Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID LAUNDRY DETERGENT COMPOSITIONS
COMPRISING HEDP AND POLYAMINES
FIELD OF THE INVENTION
The present invention relates to liquid laundry detergent compositions
comprising
HEDP and water soluble and/or dispersible, modified polyamines having
functionalized
backbone moieties.
BACKGROUND OF THE INVENTION
Liquid laundry detergent compositions comprising HEDP (hydroxyethane-1,1-
diphosphonate) are known and have been described for instance in FR 2,677,370,
EP 517
605, EP 384 515, and EP 37 184. In liquid laundry detergent compositions, HEDP
provides benefits of improved stain removal and whiteness on fabrics. However
there is
an issue in formulating HEDP in liquid detergents - particularly concentrated
ones - in
that poor physical stablity is obtained in the presence of high levels of
surfactants and
other detergent ingredients. EP 517 605 discloses the use of specif c salts of
HEDP in
order to improve the physical stability of the composition. It is an object of
the present
invention to formulate liquid detergent compositions which comprise HEDP and
surfactants and, optionally other detergency ingredients, and, which are
physically stable.
In response, it has now been found that the presence of certain polymers would
provide
the desrired stabilizing effect enabling the formulation of stable
compositions comprising
HEDP.
SUMMARY OF THE INVENTION
The present invention encompasses liquid laundry detergent compositions
comprising a surfactant, an effective amount of HEDP, and a stabilizing amount
of a
water-soluble or dispersible, modified polyamine comprising a polyamine
backbone
corresponding to the formula:
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H
fH2N'RJn+1-fN'RJm LN'RJri NH2
having a modified polyamine formula Vin+1 )WmYnZ or a polyamine
backbone corresponding to the formula:
~2N'RJn-k+1--[N-RJtri ~-RJn~-RJk-NH2
having a modified polyamine formula V~n_k+1)WmynY~kZ~ wherein
k is less than or equal to n, said polyamine backbone prior to
modification has a molecular weight greater than about 200 daltons,
wherein
i) V units are terminal units having the formula:
E X- O
E-N-R-' or E-N~ R'- or E-N-R-
E E E
ii) W units are backbone units having the formula:
E O
N R or -N-ft- or -N-R-
E E E
iii) Y units are branching units having the formula:
E O
R or - ~ -R- or - ~ -R'_
and
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iv) Z units are terminal units having the formula:
E O
X-
-N-E or -N~ E or -N-E
E E E
wherein backbone linking R units are selected from the group consisting
of C2-C 12 alkylene, C4-C 12 alkenylene, C3-C 12 hydroxyalkylene, C4-
C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -(R10)xRl-, -
(R1 O~RS(OR1)x-, -(CH2CH(OR2)CH20)(Rl Oh,-
R10(CH2CH(OR2)CH2)~,~-, -C(O)(R4)rC(O)-, -CH2CH(OR2)CH2-, and
mixtures thereof; wherein Rl is C2-C6 alkylene and mixtures thereof; RZ
is hydrogen, -(R10~B, and mixtures thereof; R3 is C1-Clg alkyl, C~-
C 12 arylalkyl, C~-C 12 alkyl substituted aryl, C6-C 12 aryl, and mixtures
thereof; R4 is C 1-C 12 alkylene, C4-C 12 alkenylene, Cg-C 12
arylalkylene, C6-C 1 p arylene, and mixtures thereof; RS is C 1-C 12
alkylene, C3-C 12 hydroxy-alkylene, C4-C 12 dihydroxyalkylene, Cg-C 12
dialkylarylene, -C(O)-, -C(O)NHR6-NHC(O)-, -C(O)(R4)rC(O)-, -
CH2CH(OH~H20(R10~,R10-CH2CH(OH)CH2-, and mixtures
thereof; R6 is C2-C 12 alkylene or C6-C 12 arylene; E units are selected
from the group consisting of hydrogen, Cl-C22 alkyl, C3-C22 alkenyt.
C7-C22 ~YlaIk3'l, C2-C22 hydroxyalkyl, -(CH2)p-C02M, _
(CH2)qS03M, -CH(CH2C02M)-C02M, -(CH2)pP03M, -(R10)xB, -
C(O)R3, and mixtures thereof; provided that when any E unit of a
nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B i s
hydrogen, C1-C6, alkyl, -(CH2)qS03M, -(CH2~C02M.
(CH2)qCH(S03M)CH2S03M, -(CH2)qCH(S02M)CH2S03M, -
(CH2~P03M, -P03M, and mixtures thereof; M is hydrogen or a water
soluble cation in sufficient amount to satisfy charge balance; X is a water
soluble anion; m has the value from 4 to about 400; n has the value from i ~
to about 200; p has the value from 1 to 6, q has the value from 0 to 6: r
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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.
All percentages, ratios and proportions herein are by weight of the total
composition, unless otherwise specified. All temperatures are in degrees
Celsius (o C)
unless otherwise specified, and ratios are by weight. All documents cited are
in relevant
part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The liquid detergent composition
The compositions herein are liquid detergent compositions and as such, they
typically but not necessarily comprise water, in amounts of from 20% to 70% by
weight
of the total composition, preferably 25% to .60% , most preferably 30% to 40%.
Compositions comprising less than 40% water are generally referred to as
concentrated
compositions, and it is in those compositions that the stability problem of
HEDP is
particularly acute.
HEDP
The compositions herein comprise an effective amount of HEDP (hydroxy-
ethane-1,1-diphosphonate). By effective amount, it is meant herein an amount
sufficient
so as to improve the stain removal properties of the detergent compositon,
and/or to
improve the whiteness performance of that compositon. Typically such amounts
are in
the range of from 0.01 % to 10% by weight of the total composition, preferably
0.7% to
5%, most preferably 0.2% to 2%. Suitable for use herein are HEDP in its acid
form, or
in the form of any of its salts. A suitable commercial form of HEDP is
bequest~2010,
from Monsanto.
The~ol
The compositions herein further comprise a stabilizing amount of a water-
soluble
or dispersible, modified polyamine. These polyamines comprise backbones that
can be
either linear or cyclic. The polyamine backbones can also comprise polyamine
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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),
quaternizing a
backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-
oxide
(oxidized). The terms "modification" and "substitution" are used
interchangably when
refernng 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 preferably is accompanied by oxidation
or
quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones have the general formula:
H I
~2N'R]n+1 WN'R]rri (N'R]ri NHz
said backbones prior to subsequent modification, comprise primary, secondary
and
tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine
backbones have the general formula:
I
IH2N'R]mk+t-~N-R]m LN-R]n'_'iN_R]k'NH2
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 "ternvnal"
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]-
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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 unmodified subject to the
restrictions
farther 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
-II't_Rl-
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.
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
-(N_Rl-
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
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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+I )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
-LI'I_R~-
serves as a branch point for a backbone or branch ring. For every Y' unit
there is a Y unit
having the formula
-(N _ Rl-
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
fH2N-RJn-(N'Rlrri II'1'RJri
therefore comprising no Z terminal unit and having the formula
Vn-kWmYnY~k
wherein k is the number of ring forming branching units. Preferably the
polyamine
backbones of the present invention comprise no rings.
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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
VWmZ
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; simply 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 pri~rcary 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) quatennized 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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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-
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-
I ,
b) quaternized units having the structure:
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E
X-
-N~ R-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-E
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
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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.
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 vn the R
unit chain
except the carbon atoms directly connected to the polyamine backbone
nitrogens; C4-
C 12 dihydroxyalkylene 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)4 / ' (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~R5(ORI)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~R1-, -
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CH2CH(OR2)CH2-, -(CH2CH(OH)CH20)z(R10)yRl(OCH2CH-(OH)CH2)~,-, -
(R1 O)xRS(OR1 )x-, more preferred R units are C2-C 12 alkylene, C3-C 12
hydroxy-
alkylene, C4-C12 dihydroxyalkylene, -(R10)xRl-, -(R10)xRS(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 50% R units that are ethylene.
R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is
hydrogen, and -(R1 O)xB, preferably hydrogen.
R3 is C 1-C 1 g alkyl, C~-C 12 arylalkylene, C~-C 12 alkyl substituted aryl,
C6-C 12
aryl, and mixtures thereof , preferably C 1-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.
R4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-C10
arylene, preferably C 1-C 1 p 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-C12 dialkylarylene, -C(O~, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-,
-R1(ORl)-, -CH2CH(OH)CH20(Rl0h,R10CH2CH(OH)CH2-, -C(O)(R4)rC(O)-,
-CH2CH(OH)CH2-, RS is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
-R1{ORl)-, -CH2CH(OH)CH2-, -CH2CH{OH)CH20(Rl0h,R10CH2CH-(OH)CH2-,
more preferably -CH2CH(OH)CH2-.
R6 is C2-C12 alkylene or C6-C12 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 R1, 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.
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i) Substituting more preferred RS into -(CH2CH20)xR5(OCH2CH2)x-
yields -(CH2CH20)xCH2CHOHCH2(OCH2CH2~-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH20)z-
(R10)yRlO(CH2CH(OR2)CH2~,- yields -(CH2CH(OH)CH20)z-
(CH2CH20h,CHZCH20(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, C1-C22 alkyl, C3-
C2z alkenyl, C~-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2~C02M, -(CH2)qS03M, -
CH(CH2C02M)C02M, -(CH2)pP03M, -(R10)mB, -C(O)R3, preferably hydrogen, C2-
C22 hydroxyalkylene, benzyl, C1-C22 alkylene, -(R10)mB, -C(O)R3, -(CH2~C02M, -
(CH2)qS03M, -CH(CH2COZM)C02M, more preferably C1-C22 alkylene, -(R10)xB,
-C(O)R3, -(CH2)pC02M, -(CH2)qS03M, -CH(CHZC02M)C02M, most
preferably C1-C22 alkylene, -(R10~B, and -C(O)R3. When no
modification or substitution is made on a nitrogen then hydrogen atom will
remain as the
moiety representing E.
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 ~-
oxide modified nitrogen, that is, there are no N-oxide amides having the
structure
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-N-R or R3-C-N-R or -N-C-R3
C=O E E
R3
nor combinations thereof.
B is hydrogen, C1-C6 alkyl, -(CH2)qS03M, -(CH2)pC02M, -(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 ration in sufficient amount to satisfy charge
balance. For example, a sodium ration equally-satisfies -(CH2)pC02M, and -
(CH2)qS03M, thereby resulting in -{CHZ)pC02Na, and -(CH2)qS03Na moieties.
More than one monovalent ration, {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 ration, or more than one mono-valent ration 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~P03Na3.
Divalent rations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted
for or
combined with other suitable mono-valent water soluble rations. Preferred
rations are
sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine {Cl-), bromine (Br-) and iodine
(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, preferably 5 to 30; y has the value from 0 to 100; z has the value 0
or 1; 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.
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The preferred polyamines of the present invention comprise 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 polyamines which comprise no "oxy" R units comprise
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-C 12
alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
The cotton polyamines 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
a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-
homogeneous backbone.
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Preferred polyamines of the present invention comprise homogeneous polyamine
backbones that are totally or partially substituted by polyethyleneoxy
moieties, totally or
partially quaternized 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), polyaIkyleneimines
(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
disdlladon. The common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,
heptamines,
octamines and possibly nona~riines, 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 INCH2CH2Im ~CH2CH2Jri NH2
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17
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,
preferably up
to 3000.
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
of preparation. Each hydrogen atom attached to each nitrogen atom of the
polyamine
backbone chain represents a potential site for subsequent substitution,
quaternization or
oxidation.
These polyamines can be prepared, for example, by polymerizing ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulfate,
sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing
these polyamine backbones are disclosed in U.S. Patent 2,182,306, 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 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21,
1951; all
herein incorporated by reference.
Examples of polyamines of the present invention comprising PEI's, are
illustrated
in Formulas I - V:
Formula I depicts a preferred polyamines comprising a PEI backbone wherein all
substitutable nitrogens are modified by replacement of hydrogen with a
polyoxyalkyleneoxy unit, -(CH2CH20)2pH, having the formula:
M(Cn~:C~t:o~z
'NJ tuocH_a-izyzo.N.(~z~zo~
(C~hCHzoy~H ~ ~ ((I-izCHi~y~H
IH(~Z~olz~N~~N~ iI~N~N~N~N[(C~i;CHZO~o~
(C7i,C~i;O~H
Nf(~z~z~ho~ M(~ZCHz~hoBlz
Formula I
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Formula II depicts a polyamine comprising a PEI backbone wherein all
substitutable nitrogens are modified by replacement of hydrogen with a
polyoxyalkyleneoxy unit, -(CH2CH20)~H, having the formula
(cHzcHzohH
=HzOhH)z
Formula II
This is an example of a polyamine that is fully modified by one type of
moiety.
Formula III depicts a polyamine 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
polyamine
having the formula
H(OQi n,~ _N, v-......~....~n..~
~O o(CthCHiO~~ O(C~izCFIzo~
p 0O
~~~~~~N~N~N~N~N~'~N~~~NI(~h~zoh~z
O(~z~z0)6H ~ O(CH,CFi,OI~H
O
NI(~z~'hohNlz
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Formula III
Formula IV depicts a polyamine 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 polyamine has the formula
cH,
~"~(~z~)zN N(CHZCHZO}~H
CI_ CH3,~N(~z~OhH
~3, .~
IH(OCHzCHz~rIz~t+~1~'~N~I~1~N~~ C~~N«;~
CI' c~-1. ~u_
CI'
Formula IV
+ CI_
N(CH3lz
Formula V depicts a polyamine 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
polyamine has
the formula
+. _ _ . O
Cr
~ rv ~ + CI__ _
O
CH3 ~ ~3. .~3 t
IH(~z~z~rlz~+r~1~1~ i ~~N~tJ~I+~_ IV'~N~~~~Z
Cl' ~3 O i ~ CI
O
Cl +_. ~.
+ CI_
,iN(~3)3
N(C~i~}~
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Formula V
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.
Highly preferred for use herein are ethoxylated PEIs with a molecular weight
of
from 200 to 3000, preferably 400 to 700, and an average degree of ethoxylation
of from 4
to 30, preferably 15 to 25.
The compositions herein comprise a stabilizing amount of a polyamine, i.e. an
amount which is sufficient to solve the instability problem caused by the
presence of the
HEDP. The amount of polyamine needed will depend on the amount of HEDP which
is
present, but will typically lie in the range of from 0.05% to 20% by weight of
the total
composition, preferably 0.1% to 10%, most preferably 0.2% to 5%. In addition,
the
polyamines herein have the advantage that they provide stain removal and
whiteness
benefits.
The detersive surfactants
The compositions herein comprise a surfactant. In addition to the preferred
anionic and nonionic detersive surfactants described herein, other detersive
surfactants
that are suitable for use in the present invention are cationic, anionic,
nonionic,
ampholytic, zwitterionic, and mixtures thereof, further described herein
below.
Nonlimiting examples of other 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"), the C10-Clg secondary (2,3) alkyl sulfates of the formula
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21
CH3(CH2~(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,
C 10-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-
1 g glycerol ethers, the C 10-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-C 12
alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12-C 1 g
betaines and
sulfobetaines ("sultaines"), C 10-C 1 g amine oxides, and the like, can also
be included in
the overall compositions. The C 10-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 10-C 1 g N-(3-methoxypropyl) glucamide. C 10-C2p
conventional soaps
may also be used. If high sudsing is desired, the branched-chain C 10-C 16
soaps may be
used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful surfactants are listed in standard texts.
Other anionic surfactants useful for detersive purposes can also be included
in the
compositions hereof. These can include salts (including, for example, sodium
potassium,
ammonium, and substituted ammonium salts such a mono-, di- and triethanolamine
salts)
of soap, Cg-C2p linear alkylbenzenesulphonates, Cg-C22 primary or secondary
alkanesulphonates, Cg-C24 olefinsulphonates, sulphonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfates, alkyl
phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,
isothionates
such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl
tauride, alkyl
succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and
unsaturated C 12-C 1 g monoesters) diesters of sulfosuccinate (especially
saturated and
unsaturated C6-C 14 diesters), N-acyl sarcosinates, sulfates of
alkylpolysaccharides such
as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl
polyethoxy
carboxylates such as those of the formula RO(CH2CH20)kCH2C00-M+ wherein R is a
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zz
Cg-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming
cation, and
fatty acids esterified with isethionic acid and neutralized with sodium
hydroxide. Further
examples are given in Surface Active Agents and Detergents (Vol. I and II by
Schwartz,
Perry and Berch).
The compositions of the present invention preferably comprise at least about
0.01%, preferably at least 0.1%, more preferably from about 1% to about 95%,
most
preferably from about 1 % to about 80% by weight, of an anionic detersive
surfactant.
Alkyl sulfate surfactants, either primary or secondary, are a type of anionic
surfactant of
importance for use herein. Alkyl sulfates have the general formula ROS03M
wherein R
preferably is a C 10-C24 hydrocarbyl, preferably an alkyl straight or branched
chain or
hydroxyalkyl having a C 1 p-C20 alkyl component, more preferably a C 12-C 1 g
alkyl or
hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali
metal cation
(e.g., sodium potassium, lithium), substituted or unsubstituted ammonium
cations such as
methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations,
e.g.,
tetramethyl-ammonium and dimethyl piperdinium, and cations derived from
alkanoiamines
such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof,
and the like.
Typically, alkyl chains of C 12-C 16 are preferred for lower wash temperatures
(e.g., below
about 50°C) and C 16-C 1 g alkyl chains are preferred for higher wash
temperatures (e.g.,
about 50°C).
Alkyl alkoxylated sulfate surfactants are another category of preferred
anionic
surfactant. These surfactants are water soluble salts or acids typically of
the formula
RO(A~S03M wherein R is an unsubstituted C 10-C24 alkyl or hydroxyalkyl group
having a C 10-C24 alkyl component, preferably a C 12-C20 alkyl or
hydmxyallcyl, more
preferably C12-Clg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
greater
than zero, typically between about 0.5 and about 6, more preferably between
about 0.5 and
about 3, and M is hydrogen or a water soluble canon which can be, for example,
a metal
cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium
or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl
propoxylated
sulfates are contemplated herein. Specific examples of substituted ammonium
cations
include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cadons,
such
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23
as tetramethyl-ammonium, dimethyl piperdiniurn and cations derived from
alkanolamines,
e.g., monoethanolamine, diethanolamine, and triethanolamine, and mixtures
thereof.
Exemplary surfactants are C 12C 1 g alkyl polyethoxylate ( 1.0) sulfate, C 12-
C 1 g alkyl
polyethoxylate (2.25) sulfate, C 12-C 1 g alkyl polyethoxylate (3.0) sulfate,
and C 12-C 18
alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from
sodium and
potassium.
The compositions of the present invention also preferably comprise at least
about
0.01 %, preferably at least 0.1 %, more preferably from about 1 % to about
95%, most
preferably from about 1% to about 80% by weight, of an nonionic detersive
surfactant.
Preferred nonionic surfactants such as 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), block alkylene oxide condensate of C6
to C 12
alkyl phenols, alkylene oxide condensates of Cg-C22 alkanols and ethylene
oxide/propylene oxide block polymers (PluronicT""-BASF Corp.), as well as semi
polar
nonionics (e.g., amine oxides and phosphine oxides) can be used in the present
compositions. An extensive disclosure of these types of surfactants is found
in U.S. Pat.
3,929,678, Laughlin et al., issued December 30, 1975, incorporated herein by
reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado
(incorporated herein by reference) are also preferred nonionic surfactants in
the
compositions of the invention.
Further preferred nonionic surfactants are the polyhydroxy fatty acid amides
having
the formula:
O R8
R7-C-N-Q
wherein R7 is CS-C31 alkyl, preferably straight chain C7-C19 alkyl or alkenyl,
more
preferably straight chain Cg-C 17 alkyl or alkenyl, most preferably straight
chain C 1 l -C' 1 s
alkyl or alkenyl, or mixtures thereof; R8 is selected from the group
consisting of hydrogen.
C1-C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, more preferably
methyl. c ~
is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3
hydroxyls dirertlv
connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy
is ethoxv ar
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24
propoxy, and mixtures thereof. Preferred Q is derived from a reducing sugar in
a reductive
amination reaction. More preferably Q is a glycityl moiety. Suitable reducing
sugars
include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
As raw
materials, high dextrose corn syrup, high fivctose corn syrup, and high
maltose corn syrup
can be utilized as well as the individual sugars listed above. These corn
syrups may yield a
mix of sugar components for Q. It should be understood that it is by no means
intended to
exclude other suitable raw materials. Q is more preferably selected from the
group
consisting of -CH2(CHOH~CH20H, -CH(CH20H)(CHOH~-1CH20H, -
CH2(CHOH)2-(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof, wherein n
is
an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic
monosaccharide. Most preferred substituents for the Q moiety are glycityls
wherein n is 4,
particularly -CH2(CHOH)4CH20H.
RICO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Rg can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy
ethyl, or
2-hydroxy pmpyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions
herein is
alkyl-N-methyl glucomide, a compound of the above formula wherein R~ is alkyl
(preferably C11-CI3), R8, is methyl and Q is 1-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C 10-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 10-C2p conventional
soaps
may also be used. If high sudsing is desired, the branched-chain C ~ 0-C 16
soaps may be
used.
tionals
The compositions herein can further comprise a variety of optional
ingredients.
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WO 99/49009 PCT/IB99/00470
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 1 p-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, 0.1 %-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 sand 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 C13-15 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
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26
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 carriers.
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 6.0
and about 11, preferably between about 7.0 and 10Ø Laundry liquid products
are
typically at pH 7-9. 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.
Enz~~mes
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 hydmlases 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
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WO 99/49009 PCT/IB99/00470
27 '
enzyme per gram of the detergent composition. Stated otherwise, the
compositions
herein will typically comprise from 0.001% to S%, 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 to
increase the active enzyme content of the commercial preparation in order to
minimize
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.
Amylases suitable herein include, for example, a-amylases described in GB
1,296,839 to Novo; ItAPIDASE~, 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. I1, 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
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 11, 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
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WO 99/49009 PCT/IB99/00470
28
from chlorine bleaching, detergent compositions herein. Such preferred
amylases include
(a) an amylase according to the hereinbefore incorporated 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.licheniformis alpha-amylase, known as TERMAMYL~, or the homologous position
variation of a similar parent amylase, such as B. amyloliquefaciens,
B.subtilis, or
B.stearothermophilus; (b) stability-enhanced amylases as described by Genencor
International 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.licheniformis NCIB8061. Methionine (Met) was identified as
the
most likely residue to be modified. Met was substituted, one at a time, in
positions 8, 1 S,
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
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,
1981.
discloses suitable fungal cellulases from Humicola insolens or Humicola strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auriculu
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.? 7
CA 02324470 2000-09-19
WO 99/49009 PCT/IB99/00470
29
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 name 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 ~2ladioli. LIPOLASE~
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.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease
is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of
8-12,
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 130,756 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
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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.
The preferred liquid laundry detergent compositions according to the present
invention further comprise at least 0.001% by weight, of a protease enzyme.
However,
an effective amount of protease enzyme is sufficient for use in the liquid
laundry
detergent compositions described herein. The term "an 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.
The protease enzymes of the present invention 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.
Preferred liquid laundry detergent compositions of the present invention
comprise
a protease enzyme, referred to as "Protease D", which 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
amyloliquefaciens 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
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3I
Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published
Novenber 9, 1995 by The Procter & Gamble Company.
Preferred proteolytic enzymes are also modified bacterial serine proteases,
such
as those described in European Patent Application Serial Number 87 303,761.8,
filed
April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein
"Protease
B", and in European Patent Application 199,404, Venegas, published October 29,
1986,
which refers to a modified bacterial serine proteolytic enzyme which is called
"Protease
A" herein, Protease A as disclosed in EP 130,756 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.
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 $908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to
McCarty et ai. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18,
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
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32
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
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
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33
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 alkaiine
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, bisulfite, thiosulfite, thiosulfate,
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
enzymr-
containing embodiment of the invention; even then, the scavenger is added only
tim
optimum results. Moreover, the formulator will exercise a chemist's normal ski
I I i n
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34
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
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.
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 level 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 1 % builder. Liquid formulations typically
comprise
from about 5% to about 50%, more typically about 5% to about 30%, by weight,
of
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 allcanolammonium 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 compared 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 Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as the
layered sodium silicates described in U.S. Patent 4,664,839.
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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 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~(~02)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,
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36
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972.
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, 1, 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 polycarboxylate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
biodegradability. 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, pa.imitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates
are the preferred builders of this group, and are described in European Patent
Application
86200690.5/0,200,263, 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.
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37
Fatty acids, e.g., C 12-C I g 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.
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 (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.
Chelatine 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, poiyfunctionally-
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,
triethylenetetraacninehexacetates,
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 and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not
contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
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38
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 0.1% to about 3.0% by weight of
such
compositions.
Clay Soil RemovaUAnti-redeposition Agents
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 typically 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.
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
112,59?,
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
celluio~r
(CMC) materials. These materials are well known in the art.
Polymeric Dispersing Agents
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39
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 vinylmethyl 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
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
6,000. The
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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
acrylic 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 I5, 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 500 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.
Bri h
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 classified into subgroups, which include, but
are not
necessarily limited to, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acid,
methinecyanines, dibenzothiphene-5,5-dioxide, 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
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41
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners
from Verona. Other brighteners disclosed in this reference include: Tinopal
UNPA,
Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Antic White 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-diphenyl-
phrazolines;
2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-
(stilbene-4-yl)-
2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February
29, 1972 to
Hamilton. Anionic brighteners are preferred herein.
Suds Suppressors
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
alcohols, aliphatic C 1 g-C4p ketones (e.g., stearone), etc. Other suds
inhibitors include
N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra-
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42
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
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 100°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.
The 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 polyorganosiloxane 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 S,
1981 to
Gandolfo et al and European Patent Application No. 89307851.9, 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.
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43
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 Si01~2 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
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, 1990, 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
an~i
a copolymer of polyethylene glycol/polypropylene glycol, all having an average
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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 %, preferably more
than about
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 200 and 400, and a copolymer of polyethylene
glycol/polypropylene
glycol, preferably PPG 200/PEG 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
block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
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
secondary alcohols are available under the trademark ISALCHEM I23 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
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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 0.0I % 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 4,062,64?, 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 A ents
The compositions of the present invention may also include one or more
materials
effective for inhibiting the transfer of dyes from one 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
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46
composition, preferably from about 0.01% to about 5%, and more preferably from
about
0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form
part of the polymerizable unit or the N-O group can be attached to both units;
A is one of
the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R
is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-O group can be attached or the N-O
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives
thereof.
The N-O group can be represented by the following general structures:
O O
With-- i w(R2~y; =N-~thc
(R3h
wherein R 1, 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
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47
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 I :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. "Modem Methods of Polymer Characterization", the disclosures of which
are
incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of
N-vinylimidazole to N-vinylpyrrolidone from I :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 I 00,000, 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:
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R1 R2
>--N H H N
N N ~ ~ ~ NEON
/ N H H N
R2 S03M S03M Rt
wherein RI 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 cation 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-6-(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 tradename Tinopal-UNPA-
GX by
Ciba-Geigy Corporation. Tinopal-LJNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, RI is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
commercially marketed under the tradename 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
ancLor
PVPVI) with such selected optical brighteners (e.g., Tinopal LJNPA-GX, Tinopal
5811-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous wash solutions than does either of these two detergent composition
component,
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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
fabric "brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage
is conventional and well-known to detergent formulations.
Preparation of polvamines
EXAMPLE 1
Ethoxvlation of polv(ethyleneimine) with averaste molecular wei~~ht of 1 800 -
To
a 250m1 3-neck round bottom flask equipped with a Claisen head, thermometer
connected to a temperature controller (Therm-O-Watch'~'M, I2R), sparging tube,
and
mechanical stirrer is added poly(ethyleneimine) MW 1800 (Polysciences, SO.Og,
0.028
mole). Ethylene oxide gas (Liquid Carbonics) is added via the sparging tube
under argon
at approximately 140oC with very rapid stirring until a weight gain of 52g
(corresponding to 1.2 ethoxy units) is obtained. A SOg portion of this yellow
gel-like
material is saved. To the remaining material is added potassium hydroxide
pellets
(Baker, 0.30g, 0.0053 mol). after the potassium hydroxide dissolves, ethylene
oxide is
added as described above until a weight gain of 60g (corresponding to a total
of 4.2
ethoxy units) is obtained. A 53g portion of this brown viscous liquid is
saved. Ethylene
oxide is added to the remaining material as described above until a weight
gain of 35.9g
(corresponding to a total of 7.1 ethoxy units) is obtained to afford 94.9g of
dark brown
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liquid. The potassium hydroxide in the latter two samples is neutralized by
adding the
theoretical amounts of methanesulfonic acid.
EXAMPLE 2
S?uaternization of PEI 1800 E7
To a S00 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) (207.38, 0.590 mol nitrogen, prepared as in Example I) and
acetonitrile (120
g). Dimethyl sulfate (28.38, 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
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 E7
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
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51
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
alumina
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
Formation of amine oxide of quaternized PEI 1800 E7
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 about 7 ethyleneoxy residues per nitrogen (PEI
1800 E7) and
then further modified by quaternization to approximately 38% with dimethyl
sulfate (130
g, 0.20 mol oxidizeable nitrogen, prepared as in Example II), hydrogen
peroxide (48 g
of a 30 wt % solution in water, 0.423 mol), and water (~50 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 taken from the reaction mixture
indicates
complete conversion of the resonances attributed to the methylene peaks
previously
observed in the range of 2.5-3.0 ppm to a material having methylenes with a
chemical
shift of approximately 3.7 ppm. To the reaction solution is added
approximately S g of
0.5% Pd on alumina 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 desired material with ~38% of the nitrogens quaternized
and 62%
of the nitrogens oxidized to amine oxide is obtained and is suitably stored as
a 44.9%
active solution in water.
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EXAMPLE 5
Preparation of PEI 1200 E7
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 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 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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53
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
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
methanesulfonic 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 withwitrogen.
In other preparations the neutralization and deodorization is accomplished in
the
reactor before discharging the product.
Other preferred examples such as PEI 1200 E 15 and PEI 1200 E20 can t~:
prepared by the above method by adjusting the reaction time and the relative
amount ut
ethylene oxide used in the reaction.
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54
EXAMPLE 6
9.7% Ouaternization of PEI 1200 E7
To a 500m1 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
afford ~220g of the desired material as a dark brown viscous liquid. A 13C-NMR
(D20)
spectrum shows the absence of a peak at ~58ppm corresponding to dimethyl
sulfate. A
1H-NMR (D20) spectrum shows the partial shifting of the peak at 2.5ppm
(methylenes
attached to unquaternized nitrogens) to ~3.Oppm.
EXAMPLE 7
Preparation of PEI 600 E20
The ethoxyladon 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 250 g portion of polyethyleneimine (PEI) (Nippon Shokubai, having a listed
average molecular weight of 600 equating to about 0.417 moles of polymer and
6.25
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
CA 02324470 2000-09-19
WO 99/49009 PCT/IB99/00470
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 275 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 135 g of a 25% sodium methoxide in methanol solution
(0.625
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 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
approximately 5225 g of ethylene oxide (resulting in a total of 20 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.
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56
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 60 g
methanesulfonic acid
(0.625 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.
The following describe high density liquid detergent compositions according to
the present invention:
TABLEI
wei hg_ t
In redient 8 9 10 11
Polyhydroxy Coco-Fatty Acid 2.50 2.50 -- --
Amide
C i 2-C 13 Alcohol Ethoxylate-- -- 3.65 0.80
E9
Sodium C 12-C I 5 Alcohol - -- 6.03 2.50
Sulfate
Sodium C I 2-C 15 Alcohol 20.15 20. - --
Ethoxylate I 5
E I , g Sulfate
Sodium C 14-C I 5 Alcohol -- -- 18.00 I 8.00
Ethoxylate
E2.25 S~fate
Alkyl N-Methyl Glucose Amide -- -- 4.50 4.50
C I 0 Amidopropyl Amine 0.50 0.50 1.30 -
Citric Acid 2.44 3.00 3.00 3.00
Fatty Acid (C I 2-C 14) -- -- 2.00 2.00
NEODOL 23-9' 0.63 0.63 -- --
Ethanol 3.00 2.81 3.40 3.40
Monoethanolamine 1.50 0.75 1.00 I.00
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Propanediol 8.00 7.50 7.50 7.00
i
Boric Acid 3.50 3.50 3.50 3.50
Ethoxylated tetraethylenepentamine0.50 -- _ __
Tetraethylenepentamine -- 1.18 -- -_
Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50
NaOH 2.08 2.43 2.62 2.62
Protease enzyme 0.78 0.70 -- -_
Protease enzyme' __ __ 0.88 --
ALCALASEr -- - -- 1.00
HEDP 0.5 0.7 2.5 0.5
Polyamineb 0.50 0.50 -- __
Polyamine ' -- -- 2.00 1.00
Water balance balancebalancebalance
t r._ r~t_____~_~~
-. -ry .....~~.>>~cma.aa cmwuma a~ ~Vlu Dyne anell v11 l:o.
2. Ethoxylated tetraethylenepentamine (PEI 189 E 15-E 1 g) according to U.S.
4,597,898
Vander Meer issued July 1, 1986.
3. Bleach stable variant of BPN' (Protease A-BSV) as disclosed in EP 130,756 A
January 9, 1985.
4. Subtilisin 309 Loop Region 6 variant.
5. Proteolytic enzyme as sold by Novo.
6. Polyamine according to Example 7 (PEI 600 E20).
7. Polyamine according to Example 5 (PEI 1200 E20).
8. Balance to 100% can, for example, include minors like optical brightener,
perfume,
suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting
agents.
additional water, and fillers, including CaC03, talc, silicates, etc.
TABLE II
weight
12 ~ 13 ~ 14 15
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WO 99/49009 PCT/IB99/00470
58
Yolyhydroxy Coco-Fatty Acid 3.65 3.50 -- __
Amide
C 12-C 13 Alcohol Ethoxylate 3.65 0.80 -
E9
Sodium C 12-C 1 S Alcohol Sulfate6.03 2.50 _
Sodium C 12-C 1 S Alcohol Ethoxylate9.29 15.10 -- __
E2,5 Sulfate
Sodium C 14-C 1 S Alcohol Ethoxylate-- -- 18.00 18.00
E2.25 Sulfate
Alkyl N-Methyl Glucose Amide - -- 4.50 4.50
C 10 Amidopropyl Amine -- 1.30 - __
Citric Acid 2.44 3.00 3.00 3.00
Fatty Acid (C 12-C 14) 4.23 2.00 2.00 2.00
NEODOL 23-9' -- -- 2.00 2.00
Ethanol 3.00 2.81 3.40 3.40
Monoethanolamine 1.50 0.75 1.00 1.00
Propanediol 8.00 7.50 7.50 7.00
Boric Acid 3.50 3.50 3.50 3.50
Tetraethylenepentamine - 1.18 -- --
Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50
NaOH 2.08 2.43 2.62 2.62
Protease enzyme' 0.78 0.70 __ __
_
Protease enzyme' __ __ 0.88 __
ALCALASE' _ _ __ 1.00
HEDP 1.5 1.5 1.5 0.5
Polyamine5 0.50 0.50 -- -
Polyamineb - -- 2.00 1.00
Water' balancebalance balancebalance
t r._ r.L_____~. , .,
~. ~y ~mvaytaiea H1COI101S aS SO1C1 by the shell Uil (:o.
2. Bleach stable variant of BPN' (Protease A-BSV) as disclosed in EP 130,756
:~
January 9, 1985.
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WO 99/49009 PCT/IB99/00470
59 -
3. Subtilisin 309 Loop Region 6 variant.
4. Proteolytic enzyme as sold by Novo.
5. Polyamine according to Example 1 (PEI 1200 E7).
6. Polyamine according to Example 7 (PEI 600 E20).
7. Balance to 100% can, for example, include minors like optical brightener,
perfume,
suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting
agents,
additional water, and fillers, including CaC03, talc, silicates, etc.
TABLE III
Inaeredient 16 17 18 19
Sodium C 14-C 1 S Alcohol 13.00 - - 8.43
Ethoxylate
E2.25 Sulfate
Sodium C 12-C 15 Alcohol Ethoxylate-- 18.00 13.00 --
E2,5 Sulfate
Sodium C 12-C 13 linear alkylbenzene9.86 -- -- 8.43
sulfonate
Fatty Acid (C 12-C 14) -- 2.00 2.00 2.95
C 12-C 13 Alcohol Ethoxylate -- -- -- 3.37
E9
C 1 p Amidopropyl Amine _ __ 0.80 __
NEODOL 23-91 2.22 2.00 1.60 --
Alkyl N-Methyl Glucose Amide -- 5.00 2.50 --
Citric Acid 7.10 3.00 3.00 3.37
Ethanol 1.92 3.52 3.41 1.47
Monoethanolamine 0.71 1.09 1.00 1.05
Propanediol 4.86 8.00 6.51 6.00
Boric Acid 2.22 3.30 2.50 --
Ethoxylated Tetraethylenepentamine1.18 1.18 -- 1.48
Sodium Cumene Sulfonate 1.80 3.00 - 3.00
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WO 99/49009 PCT/IB99/00470
Sodium Toluene Sulfonate -- -- ~ 2.50 --
~~ ~
NaOH 6.60 2.82 2.90 2.10
Dodecyitrimethylammonium Chloride-- -- - 0.51
Sodium Tartrate Mono and Di-succinate-- -- - 3.37
Sodium Formate -- - -- 0.32
Protease DL 0.88 0.88 -- -_
Protease subtilisin 309 variant-- -- 0.78 0.56
HEDP 0.3 0.7 1.5 2.5
Polyamine'~ 0.50 2.00 -- --
Polyamine~ 1.50 -- 2.00 3.00
Waters balance balancebalance balance
r r~~tn
.. Ly L;mv~yatcu tll~:VIIV1J tIS SOIa Dyne ~neu ui1 c:o.
2. Protease B variant of BPN' wherein Tyr 217 is replaced with Leu.
3. Subtilisin 309 variant having a modified amino acid sequence of subtilisin
309 wild-
type amino acid sequence wherein substitutions occur at one or more of
positions
194, 195, I 96, 199 or 200.
4. Polyamine according to Example 4.
S. Polyamine according to Example 7.
6. Balance to 100% can, for example, include minors like optical brightener,
perfume,
suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting
agents,
additional water, and fillers, including CaC03, talc, silicates, etc.
TABLE IV
In edient 20 21 22 23
;- -.-._,
Sodmm C I4-C I 5 Alcohol EthoxylateI 3.00 -- - 8.43
E2.25 S~fate
Sodium C I 2-C 15 Alcohol - 18.00 I 3.00 --
Ethoxylate
E2,g Sulfate
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61
Sodium C 12-C 13 lin ylbenzene9.86 -- -- 8.43
sulfonate
Fatty Acid (C 12-C 14) -- 2.00 2.00 2.95
C 12-C 13 Alcohol Ethoxylate - -- - 3.37
E9
C 10 Amidopropyl Amine -- -- 0.80 --
NEODOL 23-91 2.22 2.00 1.60 --
Alkyl N-Methyl Glucose Amide -- 5.00 2.50 --
Citric Acid 7.10 3.00 3.00 3.37
Ethanol . 1.92 3.52 3.41 1.47
Monoethanolamine 0.71 1.09 1.00 1.05
Propanediol 4.86 8.00 6.51 6.00
Boric Acid 2.22 3.30 2.50
Ethoxylated Tetraethylenepentamine1.18 1.18 - 1.48
Sodium Cumene Sulfonate 1.80 3.00 - 3.00
Sodium Toluene Sulfonate -- -- 2.50 --
NaOH 6.60 2.82 2.90 2.10
Dodecyltrimethylammonium Chloride-- -- -- 0.51
Sodium Tartrate Mono and Di-succinate-- -- - 3.37
Sodium Formate -- - -- 0.32
Protease D~ 0.88 0.88 -- __
Protease subtilisin 309 variant- -- 0.78 0.56
HEDP 0.3 0.7 2.5 3.5
Polyamine4 0.50 2.00 -- -
Polyamine~ 1.50 - 2.00 3.00
Waters balancebalance balancebalance
~ r r.~,,
-. Ly a.uavnyiutcu lll~:unulS ~iS SOIa Dy me ~neu uu Lo.
2. Protease B variant of BPN' wherein Tyr 217 is replaced with Leu.
3. Subtilisin 309 variant having a modified amino acid sequence of subtilisin
309 wild-
type amino acid sequence wherein substitutions occur at one or more of
positions
194, 195, 196, 199 or 200.
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62
4. Polyamine according to Example 7.
5. Polyamine according to Example 1.
6. Balance to 100% can, for example, include minors like optical brightener,
perfume,
suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting
agents,
additional water, and fillers, including CaC03, talc, silicates, etc.
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63
TABLE V
Ingredients 24 25 26 27 28
-~~~
-
Polyhydroxy coco-fatty acid 3.50 3.50 3.15 3.50 3.00
amide
NEODOL 23-9 1 2.00 0.60 2.00 0.60 0.60
C25 Alkyl ethoxylate sulphate 19.00 19.40 19.00 17.40 14.00
C25 Alkyl sulfate -- -- - 2.85 2.30
C 10 -AminopropyIamide -- - -- 0.75 0.50
Citric acid 3.00 3.00 3.00 3.00 3.00
Tallow fatty acid 2.00 2.00 2.00 2.00 2.00
Ethanol 3.41 3.47 3.34 3.59 2.93
Propanediol 6.22 6.35 6.21 6.56 5.75
Monomethanol amine 1.00 0.50 0.50 0.50 0.50
Sodium hydroxide 3.05 2.40 2.40 2.40 2.40
Sodium p-toluene sulfonate 2.50 2.25 2.25 2.25 2.25
B~ 2.50 2.50 2.50 2.50 2.50
Protease 1 0.88 0.$8 0.88 0.88 0.88
Lipolase s 0.04 0.12 0.12 0.12 0.12
Y14 0.10 0.10 0.10 0.10 0.40
CAREZYME 0.053 0.053 0.053 0.053 0.053
Optical Brightener 0.15 0.15 0.15 0.15 0.15
HEDP 0.7 0.5 0.7 0.7 0.9
Polyamine ~ 1.18 1.18 1.18 1.18 1.75
Fumed silica 0.119 0.119 0.119 0.119 0.119
Minors, aestetics, water balancebalancebalancebalancebalance
t f :..l'._ ..11._.t rn _~L___~_~
'~ 1 L-~ 1 s °~yi ~7 Gu~~xyaie as solo Dy ~11e11 U11 C;O.
2. Bacillus amyloliguefaciens subtilisin as described in WO 95/10615 published
April
20, 1995 by Genencor International.
3. Derived from Humicola lanuginosa and commercially available from Novo.
4. Disclosed in WO 9510603 A and available from Novo.
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64
5. Polyamine according to Example 7.
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WO 99/49009 PCT/IB99/004~0
6S
TABLE VI
Composition 29 30
C 14 14
,2.,5
Alkyl
sulfate
C 4 4
,Z_,5
Alkyl
sulfate
3
ethoxylate
C 4.S 4.S
,3.,5
Alkyl
7
ethoxylate
C 4 4
,2."
alkyl
glucoseamide
C 1.3 1.3
&,o
alkylamidopropyl
dimethylamine
Citric 3.S 3.S
acid
Fatty 10.5 10.5
acid
HEDP O.S O.S
Polyamine' 0.7 -
PolyamineZ _ 0.7
Ethanol 2 2
1,2 9 9
propandiol
Tetraethylenepentamine, 0.7 0.7
1
S
ethoxylate
Diethyienetriamine 0.9 O.S
pentamethylene
phosphoric
acid
Enzymes 2 2
Boric 2 2
acid
MEA pH 7.S pH 7.S
(monoethanolamine)
+
NaOH
Minors, balancebalance
additives,
water
n_~_-___._
....
.. . vayaauiua m ~xitmple ~.
2. Polyamine of Example 1.
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WO 99/49009 PCT/IB99/00470
66
TABLE VII
Composition 3 32 33 34 35
C ,Z.,s Alkyl sulfate, 10 14 16 16 15
MEA salt
C ,z_,s Alkyl sulfate 9 8 4 4 3
3 ethoxylate,
Na salt
C ,3.,5 Alkyl 7 ethoxylate6 3 _
C ,z.,4 alkyl glucoseamide3 S 6 6 2
C ~.,o alkylamidopropyl 1 - - - 0.5
dimethylamine
Citric acid 1 3 2 2 5
Fatty acid 10 9 10 10 2
HEDP 1.1 0.7 2.5 1.5 2.0
Polyamine ' 1.5 1.2 1.5 - 0.5
Polyamine Z _ - _ _
Polyamine 3 - - 1.5 -
Ethanol 4 3 2 2 3
1,2 propandiol 7 10 5 S 7
Tetraethylenepentamine, 0.5 0.9 - 1
15
ethoxylate
Diethylenetriamine 0.5 _ _
pentamethylene phosphoric
acid
Enzymes 1 3 _ _
Boric acid 3 1 _ - 3
MEA(monoethanolamine)+NaOHpH 8 pH pH pH pH 8
8 8 8
Minors, additives, water balancebalancebalancebalancebalance
1 P1
o yamme of example 7.
2. Polyamine of example 1.
3. Polyamine of example 5.
