FIELD OF THE INVENTION
[0001] 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
[0002] 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 specific 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
[0003] 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:

having a modified polyamine formula V
(n+1)W
mY
nZ or a polyamine backbone corresponding to the formula:

having a modified polyamine formula V
(n-k+1)W
mY
nY'
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:

ii) W units are backbone units having the formula:

iii) Y units are branching units having the formula:

iv) Z units are terminal units having the formula:

wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -(R1O)xR1-, - (R1O)xR5(OR1)x-, -(CH2CH(OR2)CH2O)(R1O)y-R1O(CH2CH(OR2)CH2)w-, -C(O)(R4)rC(O)-, -CH2CH(OR2)CH2-, and mixtures thereof, wherein R1 is C2-C6 alkylene and mixtures thereof, R2 is hydrogen, -(R1O)xB, and mixtures thereof, R3 is C1-C18 alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof, R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof, R5 is C1-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, - C(O)-, -C(O)NHR6-NHC(O)-, -C(O)(R4)rC(O)-, - CH2CH(OH)CH2O(R1O)yR1O-CH2CH(OH)CH2-, and mixtures thereof, R6 is C2-C12 alkylene or C6-C12 arylene; E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)p-CO2M, - (CH2)qSO3M, -CH(CH2CO2M)-CO2M, -(CH2)pPO3M, -(R1O)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 is hydrogen, C1-C6 alkyl, -(CH2)qSO3M, -(CH2)pCO2M, - (CH2)qCH(SO3M)CH2SO3M, -(CH2)qCH(SO2M)CH2SO3M, - (CH2)pPO3M, -PO3M, 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 0 to about 200; p has the value from 1 to 6, q has the value
from 0 to 6; r has the value of 0 or 1; w has the value 0 or 1; x has the value from
1 to 100; y has the value from 0 to 100; z has the value 0 or 1.
[0004] All percentages, ratios and proportions herein are by weight of the total composition,
unless otherwise specified. All temperatures are in degrees Celsius (° 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
[0005] 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
[0006] 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 Dequest® 2010, from Monsanto.
The polyamine
[0007] 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 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
[0008] 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 referring
to the process of replacing a hydrogen atom attached to a backbone nitrogen with an
E unit. Quaternization or oxidation may take place in some circumstances without substitution,
but substitution preferably is accompanied by oxidation or quaternization of at least
one backbone nitrogen.
[0009] The linear or non-cyclic polyamine backbones have the general formula:

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:

said backbones prior to subsequent modification, comprise primary, secondary and
tertiary amine nitrogens connected by R "linking" units
[0010] For the purpose of the present invention, primary amine nitrogens comprising the
backbone or branching chain once modified are defined as V or Z "terminal" units.
For example, when a primary amine moiety, located at the end of the main polyamine
backbone or branching chain having the structure
H
2N-R]-
is modified according to the present invention, it is thereafter defined as a V "terminal"
unit, or simply a V unit. However, for the purposes of the present invention, some
or all of the primary amine moieties can remain unmodified subject to the restrictions
further described herein below. These unmodified primary amine moieties by virtue
of their position in the backbone chain remain "terminal" units. Likewise, when a
primary amine moiety, located at the end of the main polyamine backbone having the
structure
-NH
2
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
further described herein below.
[0011] 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

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.
[0012] 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

is modified according to the present invention, it is thereafter defined as a Y "branching"
unit, or simply a Y unit. However, for the purposes of the present invention, some
or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary
amine moieties by virtue of their position in the backbone chain remain "branching"
units. The R units associated with the V, W and Y unit nitrogens which serve to connect
the polyamine nitrogens, are described herein below.
[0013] The final modified structure of the polyamines of the present invention can be therefore
represented by the general formula
V
(n+1)W
mY
nZ
for linear polyamine cotton soil release polymers and by the general formula
V
(n-k+1)W
mY
nY'
kZ
for cyclic polyamine cotton soil release polymers. For the case of polyamines comprising
rings, a Y' unit of the formula

serves as a branch point for a backbone or branch ring. For every Y' unit there is
a Y unit having the formula

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

therefore comprising no Z terminal unit and having the formula
V
n-kW
mY
nY'
k
wherein k is the number of ring forming branching units. Preferably the polyamine
backbones of the present invention comprise no rings.
[0014] 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
VW
mZ
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.
[0015] Each polyamine nitrogen whether primary, secondary or tertiary, once modified according
to the present invention, is further defined as being a member of one of three general
classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units
not modified are classed into V, W, Y, or Z units depending on whether they are primary,
secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V
or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary
amine nitrogens are Y units for the purposes of the present invention.
[0016] Modified primary amine moieties are defined as V "terminal" units having one of three
forms:
a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:

[0017] Modified secondary amine moieties are defined as W "backbone" units having one of
three forms:
a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:

[0018] Modified tertiary amine moieties are defined as Y "branching" units having one of
three forms:
a) unmodified units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:

[0019] Certain modified primary amine moieties are defined as Z "terminal" units having
one of three forms:
a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:

[0020] When any position on a nitrogen is unsubstituted of unmodified, it is understood
that hydrogen will substitute for E. For example, a primary amine unit comprising
one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula
(HOCH
2CH
2)HN-
.
[0021] 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 -NH
2. 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.
[0022] 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 C
2-C
12 alkylene, C
4-C
12 alkenylene, C
3-C
12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain
except the carbon atoms directly connected to the polyamine backbone nitrogens; C
4-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; C
8-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

although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substituted
C
2-C
12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably
ethylene. The "oxy" R units comprise -(R
1O)
xR
5(OR
1)
x-, CH
2CH(OR
2)CH
2O)
z(R
1O)
yR
1(OCH
2CH(OR
2)CH
2)
w-, -CH
2CH(OR
2)CH
2-, (R
1O)
xR
1-, and mixtures thereof. Preferred R units are C
2-C
12 alkylene, C
3-C
12 hydroxyalkylene, C
4-C
12 dihydroxyalkylene, C
8-C
12 dialkylarylene, -(R
1O)
xR
1-, - CH
2CH(OR
2)CH
2-, -(CH
2CH(OH)CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH)CH
2)
w-, - (R
1O)
xR
5(OR
1)
x-, more preferred R units are C
2-C
12 alkylene, C
3-C
12 hydroxy-alkylene, C
4-C
12 dihydroxyalkylene, -(R
1O)
xR
1-, -(R
1O)
xR
5(OR
1)
x-, (CH
2CH(OH)CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH)CH
2)
w-, and mixtures thereof, even more preferred R units are C
2-C
12 alkylene, C
3 hydroxyalkylene, and mixtures thereof most preferred are C
2-C
6 alkylene. The most preferred backbones of the present invention comprise at least
50% R units that are ethylene.
[0023] R
1 units are C
2-C
6 alkylene, and mixtures thereof, preferably ethylene. R
2 is hydrogen, and -(R
1O)
xB, preferably hydrogen.
[0024] R
3 is C
1 -C
18 alkyl, C
7-C
12 arylalkylene, C
7-C
12 alkyl substituted aryl, C
6-C
12 aryl, and mixtures thereof , preferably C
1-C
12 alkyl, C
7-C
12 arylalkylene, more preferably C
1-C
12 alkyl, most preferably methyl. R
3 units serve as part of E units described herein below.
[0025] R
4 is C
1-C
12 alkylene, C
4-C
12 alkenylene, C
8-C
12 arylalkylene, C
6-C
10 arylene, preferably C
1-C
10 alkylene, C
8-C
12 arylalkylene, more preferably C
2-C
8 alkylene, most preferably ethylene or butylene.
[0026] R
5 is C
1-C
12 alkylene, C
3-C
12 hydroxyalkylene, C
4-C
12 dihydroxyalkylene, C
8-C
12 dialkylarylene, -C(O)-, -C(O)NHR
6NHC(O)-, -C(O)(R
4)
rC(O)-, R
1(OR
1)-, CH
2CH(OH)CH
2O(R
1O)
yR
1OCH
2CH(OH)CH
2-, C(O)(R
4)
rC(O)-, -CH
2CH(OH)CH
2-, R
5 is preferably ethylene, -C(O)-, -C(O)NHR
6NHC(O)-, R
1(OR
1)-, -CH
2CH(OH)CH
2-, CH
2CH(OH)CH
2O(R
1O)
yR
1OCH
2CH-(OH)CH
2-, more preferably -CH
2CH(OH)CH
2-.
[0027] R
6 is C
2-C
12 alkylene or C
6-C
12 arylene.
[0028] The preferred "oxy" R units are further defined in terms of the R
1, R
2, and R
5 units. Preferred "oxy" R units comprise the preferred R
1, R
2, and R
5 units. The preferred cotton soil release agents of the present invention comprise
at least 50% R
1 units that are ethylene. Preferred R
1, R
2, and R
5 units are combined with the "oxy" R units to yield the preferred "oxy" R units in
the following manner.
i) Substituting more preferred R5 into -(CH2CH2O)xR5(OCH2CH2)x-yields -(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH2O)z-(R1O)yR1O(CH2CH(OR2)CH2)w- yields -(CH2CH(OH)CH2O)z-(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields -CH2CH(OH)CH2-.
[0029] E units are selected from the group consisting of hydrogen, C
1-C
22 alkyl, C
3-C
22 alkenyl, C
7-C
22 arylalkyl, C
2-C
22 hydroxyalkyl, -(CH
2)
pCO
2M, -(CH
2)
qSO
3M, - CH(CH
2CO
2M)CO
2M, -(CH
2)
pPO
3M, -(R
1O)
mB, -C(O)R
3, preferably hydrogen, C
2-C
22 hydroxyalkylene, benzyl, C
1-C
22 alkylene, -(R
1O)
mB, -C(O)R
3, -(CH
2)
pCO
2M, - (CH
2)
qSO
3M, -CH(CH
2CO
2M)CO
2M, more preferably C
1-C
22 alkylene, -(R
1O)
xB, -C(O)R
3, -(CH
2)
pCO
2M, -(CH
2)
qSO
3M, -CH(CH
2CO
2M)CO
2M, most preferably C
1-C
22 alkylene, -(R
1O)
xB, and -C(O)R
3. When no modification or substitution is made on a nitrogen then hydrogen atom will
remain as the moiety representing E.
[0030] 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:

[0031] 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)R
3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide
amides having the structure

nor combinations thereof.
[0032] B is hydrogen, C
1-C
6 alkyl, (CH
2)
qSO
3M, -(CH
2)
pCO
2M, -(CH
2)
q -(CHSO
3M)CH
2SO
3M, -(CH
2)
q(CHSO
2M)CH
2SO
3M, -(CH
2)
pPO
3M, -PO
3M, preferably hydrogen, -(CH
2)
qSO
3M, -(CH
2)
q(CHSO
3M)CH
2SO
3M, -(CH
2)
q-(CHSO
2M)CH
2SO
3M, more preferably hydrogen or -(CH
2)
qSO
3M.
[0033] M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
For example, a sodium cation equally satisfies -(CH
2)
pCO
2M, and - (CH
2)
qSO
3M, thereby resulting in -(CH
2)
pCO
2Na, and -(CH
2)
qSO
3Na moieties. More than one monovalent cation, (sodium, potassium, etc.) can be combined
to satisfy the required chemical charge balance. However, more than one anionic group
may be charge balanced by a divalent cation, or more than one mono-valent cation may
be necessary to satisfy the charge requirements of a poly-anionic radical. For example,
a - (CH
2)
pPO
3M moiety substituted with sodium atoms has the formula -(CH
2)
pPO
3Na
3. Divalent cations such as calcium (Ca
2+) or magnesium (Mg
2+) may be substituted for or combined with other suitable mono-valent water soluble
cations. Preferred cations are sodium and potassium, more preferred is sodium.
[0034] 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 (SO
42-) and methosulfate (CH
3SO
3-).
[0035] 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.
[0036] 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.
[0037] 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 C
2-C
12 alkylene, preferred is C
2-C
3 alkylene, most preferred is ethylene.
[0038] 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.
[0039] 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.
[0040] 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.
[0041] The preferred polyamines that comprise the backbone of the compounds of the present
invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably
polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected
by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's. A
common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions
involving ammonia and ethylene dichloride, followed by fractional distillation. The
common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines,
the cogenerically derived mixture does not appear to separate by distillation and
can include other materials such as cyclic amines and particularly piperazines. There
can also be present cyclic amines with side chains in which nitrogen atoms appear.
See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation
of PEA's.
[0042] Preferred amine polymer backbones comprise R units that are C
2 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:

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.
[0043] 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.
[0044] These polyamines can be prepared, for example, by polymerizing ethyleneimine in the
presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen
peroxide, hydrochloric acid, 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.
[0045] Examples of polyamines of the present invention comprising PEI's, are illustrated
in Formulas I - V:
[0046] Formula I depicts a preferred polyamines comprising a PEI backbone wherein all substitutable
nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit,
-(CH
2CH
2O)
20H, having the formula:

[0047] Formula II depicts a polyamine comprising a PEI backbone wherein all substitutable
nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit,
-(CH
2CH
2O)
7H, having the formula

This is an example of a polyamine that is fully modified by one type of moiety.
[0048] 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, -(CH
2CH
2O)
7H, the molecule is then modified by subsequent oxidation of all oxidizable primary
and secondary nitrogens to N-oxides, said polyamine having the formula

[0049] 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, -(CH
2CH
2O)
7H, or methyl groups. The modified PEI polyamine has the formula

[0050] Formula V depicts a polyamine comprising a PEI backbone wherein the backbone nitrogens
are modified by substitution (i.e. by -(CH
2CH
2O)
7H or methyl), quaternized, oxidized to N-oxides or combinations thereof The resulting
polyamine has the formula

[0051] 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.
[0052] 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.
[0053] 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
[0054] 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.
[0055] Nonlimiting examples of other surfactants useful herein typically at levels from
about 1% to about 55%, by weight, include the conventional C
11-C
18 alkyl benzene sulfonates ("LAS"), the C
10-C
18 secondary (2,3) alkyl sulfates of the formula CH
3(CH
2)
x(CHOSO
3-M
+) CH
3 and CH
3 (CH
2)
y(CHOSO
3-M
+) CH
2CH
3 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
18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C
10- 18 glycerol ethers, the C
10-C
18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C
12-C
18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C
12-C
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol sulfobetaines ("sultaines"), C
10-C
18 amine oxides, and the like, can also be included in the overall compositions. The
C
10-C
18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include
the C
12-C
18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the
N-alkoxy polyhydroxy fatty acid amides, such as C
10-C
18 N-(3-methoxypropyl) glucamide. C
10-C
20 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.
[0056] 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, C
9-C
20 linear alkylbenzenesulphonates, C
8-C
22 primary -or secondary alkanesulphonates, C
8-C
24 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
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C
6-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(CH
2CH
2O)
kCH
2COO-M
+ wherein R is a C
8-C
22 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).
[0057] 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 ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably an alkyl straight or branched chain or hydroxyalkyl having
a C
10-C
20 alkyl component, more preferably a C
12-C
18 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 alkanolamines 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
18 alkyl chains are preferred for higher wash temperatures (e.g., about 50°C).
[0058] 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)
mSO
3M wherein R is an unsubstituted C
10-C
24 alkyl or hydroxyalkyl group having a C
10-C
24 alkyl component, preferably a C
12-C
20 alkyl or hydroxyalkyl, more preferably C
12-C
18 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 cation which can be, for example, a metal cation
(e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium
cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium,
dimethyl piperdinium and cations derived from alkanolamines, e.g., monoethanolamine,
diethanolamine, and triethanolamine, and mixtures thereof Exemplary surfactants are
C
12C
18 alkyl polyethoxylate (1.0) sulfate, C
12-C
18 alkyl polyethoxylate (2.25) sulfate, C
12-C
18 alkyl polyethoxylate (3.0) sulfate, and C
12-C
18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium
and potassium.
[0059] 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
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block
alkylene oxide condensate of C
6 to C
12 alkyl phenols, alkylene oxide condensates of C
8-C
22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic™-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.
[0060] 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.
[0061] Further preferred nonionic surfactants are the polyhydroxy fatty acid amides having
the formula:

wherein R
7 is C
5-C
31 alkyl, preferably straight chain C
7-C
19 alkyl or alkenyl, more preferably straight chain C
9-C
17 alkyl or alkenyl, most preferably straight chain C
11-C
15 alkyl or alkenyl, or mixtures thereof, R
8 is selected from the group consisting of hydrogen, C
1-C
4 alkyl, C
1-C
4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl
moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative thereof, preferred alkoxy is ethoxy or 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 fructose 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 CH
2(CHOH)
nCH
2OH, -CH(CH
2OH)(CHOH)
n-1CH
2OH, - CH
2(CHOH)
2-(CHOR')(CHOH)CH
2OH, 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 -CH
2(CHOH)
4CH
2OH.
[0062] R
7CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide,
capricamide, palmitamide, tallowamide, etc.
[0063] R
8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or
2-hydroxy propyl.
[0064] Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl,
1-deoxymannityl, 1-deoxymaltotriotityl, etc.
[0065] 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
7 is alkyl (preferably C
11-C
13), R
8, is methyl and Q is 1-deoxyglucityl.
[0066] Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides,
such as C
10-C
18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C
12-C
18 glucamides can be used for low sudsing. C
10-C
20 conventional soaps may also be used. If high sudsing is desired, the branched-chain
C
10-C
16 soaps may be used.
Optionals
[0067] The compositions herein can further comprise a variety of optional ingredients.
[0068] A wide variety of other ingredients useful in detergent compositions can be included
in the compositions herein, including other active ingredients, carriers, hydrotropes,
processing aids, dyes or pigments, solvents for liquid formulations, solid fillers
for bar compositions, etc. If high sudsing is desired, suds boosters such as the C
10-C
16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
The C
10-C
14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCl
2, MgSO
4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional
suds and to enhance grease removal performance.
[0069] Various detersive ingredients employed in the present compositions optionally can
be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate,
then coating said substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a surfactant before being absorbed into the porous substrate.
In use, the detersive ingredient is released from the substrate into the aqueous washing
liquor, where it performs its intended detersive function.
[0070] To illustrate this technique in more detail, a porous hydrophobic silica (trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5%
of C
13-15 ethoxylated 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.
[0071] Liquid detergent compositions can contain water and other solvents as carriers. Low
molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol,
and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant,
but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to
about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol)
can also be used. The compositions may contain from 5% to 90%, typically 10% to 50%
of such carriers.
[0072] 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 10.0. 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.
Enzymes
[0073] 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.
[0074] "Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing
or otherwise beneficial effect in a laundry, hard surface cleaning or personal care
detergent composition. Preferred detersive enzymes are hydrolases such as proteases,
amylases and lipases. Preferred enzymes for laundry purposes include, but are not
limited to, proteases, cellulases, lipases and peroxidases.
[0075] Enzymes are normally incorporated into detergent or detergent additive compositions
at levels sufficient to provide a "cleaning-effective amount". The term "cleaning
effective amount" refers to any amount capable of producing a cleaning, stain removal,
soil removal, whitening, deodorizing, or freshness improving effect on substrates
such as fabrics. In practical terms for current commercial preparations, typical amounts
are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per
gram of the detergent composition. Stated otherwise, the compositions herein will
typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such commercial preparations
at levels sufficient to provide from 0.005 to 0.1 Anson 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.
[0076] Amylases suitable herein include, for example, α-amylases described in GB 1,296,839
to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL®
from Novo is especially useful. Engineering of enzymes for improved stability, e.g.,
oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No.
11, 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 60°C; 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 α-amylases, regardless of whether one, two or multiple amylase strains are the immediate
precursors. Oxidative stability-enhanced amylases vs. the above-identified reference
amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching,
as distinct from chlorine bleaching, detergent compositions herein. Such preferred
amylases include (a) an amylase according to the hereinbefore 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, 15, 197, 256, 304, 366 and 438
leading to specific mutants, particularly important being M197L and M197T with the
M197T 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.
[0077] Cellulases usable herein include both bacterial and fungal types, preferably having
a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984,
discloses suitable fungal cellulases from
Humicola insolens or
Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME® (Novo) is especially useful. See also WO 9117243 to Novo.
[0078] 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 gladioli. 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.
[0079] Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
[0080] 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 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.
[0081] 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 Anson units (AU) of activity per gram of composition.
[0082] 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.
[0083] Useful proteases are also described in PCT publications: WO 95/30010 published Novenber
9, 1995 by The Procter & Gamble Company; WO 95/30011 published Novenber 9, 1995 by
The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter
& Gamble Company.
[0084] 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.
[0085] 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.
[0086] A range of enzyme materials and means for their incorporation into synthetic detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International,
WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes
are further disclosed in U.S. 4,101,457, Place et al, July 18, 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
[0087] 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.
[0088] 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.
[0089] 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 levels of total boron in
detergent compositions may be possible though the use of such substituted boron derivatives.
[0090] Stabilizing systems of certain cleaning compositions may further comprise from 0
to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach
scavengers, added to prevent chlorine bleach species present in many water supplies
from attacking and inactivating the enzymes, especially under alkaline conditions.
While chlorine levels in water may be small, typically in the range from about 0.5
ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes
in contact with the enzyme, for example during fabric-washing, can be relatively large;
accordingly, enzyme stability to chlorine in-use is sometimes problematic. Since perborate
or percarbonate, which have the ability to react with chlorine bleach, may present
in certain of the instant compositions in amounts accounted for separately from the
stabilizing system, the use of additional stabilizers against chlorine, may, most
generally, not be essential, though improved results may be obtainable from their
use. Suitable chlorine scavenger anions are widely known and readily available, and,
if used, can be salts containing ammonium cations with sulfite, 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 enzyme-containing embodiment of the invention; even then, the scavenger
is added only for optimum results. Moreover, the formulator will exercise a chemist's
normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly
incompatible, as formulated, with other reactive ingredients, if used. In relation
to the use of ammonium salts, such salts can be simply admixed with the detergent
composition but are prone to 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
[0091] 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.
[0092] 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.
[0093] Inorganic or P-containing detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders are required in some
locales. Importantly, the compositions herein function surprisingly well even in the
presence of the so-called "weak" builders (as compared with phosphates) such as citrate,
or in the so-called "underbuilt" situation that may occur with zeolite or layered
silicate builders.
[0094] Examples of silicate builders are the alkali metal silicates, particularly those
having a SiO
2:Na
2O 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.
[0095] 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.
[0096] Aluminosilicate builders are useful in the present invention. Aluminosilicate builders
include those having the empirical formula:
M
z(zAlO
2)
y]·xH
2O
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.
[0097] 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:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
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.
[0098] 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.
[0099] 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,
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.
[0100] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-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.
[0101] 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.
[0102] 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 C
5-C
20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound
of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (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.
[0103] 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.
[0104] Fatty acids, e.g., C
12-C
18 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.
[0105] 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.
Chelating Agents
[0106] The detergent compositions herein may also optionally contain one or more iron and/or
manganese chelating agents. Such chelating agents can be selected from the group consisting
of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating
agents and mixtures therein, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is due in part to their
exceptional ability to remove iron and manganese ions from washing solutions by formation
of soluble chelates.
[0107] Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
[0108] 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.
[0109] 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. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
[0110] 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.
[0111] 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 Removal/Anti-redeposition Agents
[0112] 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%.
[0113] 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 112,592, Gosselink, published July 4, 1984;
and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985. Other clay soil removal and/or anti redeposition agents known in the art can
also be utilized in the compositions herein. Another type of preferred antiredeposition
agent includes the carboxy methyl cellulose (CMC) materials. These materials are well
known in the art.
Polymeric Dispersing Agents
[0114] 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.
[0115] 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, maleic acid (or maleic 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.
[0116] 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.
[0117] 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 maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably
from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio
of acrylate to maleate segments in such copolymers will generally range from about
30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of
such 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 15, 1982, as well as in EP 193,360, published September 3, 1986,
which also describes such polymers comprising hydroxypropylacrylate. Still other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials
are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer
of acrylic/maleic/vinyl alcohol.
[0118] 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.
[0119] Polyaspartate and polyglutamate dispersing agents may also be used, especially in
conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably
have a molecular weight (avg.) of about 10,000.
Brightener
[0120] 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).
[0121] Specific examples of optical brighteners which are useful in the present compositions
are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 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
[0122] 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.
[0123] 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.
[0124] 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
18-C
40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines
such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed
as products of cyanuric chloride with two or three moles of a primary or secondary
amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates
such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.,
K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin
and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid
at room temperature and atmospheric pressure, and will have 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.
[0125] 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 5, 1981 to Gandolfo
et al and European Patent Application No. 89307851.9, published February 7, 1990,
by Starch, M. S.
[0126] 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.
[0127] 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.
[0128] 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)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 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.
[0129] 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.
[0130] 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.
[0131] The silicone suds suppressor herein preferably comprises polyethylene glycol and
a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular
weight of less than about 1,000, preferably between about 100 and 800. The polyethylene
glycol and polyethylene/polypropylene copolymers herein have a solubility in water
at room temperature of more than about 2 weight %, preferably more than about 5 weight
%.
[0132] 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.
[0133] 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.
[0134] 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 C
6-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 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol
+ silicone at a weight ratio of 1:5 to 5:1.
[0135] 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.
[0136] The compositions herein will generally comprise from 0% to about 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein,
will be present typically in amounts up to about 5%, by weight, of the detergent composition.
Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is
utilized. Silicone suds suppressors are typically utilized in amounts up to about
2.0%, by weight, of the detergent composition, although higher amounts may be used.
This upper limit is practical in nature, due primarily to concern with keeping costs
minimized and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more
preferably from about 0.25% to about 0.5%. As used herein, these weight percentage
values include any silica that may be utilized in combination with polyorganosiloxane,
as well as any adjunct materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about 0.1% to about 2%,
by weight, of the composition. Hydrocarbon suds suppressors are typically utilized
in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
Fabric Softeners
[0137] Various through-the-wash fabric softeners, especially the impalpable smectite clays
of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as
other softener clays known in the art, can optionally be used typically at levels
of from about 0.5% to about 10% by weight in the present compositions to provide fabric
softener benefits concurrently with fabric cleaning. Clay softeners can be used in
combination with amine and cationic softeners as disclosed, for example, in U.S. Patent
4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued
September 22, 1981.
Dye Transfer Inhibiting Agents
[0138] 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 composition, preferably from about 0.01% to about 5%, and more preferably from
about 0.05% to about 2%.
[0139] More specifically, the polyamine N-oxide polymers preferred for use herein contain
units having the following structural formula: R-A
x-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.
[0140] The N-O group can be represented by the following general structures:

wherein R
1, R
2, R
3 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.
[0141] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof These polymers include random or block copolymers where one monomer
type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide
polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
The polyamine oxides can be obtained in almost any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more preferred
1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials
can be referred to as "PVNO".
[0142] The most preferred polyamine N-oxide useful in the detergent compositions herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000
and an amine to amine N-oxide ratio of about 1:4.
[0143] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light scattering as described in Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably
from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be
either linear or branched.
[0144] The present invention compositions also may employ a polyvinylpyrrolidone ("PVP")
having an average molecular weight of from about 5,000 to about 400,000, preferably
from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897
and EP-A-256,696, incorporated herein by reference. Compositions containing PVP can
also contain polyethylene glycol ("PEG") having an average molecular weight from about
500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the
ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to
about 50:1, and more preferably from about 3:1 to about 10:1.
[0145] 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.
[0146] The hydrophilic optical brighteners useful in the present invention are those having
the structural formula:

wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R
2 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.
[0147] When in the above formula, R
1 is anilino, R
2 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-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent compositions
herein.
[0148] When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener
is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
[0149] When in the above formula, R
1 is anilino, R
2 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.
[0150] 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 and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX
and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous
wash solutions than does either of these two detergent composition components when
used alone. Without being bound by theory, it is believed that such brighteners work
this way because they have high affinity for fabrics in the wash solution and therefore
deposit relatively quick on these fabrics. The extent to which brighteners deposit
on fabrics in the wash solution can be defined by a parameter called the "exhaustion
coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in the wash
liquor. Brighteners with relatively high exhaustion coefficients are the most suitable
for inhibiting dye transfer in the context of the present invention.
[0151] 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 polyamines
EXAMPLE 1
[0152] Ethoxylation of poly(ethyleneimine) with average molecular weight of 1,800 - To a 250ml 3-neck round bottom flask equipped with a Claisen head, thermometer
connected to a temperature controller (Therm-O-Watch™, I
2R), sparging tube, and mechanical stirrer is added poly(ethyleneimine) MW 1800 (Polysciences,
50.0g, 0.028 mole). Ethylene oxide gas (Liquid Carbonics) is added via the sparging
tube under argon at approximately 140°C with very rapid stirring until a weight gain
of 52g (corresponding to 1.2 ethoxy units) is obtained. A 50g 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 liquid. The potassium hydroxide in the latter two samples is neutralized
by adding the theoretical amounts of methanesulfonic acid.
EXAMPLE 2
Quaternization of PEI 1800 E7
[0153] To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine
having a molecular weight of 1800 which is further modified by ethoxylation to a degree
of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E
7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and acetonitrile (120 g).
Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly stirring
solution, which is then stoppered and stirred at room temperature overnight. The acetonitrile
is removed by rotary evaporation at about 60°C, followed by further stripping of solvent
using a Kugelrohr apparatus at approximately 80°C to afford 220 g of the desired partially
quaternized material as a dark brown viscous liquid. The
13C-NMR (D
2O) spectrum obtained on a sample of the reaction product indicates the absence of
a carbon resonance at ∼58ppm corresponding to dimethyl sulfate. The
1H-. NMR (D
2O) 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
[0154] 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, E
7) (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.
1H-NMR (D
2O) spectrum obtained on a sample of the reaction mixture indicates complete conversion.
The resonances ascribed to methylene protons adjacent to unoxidized nitrogens have
shifted from the original position at ∼2.5 ppm to ∼3.5 ppm. To the reaction solution
is added approximately 5 g of 0.5% Pd on 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
[0155] 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 E
7) 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.
1H-NMR (D
2O) 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 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 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.
EXAMPLE 5
Preparation of PEI 1200 E7
[0156] 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.
[0157] 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.
[0158] Next, vacuum is continuously applied while the autoclave is cooled to about 50 °
C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles,
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide
solution is sucked into the autoclave under vacuum and then the autoclave temperature
controller setpoint is increased to 130 °C. A device is used to monitor the power
consumed by the agitator. The agitator power is monitored along with the temperature
and pressure. Agitator power and temperature values gradually increase as methanol
is removed from the autoclave and the viscosity of the mixture increases and stabilizes
in 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.
[0159] 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.
[0160] The final reaction product is cooled slightly and collected in glass containers purged
with nitrogen.
[0161] In other preparations the neutralization and deodorization is accomplished in the
reactor before discharging the product.
[0162] Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 can be prepared by
the above method by adjusting the reaction time and the relative amount of ethylene
oxide used in the reaction.
EXAMPLE 6
9.7% Quaternization of PEI 1200 E7
[0163] To a 500ml 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 (D
2O) spectrum shows the absence of a peak at ∼58ppm corresponding to dimethyl sulfate.
A
1H-NMR (D
2O) spectrum shows the partial shifting of the peak at 2.5ppm (methylenes attached
to unquaternized nitrogens) to ∼3.0ppm.
EXAMPLE 7
Preparation of PEI 600 E20
[0164] 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.
[0165] 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 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.
[0166] 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.
[0167] 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. 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.
[0168] The final reaction product is cooled slightly and collected in glass containers purged
with nitrogen.
[0169] In other preparations the neutralization and deodorization is accomplished in the
reactor before discharging the product.
[0170] The following describe high density liquid detergent compositions according to the
present invention:
TABLE I
|
weight % |
Ingredient |
8 |
9 |
10 |
11 |
Polyhydroxy Coco-Fatty Acid Amide |
2.50 |
2.50 |
-- |
-- |
C12-C13 Alcohol Ethoxylate E9 |
-- |
-- |
3.65 |
0.80 |
Sodium C12-C15 Alcohol Sulfate |
-- |
-- |
6.03 |
2.50 |
Sodium C12-C15 Alcohol Ethoxylate E1.8 Sulfate |
20.15 |
20.15 |
-- |
-- |
Sodium C14-C15 Alcohol Ethoxylate E2.25 Sulfate |
-- |
-- |
18.00 |
18.00 |
Alkyl N-Methyl Glucose Amide |
-- |
-- |
4.50 |
4.50 |
C10 Amidopropyl Amine |
0.50 |
0.50 |
1.30 |
-- |
Citric Acid |
2.44 |
3.00 |
3.00 |
3.00 |
Fatty Acid (C12-C14) |
-- |
-- |
2.00 |
2.00 |
NEODOL 23-91 |
0.63 |
0.63 |
-- |
-- |
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 |
Ethoxylated tetraethylenepentamine2 |
0.50 |
-- |
-- |
-- |
Tetraethylenepentamine |
-- |
1.18 |
-- |
-- |
Sodium Toluene Sulfonate |
2.50 |
2.25 |
2.50 |
2.50 |
NaOH |
2.08 |
2.43 |
2.62 |
2.62 |
Protease enzyme3 |
0.78 |
0.70 |
-- |
-- |
Protease enzyme4 |
-- |
-- |
0.88 |
-- |
ALCALASE5 |
-- |
-- |
-- |
1.00 |
HEDP |
0.5 |
0.7 |
2.5 |
0.5 |
Polyamine6 |
0.50 |
0.50 |
-- |
-- |
Polyamine 7 |
-- |
-- |
2.00 |
1.00 |
Water8 |
balance |
balance |
balance |
balance |
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co. |
2. Ethoxylated tetraethylenepentamine (PEI 189 E15-E18) 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 CaCO3, talc, silicates, etc. |
TABLE II
|
weight % |
Ingredient |
12 |
13 |
14 |
15 |
Polyhydroxy Coco-Fatty Acid Amide |
3.65 |
3.50 |
-- |
-- |
C12-C13 Alcohol Ethoxylate E9 |
3.65 |
0.80 |
-- |
-- |
Sodium C12-C15 Alcohol Sulfate |
6.03 |
2.50 |
-- |
-- |
Sodium C12-C15 Alcohol Ethoxylate E2.5 Sulfate |
9.29 |
15.10 |
-- |
-- |
Sodium C14-C15 Alcohol Ethoxylate E2.25 Sulfate |
-- |
-- |
18.00 |
18.00 |
Alkyl N-Methyl Glucose Amide |
-- |
-- |
4.50 |
4.50 |
C10 Amidopropyl Amine |
-- |
1.30 |
-- |
-- |
Citric Acid |
2.44 |
3.00 |
3.00 |
3.00 |
Fatty Acid (C12-C14) |
4.23 |
2.00 |
2.00 |
2.00 |
NEODOL 23-91 |
-- |
-- |
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 enzyme2 |
0.78 |
0.70 |
-- |
-- |
Protease enzyme3 |
-- |
-- |
0.88 |
-- |
ALCALASE4 |
-- |
-- |
-- |
1.00 |
HEDP |
1.5 |
1.5 |
1.5 |
0.5 |
Polyamine5 |
0.50 |
0.50 |
-- |
-- |
Polyamine6 |
-- |
-- |
2.00 |
1.00 |
Water7 |
balance |
balance |
balance |
balance |
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co. |
2. Bleach stable variant of BPN' (Protease A-BSV) as disclosed in EP 130,756 A January
9, 1985. |
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 CaCO3, talc, silicates, etc. |
TABLE III
Ingredient |
16 |
17 |
18 |
19 |
Sodium C14-C15 Alcohol Ethoxylate E2.25 Sulfate |
13.00 |
-- |
-- |
8.43 |
Sodium C12-C15 Alcohol Ethoxylate E2.5 Sulfate |
-- |
18.00 |
13.00 |
-- |
Sodium C12-C13 linear alkylbenzene sulfonate |
9.86 |
-- |
-- |
8.43 |
Fatty Acid (C12-C14) |
-- |
2.00 |
2.00 |
2.95 |
C12-C13 Alcohol Ethoxylate E9 |
-- |
-- |
-- |
3.37 |
C10 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 Tetraethylenepentamine |
1.18 |
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 D2 |
0.88 |
0.88 |
-- |
-- |
Protease subtilisin 309 variant3 |
-- |
-- |
0.78 |
0.56 |
HEDP |
0.3 |
0.7 |
1.5 |
2.5 |
Polyamine4 |
0.50 |
2.00 |
-- |
-- |
Polyamine5 |
1.50 |
-- |
2.00 |
3.00 |
Water6 |
balance |
balance |
balance |
balance |
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co. |
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. |
4. Polyamine according to Example 4. |
5. 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 CaCO3, talc, silicates, etc. |
TABLE IV
Ingredient |
20 |
21 |
22 |
23 |
Sodium C14-C15 Alcohol Ethoxylate E2.25 Sulfate |
13.00 |
-- |
-- |
8.43 |
Sodium C12-C15 Alcohol Ethoxylate E2.5 Sulfate |
-- |
18.00 |
13.00 |
-- |
Sodium C12-C13 linear alkylbenzene sulfonate |
9.86 |
-- |
-- |
8.43 |
Fatty Acid (C12-C14) |
-- |
2.00 |
2.00 |
2.95 |
C12-C13 Alcohol Ethoxylate E9 |
-- |
-- |
-- |
3.37 |
C10 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 Tetraethylenepentamine |
1.18 |
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 D2 |
0.88 |
0.88 |
-- |
-- |
Protease subtilisin 309 variant3 |
-- |
-- |
0.78 |
0.56 |
HEDP |
0.3 |
0.7 |
2.5 |
3.5 |
Polyamine4 |
0.50 |
2.00 |
-- |
-- |
Polyamine5 |
1.50 |
-- |
2.00 |
3.00 |
Water6 |
balance |
balance |
balance |
balance |
1. E9 Ethoxylated Alcohols as sold by the Shell Oil Co. |
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. |
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 CaCO3, talc, silicates, etc. |
TABLE V
Ingredients |
24 |
25 |
26 |
27 |
28 |
Polyhydroxy coco-fatty acid amide |
3.50 |
3.50 |
3.15 |
3.50 |
3.00 |
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 |
C10-Aminopropylamide |
-- |
-- |
-- |
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 |
Borax |
2.50 |
2.50 |
2.50 |
2.50 |
2.50 |
Protease2 |
0.88 |
0.88 |
0.88 |
0.88 |
0.88 |
Lipolase3 |
0.04 |
0.12 |
0.12 |
0.12 |
0.12 |
Duramyl4 |
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 |
Polyamine5 |
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 |
balance |
balance |
balance |
balance |
balance |
1. C12-C13 alkyl E9 ethoxylate as sold by Shell Oil Co. |
2. Bacillus amyloliquefaciens 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. |
5. Polyamine according to Example 7. |
TABLE VI
Composition |
29 |
30 |
C 12-15 Alkyl sulfate |
14 |
14 |
C 12-15 Alkyl sulfate 3 ethoxylate |
4 |
4 |
C 13-15 Alkyl 7 ethoxylate |
4.5 |
4.5 |
C 12-14 alkyl glucoseamide |
4 |
4 |
C8-10 alkylamidopropyl dimethylamine |
1.3 |
1.3 |
Citric acid |
3.5 |
3.5 |
Fatty acid |
10.5 |
10.5 |
HEDP |
0.5 |
0.5 |
Polyamine1 |
0.7 |
- |
Polyamine2 |
- |
0.7 |
Ethanol |
2 |
2 |
1,2 propandiol |
9 |
9 |
Tetraethylenepentamine, 15 ethoxylate |
0.7 |
0.7 |
Diethylenetriamine pentamethylene phosphonic acid |
0.9 |
0.5 |
Enzymes |
2 |
2 |
Boric acid |
2 |
2 |
MEA (monoethanolamine) + NaOH |
pH 7.5 |
pH 7.5 |
Minors, additives, water |
balance |
balance |
1. Polyamine of Example 7. |
2. Polyamine of Example 1. |
TABLE VII
Composition |
31 |
32 |
33 |
34 |
35 |
C 12-15 Alkyl sulfate, MEA salt |
10 |
14 |
16 |
16 |
15 |
C 12-15 Alkyl sulfate 3 ethoxylate, Na salt |
9 |
8 |
4 |
4 |
3 |
C 13-15 Alkyl 7 ethoxylate |
6 |
3 |
- |
- |
2 |
C 12-14 alkyl glucoseamide |
3 |
5 |
6 |
6 |
2 |
C 8-10 alkylamidopropyl dimethylamine |
1 |
- |
- |
- |
0.5 |
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 |
1.5 |
1.2 |
1.5 |
- |
0.5 |
Polyamine 2 |
- |
- |
- |
- |
- |
Polyamine 3 |
- |
- |
- |
1.5 |
- |
Ethanol |
4 |
3 |
2 |
2 |
3 |
1,2 propandiol |
7 |
10 |
5 |
5 |
7 |
Tetraethylenepentamine, 15 ethoxylate |
0.5 |
0.9 |
- |
- |
1 |
Diethylenetriamine pentamethylene phosphonic acid |
0.5 |
- |
- |
- |
- |
Enzymes |
1 |
3 |
- |
- |
3 |
Boric acid |
3 |
1 |
- |
- |
3 |
MEA(monoethanolamine)+NaOH |
pH 8 |
pH 8 |
pH 8 |
pH 8 |
pH 8 |
Minors, additives, water |
balance |
balance |
balance |
balance |
balance |
1. Polyamine of example 7. |
2. Polyamine of example 1. |
3. Polyamine of example 5. |