate chlorine
scavenger unless a
compound performing that function to the desired extent is absent from an
enzyme-
containing embodiment of the invention; even then, the scavenger is added only
for
optimum results. Moreover, the formulator will exercise a chemist's normal
skill in
avoiding the use of any enzyme scavenger or stabilizer which is majorly
incompatible, as
formulated, with other reactive ingredients, if used. In relation to the use
of ammonium
salts, such salts can be simply admixed with the detergent composition but are
prone to
CA 02252855 2003-05-02
adsorb water and/or liberate ammonia during storage. Accordingly, such
materials, if
present, are desirably protected in a particle such as that described in US
4,652,392,
Baginski et al.
Bleachirn~C_ompounds - Bleachinn Aeents and Bleach Activators - The detergent
compositions herein may optionally contain bleaching agents or bleaching
compositions
containing a bleaching agent and one or more bleach activators. When present,
bleaching agents will typically be at levels of from about 1% to about 30%,
more
typically from about 5% to about 20%, of the detergent composition, especially
for fabric
laundering. If present, the amount of bleach activators will typically be from
about 0.1%
to about 60%, more typically from about 0.5% to about 40% of the bleaching
composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning that are now known or become known.
These
include oxygen bleaches as well as other bleaching agents. Perborate bleaches,
e.g.,
sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof Suitable
examples of
this class of agents include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid
and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
Patent
4,483,781, Hartman, issued November 20, 1984, U.S. Patent No. 4,634,551, Burns
et al,
issued January 6, 1987, European Patent Application 0,133,354, Banks et al,
published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid
as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhydMate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can
also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers, not
more than about 10% by weight of said particles being smaller than about 200
micrometers and not more than about 10% by weight of said particles being
larger than
about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate,
CA 02252855 2003-05-02
31
borate or water-soluble surfactants. Percarbonate is available from various
commercial
sources such as FMC, Solway and T'okai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably
combined with bleach activators, which lead to the in situ production in
aqueous solution
(i.e., during the washing process) of the peroxy acid con-esponding to the
bleach
activator. Various nonlimiting examples of activators are disclosed in U.S.
Patent
4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The
nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,551 for
other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(R')R2C(O)L
wherein R 1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group.
A leaving group is any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis
anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproy.l)oxybenzenesulfonate,
(6-decanamido-caproyl~xybenzenesulfonate, and mixtures thereof as described in
U.S.
Patent 4,634,551.
Another class of bleach activators comprises the benzoxaxin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
A highly preferred activator of the benzoazin-type is:
O
(I
of
..~ o
N
Still another class of preferred bleach activators includes ttve acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
CA 02252855 2003-05-02
32
0 O
O C-CHZ-CH2 O C-CH2-CH2
R6 C N~ -CH ~CHZ R6-C-N~ H -
C H2 z C 2 C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from I to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam,
decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
Patent
4,545,784, issued to Sanderson, October 8, 1985, which
discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
sodium
perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum
phthaiocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et
al. If
used, detergent compositions will typically contain from about 0.025% to about
1.25%,
by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S.
Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
549,271A1,
549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts
include
~IV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane~(PF6)2, M',nIII2(u-O)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_(C104)2, MnIV4(u-O)~(1,4,7-
triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(CI04)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include
those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese
with
various complex ligands to enhance bleaching is also reported in the following
United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,11?;
5,274,147;
5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per ten
million of the active bleach catalyst species in the aqueous washing liquor,
and will
CA 02252855 2003-05-02
33
preferably provide from about 0. l ppm to about 700 ppm, more preferably from
about 1
ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders can
be used. Builders are typically used in fabric laundering compositions to
assist in the
removal of particulate soils.
The teve) of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about I % builder. Liquid formulations typically
comprise
from about 5% to about 50%, more typically about 5% to about 30%, by weight,
of
detergent builder. Granular formulations typically comprise from about 10% to
about
80°l0, more typically from about 15% to about 50% by weight, of the
detergent builder.
Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by
the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
builders are
required in some locales. Importantly, the compositions herein function
surprisingly
well even in the presence of the so-called "weak" builders (as cornpared with
phosphates)
such as citrate, or in the so-called "underbuilt" situation that may occur
with zeolite or
layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si42:Na20 ratio in the range I .6:1 to 3.2:1 and layered silicates,
such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12,
198? to H.
P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed
by
Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the
Na
SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-
Na2Si05
morphology form of layered silicate. It can be prepared by methods such as
those
described in Getrnan DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly
preferred
layered silicate for use herein, but other such layered silicates, such as
those having the
general formula NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a
number
from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can
be used
TM TM
herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7
and
NaSKS-11 Tas the alpha, beta and gamma forms. As noted above, the delta-
Na~Si05
(NaSKS-6 form) is most preferred for use herein. Other silicates may also be
useful such
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
34
as for example magnesium silicate, which can serve as a crispening agent in
granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component
of suds
control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates
as disclosed in German Patent Application No. 2,321,001 published on November
15,
1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical
formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0
to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-
occurring aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669,
Krummel,
et al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion
exchange materials useful herein are available under the designations Zeolite
A, Zeolite
P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material has the formula:
Nal2~(AI02)12(Si02)12]'~20
wherein x is from about 20 to about 30, especially about 27. This material is
known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As used
herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287,
CA 02252855 2003-05-02
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 197?.
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on
May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, I, 3, S-
trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the
various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates
such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxyiate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
biodegradability. Citrates can also be used in granular compositions,
especially in
combination with zeolite andlor layered silicate builders. Oxydisuccinates are
also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
Patent
4,566.984, Bush, issued January 28, 1986. Useful succinic acid builders
include the CS-
C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred
compound of this type is dodecenylsuccinic acid. Specific examples of
succinate
builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (prefer ed), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates
are the preferred builders of this group, and are described in European Patent
Application
0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into
the compositions alone, or in combination with the aforesaid builders,
especially citrate
and/or the succinate builders, to provide additional builder activity. Such
use of fatty
acids will generally result in a diminution of sudsing, which should be taken
into account
by the formulator.
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
36
In situations where phosphorus-based builders can be used, and especially in
the
formulation of bars used for hand-laundering operations, the various alkali
metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate
and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-
hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.
S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be
used.
Polymeric Soil Release Agent - In addition to the preferred soil release
agents
noted hereinbefore, known polymeric soil release agents, hereinafter "SRA",
can
optionally be employed in the present detergent compositions. If utilized,
SRA's will
generally comprise from 0.01 % to 10.0%, typically from 0.1 % to 5%,
preferably from
0.2% to 3.0% by weight, of the compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of
hydrophobic fibers such as polyester and nylon, and hydrophobic segments to
deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can
enable stains occurring subsequent to treatment with the SRA to be more easily
cleaned
in later washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic
species, see
U.S. 4,956,447, issued September 11, 1990 to Gosselink, et al., as well as
noncharged
monomer units, and their structures may be linear, branched or even star-
shaped. They
may include capping moieties which are especially effective in controlling
molecular
weight or altering the physical or surface-active properties. Structures and
charge
distributions may be tailored for application to different fiber or textile
types and for
varied detergent or detergent additive products.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes involving at least one transesterification/oligomerization, often
with a metal
catalyst such as a titanium(IV) alkoxide. Such esters may be made using
additional
monomers capable of being incorporated into the ester structure through one,
two, three,
four or more positions, without, of course, forming a densely crosslinked
overall
structure.
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat
units and allyl-derived sulfonated terminal moieties covalently attached to
the backbone,
for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel
and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl
alcohol; (b)
reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-
propylene
CA 02252855 2003-05-02
37
glycol ("PG") in a two-stage transesterification/oligomerization procedure;
and (c)
reacting the product of (b) with sodium metabisulfite in water. Other SRA's
include the
nonionic end-capped 1,2-propylenelpolyoxyethylene terephthalate polyesters of
U.S.
4,711,730, December 8, 1987 to Gosselink et al., for example those produced by
transesterificationloligomerization of poly(ethyleneglycol) methyl ether, DMT,
PG and
poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and
fully-
anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to
Gosselink,
such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
compounds of
U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT,
methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG andlor
PG,
Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
Maldonado, Gosselink et al., the latter being typical of SR,A's useful in both
laundry and
fabric conditioning products, an example being an ester composition made from
m-
sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably
further
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July
8, 1975;
cellulosic derivatives such as the hydroxyether cellulosic polymers available
as
TM
METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses,
see
U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose
ethers
having an average degree of substitution (methyl) per anhydroglucose unit from
about
1.6 to about 2.3 and a solution viscosity of from about 80 to about 120
centipoise
measured at 20°C as a 2% aqueous solution. Such materials are available
as
TM
METOLOSE SM 100 and METOLOSE SM200, which are the trade names of methyl
cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Suitable SRA's characterised by polyvinyl ester) hydrophobe segments include
graft copolymers of polyvinyl ester), e.g., Cl-C6 vinyl esters, preferably
polyvinyl
acetate), grafted onto polyalkylene oxide backbones. See European Patent
Application 0
219 048, published April 22, 1987 by Kud, et al. Commercially available
examples
TM
include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany.
Other SRA's are polyesters with repeat units containing 10-15% by weight of
ethylene
terephthalate together with 80-90% by weight of polyoxyethylene terephthalate
derived
CA 02252855 2003-05-02
38
from a polyoxyethylene glycol of average molecular weight 300-5,000.
Commercial
TM TM
examples include 2ELC~N 5126 from Dupont and MILEASE T fiom ICI.
Another preferred SRA is an oligomer having empirical formula
(CAP)2(EG/PG)5(T)5(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl
(SIP),
oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably
terminated with end-caps (CAP), preferably modified isethionates, as in an
oligomer
comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-
1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about
10:1, and two
end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said
SRA
preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a
crystallinity-reducing stabiliser, for example an anionic surfactant such as
linear sodium
dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and
toluene-
sulfonates or mixtures thereof, these stabilizers or modifiers being
introduced into the
synthesis vessel, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and
Hall, issued
May 16, 1995. Suitable monomers for the above SRA include Na-2-(2-
hydroxyethoxy)-
ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.
Yet another group of preferred SR.A.'s are oligomeric esters comprising: ( 1 )
a
backbone comprising (a) at least one unit selected from the group consisting
of
dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least
trifunctional
whereby ester linkages are formed resulting in a branched oligomer backbone,
and
combinations thereof; (b) at least one unit which is a terephthaloyl moiety;
and (c) at
least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one
or more
capping units selected from nonionic capping units, anionic capping units such
as
alkoxylated, preferably ethoxylated, isethionates, alkoxylated
propanesulfonates,
alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl
derivatives
and mixtures thereof. Preferred are esters of the empirical fon,nula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(S1P)z'(SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)
represents
di(oxyethylene)oxy units, (SEG) represents units derived from the sulfoethyl
ether of
glycerin and related moiety units, (B) represents branching units which are at
least
trifunctional whereby ester linkages are formed resulting in a branched
oligomer
backbone, x is from about 1 to about 12, y' is from about 0.5 to about 25, y"
is from 0 to
about 12, y"' is from 0 to about 10, y'+y"+y"' totals from about 0.5 to about
25, z is from
about 1.5 to about 25, z' is from 0 to about 12; z + z' totals from about 1.5
to about 25, q
is from about 0.05 to about 12; rn is from about 0.01 to about 10, and x, y',
y", y"', z, z', q
CA 02252855 1998-10-29
WO 97/42292 PCTIUS97/07057
39
and m represent the average number of moles of the corresponding units per
mole of said
ester and said ester has a molecular weight ranging from about 500 to about
5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-
dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products
of
ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class
include the
product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxy-
ethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)ethoxy}-
ethoxyJethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate,
EG,
and PG using an appropriate Ti(IV) catalyst and can be designated as
(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+p3S[CH2CH20]3.5)-
and B is a unit from glycerin and the mole ratio EG/PG is about I .7:1 as
measured by
conventional gas chromatography after complete hydrolysis.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate coupling agents to link polymeric ester structures, see U.S.
4,201,824,
Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with
carboxylate
terminal groups made by adding trimellitic anhydride to known SRA's to convert
terminal hydroxyl groups to trimellitate esters. With the proper selection of
catalyst, the
trimellitic anhydride forms linkages to the terminals of the polymer through
an ester of
the isolated carboxylic acid of trimellitic anhydride rather than by opening
of the
anhydride linkage. Either nonionic or anionic SRA's may be used as starting
materials as
long as they have hydroxyl terminal groups which may be esterified. See U.S.
4,525,524
Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of
the
urethane-linked variety, see U.S. 4,201,824, Violland et al.; (IV) polyvinyl
caprolactam)
and related co-polymers with monomers such as vinyl pyrrolidone and/or
dimethylaminoethyl methacrylate, including both nonionic and cationic
polymers, see
U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the
SOKALAN types
from BASF, made by grafting acrylic monomers onto sulfonated polyesters. These
SRA's assertedly have soil release and anti-redeposition activity similar to
known
cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie. Still other
classes
include: (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate
onto
proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) polyester-
polyamide SRA's prepared by condensing adipic acid, caprolactam, and
polyethylene
glycol, especially for treating polyamide fabrics, see Bevan et al., DE
2,335,044 to
Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents
4,240,918,
4,787,989 and 4,525,524.
CA 02252855 2003-05-02
Chelating Agents - The detergent compositions herein may also optionally
contain one or more iron and/or manganese chelating agents. Such chelating
agents can
be selected from the group consisting of amino carboxylates, amino
phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures therein,
all as
hereinafter defined. Without intending to be bound by theory, it is believed
that the
benefit of these materials is due in part to their exceptional ability to
remove iron and
manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted
in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates)
TM
as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or
alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic cheiating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et a!.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5~disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November
3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1 %
to
about 10% by weight of the detergent compositions herein. More preferably, if
utilized,
the chelating agents will comprise from about 0. I % to about 3.0% by weight
of such
compositions.
CIa~Soil Removat/Anti-redeposition Aeents - The compositions of the present
invention can also optionally contain water-soluble ethoxylated amines having
clay soil
removal and antiredeposition properties. Granular detergent compositions which
contain
these compounds typically contain from about 0.01 % to about 10.0% by weight
of the
water-soluble ethoxylates amines; liquid detergent compositions t)~pically
contain about
0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
CA 02252855 1998-10-29
WO 97/42292 PCT/ITS97/07057
41
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil
removal-antiredeposition agents are the cationic compounds disclosed in
European
Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil
removal/antiredeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti
redeposition agents known in the art can also be utilized in the compositions
herein.
Another type of preferred antiredeposition agent includes the carboxy methyl
cellulose
(CMC) materials. These materials are well known in the art.
Polymeric DispersingA~ents - Polymeric dispersing agents can advantageously
be utilized at levels from about 0.1% to about 7%, by weight, in the
compositions herein,
especially in the presence of zeolite and/or layered silicate builders.
Suitable polymeric
dispersing agents include polymeric polycarboxylates and polyethylene glycols,
although
others known in the art can also be used. It is believed, though it is not
intended to be
limited by theory, that polymeric dispersing agents enhance overall detergent
builder
performance, when used in combination with other builders (including lower
molecular
weight polycarboxylates) by crystal growth inhibition, particulate soil
release
peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segments,
containing no carboxylate radicals such as vinylrnethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
form preferably ranges from about 2,000 to 10,000, more preferably from about
4,000 to
7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of
such acrylic
acid polymers can include, for example, the alkali metal, ammonium and
substituted
ammonium salts. Soluble polymers of this type are known materials. Use of
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
42
polyacrylates of this type in detergent compositions has been disclosed, for
example, in
Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the dispersing/anti-redeposition agent. Such materials include the water-
soluble salts of
copolymers of acrylic acid and malefic acid. The average molecular weight of
such
copolymers in the acid form preferably ranges from about 2,000 to 100,000,
more
preferably from about 5,000 to 75,000, most preferably from about 7,000 to
65,000. The
ratio of acrylate to maleate segments in such copolymers will generally range
from about
30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts
of such
acryli ~ acid/maleic acid copolymers can include, for example, the alkali
metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers
of
this type are known materials which are described in European Patent
Application No.
66915, published December 15, 1982, as well as in EP 193,360, published
September 3,
1986, which also describes such polymers comprising hydroxypropylacrylate.
Still other
useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
Such
materials are also disclosed in EP 193,360, including, for example, the
45/45/10
terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil
removal-
antiredeposition agent. Typical molecular weight ranges for these purposes
range from
about S00 to about 100,000, preferably from about 1,000 to about 50,000, more
preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably
have a molecular weight (avg.) of about 10,000.
Brightener - Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels typically from about 0.05% to
about 1.2%,
by weight, into the detergent compositions herein. Commercial optical
brighteners
which may be useful in the present invention can be c~_ ssified into
subgroups, which
include, but are not necessarily limited to, derivatives c~. ~;tilbene,
pyrazoline, coumarin,
carboxylic acid, methinecyanines, dibenzothiphene-5, ~-:~roxia, azoles, 5- and
6-
membered-ring heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of Fluorescent
Brightening
Agents", M. Zahradnik, Published by John Wiley & Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
CA 02252855 2003-05-02
43
December 13, 1988. These brighteners include the PHORWHITE series
oTMrighteners
from Verona. Other brighteners disclosed in this reference include: Tinopal
UNPA,
Tinopal CBS and Tinopal SHM; available from Ciba-Geigy; Antic Whiff CC and
Antic
White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-
phenyl)-2H-
napthol[1,2-dJtriazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-
bis(stryl)bisphenyls;
and the aminocoumarins. Specific examples of these brighteners include 4-
methyl-7-
diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 1,3-Biphenyl-
phrazolines;
2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-
(stilbene-4-yl)-
2H-naphtho- [I,2-d)triazole. See also U.S. Patent 3,646,015, issued February
29, 1972 to
Hamilton. Anionic brighteners are preferred herein.
Suds Sup~ressors - Compounds for reducing or suppressing the formation of suds
can be incorporated into the compositions of the present invention. Suds
suppression can
be of particular importance in the so-called "high concentration cleaning
process" as
described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style
washing
machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer
Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447
(John
Wiley & Sons, Inc., 1979). One category of suds suppressor of particular
interest
encompasses monocarboxylic fatty acid and soluble salts therein. See U.S.
Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic
fatty
acids and salts thereof used as suds suppressor typically have hydrocarbyl
chains of 10 to
about 24 carbon atoms, preferably 12 'to 18 carbon atoms. Suitable salts
include the
alkali metal salts such as sodium, potassium, and lithium salts, and ammonium
and
alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such as
paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid
esters of monovalent
aicohols, aliphatic C 1 g-C4p ketones (e.g., stearone), etc. Other suds
inhibitors include
N-alkylated amino triazines such as tri- to hexa-alkylmelamines ar di- to
tetra-
alkyldiamine chlortriazines formed as products of cyanuric chloride with two
or three
moles of a primary or secondary amine containing 1 to 24 carbon atoms,
propylene
oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester
and
monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate
esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in .liquid
form. The liquid
hydrocarbons will be liquid at room temperature and atmospheric pressure, and
will have
CA 02252855 2003-05-02
44
a pour point in the range of about -40°C and about 50°C, and a
minimum boiling point
not less than about 110°C (atmospheric pressure). It is also known to
utilize waxy
hydrocarbons, preferably having a melting point below about l Otl°C.
The hydrocarbons
constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779,
issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include
aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from
about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds
suppressor
discussion, is intended to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone
suds suppressors. This category includes the use of polyorganosiloxane oils,
such as
polydimethylsiloxane, dispersions or emulsions of polyorganosilaxane oils or
resins, and
combinations of polyorganosiloxane with silica particles wherein the
polyorganosiloxane
is chemisorbed or fused onto the silica. Silicone suds suppressors are well
known in the
art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5,
1981 to
Gandolfo et al and European Publication No. 354016, published February 7,
1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating
therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling
agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672,
Bartolotta et al,
and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing
amount of a suds controlling agent consisting essentially of
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about
1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01~2 units of Si02 units in a ratio of from
(CH3)3 Si0I~2 units and to Si02 units of from about 0.6:1 to about 1.2:1;
and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica
gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous
phase is made up of certain polyethylene glycols or polyethylene-polypropylene
glycol
CA 02252855 2003-05-02
copolymers or mixtures thereof (preferred), or polypropylene glycol. The
primary
silicone suds suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with
controlled suds will optionally comprise from about 0.001 to about 1,
preferably from
about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight
% of said
silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a
primary
antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous
siloxane or
a silicone resin-producing silicone compound, (c) a finely divided filler
material, and (d)
a catalyst to promote the reaction of mixture components (a), (b) and (c), to
form
silanolates; (2) at least one nonionic silicone surfactant; and (3)
polyethylene glycol or a
copolymer of polyethylene-polypropylene glycol having a solubility in water at
room
temperature of more than about 2 weight %; and without polypropylene glycol.
Similar
amounts can be used in granular compositions, gels, etc. See also U.S. Patents
4,978,471, Starch, issued December 18, I990, and 4,983,316, Starch, issued
January 8,
1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents
4,639,489 and
4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and
a copolymer of polyethylene glycoUpolypropylene glycol, all having an average
molecular weight of less than about 1,000, preferably between about 100 and
800. The
polyethylene glycol and polyethylene/polypropylene copolymers herein have a
solubility
in water at room temperature of more than about 2 weight °l°,
preferably more than about
5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular
weight of less than about 1,000, more preferably between about 100 and 800,
most
preferably between 240 and 400, and a copolymer of polyethylene
glycol/polypropylene
glycol, preferably PPG 2001PEG 300. Preferred is a weight ratio of between
about 1:1
and 1:10, most preferably between 1:3 and 1:6, of polyethylene
glycol:copolymer of
polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
polypropylene
glycol, particularly of 4,000 molecular weight. They also preferably do not
contain
TM
block copolymers of ethylene oxide and propylene oxide, like PL,URONIC L 101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include
the C6-C 16 alkyl alcohols having a C 1-C 16 chain. A preferred alcohol is 2-
butyl
octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of
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46
secondary alcohols are available under the trademark ISALCHEM 123 from
Enichem.
Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a
weight
ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine.
Suds suppressors, when utilized, are preferably present in a "suds suppressing
amount.
By "suds suppressing amount" is meant that the formulator of the composition
can select
an amount of this suds controlling agent that will sufficiently control the
suds to result in
a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and
salts
therein, will be present typically in amounts up to about 5%, by weight, of
the detergent
composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate
suds
suppressor is utilized. Silicone suds suppressors are typically utilized in
amounts up to
about 2.0%, by weight, of the detergent composition, although higher amounts
may be
used. This upper limit is practical in nature, due primarily to concern with
keeping costs
minimized and effectiveness of lower amounts for effectively controlling
sudsing.
Preferably from about 0.01 % to about 1 % of silicone suds suppressor is used,
more
preferably from about 0.25% to about 0.5%. As used herein, these weight
percentage
values include any silica that may be utilized in combination with
polyorganosiloxane, as
well as any adjunct materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about 0.1 % to
about 2%, by
weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in
amounts ranging from about 0.01 % to about 5.0%, although higher levels can be
used.
The alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished
compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued
December
13, 1977, as well as other softener clays known in the art, can optionally be
used
typically at levels of from about 0.5% to about 10% by weight in the present
compositions to provide fabric softener benefits concurrently with fabric
cleaning. Clay
softeners can be used in combination with amine and cationic softeners as
disclosed, for
example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071,
Hams et al, issued September 22, 1981.
DYe Transfer Inhibiting Agents - The compositions of the present invention may
also include one or more materials effective for inhibiting the transfer of
dyes from one
CA 02252855 1998-10-29
WO 97142292 PCT/US97/07057
47
fabric to another during the cleaning process. Generally, such dye transfer
inhibiting
agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers,
copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine,
peroxidases, and mixtures thereof. If used, these agents typically comprise
from about
0.01 % to about 10% by weight of the composition, preferably from about 0.01 %
to about
5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form
part of the polymerizable unit ar the N-O group can be attached to both units;
A is one of
the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R
is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-O group can be attached or the N-O
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives
thereof.
The N-O group can be represented by the following general structures:
O O
I I
~uc- i -(R2~~ =N-(R~)x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of the
polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of 10:1
to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine
oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree
of N-oxidation. The polyamine oxides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the range of
500 to
CA 02252855 2003-05-02
48
1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
This
preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight
of about
50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has an
average molecular weight range from 5,000 to 1,000,000, more preferably from
5,000 to
200,000, and most preferably from 10,000 to 20,000. (The average molecular
weight
range is determined by light scattering as described in Barth, et al.,
Chemical Analysis,
Vol 113. "Modern Methods of Polymer Characterization"). The
PVPVI copolymers typically have a molar ratio of
N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8:1 to
0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or
branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000 to
about 50,000. PVP's are known to persons skilled in the detergent field; see,
for example,
EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions
containing PVP can also contain polyethylene glycol ("PEG") having an average
molecular weight from about 500 to about 100,000, preferably from about 1,000
to about
10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions
is from about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners
which also
provide a dye transfer inhibition action. If used, the compositions herein
will preferably
comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
Rt R2
N H H N
N N C-C N N
N H H N
SO M R
RZ SO3M 3 1
CA 02252855 2003-05-02
49
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-b-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the trademark Tinopal-UNPA-
GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino}-s-triazine-2-yl)aminoJ2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-anilino-b-morphilincr-s-triazine-
2-
yl)aminoJ2,2'-stilbenedisuifonic acid, sodium sail. This particular brightener
species is
commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
andlor
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
SBM-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous wash solutions than does either of these two detergent composition
components
when used alone. Without being bound by theory, it is believed that such
brighteners
work this way because they have high affinity for fabrics in the wash solution
and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners
deposit on fabrics in the wash solution can be defined by a parameter called
the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the
brightener material deposited on fabric to b) the initial brightener
concentration in the
wash liquor. Brighteners with relatively high exhaustion coefficients are the
most
suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types
of compounds can optionally be used in the present compositions to provide
conventional
CA 02252855 2003-05-02
fabric "brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage
is conventional and well-known to detergent formulations.
EXAMPLE 1
Preearation of PEI 1800 E_7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for temperature measwement and control, presswe measwement, vacuum
and
inert gas purging, sampling, and for introduction of ethylene oxide as a
liquid. A ~20 lb.
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a
pump to the autoclave with the cylinder placed on a scale so that the weight
change of
the cylinder could be monitored.
A ?50 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-018
having a listed average molecular weight of 1800 equating to about 0.417 moles
of
polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The
autoclave
is then sealed and pwged of air (by applying vacuum to minus 28" Hg followed
by
pressurization with nitrogen to 250 psia, then venting to atmospheric
pressure). The
autoclave contents are heated to 130 °C while applying vacuum. After
about one hour,
the autoclave is charged with nitrogen to about 250 psia while cooling the
autoclave to
about 1 OS °C. Ethylene oxide is then added to the autoclave
incrementally over time
while closely monitoring the autoclave pressure, temperature, and ethylene
oxide flow
rate. The ethylene oxide pump is turned off and cooling is applied to limit
any
temperatwe increase resulting from any reaction exothenm. The temperature is
maintained between 100 and 110 °C while the total pressure is allowed
to gradually
increase during the course of the reaction. After a total of 750 grams of
ethylene oxide
has been charged to the autoclave (roughly equivalent to one mole ethylene
oxide per
PEI nitrogen function), the temperature is increased to 110 °C and the
autoclave is
allowed to stir for an additional hour. At this point, vacuum is applied to
remove any
residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50
°
C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74
moles,
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The
methoxide
solution is sucked into the autoclave under vacuum and then the autoclave
temperature
controller setpoint is increased to 130 °C. A device is used to monitor
the power
consumed by the agitator. The agitator power is monitored along with the
temperature
and pressure. Agitator power and temperature values gradually increase as
methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in
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WO 97/42292 PCT/US97/07057
51
about 1 hour indicating that most of the methanol has been removed. The
mixture is
further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is
charged to 200 psia with nitrogen. Ethylene oxide is again added to the
autoclave
incrementally as before while closely monitoring the autoclave pressure,
temperature,
and ethylene oxide flow rate while maintaining the temperature between 100 and
110 °C
and limiting any temperature increases due to reaction exotherm. After the
addition of
4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide
per mole of
PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110
°C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually
transferred into a 22 L three neck round bottomed flask equipped with heating
and
agitation. The strong alkali catalyst is neutralized by adding 167 g
rnethanesulfonic acid
( 1.74 moles). The reaction mixture is then deodorized by passing about 100
cu. ft. of
inert gas (argon or nitrogen) through a gas dispersion frit and through the
reaction
mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the
reactor before discharging the product.
EXAMPLE 2
Ouaternization of PEI 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified
by
ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen
(PEI
1800, E7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and
acetonitrile (120
g). Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly
stirring
solution, which is then stoppered and stirred at room temperature overnight.
The
acetonitrile is removed by rotary evaporation at about 60°C, followed
by further stripping
of solvent using a Kugelrohr apparatus at approximately 80°C to afford
220 g of the
desired partially quaternized material as a dark brown viscous liquid. The 13C-
NMR
(D20) spectrum obtained on a sample of the reaction product indicates the
absence of a
carbon resonance at ~58ppm corresponding to dimethyl sulfate. The 1 H-NMR
(D20)
spectrum shows a partial shifting of the resonance at about 2.5 ppm for
methylenes
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WO 97/42292 PCT/US97/07057
52
adjacent to unquaternized nitrogen has shifted to approximately 3.0 ppm. This
is
consistent with the desired quaternization of about 38% of the nitrogens.
EXAMPLE 3
Formation of amine oxide of PEI 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 and ethoxylated to a
degree of
about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 mol nitrogen,
prepared
as in Example I), and hydrogen peroxide ( 120 g of a 30 wt % solution in
water, 1.06
mol). The flask is stoppered, and after an initial exotherm the solution is
stirred at room
temperature overnight. 1 H-NMR (D20) spectrum obtained on a sample of the
reaction
mixture indicates complete conversion. The resonances ascribed to methylene
protons
adjacent to unoxidized nitrogens have shifted from the original position at
~2.5 ppm to
~3.5 ppm. To the reaction solution is added approximately 5 g of 0.5% Pd on
alununa
pellets, and the solution is allowed to stand at room temperature for
approximately 3
days. The solution is tested and found to be negative for peroxide by
indicator paper.
The material as obtained is suitably stored as a 51.1 % active solution in
water.
EXAMPLE 4
Oxidation of Ouaternized PEI 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified
by
ethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E7)
subsequently quaternized with dimethyl sulfate to approximately 4.7% (121.7 g,
0.32
mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution in
water, 0.588
mol), and water (109.4 g). The flask is stoppered, and after an initial
exotherm the
solution is stirred at room temperature overnight. ' H-NMR (D20) spectrum
obtained on
a sample of the reaction mixture indicates the methylene peaks at 2.5-3.0 ppm
have
shifted to ~3.5 ppm. To the reaction solution is added ~5 g of 0.5 % Pd on
alumina
pellets, and the solution is allowed to stand at room temperature for ~3 days.
The
solution is tested and found to be negative for peroxide by indicator paper.
The desired
material with ~4.7% of the nitrogens quaternized and 95.3% of the nitrogens
oxidized
to the amine oxide is obtained and is suitably stored as a 46.5% solution in
water.
Granular compositions, for example, are generally made by combining base
granule ingredients (e.g. surfactants, builders, water, etc.) as a slurry, and
spray drying
the resulting slurry to a low level of residual moisture (5-12%). The
remaining dry
ingredients can be admixed in granular powder form with the spray dried
granules in a
rotary mixing drum and the liquid ingredients (e.g. enzymes, binders and
perfumes) can
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
53
be sprayed onto the resulting granules to form the finished detergent
composition.
Granular compositions according to the present invention can also be in
"compact form",
i.e. they may have a relatively higher density than conventional granular
detergents, i.e.
from 550 to 950 gll. In such case, the granular detergent compositions
according to the
present invention will contain a lower amount of "inorganic filler salt",
compared to
conventional granular detergents; typical filler salts are alkaline earth
metal salts of
sulfates and chlorides, typically sodium sulfate; "compact" detergents
typically comprise
not more than 10% filler salt.
EXAMPLE 5
Preparation of PEI 1200 E_7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for temperature measurement and control, pressure measurement, vacuum
and
inert gas purging, sampling, and for introduction of ethylene oxide as a
liquid. A ~20 Ib.
net cylinder of ethylene oxide {ARC) is set up to deliver ethylene oxide as a
liquid by a
pump to the autoclave with the cylinder placed on a scale so that the weight
change of
the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) ( having a listed average molecular
weight of 1200 equating to about 0.625 moles of polymer and 17.4 moles of
nitrogen
functions) is added to the autoclave. The autoclave is then sealed and purged
of air (by
applying vacuum to minus 28" Hg followed by pressurization with nitrogen to
250 psia,
then venting to atmospheric pressure). The autoclave contents are heated to
130 °C
while applying vacuum. After about one hour, the autoclave is charged with
nitrogen to
about 250 psia while cooling the autoclave to about 105 °C. Ethylene
oxide is then
added to the autoclave incrementally over time while closely monitoring the
autoclave
pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump
is turned
off and cooling is applied to limit any temperature increase resulting from
any reaction
exotherm. The temperature is maintained between 100 and 110 °C while
the total
pressure is allowed to gradually increase during the course of the reaction.
After a total
of 750 grams of ethylene oxide has been charged to the autoclave {roughly
equivalent to
one.mole ethylene oxide per PEI nitrogen function), the temperature is
increased to 110 °
C and the autoclave is allowed to stir for an additional hour. At this point,
vacuum is
applied to remove any residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50
°
C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74
moles,
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The
methoxide
solution is sucked into the autoclave under vacuum and then the autoclave
temperature
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WO 97/42292 PCT/US97/07057
54
controller setpoint is increased to I30 °C. A device is used to monitor
the power
consumed by the agitator. The agitator power is monitored along with the
temperature
and pressure. Agitator power and temperature values gradually increase as
methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in
about I hour indicating that most of the methanol has been removed. The
mixture is
further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is
charged to 200 psia with nitrogen. Ethylene oxide is again added to the
autoclave
incrementally as before while closely monitoring the autoclave pressure,
temperature,
and ethylene oxide flow rate while maintaining the temperature between 100 and
110 °C
and limiting any temperature increases due to reaction exotherm. After the
addition of
4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide
per mole of
PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110
°C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually
transferred into a 22 L three neck round bottomed flask equipped with heating
and
agitation. The strong alkali catalyst is neutralized by adding 167 g
methanesuIfonic acid
( I .74 moles). The reaction mixture is then deodorized by passing about 100
cu. ft. of
inert gas (argon or nitrogen) through a gas dispersion frit and through the
reaction
mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the
reactor before discharging the product.
Other preferred examples such as PEI 1200 E 1 S and PEI 1200 E20 can be
prepared by the above method by adjusting the reaction time and the relative
amount of
ethylene oxide used in the reaction.
EXAMPLE 6
9.7% Ouaternization of PEI 1200 E7
To a SOOmI erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4g, 0.707 mol
nitrogen,
prepared as in Example 5) and acetonitrile (Baker, 200 mL). Dimethyl sulfate
(Aldrich,
8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which
is then
stoppered and stirred at room temperature overnight. The acetonitrile is
evaporated on
the rotary evaporator at ~60°C, followed by a Kugelrohr apparatus
(Aldrich) at ~80°C to
CA 02252855 2003-05-02
afford --220g of the desired material as a dark brown viscous liquid. A I 3C-
NMR (D20)
spectrum shows the absence of a peak at -58ppm corresponding to dimethyi
sulfate. A
I H-NMR (D20) spectrum shows the partial shifting of the peak at 2.Sppm
(methylenes
attached to unquatemized nitrogens) to --3.Oppm.
TABLEI
Granular Laundry Deterg-ent Com op Sitions
Weight
Ingredients 7 8 9 10
C12-C15 Linear alkyl benzene19.30 18.30 18.00 12.25
sulfonate
C25 Ethoxylated (3) sulfate-- -- 1.50 --
NEODOLT 45-7 ~ 0.90 0.93 0.90 0.91
C 12-C 14 Dimethyl hydroxyethyl0.63 0.62 0.70 0.65
ammonium chloride
Coco fatty acid -- -- -- 3.45
Tallow fatty acid -- -- -- 2.40
Sodium tripolyphosphate 25.00 23.50 22.50 23.00
Acrylic acid/maleic acid I .00 0.80 0.90 --
co-
polymer
Sodium carbonate 5.00 4.80 5.00 5.00
Sodium silicate 7.60 7.70 7.60 7.50
Savinase (4T) 0.60 0.57 0.60 0.60
Termamyl (60T) 0.36 0.34 0.36 0.36
Lipolase (100T) 0.15 0.14 0.10 0.15
Carczyme ( 1 T) 0.20 0.19 0.20 0.20
Diethylenetriamine pentamethyl0.50 0.70 0.60 0.50
phosphonic acid (DETAPMPA)
Carboxymethylcellulose 0.30 0.28 0.78 0.50
Polyamine dispersant 2 0.30 0.30 0.25 0.25
Soil release agent 3 0.14 0.13 0.20 0.13
Bleaching agent 4 0.0015 0.0017 O.U015 0.0015
Optical brightener 0.20 0.20 O.I6 0.17
Magnesium sulfate 0.66 0.65 0.80 0.66
Minors and water balance balance balancebalance
1. C45 ethoxylated (7} alcohol as sold by Shell Oil Co.
CA 02252855 2003-05-02
56
2. As described in Example 1 hereinabove.
3. Soil release agent as disclosed in U.S. 5,415,807, Gosselink et al., issued
May 16,
1995.
4. Zinc phthalocyanine sulfonate photobleach according to U.S. Patent
4,033,718
Holcombe et al., issued July S, 1977.
The laundry detergent compositions of the present invention also comprise
peroxygen bleaches and bleach activators as illustrated in Table II below.
TABLE II
Granular Laundry Detergent Compositions Compr~sin Oxygen Bleach
Weight
Ingredients 11 12 13 14
C 12-C 15 Linear alkyl 19.30 16.40 18.00 13.00
benzene
suf fonate
C25 Ethoxylated (3) sulfate-- -- 1.50 --
NEODOL 45-7 ~ 0.90 0.84 0.90 0.91
C 12-C 14 Dimethyl hydroxyethylO.b3 0.54 0.70 0.65
ammonium chloride
Coco fatty acid -- -- -- 3.45
Tallow fatty acid -- -- -- 2.40
Sodium tripolyphosphate 25.00 20.50 22.50 23.00
Acrylic acid/maleic acid 1.00 0.60 0.91? --
co-
polymer
Sodium carbonate 5.00 4.25 5.00 5.00
Sodium silicate 7.60 7.00 7.6U 7.50
Savinase (4T) 0.60 0.51 0.60 0.60
TermamylT(60T) 0.36 0.30 0.36 0.36
Lipolase ( 1 OOT) 0.15 0.13 0.1 0.15
U
Carezytrie ( I T) 0.20 0.17 0.20 0.20
Diethylenetrianvne pentamethyl0.50 0.60 0.60 0.50
phosphonic acid (DETAPMPA)
Carboxymethylceliulose 0.30 0.25 -- --
Polyamine dispersant z 0.30 0.30 0.25 0.25
Soil release agent 3 0.14 0.11 2.20 2.5
NOBS 1.00 1.00 I.OG 1.15
Sodium perborate monohydrate3.30 3.30 3.50 3.60
CA 02252855 1998-10-29
WO 97/42292 PCT/US97/07057
57
Optical brightener 0.20 0.16 0..14 0.13
Magnesium sulfate 0.66 0.60 0.80 0.66
Minors and water balance balancebalancebalance
1. C45 ethoxylated (7) alcohol as sold by Shell Oil Co.
2. As described in Example 4 hereinabove.
3. Soil release agent as disclosed in U.S. 5,415,807, Gosselink et al., issued
May 16,
1995.
Method of Use
The present invention also provides a method for laundering fabrics wherein an
improved soil removal benefit is obtained. Such a method employs contacting
these
fabrics with an aqueous washing solution formed from an effective amount of
the
detergent compositions hereinbefore described. Contacting of fabrics with
washing
solution will generally occur under conditions of agitation.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is preferably followed by drying the wet fabric in a conventional
clothes dryer.
An effective amount of the detergent composition (either in liquid or granular
form) in
the aqueous wash solution in the washing machine is preferably from about 500
to about
7000 ppm, more preferably from about 1000 to about 3000 ppm.
