Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING MODIFIED POLYAMINE POLYMERS AND CELLULASE
ENZYMES
FIELD OF THE nNVENTION
The present invention relates to detergent compositions comprising cellulase
enzymes and water soluble and/or dispersible, modified polyamines having
functionalized backbone moieties which provide depilling benefits. The cellulaseenzymes are present in an amount capable of degrading cellulose. In addition, atleast about 0.1% by weight of the detergent composition is a surfactant.
BACKGROUND OF THE INVENTION
Conventional detergent formulations usually contain surf~t~nt.c, builders and
other additives to improve the removal of soil. It is recognized by those skilled in
the art of formulating detergents that enzymes, a unique class of proteins, can be
added to conventional detergents to improve the cleaning of fabrics, dishes, andother hard surfaces. Enzymes are substances formed by living cells which catalyze
biochemical reactions, and when used in detergent formulations, they enh~n~e thecleaning ability of the detergent. Likewise, it is also known to those skilled in the
art of laundry detergents that when conventional enzyme-cont~ining laundry
detergents are used in the wash process, the surfactant and builder present in the
formulation enh~nre the action of the enzyme. Common enzymes included in
conventional laundry d~lelg~ include: amylase, which breaks down starch;
protease, which catalyzes reactions that break down proteins; lipases which work on
lipids; and cellulase which breaks down cellulose.
Cellulases are known in the art as enzymes that hydrolyze cellulose (n-1,4-
glucan linkages) to form glucose, cellobiose, cellooligosaccharides, etc. Celluloytic
enzymes are recognized by those skilled in the art of detergent formulation not only
as agents that Pnh~n~e the cleaning ability of detergents but also as agents that
modify the fabric surface by softening and improving its feel. Repeated washing of
cotton-cont~ininp~ fabric can result in the fabric a~s--ming a harsh and unpleasant
stiffness and result in pilling. Pilling is the presence of small bundles or "pills" of
fibers which gather on cotton fabrics aRer repeated washings. The use of laundrydetergent formulations cont~ininE cellulase can reduce or elimin~te the stiffn~ss and
harshness of fabrics which contain cotton. In addition cellulase enzymes also assist
in reducing the pilling effect from repeated washings and assist in m~int~ining the
whiteness of fabrics. Moreover, cellulase enzymes in laundry detergent
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compositions are employed as stain removers and contribute to the overall
impression of cleaning performance perceived by the consumer.
However, it is recognized by those skilled in the art of detergent enzymology
that cellulase ~lepatd~ions are complex mixtures of which only a certain fraction is
effective as a catalyst in the washing process. Further, it is well known in the art
that certain cellulases can produce negative effects on cotton garments, such asweight loss and tensile strength loss. These negative effects can be minimi7ed by
choosing a combination of cellulase with specific detergent components which help
to modify the surface of fabrics without the negative effects.
Various fabric surface modifying agents have been commercialized and are
currently used in delelgellt compositions and fabric softener/~nti~t~tic articles and
compositions. Examples of surface modifying agents are soil release polymers. Soil
release polymers typically comprise an oligomeric or polymeric ester "backbone"
and are generally very effective on polyester or other synthetic fabrics where the
grease or similar hydrophobic stains form an attached film and are not easily
removed in an aqueous laundering process. The soil release polymers have a less
drarnatic effect on "blended" fabrics, that is on fabrics that comprise a mixture of
cotton and synthetic material, and have little or no effect on cotton articles.
Until now the development of effective fabric surface modifying agents for use
on cotton fabrics has been elusive. Attempts by others to apply the paradigm of
matching the structure of a soil release polymer with the structure of the fabric, a
method s~-cces~ful in the polyester soil release polymer field, has neverthelessyielded marginal results when applied to other fabric surface modifying agents,
especially for cotton fabrics. For example, the use of methylcellulose, a cottonpolysaccharide with modified oligomeric units, proved to be more effective on
polyesters than on cotton.
It has now been surprisingly discovered that effective surface modifying agents
for textile articles can be picp~ed from certain modified polyarnines. This
unexpected result has yielded compositions that are effective at providing desirable
surface modifying effects, such as soil release benefits, not only to synthetic and
synthetic-cotton blended fabric, but also to cotton fabrics.
The modified polyamines of the present invention are equally effective when
the laundry detergent compositions disclosed herein are solid or liquid. The solid
laundry detergents may be in the form of granules, flakes or laundry bars. The
liquid detergents can have a wide range of viscosity and may include heavy
concentrates, pourable "ready" detergents, or light duty fabric pre-ll~dlme,ll~.
.. . .. .
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Moreover, the modified polyamines disclosed in the present method are especiallycompatible with other laundry detergent additives and adjuncts.
Accordingly, despite the aforementioned disclosures in the art, the need exists
for a detergent composition cont~ining cellulase which enhances the cleaning ability
of laundry detergents and which softens and improves the feel of cotton. There is
also a need for such a detergent composition which removes stains. Furthermore,
despite disclosures in the art, there still remains a need for such a detergent
composition comprising a specific combination of cellulases and modified
polyamine polymers that are capable of delivering enhanced cleaning, softening,
and depilling without concomitant weight loss and tensile strength loss in cOnongarments.
It is, therefore, an object of the present invention to provide laundry detergent
compositions that comprise an effective cellulase enzyme together with a water
soluble and/or dispersible, modified polyamine fabric surface modifying agents of
the present invention. This combination provides a laundry detergent compositionthat is effective for providing surface modifying benefits, depilling and cleaning
benefits to all fabric.
It is still a further object of the present invention to provide a method for
modifiying fabric surface during laundering concicting of cont~cting said fabricsurface with an aqueous solution of a laundry detergent composition.
BACKGROUND ART
U.K. 1,314,897, published April 26, 1973 teaches a hydroxypropyl methyl
cellulose material for the prevention of wet-soil redeposition and improving stain
release on laundered fabric. U. S. Patent No. 3,897,026 issued to Kearney, discloses
cellulosic textile materials having improved soil release and stain resistance
pl~p~ ies obtained by reaction of an ethylene-maleic anhydride co-polymer with the
hydroxylmoietiesofthecononpolymers. U.S. PatentNo. 3,912,681 issuedto
Dickson teaches a composition for applying a non-permanent soil release finish
co~ isillg a polycarboxylate polymer to a cOnon fabric. U.S. Patent No. 3,948,838
issued to Hinton, et a/ia describes high molecular weight (500,000 to 1,500,000)polyacrylic polymers for soil release. U.S. Patent 4,559,056 issued to Leigh, et alia
discloses a process for treating cOnon or synthetic fabrics with a composition
comprising an organopolysiloxane elastomer, an organosiloxaneoxyalkylene
copolymer cro~clinkin~ agent and a siloxane curing catalyst. See also U.S. Patent
Nos. 4,579,681 and 4,614,519. These disclose vinyl caprolactam materials have
their effectiveness limited to polyester fabrics, blends of cotton and polyester, and
cotton fabrics rendered hydrophobic by finiching agents.
....
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Examples of alkoxylated polyamines and quaternized alkoxylated polyamines
are disclosed in European Patent Application 206,513 as being suitable for use as
soil dispersents, however their possible use as fabric surface modifying agents are
not disclosed. In addition, these materials do not comprise N-oxides, a key
modification made to the polyamines of the present invention and a component of
the increased bleach stability exhibited by the presently disclosed compounds.
In addition to the above cited art, the following disclose various soi} release
polymers or modified poly~n-inPs; U.S. Patent 4,54~,744, Connor, issued October
22, 1985; U.S. Patent 4,597,898, Vander Meer, issued July 1, 1986; U.S. Patent
4,877,896, Maldonado, et al., issued October 31, 1989; U.S. Patent 4,891,160,
Vander Meer, issued January 2, 1990; U.S. Patent 4,976,879, Maldonado, et al.,
issued December 11, 1990; U.S. Patent 5,415,807, Gosselink, issued May 16,1995;
U.S. Patent 4,235,735, Marco, et al., issued November 25, 1980; U.K. Patent
1,537,288, published December 29, 1978; U.K. Patent 1,498,520, published January18, 1978; WO 95/32272, published November 30, 1995; German Patent DE 28 29
022, issued January 10, 1980; J~p~ se Kokai JP 06313271, published April 27,
1994.
The following patents and publications disclose detergent compositions
cont~ininp~ cellulase enzymes: Bjork et al, U. S. Pat. No. 5,120,463 (GenPnter~llnt~ tional, Inc.); Boyer et al, WO 93/11215 (The Procter & Gamble Company);
Convents et al, U. S. Pat. No. 5,443,750 (The Procter & Gamble Company); Suzuki
et al, U. S. Pat. No. 4,822,516 (Kao Co~,o,alion); Suzuki et al, U. S. Pat. No.
4,978,470 (Kao Corporation). The following patent discloses a cellulase
prep~dlion: Barbesgaard et al, U. S. Pat. No. 4,435,307 (Novo Industri A/S);
Rasmussen et al, EP 0,531,372 (Novo Nordisk A/S).
SUMMARY OF THE INVENTION
The present invention relates to detelgenl compositions comprising:
a) at least about 0.1 % by weight, of a detersive surfactant;
b) at least about 0.001 % by weight, of cellulase enzyme; and
c) at least about 0.05%, preferably from about 0.5% to about 10%, more
p~fe~ably from about 1% to about 7%, by weight, of a water-soluble or
dispersible, modified polyamine fabric surface modifying agent, said agent
comprising a polyamine backbone corresponding to the formula:
,H
[H2N-Rln+~ R~m--[N~R]n-NH2
having a modified polyamine formula V(n+1)WmYnZ or a
polyamine backbone corresponding to the formula:
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H I R
[H2N ~R]n-k+ ~N ~R]m--[N-R]n~N-R]k-NH2
having a modified polyarnine formula V(n-k+l )WmYnY kZ, wherein
k is less than or equal to n, said polyamine backbone prior to
modification has a molecular weight greater than about 200 daltons,
wherein
i) V units are terminal units having the formula:
E X~ O
E--I--Ror E--I--R or E--I--R--
E E E
ii) W units are backbone units having the forrnula:
E X~ O
--I--Ror --I--R or --I--R
E E E
iii) Y units are br~n~lin~ units having the forrnula:
E X~ O
7 - Ror --I--R or --I--R
; and
iv) Z units are t~nnin~l units having the forrnula:
E X~ O
--I--E or --I--E or --I--E
E E E
wherein backbone linking R units are selected from the group
conci~tin~ of C2-C12 alkylene, C4-C12 alkenylene, C3-C12
hydroxyalkylene, C4-C 1 2 dihydroxy-alkylene, Cg-C 1 2
dialkylarylene, (Rl O)XRl , (Rl o)xR5(oRl )x-, -
(CH2CH(OR2)CH20)(Rl O)y~Rl O(CH2CH(OR2)CH2)W-, -
C(o)(R4)rC(o)-, -CH2CH(OR2)CH2-, and mixtures thereof;
wherein Rl is C2-C6 alkylene and mixtures thereof; R2 is hydrogen,
-(RIO)xB, and mixtures thereof; R3 is Cl-Clg alkyl, C7-C12
arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures
thereof; R4 is Cl-C12 alkylene, C4-C12 alkenylene, Cg-C12
arylalkylene, C6-Clo arylene, and mixtures thereof; RS is Cl-Cl2
_ .
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alkylene, C3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, Cg-
C 1 2 dialkylarylene, -C(O)-, -C(O)NHR6-NHC(O)-, -C(o)(R4)rC(o)-
, -CH2CH(OH)CH2O(RIO)yRlO-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, C 1 -C22 alkyl, C3-
C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)p-
C02M~ ~(CH2)qs03M~ -CH(CH2C02M)-C02M, -(CH2)pP03M, -
(RlO)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, C l-C6 alkyl, -(CH2)qSo3M~
(CH2)pc02M~ ~(CH2)qCH(S03M)CH2S03M~ -
(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.
The detergent compositons will further, optionally but preferably, comprises
effective arnounts of adjunct ingredients selected from builders, optical brighteners,
bleaches, bleach boosters, bleach activators, noncellulase enzymes, enzyme
activators, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and
mixtures thereof.
All percentages, ratios and ~lopo.lions herein are by weight, unless otherwise
specified. All ten~ Lul~s are in degrees Celsius (~ C) unless otherwise specified.
All documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises detergent compositions especially suitable for
use on cotton, non-cotton, or mixtures of cotton and non-cotton fabric The present
invention comprises the following formulations.
A plef~.led li~uid laundry detergent composition providing fabric modifying
benefits comprises:
a) at least about 10%, by weight, of a detersive surfactant selected from
anionic and nonionic detersive surfactants;
b) from about 0.05% to about 2%, by weight, of a cellulase enzyme; and
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c) from about 0.5% to about 10%, by weight, of a water-soluble or
dispersible, modified polyarnine fabric surface modifying agent, said
agent comprising a polyamine backbone corresponding to the formula:
H
[H2N~R]n+l--[N-R]m--[N~R]n-N~2
having a modified polyamine formula V(n+l)wmynz or a
polyamine backbone corresponding to the formula:
H I R
[H2N ~R]n-k+ ~[N-R]m--[N ~R]n~N-R]k-NH2
having a modified polyarnine formula V(n-k+l )WmYnY kZ, wherein
k is less than or equal to n, said polyamine backbone prior to
modification has a molecular weight greater than about 200 daltons,
wherein
i)V units are terTnin~l units having the formula:
E X~ ~
E--I--Ror E--I--R or E--I--R--
E E E
ii) W units are backbone units having the formula:
E X ~O
--I--Ror --I--R-- or --I--R
E E E
iii)Y units are br~n~hing units having the formula:
E X~ ~
_7 R--7+ R --7 R
; and
iv) Z units are terrninal units having the formula:
IE X- ~\
--I--E or --I--E or --I--E
E E E
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, C g-C 12 dialkylarylene, -(R 1 O)XR 1
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(R 1 O)XRS(OR 1 )x~, ~(CH2CH(OR2)CH20)z-
(R 1 O)yR 1 (OCH2CH(OR2)CH2)W-, -C(o)(R4)rC(o)-,
CH2CH(OR2)CH2-, and mixtures thereof; wherein Rl is C2-C6 alkylene
and mixtures thereof; R2 is hydrogen, -(RlO)XB, and mixtures thereof; R3 is
Cl-CIg alkyl, C7-C12 arylalkyl, C7-C12 alkyl substitutedaryl, C6-C12 aryl,
and mixtures thereof; R4 is Cl-C12 alkylene, C4-C12 alkenylene, Cg-C12
arylalkylene, C6-CIo arylene, and mixtures thereof; R5 is Cl-C12 alkylene,
C3-C 1 2 hydroxy-alkylene, C4-C 1 2 dihydroxyalkylene, Cg-C 1 2
dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -R 1 (OR 1 ) , -C(o)(R4)rC(o)-
-CH2CH(OH)CH2-, -CH2CH(OH)CH20(Rl O)yRl -
OCH2CH(OH~CH2-, and mixtures thereof; R6 is C2-C 12 alkylene or C6-
C 12 arylene; E units are selected from the group consisting of hydrogen, Cl -
C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -
(CH2)pC02M, ~(C~I2)qS03M~ -CH(CH2C02M)-C02M, -(CH2)pP03M, -
~Rl O)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,
Cl-C6 alkyl, ~(C~I2)q~SO3M~ -(CH2)pC02M,
(cH2)q(cHso3M)cH2so3M~ -(cH2)q-(cHso2M)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; and
d) sufficient ~Ik~line material to provide the composition with a pH of
from about 7 to about 9.5 when measured as a 10% solution in water.
Also included in the invention herein is a method for modifiying fabric surface
during laundering con.~i~ting of contacting said fabric surface with an aqueous
solution of a laundry detergent composition of this invention.
Moreover, included herein is a method for laundering and depilling fabrics
with pilled fibers, said method comprising contacting said pilled fabrics with an
aqueous washing solution formed from an effective amount of the detergent
composition of this invention.
The laundry detergent compositions of the present invention comprise the
following ingredients.
Cellulase Enzymes - The laundry detergent compositions according to the
present invention comprise at least 0.001% by weight, preferably at least about
.. . .
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0.01 %. of a cellulase enzyme. However, an effective amount of cellulase enzyme is
sufficient for use in the laundry detergent compositions described herein. The term
"an effective amount" refers to any arnount capable of producing a cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect on
substrates such as fabrics, dishware and the like. The compositions herein will
typically comprise from about 0.05% to about 2%, preferably from about 0.1% to
about 1.5% by weight of a commercial enzyme ~ pd~dlion. The cellulase enzymes
of the present invention are usually present in such commercial p,c~dlions at
levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per grarn
of composition. Preferably, the optimum pH of the enzyme-cont~ining composition
is between about 7 and about 9.5.
U. S. Patent No. 4,435,307, Barbesgaard et al, issued March 6, 1984, discloses
cellulase produced from Humicola insolens. Examples of other suitable cellulasesinclude those produced by a strain of Humicola insolens, Humicola grisea var.
thermoidea, and cellulases produced by a species of Bacillus sp. or Aeromonas sp.
Other useful cellulases are those extracted from the hepatopanc~as of the marinemollusc Dolabella Auricula Solander. Suitable cellulases are also disclosed in the
following: GB 2,075,028 A (Novo Industri A/S); GB 2,095,275 A (Kao Soap Co.,
Ltd.); and Horikoshi et al, U.S. Patent No. 3,844,890 (Rikagaku Kenkyusho). In
addition, suitable cellulases and methods for their plel)dld~ion are described in PCT
International Publication Number WO 91/17243, published November 14, 1991, by
Novo Nordisk A/S.
Cellulases are known in the art and can be obtained from suppliers under the
traden~m.os: Celluzyme@~, Endolase~, and Carezyme(~.
For industrial production of the cellulases herein it is plefe.l~d that
recombinant DNA techniques be employed. However other techniques involving
adj--~tm~ nt~ of f~rm~nt~tions or mutation of the microorg~ni~m~ involved can beemployed to ensure overproduction of the desired enzymatic activities. Such
methods and techniques are known in the art and may readily be carried out by
persons skilled in the art.
Modified PolYamine Polvmers - The fabric surface modifying agents of the
present invention are water-soluble or dispersible, modified polyamines. These
polyamines comprise backbones that can be either linear or cyclic. The polyaminebackbones can also comprise polyamine br~nching 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.
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For the purposes of the present invention the terrn "modification" is defined asreplacing 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 terrns "modification" and "substitution" are used interch~ng~blywhen 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
circurnstances without substitution, but substitution preferably is accompanied by
oxidation or qu~ ion of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the fabric surface
modifying agents of the present invention have the general formula:
,H
rH2N ~R3n+ 1--[N-R]m--[N-R]n-NH2
said backbones prior to subsequent modification, comprise primary, secondary andtertiary arnine nitrogens connected by R "linking" units. The cyclic polyamine
backbones comprising the agents of the present invention have the general formula:
H I R
rH2N ~R]n-k+ ~[N ~R]m--[N ~R]n{N -R]k-NH2
said backbones prior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising
the backbone or br~nrllin~ 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 ~ g chain having the structure
H2N-R]-
is modified according to the present invention, it is thereafter defined as a V
"terrnin~l " unit, or simply a V unit. However, for the purposes of the present
invention, some or all of the primary amine moieties can remain Immo~lifie~ subject
to the restrictions further described herein below. These unmodified primary amine
moieties by virtue of their position in the backbone chain remain "t~rrnin~l" units.
Likewise, when a primary amine moiety, located at the end of the main polyamine
backbone having the structure
-NH2
is modified according to the present invention, it is thereafter defined as a Z
"terminal" unit, or simply a Z unit. This unit can remain unrnodified subject to the
- restrictions further described herein below.
.
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11
In a similar manner, secondary amine nitrogens comprising the backbone or
branching chain once modified are defined as W "backbone" units. For example,
when a secondary amine moiety, the major constituent of the backbones and
branching chains of the present invention, having the structure
H
[N-R]--
is modified according to the present invention, it is thereafter defined as a W
"backbone" unit, or simply a W unit. However, for the purposes of the present
invention, some or all of the secondary amine moieties can remain unmodified.
These unmodified secondary amine moieties by virtue of their position in the
backbone chain remain "backbone" units.
In a further similar nlallllel, tertiary amine nitrogens comprising the backboneor branching chain once modified are further referred to as Y "br~nehing" units. For
example, when a tertiary amine moiety, which is a chain branch point of either the
polyamine backbone or other br~n~hing chains or rings, having the structure
I
[N-R]--
is modified according to the present invention, it is thereafter defined as a Y
"br~n~hing" unit, or simply a Y unit. However, for the purposes of the present
invention, some or all or the teniary amine moieties can remain unmodified. These
unmodified tertiary amine moieties by virtue of their position in the backbone chain
remain "br~n- hing" units. The R units associated with the V, W and Y unit
nitrogens which serve to connect the polyamine nitrogens, are described herein
below.
The final modified structure of the polyamines of the present invention can be
therefore leplesented by the general formula
V(n+l)wmynz
for linear polyamine polymers and by the general formula
V(n-k+1)wmYnY kZ
for cyclic polyamine polymers. For the case of polyamines comprising rings, a Y'unit of the formula
R
R]--
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12
serves as a branch point for a backbone or branch ring. For every Y' unit there is a
Y unit having the formula
I
~N-R]--
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 polyarnine backbone
has the formula
H
~ H2N-R~n~ R]m--[N~R]n--
therefore comprising no Z terminal unit and having the formula
Vn kwmyny k
wherein k is the number of ring forming br~nçhing units. Preferably the polyarnine
backbones of the present invention comprise no rings.
In the case of non-cyclic poly~mine~, the ratio of the index n to the index m
relates to the relative degree of br~nrhing. A fully non-branched linear modified
polyamine according to the present invention has the formula
VWmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the
greater the degree of br~n~hing in the molecule. Typically the value for m ranges
from a minimum value of 4 to about 400, however larger values of m, especially
when the value of the index n is very low or nearly 0, are also preferred.
Each polyamine nitrogen whether primary, secondary or tertiary, once
modified according to the present invention, is further defined as being a member of
one of three general classes; simple substituted, qu~terni7~ d or oxidized. Those
polyamine nitrogen units not modified are classed into V, W, Y, or Z units
depending on whether they are primary, secondary or tertiary nitrogens. That is
unmodified primary amine nitrogens are V or Z units, unmodified secondary amine
nitrogens are W units and unmodified tertiary amine nitrogens are Y units for the
purposes of the present invention.
Modified primary amine moieties are defined as V "t~rmin~l" units having one
of three forms:
a) simple substituted units having the structure:
,,
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13
E--N--R
E
b) quatemized units having the structure:
E--N--R
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
E--I--R--
E
Modified secondary amine moieties are defined as W "backbone" units having
one of three forms:
a) simple substituted units having the structure:
--N-R--
E
b) qll~terni7lod units having the structure:
E X~
--I--R
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
--N--R
Modified tertiary amine moieties are defined as Y "br~nrhing" units having
one of three forms:
a) unmodified units having the structure:
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14
--I -R--
b)quaternized units having the structure:
lE+x-
--I--R-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
_7 R--.
Certain modified primary amine moieties are defined as Z "terrninal" units
having one of three forms:
a) simple substituted units having the structure:
--N-E
E
b) qu~terni7.~cl units having the structure:
--I +--E
wherein X is a suitable counter ion providing charge b~l~n.~e; and
c) oxidized units having the structure:
--I--E
When any position on a nitrogen is unsubstituted of unrnodified, it is
understood that hydrogen will substitute for E. For example, a primary amine unit
CA 022~28~3 1998-10-29
WO 97142294 PCT/US97/07058
comprising one E unit in the forrn of a hydroxyethyl moiety is a V terminal unithaving the forrnula (HOCH2CH2)HN-.
For the pu~poses of the present invention there are two types of chain
termin~tin~ units, the V and Z units. The Z "terminal" unit derives from a terminal
primary arnino moiety of the structure -NH2. Non-cyclic polyarnine backbones
according to the present invention comprise only one Z unit whereas cyclic
polyamines can comprise no Z units. The Z "terminal" unit can be substituted with
any of the E units described further herein below, except when the Z unit is modified
to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide,
the nitrogen must be modified and therefore E cannot be a hydrogen.
The polyamines of the present invention comprise backbone R "linking" units
that serve to connect the nitrogen atoms of the backbone. R units comprise unitsthat for the purposes of the present invention are referred to as "hydrocarbyl R" units
and "oxy R" units. The "hydrocarbyl" R units are C2-C12 alkylene, C4-C12
alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any
position on the R unit chain except the carbon atoms directly connectPd to the
polyamine backbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl
moieties may occupy any two of the carbon atoms of the R unit chain except thosecarbon atoms directly connected to the polyamine backbone nitrogens; Cg-C12
dialkylarylene which for the purpose of the present invention are arylene moieties
having two alkyl substituent groups as part of the linking chain. For exarnple, a
dialkylarylene unit has the formula
--(CH2)2~3CH2 - --(CH2)4~3(CH2)2--
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substituted
C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more
preferably ethylene. The "oxy" R units comprise -(RlO)xRS(oRl)x-~ -
CH2CH(OR2)CH20)z(RIO)yRI(OCH2CH(OR2)CH2)w~~-CH2CH(OR2)CH2-,
-(R10)XR1-, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(R10)XRl-,
-CH2CH(OR2)CH2-, -(CH2CH(OH)CH20)z(R 1 O)yR 1 (OCH2CH-(OH)CH2)W-,
-(RlO)xRS(oRl)x-7 more preferred R units are C2-C12 alkylene, C3-C12 hydroxy-
alkylene, C4-C12 dihydroxyalkylene, -(R10)XRI-, -(RlO)xRS(oRl)x-~
-(CH2CH(OH)CH20)z(R1O)yR1(OCH2CH~(OH)CH2)w~7 and mixtures thereof,
even more prc~..ed R units are C2-C12 alkylene, C3 hydroxyalkylene, and
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16
mixtures thereof, most preferred are C2-C6 alkylene. The most preferred backbones
of the present invention comprise at least 50% R units that are ethylene.
Rl units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R10)XB, preferably hydrogen.
R3 is Cl-Clg alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-
C12 aryl, and mixtures thereof, preferably C1-C12 alkyl, C7-C12 arylalkylene,
more preferably C l-C12 alkyl, most preferably methyl. R3 units serve as part of E
units described herein below.
R4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-C1o
arylene, preferably C1-C1o alkylene, Cg-C12 arylalkylene, more preferably C2-C~
alkylene, most preferably ethylene or butylene.
R5 is Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,
Cg-C 1 2 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-~ -C(o)(R4)rC(o)-
~Rl (OR I )-, -CH2CH(OH)CH20(R1 o)yRl OCH2CH(OH)CH2-, -C(o)(R4)rC(o)-,
-CH2CH(OH)CH2-, R5 is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
-Rl (ORl )-, -CH2CH(OH)CH2-, -CH2CH(OH)CH20(Rl O)yRl OCH2CH-
(OH)CH2-, more ~ Çel~bly -CH2CH(OH)CH2-.
R6 is C2-C12 alkylene or C6-C12 arylene.
The ~l ~r~ ,d "oxy" R units are further defined in terms of the R 1, R2, and R5
units. Preferred "oxy" R units comprise the l)refell~d Rl, R2, and R5 units. Thep~ ed surface modifying agents of the present invention comprise at least 50%
R1 units that are ethylene. Preferred R1, R2, and R5 units are combined with the"oxy" R units to yield the prefelled "oxy" R u~its in the following manner.
i) SubsliLu~ g more plef. lled R5 into -(CH2CH2o)XR5(oCH2CH2)x-
yields -(CH2CH20)XCH2CHOHCH2(0CH2CH2)x-.
ii) Sub~liluling plef~ d Rl and R2 into -(CH2CH(OR2)CH20)z-
1 O)yRI O(CH2CH(OR2)CH2)~ yields -(CH2CH(OH)CH20)z-
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)~.
iii) Sub~liLulillg preferred R2 into -CH2CH(OR2)CH2- yields
-CH2CH(OH)CH2--
E units are selected from the group consisting of hydrogen, C 1 -C22 alkyl, C3-
C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pCO2M, -
(cH2)qso3M~ -cH(cH2co2M)co2M~ -(cH2)ppo3M~ -(R l o)mB~ -c(o)R3
preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C I -C22 alkylene, -
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17
(Rl O)mB, -C(o)R3, -(CH2)pC02M, ~(CH2)qS03M~ -CH(CH2C02M)C02M,
more preferably C l -C22 alkylene, -(Rl O)xB, -C(o)R3, -(CH2)pC02M, -
(cH2)qso3M~ -CH(CH2C02M)C02M, most preferably Cl-C22
alkylene, -(R10)xB, and -C(o)R3. When no modification or substitution is made
on a nitrogen then hydrogen atom will remain as the moiety representing E.
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 branchingchains do not comprise units of the following structure:
0~ 0~ 0~
N--R or H--N--R or N--H
H H H
Additionally, E units do not comprise carbonyl moieties directly bonded to a
nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N-
oxides. According to the present invention, the E unit -C(o)R3 moiety is not
bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having
the structure
O O O
J'--R or R3--C--N--R or N--C-R3
C=O E E
R3
nor combinations thereof.
B is hydrogen, Cl-C6 alkyl, -(CH2)qS03M, -(CH2)pC02M, ~(CH2)q~
(CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2S03M, -(CH2)pP03M, -P03M,
preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M, ~(CH2)q~
(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance. For example, a sodiurn cation equally satisfies -(CH2)pC02M, and
-(CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -(CH2)qS03Na moieties.
More than one monovalent cation, (sodium, potassium, etc.) can be combined to
satisfy the required chemical charge balance. However, more than one anionic
group may be charge b~l~nced by a divalent cation, or more than one mono-valent
cation may be nPcess~ry to satisfy the charge requirements of a poly-anionic radical.
For example, a -(CH2)pP03M moiety substituted with sodium atoms has the
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18
formula -(CH2)pPO3Na3. Divalent cations such as calcium (Ca2+) or magnesium
(Mg2+) may be substituted for or combined with other suitable mono-valent water
soloble cations. Preferred cations are sodium and potassium, more preferred is
sodlum.
X is a water soluble anion such as chlorine (Cl~), bromine (Br~) and iodine
(I-) or X can be any negatively charged radical such as sulfate (S042-) and
methosulfate (CH3SO3-).
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 l, x has the
value from I to 100; 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.
The preferred modified polyarnine surface modifying agents of the present
invention comprise polyamine backbones wherein less than about 50% of the R
groups comprise "oxy" R units, pl~fclably less than about 20%, more preferably
less than 5%, most preferably the R units comprise no "oxy" R units.
The most preferred agents which comprise no "oxy" R units comprise
polyamine backbones wherein less than 50% of the R groups comprise more than 3
carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when
backbone R units are C2-C12 alkylene, p~e~l. d is C2-C3 alkylene, most preferredis ethylene.
The surface modifying agents of the present invention comprise modified
homogeneous and non-homogeneous polyamine backbones, wherein 100% or less
of the -NH units are modified. For the purpose of the present invention the terrn
"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 exarnple, it is known to those ski]led 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 br~nching Y units
- are present is a homogeneous backbone. A polyamine backbone comprising all
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19
ethylene R units is a homogeneous backbone regardless of the degree of branchingor the number of cyclic branches present.
For the purposes of the present invention the term "non-homogeneous polymer
~ backbone" refers to polyamine backbones that are a composite of various R unit
lengths and R unit types. For example, a non-homogeneous backbone comprises R
units that are a mixture of ethylene and l ,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. The proper manipulation of these "R unit
chain ~engths" provides the formulator with the ability to modify the solubility and
fabric substantivity of the polyamine agents of the present invention.
Preferred polymers of the present invention comprise homogeneous polyamine
backbones that are totally or partially substituted by polyethyleneoxy moieties,totally or partially quz~tPrni7P~l zlminps~ nitrogens totally or partially oxidized to N-
oxides, and mixtures thereof. However, not all backbone amine nitrogens must be
modified in the same ~llal~l,el, the choice of modification being left to the specific
needs of the formulator. The degree of ethoxylation is also determined by the
specific requi~l,lcnls of the formulator.
The prefe.l~d polyamines that comprise the backbone of the compounds of the
present invention are generally polyalkylenPzlminPs (PAA's), polyalkylçneimintos(PAI's), preferably polyethylenPzlmine (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 polyalkylen~zlmine (PAA) is
tetrabutylen~ t~P PEA's are obtained by reactions involving ammonia and
ethylene dichloride, followed by fractional fli~till;~tion. The common PEA's
obtained are triethyle.letel-dllline (TETA) and teraethylenepentztmine (TEPA).
Above the pentz~minPs, i.e., the he~..,inPs, heptz ll~inPs, octz~minPs and possibly
non~minPs, the cogenerically derived mixture does not appear to separate by
tillzltion and can include other materials such ~ cyclic amines and particularlypipel~l~es. 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 plep~dlion of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's have at
least moderate brzlnching, that is the ratio of m to n is less than 4: l, however PEI's
having a ratio of m to n of about 2:l are most preferred. Preferred backbones, prior
~ to modification have the general formula:
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H
[H2NCH2CH2]n--[NcH2cH2]m--[NcH2cH2]n-NH2
wherein m and n are the sarne as defined herein above. Preferred PEI's, prior tomodification, will have a molecular weight greater than about 200 daltons.
The relative plOpOI ~ions of primary, secondary and tertiary amine units in the
polyarnine backbone, especially in the case of PEI's, will vary, depending on the
manner of preparation. Each hydrogen atom att~rhe-l to each nitrogen atom of thepolyamine backbone chain le~l~sents a potential site for subsequent substitution,
quaternization or oxidation.
These polyamines can be prepared, for example, by polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide, sodiurn bisulfite,
sulfilric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specificmethods 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 Icrtr~ncc.
Examples of modified polymers of the present invention comprising PEI's, are
illustrated in Formulas I - IV:
Formula I depicts a polymer comprising a PEI backbone wherein all
substitutable nitrogens are modified by repl~cem-~nt of hydrogen with a
polyoxyalkyleneoxy unit, -(CH2CH2O)7H, having the formula
[}~OCH2CH2hl2N~ ~NI(cH2cH2ohH]2
NJ H(ocH2cH2h'N~Nl(cH2cH2ohH]2
(CH2CH20hH ~ ~ (CH2CH20)7H
H(OCH2CH2hkN~N--,N~N N~N N~N IN~NI(CH2CH20)7H]2
(CH2CH20hH (CH2CH20hH ~ (CH2CH20)7H
[H(ocH2cH2hl2N~ N~N[(CH2CH20h~2
I~Nl(cH2cH2ohH]2
Formula I
This is an example of a polymer that is fully modified by one type of moiety.
Formula II depicts a polymer comprising a PEI backbone wherein all
substitutable primary amine nitrogens are modified by replacement of hydrogen with
a polyoxyalkyleneoxy unit, -(CH2CH2O)7H, the molecule is then modified by
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21
subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides,
said agent having the formula
[H(OCH2CH2h]2N~ N[(CH2CH20)7H]2 ~ 0
N~ N~ N j(CH2cH20hH]2
H(OCH2CH2)6~ ~0 (~2CH20)6~ o (~H2CH20)~H
H(ocH2cH2h]2N ~ o oN N~Nl--N ~N ~o~NucH2cH2o)7H]2
O(CH2CH20)6H N O(CH2CH20)6H
~N[(CH.CH20hH]2
lH(OCH2CH2hkN ~N
1~, ~NUcH2cH2ohHk
Formula II
Formula III depicts a polymer comprising a PEI backbone wherein all
backbone hydrogen atoms are substituted and some backbone amine units are
qll~temi7~-~l The substituents are polyoxyalkyleneoxy units, -(CH2CH20)7H, or
methyl groups. The modified PEI polymer has the formula
~CH3
[H(ocH2cH2hl2N~ ~N(CH2CH20),H CH3
~NJ CH3~N~N(cH2cH2ohH
CH3 CH3 ~ ~ CH3 ~ CH3
[H(OCH2CH2}7]2N N. N~N N~N N~N' N~N(CH3)2
Cl- CH3 CH3 ~ Cl- CH3
~-~3 Cl-
[H(ocH2cH2)7]2N N~N(CH3h
~,N(CH3)2
Formula III
Formula IV depicts a polymer comprising a PEI backbone wherein the
backbone nitrogens are modified by substitution (i.e. by -(CH2CH20)7H or
methyl), q~?terni7~ oxidized to N-oxides or combinations thereof. The resulting
polymer has the formula
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22
C~ H3
H(OCH2CH2h]2N~ ~N(CH2CH~OhH ~ CH3
NJ CH3 ~ t ~N(CH2CH20hH
C~13 ,CH3 0 ~ CH3 ~ CH~; CH3
EH(ocH2cH2h]2N~N. - N~ ~N N~N N~~ N~N(CH3)2
Cl- CH3 0 o ~ Cl- CH3
3 Cl
[H(ocH2cH2)7]2N N~N(CH3)3
~N(CH3)2
Forrnula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of the
secondary amine nitrogens ethoxylated while having other secondary amine
nitrogens oxidized to N-oxides. This also applies to the primary amine nitrogens, in
that the formulator may choose to modify all or a portion of the primary arnine
nitrogens with one or more substituents prior to oxidation or 4u~r. ..i7~tion. Any
possible combination of E groups can be substituted on the primary and secondaryamine nitrogens, except for the restrictions described herein above.
Detersive surfactants - In addition to plefe~lcd anionic and nonionic detersive
surfactants described herein above, other detersive surfactants that are suitable for
use in the present invention are cationic, ampholytic, zwitterionic, and mixtures
thereof, further described herein below.
Anionic Detersive Surfactants - The compositions of the present invention
comprise at least about 0.1%, preferably at least 1%, more preferably at least 10%,
most preferably from about 5% to about 80% by weight, of an anionic detersive
surfactant. Alkyl sulfate surf~rt~nt~, either primary or secondary, are a type of anionic
surfactant of h~lpol ~ce for use herein. Alkyl sulfates have the general forrnula
ROSO3M wherein R preferably is a C 1 o-C24 hydrocarbyl, preferably an alkyl straight
or branched chain or hydroxyalkyl having a C 1 o-C20 alkyl component, more
preferably a C 1 2-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 amrnonium cations such as methyl-, dimethyl-, and trimethyl
ammoniurn and quaternary ammonium cations, e.g., tetramethyl-ammonium and
dimethyl pipe.dinium, and cations derived from alkanolamines such as ethanolamine,
diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl
chains of C12-C16 are preferred for lower wash temperatures (e.g., below about 50~C)
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23
and C 1 6-C 18 alkyl chains are preferred for higher wash temperatures (e.g., about S0~
C).
Alkyl alkoxylated sulfate surfactants are another category of preferred anionic
surfactant. These surfactants are water soluble salts or acids typically of the forrnula
RO(A)mSO3M wherein R is an unsubstituted Clo-C24 alkyl or hydroxyalkyl group
having a Clo-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl,
more preferably C 1 2-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, m~gn~sium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted
amrnonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary
ammonium cations, such as tetramethyl-ammonium, dimethyl pipeldinium and cationsderived from alkanol~mines, e.g., monoethanolamine, diethanolamine, and
triethanolamine, and mixtures thereof. Exemplary surfactants are C12Clg alkyl
polyethoxylate (1.0) sulfate, C12-CIg alkyl polyethoxylate (2.25) sulfate, C12-CIg
alkyl polyethoxylate (3.0) sulfate, and C12-CIg alkyl polyethoxylate ~4.0) sulfate
wherein M is conveniently selected from sodium and potassium.
Nonionic Detersive ~urfactants - The compositions of the present inventionmay
comprise at least about 0.1%, preferably at least 1%, more preferably at least about
10%, most preferably from about 5% to about 80% by weight, of an nonionic detersive
surfactant. Preferred nonionic surfactants such as C12-CIg alkyl ethoxylates ("AE")
including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide
con~len~te of C6 to C12 alkyl phenols, alkylene oxide con~lPn~tec of Cg-C22
alkanols and ethylene oxide/propylene oxide block polymers (PluronicTM-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, T ~llghlin et al., issued December 30, 1975,
incorporated herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado
(incorporated herein by reference) are also plc~lcd nonionic surfactants in the
compositions of the invention.
Further preferred nonionic surfactants are the polyhydroxy fatty acid amides
having the formula:
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WO 97142294 PCT/US97/07058
24
o R8
R7--C--N--Q
wherein R7 is Cs-C3 1 alkyl, preferably straight chain C7-C 19 alkyl or alkenyl, more
preferably straight chain Cg-C 17 alkyl or alkenyl, most preferably straight chain C I I
C 15 alkyl or alkenyl, or mixtures thereof; R8 is selected from the group consisting of
hydrogen, C 1-C4 alkyl, C I -C4 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, highfructose corn syrup, and high maltose corn syrup can be utilized as well as the
individual sugars listed above. These corn syrups may yield a mix of sugar
components for Q. It should be understood that it is by no means intended to exclude
other suitable raw materials. Q is more preferably selected from the group consisting
of -CH2(CHOH)nCH20H,-CH(CH20H)(CHOH)n ICH20H,-
CH2(CHOH)2-(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof,
wherein n is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or
aliphatic monosaccharide. Most preferred substituents for the Q moiety are glycityls
wherein n is 4, particularly -CH2(CHOH)4CH20H.
R7Co-N< can be, for exarnple, cocamide, stearamide, olearnide, laurarnide,
myristamide, capricamide, palmitamide, tallowamide, etc.
R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl,
or 2-hydroxy propyl.
Q can be l-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, l-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, l-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions herein
is alkyl-N-methyl glucomide, a compound of the above formula wherein R7 is alkyl(preferably C1 1-Cl3), R8, is methyl and Q is 1-deoxyglucityl.
Other sugar-derived surf~rt~ntc include the N-alkoxy polyhydroxy fatty acid
arnides, such as C 1 o-C 18 N-(3-methoxypropyl~ glucamide. The N-propyl through
N-hexyl C12-C1g glucamides can be used for low sudsing. C1o-C20 conventional
soaps may also be used. If high sudsing is desired, the branched-chain C 1 ~-C 16
soaps may be used. Other conventional useful surfactants are listed in standard
texts.
. .
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WO 97/42294 PCT/US97/07058
For the purposes of the present invention other detersive surfactants, describedherein below, may be used in the laundry detergent compositions.
Nonlimiting examples of other surfactants useful herein typically at levels
from about 1% to about S5%, by weight, include the conventional Cl l-Clg alkyl
ben_ene sulfonates ("LAS"), the Clo-CIg secondary (2,3) alkyl sulfates ofthe
- formulaCH3(CH2)x(CHOSO3 M )CH3 and CH3 (CH2)y(CHOSO3 M )
CH2CH3 where x and (y + I ) are integers of at least about 7, preferably at least
about 9, and M is a water-solubili_ing cation, especially sodiurn, unsaturated sulfates
such as oleyl sulfate, C I o-C 18 alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-18 glycero} ethers, the C I o-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 1 2-C 1 g alkyl ethoxylates ("AE") including the so-called narrow peaked
alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especi~lly ethoxylates and
mixed ethoxy/propoxy), C 1 2-C 18 betah.es and sulfobetaines ("sultaines"), C I o-C 18
amine oxides, and the like, can also be included in the overall compositions. The
C I o-C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical
examples include the C 1 2-C 18 N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid arnides, such
as C I o-C 18 N-(3-methoxypropyl) glucamide. C 1 0-c20 conventional soaps may
also be used. If high sU~lcin~ is desired, the branched-chain C 1 o-C 16 soaps may be
used. Mixtures of anionic and nonionic surf~ct~nt.~ are especially useful. Otherconventional useful ~u l~ .tc are listed in standard texts.
Other anionic surfactants useful for detersive purposes can also be included in
the compositions hereof. These can include salts (including, for example, sodiurn
potassium, ammonium, and su~sli~uled ammonium salts such a mono-, di- and
triethanolamine salts) of soap, Cg-C20 linear alkylben7Pnes~lphon~te~, Cg-C22
primary or secondary ~Ik~n~sl-lrhonates, Cg-C24 olefinsulphonates, sulphonated
polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty
oleyl glycerol s..lf~te~, alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl phosph~tes, isothionates such as the acyl isothionates, N-acyltaurates. fatty acid arnides of methyl tauride, alkyl succin,.,..~tes and sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 1 2-C 18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside, branched primary alkyl sulf~tec, alkyl polyethoxy carboxylates
such as those of the for nula RO(CH2CH2O)kCH2COO-M+ wherein R is a Cg-C22
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WO 97/42294 PCTIUS97/07058
26
alkyl, k is an integer from 0 to 10, and M is a soluble salt-forrning cation, and fatty
acids esterified with isethionic acid and neutralized with sodium hydroxide. Further
exarnples are given in Surface Active A~ents and Deter~ents (Vol. I and II by
Schwartz, Perry and Berch).
The laundry detergent compositions according to the present invention
comprise adjunct ingredients and carriers, said adjunct ingredients are selected from
the group consisting of builders, optical brighteners, bleaches, bleach boosters,
bleach activators, noncellulase enzymes, enzyme activators, suds suppressors, dyes,
perfumes, colorants, filler salts, hydrotropes, and mixtures thereof., and mixtures
thereof, however this list is not meant to be exhaustive or to exclude any suitable
material used by the formulator.
ADJUNCT INGREDIENTS
Non-cotton Soil Release A~ent - Known polymeric soil release agents,
hereinafter "SRA", can optionally be employed in the present detergent
compositions. If utili7~ SRA's will generally comprise from 0.01% to 10.0%,
typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the
compositions. ~l~f~lled SRA's are described herein above.
SRA's suitable for the compositions of the present invention typically have
hydrophilic segmentc to hydrophilize the surface of hydrophobic fibers such as
polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibersand remain adhered thereto through completion of washing and rinsing cycles,
thereby serving as an anchor for the hydrophilic segmentc This can enable stainsoccurring subsequent to l~ with the SRA to be more easily cleaned in later
washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic species,
see U.S. 4,956,447, issued September 11, 1990 to Gosselink, et al., as well as
noncharged monomer units, and their structures may be linear, branched or even
star-shaped. They may include capping moieties which are especially effective incontrolling molecular weight or altering the physical or surface-active plop~.lies.
Structures and charge distributions may be tailored for application to different fiber
or textile types and for varied dcte.~ent or d~t~,lgellt additive products.
SRA's include oligomeric terephth~l~te esters, typically prepal~d by processes
involving at least one tr~neesterification/oligomerization, often with a metal catalyst
such as a titanium(IV) alkoxide. Such esters may be made using additional
monomers capable of being incorporated into the ester structure through one, two,
three, four or more positions, without, of course, forming a densely cros~link~doverall structure.
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WO 97/42294 PCTNS97/07058
27
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties
covalently attached to the backbone, for example as described in U.S. 4,968,451,November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be
pl~ared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephth~lAte ("DMT") and 1,2-propylene glycol ("PG") in a two-stage
transesterification/oligomerization procedure; and (c) reacting the product of (b)
with sodium metabisulfite in water. Other SRA's include the nonionic end-capped
1,2-propylenetpolyoxyethylene terephth~l~te polyesters of U.S. 4,71 1,730,
December 8, 1987 to Gosselink et al., for example those produced by
tr~n~esterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG
and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly-
and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988
to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoct~n~slllfonate; the nonionic-capped block polyester oligomeric
compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example
produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a
combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-
sulfoisophth~l~te; and the anionic, especially sulfoaroyl, end-capped terephth~l~te
esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter
being typical of SRA's useful in both laundry and fabric conditioning products, an
example being an ester composition made from m-sulfobenzoic acid monosodium
salt, PG and DMT, optionally but preferably further comprising added PEG, e.g.,
PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephth~l~te or
propylene terephth~l~te with polyethylene oxide or polypropylene oxide
terephth~l~te, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to
R~ hlr, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosicpolymers available as METHOCEL from Dow, the C 1 -C4 alkyl celluloses and C4
kydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.;and the methyl cellulose ethers having an average degree of substitution (methyl)
per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from
about 80 to about 120 centipoise measured at 20~C as a 2% aqueous solution. Suchmaterials are available as METOLOSE SM 100 and METOLOSE SM200, which are
the trade names of methyl cellulose ethers m~nllf~ctured by Shin-etsu Kagaku
Kogyo KK.
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WO 97/42294 PCT/US97/07058
28
Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments
include graft copolymers of poly(vinyl ester), e.g., C 1 -C6 vinyl esters, preferably
poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European
Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Cornmercially available exarnples include SOKALAN SRA's such as SOKALAN
HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat
units cont~ining 10- 15% by weight of ethylene terephth~ te together with 80-90%by weight of polyoxyethylene terephth~l~te derived from a polyoxyethylene glycolof average molecular weight 300-5,000. Comrnercial exarnples include ZELCON
5126 from Dupont arld MILEASE T from ICI.
Another SRA is an oligomer having empirical forrnula
(CAP)2(EG/PG)s(T)s(SIP)l which comprises terephthaloyl (T), sulfoisophthaloyl
(SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is
preferably ~ennin~ted with end-caps (CAP), preferably modified isethionates, as in
an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units,
oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about
0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2-
hydroxyethoxy)-eth~n~sulfonate. Said SRA preferably further comprises from 0.5%
to 20%, by weight of the oligomer, of a crystallinity-reducing stabilizer, for exarnple
an anionic surfactant such as linear sodiwn dodecylbenzenesulfonate or a member
selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these
stabilizers or modifiers being introduced into the synthesis vessel, all as taught in
U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable
monomers for the above SRA include Na-2-(2-hydroxyethoxy)-eth~nes~lfonate,
DMT, Na-dimethyl-5-sulfoisophth~l~te, EG and PG.
Additional classes of SRA's include: (I) nonionic terephth~l~ttos using
diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,g24,
Violland et al. and U.S. 4,240,918 T ~g~cse et al.; and (Il) SRA's with carboxylate
termin~l groups made by adding trimellitic anhydride to known SRA's to convert
terrninal hydroxyl groups to trimellitate esters. With the proper selection of catalyst,
the trimellitic anhydride forrns linkages to the tennin~lc ofthe polymer through an
ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening
of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting
materials as long as they have hydroxyl tennin~l groups which may be esterified.See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephth~l~te-
based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; (IV)
poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl
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WO 97/42294 PCT/US97/07058
29
pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and
cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in
addition to the SOKALAN types from BASF, made by grafting acrylic monomers
onto sulfonated polyesters. These SRA's assertedly have soil release and anti-
redeposition activity similar to known cellulose ethers: see EP 279,134 A, 1988, to
Rhone-Poulenc Chemie. Still other classes include: (VI) grafts of vinyl monomerssuch as acrylic acid and vinyl acetate onto proteins such as caseins, see EP 457,205
A to BASF (1991); and (VII) polyester-polyamide SRA's prepared by condensing
adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide
fabrics, see Bevan et al., DE 2,335,044 to Unilever N. V., 1974. Other useful SRA's
are described in U.S. Patents 4,240,918, 4,787,989 and 4,525,524.
Bleachin~ Compounds - BleachinR Agents and Bleach Activators
The detergent compositions herein may optionally contain ble~ctling agents or
bleaching compositions con~ining a bleaching agent and one or more bleach
activators. When present, bleaching agents will be at levels of from about 0.05% to
about 30%, more preferably from about 1% to about 30%, most preferably from
about 5% to about 20%, of the detergent composition, especially for fabric
laundering. If present, the amount of bleach activators will typically be from about
0.1 % to about 60%, more typically from about 0.5% to about 40% of the bleachingcomposition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that are now known or become known. These include oxygen bleaches as
well as other ble~ching agents. Perborate bleaches, e.g., sodium perborate (e.g.,
mono- or tetra-hydrate) can be used herein.
Another category of bl~ching agent that can be used without restriction
encomp~cses perc~lJoxylic acid ble~ching agents and salts thereof. Suitable
examples of this class of agents include m~gn~cium monoperoxyphth~l~te
hexahydrate, the m~gn~sium salt of metachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydo-lec~ne~ioic acid. Such bleaching agents aredisclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching
agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
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WO 97/42294 PCT/US97N70~8
Peroxygen blea~hing agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can also be used.
A plef~ d percarbonate bleach comprises dry particles having an average
particle size in the range from about 5~0 micrometers to about 1,000 micrometers,
not more than about 10% by weight of said particles being smaller than about 200micrometers and not more than about 10% by weight of said particles being largerthan about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate, borate or water-soluble surfactants. Percarbonate is available from various
commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of ble~hing agents can also be used.
Peroxygen ble~ching agents, the perborates, the pc..;~l,onates, etc., are
preferably combined with bleach activators, which lead to the in situ production in
aqueous solution (i.e., during the washing process) of the peroxy acid corresponding
to the bleach activator. Various nonlimiting exarnples of activators are disclosed in
U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The nonanoyloxyben_ene sulfonate (NOBS) and tetraacetyl ethylene
rli~mine (TAED) activators are typical, and mixtures thereof can also be used. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly ~ f~ ,d arnido-derived bleach activators are those of the formulae:
RlN(R5)C(O)R2C(O)L or RlC(O)N(R5)R2C(O)L
wherein Rl is an alkyl group co..lAi~ from about 6 to about 12 carbon atoms, R2
is an alkylene CO.~ g from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, oralkaryl co.~l .inil~ from about 1 to about 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is displaced from the bleach
activator as a consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A ~r~felled leaving group is phenyl sulfonate.
Pl~fe.l~d exarnples of bleach activators of the above forrnulae include (6-
octanamido-caproyl)oxybe~7~onesulfonate, (6-no~ A...idocaproyl)oxybenzenesul-
fonate, (6-r~ec~rnido-caproyl)oxybe .7r ~e~-llfonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxa_in-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
incorporated herein by reference. A highly plef~ d activator of the benzoxazin-
type is:
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WO 97/42294 PCT/US97/07058
31
~N~C~
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the forrnulae:
O O
O C--CH2--CH2~ 0 C--CH2--CH2
C H2--C H2 ' C H2--C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~inin~ from I to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoylcaprolactam, decanoyl caprolactam, ~n~lecenoyl caprolactam, benzoyl valerolacta~n,
octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
reference, which discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
Ble~ching agents other than oxygen ble~chin~ agents are also known in the art
and can be utilized herein. One type of non-oxygen bleaching agent of particularinterest includes photoactivated ble~c~line agents such as the sulfonated zinc and/or
aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to
Holcombe et al. If used, detergent compositions will typically contain from about
0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine .
If desired, the ble~chin~ compounds can be catalyzed by means of a
m~neanese compound. Such compounds are well known in the art and include, for
example, the m~n~nese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub.Nos. 549,271Al, 549,272Al, 544,440A2, and 544,490Al; Preferred examples of
these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclo-
nonane)2(PF6)2, MnIII2(u-0) 1 (u-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)
(C104)2, MnlV4(u-0)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-0)1(u-
OAc)2 (1,4,7-trimethyl- 1,4,7-triazacyclononane)2(ClO4)3, MnIV(1,4,7-trimethyl-
1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based
I
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W O 97/42294 PCTAUS97/07058
32
bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of mAng~nese with various complex ligands to enhance
bleaching is also reported in the following United States Patents: 4,728,455;
5,284,944;5,246,612;5,256,779;5,280,117;5,274,147;5,153,161; and 5,227,084.
As a practical rnatter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part per ten
million of the active bleach catalyst species in the aqueous washing liquor, and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
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 1 o-C 16 alkanolarnides can be incorporated into the compositions, typically
at 1%-10% levels. The Clo-C14 monoethanol and diethanol amides illustrate a
typical class of such suds boosters. Use of such suds boosters with high sudsingadjunct surfactants such as the amine oxides, betaines and sultaines noted above is
also advantageous. If desired, soluble m~gn~sium salts such as MgC12, MgSO4,
and the like, can be added at levels of, typically, 0.1%-2%, to provide additional
suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing 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 theporous substrate. In use, the detersive ingredient is released from the substrate into
the aqueous washing liquor, where it pelr~ ls its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademArk SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme
solution contAinin~ 3%-5% of C13 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 em~ ified 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 surfAct~nt~ can be "protected" for use in detergents, including liquid
laundry detergent compositions.
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WO 97/42294 PCT/US97/07058
33
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 cont~ining from 2 to about 6
carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol, glycerin, and 1,2-propanediol) can also be used. The compositions may
contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between about 6.5 and about 11, preferably between about 7.5 and 10.5. Liquid
dishwashing product formulations preferably have a pH between about 6.8 and
about 9Ø Laundry products are typically at pH 9-11. Techniques for controllingpH at recommen~ed usage levels include the use of buffers, alkalis, acids, etc., and
are well known to those skilled in the art.
Other Enzymes - Noncellulase 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
or dishes, for the prevention of refugee dye transfer, for example in laundering, and
for fabric restoration. Suitable other enzymes include proteases, amylases, lipases,
peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin. Plef~ d selections are influenced by factors such
as pH-activity and/or stability optima, thermostability, and stability to activedetergents, builders and the like. In this respect bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases.
"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. Pl~fell~d enzymes for laundry purposes
include, but are not limited to, proteases, lipases and peroxidases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount". The term
"cleaning effective amount" refers to any amount capable of producing a cleaning,
stain removal, soil removal, whitening, deodorizing, or freshness improving effect
on substrates such as fabrics, dishware and the like. 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
CA 022~28~3 1998-10-29
WO 97t42294 PCT/US97/07058
34
5%, preferably 0.01 %- I % by weight of a commercial enzyme p~l)ardlion. Protease
enzymes are usually present in such cornrnercial plepardLions at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per grarn of composition.Higher active levels may be desirable in highly concentrated detergent forrnulations.
Amylases suitable herein include, for exarnple, a-arnylases 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 kno~vn.
See, for exarnple J. Biological Chem., Vol. 260, No. I 1, June 1985, pp 6518-6521.
Certain preferred embodiments of the present compositions can make use of
amylases having improved stability in detergents such as automatic dishwashing
types, especially improved oxidative stability as measured against a reference-point
of TERMAMYL~ in commercial use in 1993. These pl~fe.l~d amylases herein
share the characteristic of being "stability-enh~nce~l" arnylases, characterized, at a
minim~ , by a measurable improvement in one or more of: oxidative stability, e.g.,
to hydrogen peroxide / tetraacetylethyle~ mine in buffered solution at pH 9-10;
thermal stability, e.g., at comrnon wash telllpeldl lres such as about 60~C; or alkaline
stability, e.g., at a pH from about 8 to about 11, measured versus the above-
identified l~f~rence-point amylase. Stability can be measured using any of the art-
disclosed technical tests. See, for example, refe.el1ces disclosed in WO 9402597.
Stability-enh~nced amylases can be obtained from Novo or from Genencor
International. One class of highly pler~lled arnylases herein have the cornmonality
of being derived using site-directed mutagenesis from one or more of the Baccillus
arnylases, especi~ly the Bacillus a-amylases, regardless of whether one, two or
multiple amylase strains are the immediate precursors. Oxidative stability-enhanced
amylases vs. the above-identified reference arnylase are preferred for use, especially
in ble~rhing, more preferably oxygen ble~clling~ as distinct from chlorine ble~ ing
detergent compositions herein. Such ,orerelled 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 arnylase, such as B. amyloliquefaciens,
B~sub~ilis, or B.stearothermophilus; (b) stability-çnh~e~i amylases as described by
Genencor Tntern~tional in a paper entitled "Oxidatively Resistant alpha-Amylases"
- presented at the 207th Arnerican Chennic~l Society National Meeting, March 13- 17
1994, by C. Mitchinson. Therein it was noted that bleaches in automatic
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US97/ON58
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 ,v~ef~ ;d oxidative stability Pnh~n~e~l 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 exampleas derived by site-directed mutagenesis from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other plefel.~d enzyme modifications
are accessible. See WO 9509909 A to Novo.
Suitable lipase enzymes for detelgelll usage include those produced by
microorg~ni~m~ of the Pseudomonas group, such as Pseudomonas stu~zeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Jap~n~ose Patent
Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano
Pharm~ceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
or "Arnano-P." Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. Iipolyticum 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 con.l"e.cially available from Novo, see also EP 341,947, is a p.e~ d lipase
for use herein. Lipase and amylase variants stabilized against peroxidase enzymes
are described in WO 9414951 A to Novo. See also WO 9205249 and RD
94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
. Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution ble~ching" or
prevention of transfer of dyes or pigm-ont~ removed from substrates during the wash
to other substrates present in the wash solution. Known peroxidases include
horseradish peroxidase, li~nin~ce, and haloperoxidases such as chloro- or bromo-
CA 022~28~3 1998-10-29
WO 97/4Z294 PCT~US97/07058
36
peroxidase. Peroxidase-cont~ining detergent compositions are disclosed in WO
89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, ~anuary 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. AC 13 giving proteases, xylanases and cellulases, is described in WO
9401532 A to Novo.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. Iicheniformis. One suitable protease isobtained 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
De~ , he~.~ er "Novo". The p~ep~alion of this enzyme and analogous
enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE~) and SAVINASE g) from Novo and MAXATASE(~) from
Internation~l 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
- p~lease 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 & Garnble. A recombinant trypsin-like
protease for d~t~l~e..l~ suitable herein is described in WO 9425583 to Novo.
In more detail, an especially l,~erel,ed protease, referred to as "Protease D" is a
carbonyl hydrolase variant having an arnino acid sequence not found in nature,
which is derived from a precursor carbonyl hydrolase by substituting a differentamino acid for a plurality of amino acid residues at a position in said carbonylhydrolase equivalent to position +76, preferably also in combination with one or
CA 022~28~3 1998-10-29
WO 97/42294 PCTtUS97/07058
37
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 the patent applications of A. Baeck, et al, entitled"Protease-Cont~inin~ Cleaning Compositions" having US Serial No. 08/322,676,
and C. Ghosh, et al, "Ble~hing Compositions Comprising Protease Enzymes"
having US Serial No. 08/322,677, both filed October 13, 1994.
Preferred laundry detergent compositions of the present invention may
optionally 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 dir~,en
amino acid for a plurality of amino acid residues at a position in said carbonylhydrolase equivalent to position +76, preferably also in combination with one ormore amino acid residue positions equivalent to those selected from the group
comi~tir~g 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 the patent applications of A. Baeck, et al, entitled"Protease-Cont~inin~ Cleaning Compositions" having US Serial No. 08/322,676,
and C. Ghosh, et al, "Ble~clling Compositions Comprising Protease Enzymes"
having US Serial No. 08/322,677, both filed October 13, 1994.
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 iscalled 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.
Also ~.ref~ d proteases are subtilisin enzymes, in particular BPN', that have
been modified by mutating the various nucleotide sequences that code for the
enzyme, thereby modifying the amino acid sequence of the enzyme. These modified
subtilisin enzymes have decreased adsorption to and increased hydrolysis of an
insoluble substrate as compared to the wild-type subtilisin. Also suitable are mutant
genes encoding for such BPN' variants.
CA 022~28~3 1998-10-29
WO 97142294 PCT/US97/07058
38
Preferred BPN' variants comprise wild-type amino acid sequence wherein the
wild-type amino acid sequence at one or more of positions 199, 200, 201, 202, 203,
204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 21~, 219 or 220 is
substituted; wherein the BPN' variant has decreased adsorption to, and increasedhydrolysis of, an insoluble substrate as compared to the wild-type subtilisin BPN'.
Preferably, the positions having a substituted amino acid are 199, 200, 201, 202,
205, 207, 208, 209, 210, 211, 212, or 215; more preferably, 200, 201, 202, 205 or
207.
Preferred protease enzymes for use according to the present invention also
include the subtilisin 309 variants. These protease enzymes include several classes
of subtilisin 309 variants.
A. Loop Re~ion 6 Substitution Variants - These subtilisin 309 variants have a
modified amino acid sequence of subtilisin 309 wild-type amino acid sequence,
wherein the modified amino acid sequence comprises a substitution at one or moreof positions 193, 194, 195, 196, 197, 199, 200, 201, 202, 203, 204, 205, 206, 207,
208, 209, 210, 211, 212, 213 or 214; whereby the subtilisin 309 variant has
decreased adsorption to, and increased hydrolysis of, an insoluble substrate as
colllpal~d to the wild-type subtilisin 309. Preferably these proteases have amino
acids substituted at 193, 194, 195, 196, 199, 201, 202, 203, 204, 205, 206 or 209;
more ~re~.dbly 194, 195, 196, 199 or 200.
B. Multi-Loop Re~ions Substitution Variants - These subtilisin 309 variants
may also be a modified amino acid sequence of subtilisin 309 wild-type amino acid
sequence, wherein the modified amino acid sequence comprises a substitution at one
or more positions in one or more of the first, second, third, fourth, or fifth loop
regions; whereby the subtilisin 309 variant has decreased adsorption to, and
hlcleased hydrolysis of, an insoluble substrate as conl~ d to the wild-type
subtilisin 309.
C. Substitutions at positions other than the loop re~ions - In addition, one or
more substitution of wild-type subtilisin 309 may be made at positions other than
positions in the loop regions, for example, at position 74. If the additional
~ substitution to the subtilisin 309 is mad at position 74 alone, the substitution is
preferably with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro, preferably His or Asp.However modifications can be made to one or more loop positions as well as
position 74, for example residues 97, 99, 101, 102, 105 and 121.
Subtilisin BPN' variants and subtilisin 309 variants are further described in
WO 95129979, WO 95/30010 and WO 95/30011, all of which were published
November 9, 1995, all of which are incorporated herein by reference.
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US97/07058
39
Enzyme Stabilizin~ Svstem - Enzyme-cont~ining~ 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 forrnulation actives, or
be added separately, e.g., by the formulator or by a m~nl~f~cturer 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 del ,~ent composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
m~gn.ocium ions in the fini~h.o(l compositions which provide such ions to the
enzymes. Calcium ions are generally more effective than m~gn~sium 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 piefe,~bly from about 8 to about 12 milliml~les of
calcium ion per liter of fini~hec~ detergen~ composition, though variation is possible
depending on factors including the multiplicity, type and levels of enzymes
incorporated. Preferably water-soluble calciurn or magn~ium salts are employed,
including for example calcium chloride, calcium hydroxide, calcium formate,
calcium malate, calcium m~le~te, calciurn hydroxide and calcium acetate; more
generally, calcium sulfate or m~gnesium salts coll~i,yonding to the exemplified
calcium salts may be used. Further increased levels of Calcium and/or Magnesium
may of course be useful, for example for promoting the grease-cutting action of
certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of
the composition though more typically, levels of up to about 3% by weight of boric
acid or other borate compounds such as borax or orthoborate are suitable for liquid
detergent use. Substituted boric acids such as phenylboronic acid, butaneboronicacid, p-bromophenylboronic acid or the like can be used in place of boric acid and
reduced levels of total boron in detergent compositions may be possible though the
use of such substituted boron derivatives.
Stabilizing systems of certain cleaning compositions may further comprise
from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of
chlorine bleach scavengers, added to prevent chlorine bleach species present in
I
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US97/07058
many water supplies from ~tt~ckin~ 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 dish- or
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
cont~ining ~mmonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide,
etc. Antioxidants such as carb~m~te, ascorbate, etc., organic amines such as
ethyl~n~ min~tçtracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and n~ es thereof can likewise be used. Likewise,
special enzyme inhibition systems can be incoll,o,ated such that different enzymes
have maximum comra1ibility Other conventional scavengers such as bi~ulf~e
nitrate, chloride, sources of hydrogen peroxide such as sodium perborate
tetrahydrate, sodium pc.l.olate monohydrate and sodium l,e~;~l,onate, as well asphosph~1e, conden~ed phosphate, acetate, ben~o~te, citrate, formate, lactate, malate,
tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since
the chlorine scavenger function can be ~,~,~lll-ed by ingredients sepdldl~ly listed
under better recognized functions, (e.g., hydrogen peroxide sources), there is no
absolute re4~ enlent to add a se~ chlorine scavenger unless a compound
performing that function to the desired extent is absent from an enzyme-co~ inil-g
embodiment of the invention; even then, the scavenger is added only for optimum
results. Moreover, the forrn~ tor 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, B~gin~i et al.
Builders - Dt;telgellt 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.
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US97/07058
41
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. Granular formulations typically comprise from about
10% to about 80%, more typically from about 15% to about 50% by weight, of the
detergent builder. Lower or higher levels of builder, however, are not meant to be
excluded.
Inorganic or P-cont~inin~ 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), s-llph~tes, and aluminosilicates. However, non-phosphate
builders are required in some locales. Importantly, the compositions herein function
surprisingly well even in the presence of the so-called "weak" builders (as compared
with phosphates) such as citrate, or in the so-called "underbuilt" situation that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly thosehaving a SiO2:Na2O 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, issued May 12,
1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite
builders, the Na SKS-6 silicate builder does not contain all.minl-m NaSKS-6 has
the delta-Na2SiOs morphology form of layered silicate. It can be pl~pdled by
methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043.
SKS-6 is a highly plefel.ed layered silicate for use herein, but other such layered
silicates, such as those having the general formula NaMSixO2x+l yH2O wherein M
is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number
from 0 to 20, preferably 0 can be used herein. Various other layered silicates from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma
forms. As noted above, the delta-Na2SiOs (NaSKS-6 form) is most preferred for
use herein. Other silicates may also be useful such as for example m~gn~osium
silicate, which can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Exarnples 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.
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US97/07058
42
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty granular
detergent compositions, and can also be a significant builder ingredient in liquid
detergent formulations. Aluminosilicate builders include those having the empirical
formula:
MZ(zAlo2)y] ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range
from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful alurninosilicate ion exchange materials are comrnercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing alurninosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. P~efe..~d synthetic crystalline
alurninosilicate 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 ex~h~n~e material has the
formula:
Nal2[(Alo2)l2(sio2)l2] xH2o
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 alurninosilicate has a particle size of about 0.1 - 10 microns in diameter.
Organic d~le~ ~ent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate colllpoul,ds. 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 forrn, but can also be added in the
forrn of a neutralized salt. When utilized in salt form, alkali metals, such as sodiurn,
potassiurn, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One illlpol l~t 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.
CA 022~28~3 1998-10-29
WO 97142294 PCT/US97/070S8
43
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 amrnoniurn salts of polyacetic
acids such as ethylene(li~mine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders of particular hllpol ~Ice for heavy duty liquid
detergent formulations due to their availability from renewable resources and their
biodegradability. Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred compound of this type is dodecenylsuccinic acid. Specific examples of
succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pent~-lecçrlylsuccinate, and the like.
Laurylsucch~ales are the preferred builders of this group, and are described in
European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-cl g monocarboxylic acids, can also be incorporated intothe 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 su-icing, which should be taken
into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-laundering operations, the various alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodiurn
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as ethane- 1 -hydroxy- I, I -diphosphonate and other known phosphonates (see, for
CA 022~28~3 1998-10-29
WO 97/42294 PCT/US9710705B
44
example, U.S. Patents 3.159,581; 3,213.030; 3,422,021; 3,400,148 and 3,422,137)
can also be used.
Chelatin~ Agents - The detergent compositions herein may also optionally
contain one or more iron and/or m~ng~nese chelating agents. Such chelating agents
can be selected from the group consisting of arnino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures
therein, all as hereinafter ~lPfine~J Without intending to be bound by theory, it is
believed that the beneflt of these materials is due in part to their exceptional ability
to remove iron and m~ng~nçse ions from washing solutions by formation of soluble t~s.
Amino carboxylates useful as optional chelating agents include
ethyle~e.1i~minet~ ct~ ee, N-hydroxyethylethylene~ minPtriacetates, nitrilo-
triacetates, ethylenP~ mine lelldploplionates, triethylenetetr~min~he~cet~tes,
diethylenetriamincpentdacetates, and ethanoldiglycines, alkali metal, ammonium,
and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as ch~!~ting agents in the
compositions of the invention when at lease low levels of total phosphorus are
perrnitted in detergent compositions, and include ethylene~ minetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et
al. Plcfell~d col,lpo~ds of this type in acid form are dihydroxydisulfoben7.onloc
such as 1,2-dihydroxy-3,5-disulfobe,~e.le.
A plefcll~d biodegradable chelator for use herein is ethylen~ mine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
If lltili7~(1, these chPl~tin~ agents will generally comprise from about 0.1 % to
about 10% by weight of the detergent compositions herein. More preferably, if
lltili7e-l the chelating agents will comprise from about 0.1% to about 3.0% by
~ weight of such compositions.
Clav Soil Removal/Anti-redeposition A~ents - The compositions of the present
invention can also optionally contain water-soluble ethoxylated amines having clay
soil removal and antiredeposition plop~llies. Granular detelg~ 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 compositionstypically contain about 0.01% to about 5%.
CA 022~28~3 1998-10-29
W097/42294 PCTAUS97/07058
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepent~min~. 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 p~ ed antiredeposition agent
includes the carboxy methyl cellulose (CMC) materials. These materials are well
known in the art.
Polvmeric Dispersin~ A~ents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the
compositions herein, especially in the presence of zeolite andlor 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 intPn~led to be limited by theory, that polymeric dispersing
agents enh~nce overall d~lelge..l builder perforrn~nce, when used in combinationwith other builders (including lower molecular weight polycarboxylates) by crystal
growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be ~.epaled by polymerizing or
copolymerizing suitable ullsal~ ed 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
methylen~rn~lonic acid. The presence in the polymeric polycarboxylates herein ormonomeric se~ , cQllt~;l.i..g no carboxylate radicals such as vinylmethyl ether,styrene, ethylene, etc. is suitable provided that such segments do not constitute more
than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble salts of polymerized acrylic acid. The average molecular weight of such
polymers in the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
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46
Water-soluble salts of such acrylic acid polymers can include, for example, the
alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this
type are known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067,
issued march 7,1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of copolymers of acrylic acid and 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/vinylalcohol.
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent p.,.ro.lllàmce 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.
Polya~le and polygh1t~nn~te dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
poly~l,~le pl~f~lably have a molecular weight (avg.) of about 10,000.
Brightener - Any optical bright~ners or other bri~ht~ning or whitening agents
known in the art can be inco.~ aled at levels typically from about 0.05% to about
1.2%, by weight, into the detergent compositions herein. Cornmercial optical
brighteners which may be useful in the present invention can be classified into
subgroups, which include, but are not nPcess~rily limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinPcyanines, 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
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47
Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John
Wiley & Sons, New York (1982).
Specific exarnples 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
brightPn~rs from Verona. Other brighterl~rs 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; the2-(4-stryl-phenyl)-2H-naptholl1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil-
benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific exarnples 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 brightençrs are preferred herein.
Suds Su~p-essol~ - Compounds for reduçinp or ~upples~ g the formation of
suds can be incol~uuldled into the compositions of the present invention. Suds
suppression can be of particular hll~ol~ ce in the so-called "high concelllldlion
cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading
European-style washing m~hin~s
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 cdlego.y of suds ~u~ lessor of
particular interest encomp~c~ec 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
hy~oc~byl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and
lithium salts, and ammonium and alkanolammonium salts.
The det~,lE;t;lll compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons suchas paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of
monovalent alcohols, aliphatic C 1 g-C40 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 cont5~ining I to 24 carbon
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48
atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate ester and monostearyl di-al~ali 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 t~l,lpt:,dl~ue
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 1 00~C. The hydrocarbons constitute a preferred category
of suds suppressor ~or 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 inten~led
to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone suds suppressors. This category includes the use of polyorganosiloxane
oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane
oils or resins, and combinations of polyorganosiloxane with silica particles wherein
the polyorganosiloxane is chPmicorbed 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.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and sil~n~tPcl silica are described, for instance, in German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agentsin granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta
et al, and in U.S. Patent 4,652,392, Raginc~i et al, issued March 24,1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent conci.cting 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 SiOl/2 units and to SiO2 units of from about 0.6:1 to about
1.2:1; and
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49
(iii) from about I to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or polyethylene-
polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene
glycol. The primary silicone suds suppressor is branched/crosslinked and preferably
not linear.
To illustrate this point further, typical liquid laundry detergent compositions
with controlled suds will optionally comprise from about 0.001 to about 1,
preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about
0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueousemulsion 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 amountscan be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471,
Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991,5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and
4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds ~p~ssor herein preferably comprises polyethylene glycol
and a copolymer of polyethylene glycol/polypropylene glycol, all having an average
molecular weight of less than about I ,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 S weight %.
The ~efell~d solvent herein is polyethylene glycol having an average
molecular weight of less than about I ,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, ofpolyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
- polypropylene glycol, particularly of 4,000 molecular weight. They also preferably
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do not contain block copolymers of ethylene oxide and propylene oxide, like
PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C 16 alkyl alcohols having a C I -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.
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 ~Itili7f~ are preferably present in a "suds
sul~plessing amount. By "suds su~ essing amount" is meant that the formulator ofthe composition can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry d~t~ nt for use in
automatic laundry washing m~rhin~s
The compositions herein will generally comprise from 0% to about 5% of suds
suppressor. When utilized as suds SU~pl. SSOl~, 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 lltili7~d Silicone suds suppressors are typically
utilized in arnounts 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 minimi7.od and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about 0.01% to about
1% of silicone suds :ju~ SSOI iS used, more preferably from about 0.25% to about0.5%. As used herein, these weight l,~.c~ age values include any silica that may be
utilized in combination with polyorganosiloxane, as well as any adjunct materials
that may be ~tili7~fl Monostearyl phosphate suds supplessors are generally utilized
in arnounts ranging from about 0.1% to about 2%, by weight, of the composition.
Hydrocarbon suds supple~so~ are typically utilized in arnounts 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 fini~hed compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,062,647, Storrn and Nirschl, issued
r)ecember 13, 1977, as well as other softener clays known in the art, can optionally
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51
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 exarnple, 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 Inhibitin~ Agents - The compositions of the present invention
may also include one or more additional 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,
miqng~n~se 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% toabout 2%.
More specifically, the polyamine N-oxide polymers l~lcf~,led for use herein
contain units having the following structural formula: R-AX-P; wherein P is a
polymerizable unit to which an N-O group can be ~ ched or the N-O group can
form part of the polymerizable unit or the N-O group can be ~ d to both units; Ais 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, imi~ le, pyrrolidine,
piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
~l 1~
(R~ N--(R2)y; =N--(Rl)x
(R3)z
wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
~checl or form part of any of the aforementioned groups. The amine oxide unit ofthe polyamine N-oxides has a pKa ~10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed
is water-soluble and has dye transfer inhibiting properties. Examples of suitable
- polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include
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52
random or block copolymers where one monomer type is an arnine 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 app,op.;ate 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 preferredclass of materials can be referred to as "PVNO".
The most pler~,~ed polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of
about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to
as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has
an average molecular weight range from 5,000 to 1,000,000, more preferably from
5,000 to 200,0Q0, and most preferably from 10,000 to 20,000. (The average
molecular weight range is d~ in~d by light sc~ g as described in Barth, et al.,
Chemical AnalYsis, Vol 1 13. "Modern Methods of Polymer Characterization", the
disclosures of which are incorporated herein by reference.) The PVPVI copolymerstypically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to
0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.These copolymers can be either linear or branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about 400,000,preferably from about 5,000 to about 200,000, and more preferably from about 5,000
to about 50,000. PVP's are known to persons skilled in the detergent field; see, for
example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
Compositions co~ PVP can also contain polyethylene glycol ("PEG") having
an average molecular weight from about 500 to about 100,000, preferably from
about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis
. delivered in wash solutions is from about 2:1 to about 50:1, and more preferably
from about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners whichalso 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.
, . . .. .
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53
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
Rl R2
N 0~ 1 ~C=C~ I ~(~N
R2 SO3M SO3M Rl
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
This particular brighten~r species is commercially marketed under the tMdPn~me
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightPnPr is 4,4'-bis[(4-anilino-
6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commercially marketed
under the tr~den~me Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species
is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical bri~htçnPr 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 brighten~rs (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 bri~htenPrs work this way because they have high affinity forfabrics in the wash solution and therefore deposit relatively quick on these fabrics.
I
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54
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 dyetransfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of compounds can optionally be used in the present compositions to provideconventional fabric "brightnPs~" benefits, rather than a true dye transfer inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
Method of Use
Contacting of fabrics with washing solution will generally occur under
conditions of agitation. Agitation is preferably provided in a washing machine for
good cleaning. Washing is preferably followed by drying the wet fabric in a
conventional clothes dryer. An effective amount of the liquid or granular detergent
composition in the aqueous wash solution in the washing machine is preferably from
about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
EXAMPLE I
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
connPcted to a te.,lpe.alure controller (Therm-O-WatchTM, I2R), sparging tube, and
mech~nical 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 a~pl~killlately 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 rem~ining 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 rem~ining 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
m~oth~n.oculfonic acid.
EXAMPLE II
Quaternization of PEI 1800 E7
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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 byethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI
1800, E7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and acetonitrile
(120 g). Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly
stirring solution, which is then stoppered and stirred at room temperature overnight.
The acetonitrile is removed by rotary evaporation at about 60~C, followed by further
stripping of solvent using a Kugelrohr apparatus at approximately 80~C to afford220 g of the desired partially quaternized material as a dark brown viscous liquid.
The 13C-NMR (D2O) spectrum obtained on a sample of the reaction product
indicates the absence of a carbon resonance at ~58ppm corresponding to dimethyl
sulfate. The 1 H-NMR (D2O) spectrum shows a partial shifting of the resonance atabout 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 III
Formation of amine oxide of PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a m~gn~tic stirring bar is added
polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of
about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 mol nitrogen,
p.~dled 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. I H-NMR (D2O) spectrum obtained on a
sample of the reaction mixture indicates complete conversion. The resonances
ascribed to methylene protons adjacent to unoxidized nitrogens have shifted fromthe original position at ~2.5 ppm to ~3.5 ppm. To the reaction solution is addedapproximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to
stand at room te"l~c.dlllre for approximately 3 days. The solution is tested andfound to be negative for peroxide by indicator paper. The material as obtained is
suitably stored as a 51.1% active solution in water.
EXAMPLE IV
Formation of amine oxide of quaternized PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a m~gn~tic stirring bar is added
polyethylen~imine having a molecular weight of 1800 which is further modified byethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E7)
and then further modified by qudl~ dtion to approximately 38% with dimethyl
sulfate (130 g, ~0.20 mol oxidizeable nitrogen, l~repdl~,d as in Example II),
hydrogen peroxide (48 g of a 30 wt % solution in water, 0.423 mol), and water (~50
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56
g). The flask is stoppered, and after an initial exotherm the solution is stirred at
room temperature overnight. IH-NMR (D2O) 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 tenll,e,dlure 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 qll~t~rni7ç~1 and 62% of the nitrogens oxidized
to amine oxide is obtained and is suitably stored as a 44.9% active solution in water.
EXAMPLE V
Oxidation of Quaternized PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified byethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E7)
subsequently quaternized with dimethyl sulfate to approximately 4.7% ~121.7 g,
~0.32 mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution inwater, 0.588 mol), and water (109.4 g). The flask is ~lo~y~ed, and after an initial
exotherm the solution is stirred at room temperature overnight. IH-NMR (D2O)
spectrum obtained on a sample of the reaction mixture indicates the methylene peaks
at 2.5-3.0 ppm have shifted to ~3.5 ppm. To the reaction solution is added ~5 g of
0.5 % Pd on alumina pellets, and the solution is allowed to stand at room
temperature for ~3 days. The solution is tested and found to be negative for
peroxide by indicator paper. The desired material with ~4.7% of the nitrogens
q~ temi7efl and ~95.3% of the nitrogens oxidized to the amine oxide is obtained and
is suitably stored as a 46.5% solution in water.
EXAMPLE VI
Quaternization of PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a m~gn~tic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified byethoxylation to a degree of approximately 7 (224g, 0.637 mol nitrogen) and
- acetonitrile (150g, 3.65 mol). Dimethyl sulfate (3.8g, 0.030 mol) is added in one
portion to the rapidly stirring solution, which is stoppered and stirred at roomtemperature overnight. The acetonitrile is removed by rotary evaporation at
approximately 60~C. The last traces of solvent are removed by further stripping on
a Kugelrohr at ~80~C to afford ~220g of the desired material obtained as a dark
brown viscous liquid in which ~4.7% of the nitrogen are quaternized. The l 3C-
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57
NMR (D2O) spectrum indicates the consumption of dimethyl sulfate by the absence
of a resonance at ~58ppm. The ~H-NMR (D2O) spectrum shows a partial shifting of
the resonance at 2.5 ppm (methylene units adjacent to unquaternized nitrogens) to
~3.0 ppm.
The following describe high density liquid detergent compositions according
to the present invention:
EXAMPLE VII-X
wei~ht %
In~redient VII VIII IX X
PolyhydroxyCoco-FattyAcid Amide 3.65 3.50
C 12-c 13 Alcohol Ethoxylate Eg 3.65 0.80 -- ~~
SodiumC12-C1s AlcoholSulfate 6.03 2.50 -- --
Sodium C 12-c 15 Alcohol Ethoxylate 9.29 15.10 --
E2 5 Sulfate
Sodium C 14-C 15 Alcohol Ethoxylate -- -- 18.00 18.00
E2 25 Sulfate
Alkyl N-Methyl Glucose Amide -- -- 4.50 4.50
Clo 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 ~.00 7.50 7.50 7.00
Boric Acid 3.50 3.50 3.50 3.50
TetraethylenepentArninP 1. ~ 8
Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50
NaOH 2.08 2.43 2.62 2.62
Minors2 1.60 1.30 0.27 0.27
Fabric Surface Modifying Polymer3 0.50 0.50 -- --
Fabric Surface ModifyingPolymer4 -- -- 2.00 1.00
Carezyme (5000 Cevu/g) enzyme 0.05 0.0S 0.05 0.05
WaterS balance balance balance balance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Minors - includes optical brightener and enzymes (protease, lipase, cellulase,
and amylase).
.. .. .
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58
3. Polymer according to Example 4.
4. Polymer according to Example 1.
5. Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, chelating agents,
dye transfer inhibiting agents, additional water, and fillers, including CaC03, talc,
silicates, etc.
EXAMPLE XI-XIV
Ingredient XI XII XIII XIV
Sodium C 14-C 15 Alcohol Ethoxylate13.00 - 8.43
E2 25 Sulfate
Sodiurn C 12-C 15 Alcohol Ethoxylate -- 18.00 13.00
E2 5 Sulfate
Sodium C12-C13 linearalkylbenzene 9.86 8.43
sulfonate
Fatty Acid (C 12-C 14) 2.00 2.00 2.95
C12-C13 Alcohol Ethoxylate Eg -- -- -- 3.37
Clo 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 Tetraethylent;pe ~ P 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
Optical Brightçner 1.60 1.80 2.00 1.60
Fabric Modifying Polymer2 0.50 2.00 -- --
Fabric ModifyingPolymer3 1.50 -- 2.00 3.00
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Endolase Enzyme (5000Cevu/g) 0.1 0.1 0.5 0.2
Soil Release Polymer I .15 1.50
Water5 balance balance balance balance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Polymer according to Example 4.
3. Polymer according to Example 1.
4. Balance to 100% can, for example, include minors lil~e perfume, suds
suppresser, soil dispersant, protease, lipase, amylase, chelating agents, dye
transfer inhibiting agents, additional water, and fillers, including CaCO3, talc,
silicates, etc.
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EXAMPLE XV-XIX
Ingredients XV XVI XVII XVIIIXIX
Polyhydroxy coco-fatty acid3.50 3.50 3.15 3.503.00
amide
NEODOL 23-9 1 2.00 0.60 2.00 0.600.60
C2s Alkyl ethoxylate sulphate 19.00 19.40 19.0017.40 14.00
C2s Alkyl sulfate -- -- -- 2.852.30
C 10 -Aminopropylamide -- -- -- 0.750.50
Citric acid 3.00 3.00 3.00 3.003.00
Tallow fatty acid 2.00 2.00 2.00 2.002.00
Ethanol 3.41 3.47 3.34 3.592.93
Propanediol 6.22 6.35 6.21 6.565.75
Monomethanol amine 1.00 0.50 0.50 0.500.50
Sodium hydroxide 3.05 2.40 2.40 2.402.40
Sodium p-toluene sulfonate2.50 2.25 2.25 2.252.25
Borax 2.50 2.50 2.50 2.502.50
Protease 2 0.88 0.88 0.88 0.880.88
Lipolase 3 0.04 0.12 0.12 0.120.12
Duramyl 4 0.10 0.10 0.10 0.100.40
CAREZYME Cellulase Enzyme0.053 0.053 0.053 0.0530.053
Optical Brightçntor 0.15 0.15 0.15 0.150.15
Polyamine Fabric Surface 1.18 1.18 1.18 1.181.75
Modifying Agent5
Fumed silica 0.119 0.119 0.119 0.1190.119
Minors, aestetics, water balance balance balance balance balance
1. C12-C13 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillus amyloliquefaciens subtiîisin according to U.S. Patent Application No.
08/322,676, of A. Baeck, et al, entitled "Protease-Con~ining Cleaning
Compositions".
3. . Derived from Humicola lanuginosa and commercially available from Novo.
4. Disclosed in WO 9510603 A and available from Novo.
5. Polymer according to Example 4.
EXAMPLE XX-XXIII
Liquid Laundrv Del~ e.ll Compositions
Ingredients XX XXI ~XII XXIII
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C 12-c 15 Alkyl sulfate -- - -- --
C 12-C 15 Alkyl ethoxylated sulfate 18.0 16.0 18.0 16.0
C12-C14 N-methyl glucamide 4.5 3.1 4.5 3.1
C 12-c 14 Fatty alcohol ethoxylate 2.0 1.0 2.0 1.0
C12-C16 Fatty acid 2.0 2.0 2.0 2.0
Citric acid (anhydrous) 3.0 2.5 3.0 2.5
Monoethanolamine 0.0 0.75 0.0 0.75
Propanediol 0.0 5.1 0.0 5.1
NaOH 2.93 2.9 2.93 2.9
Ethanol 3.52 2.88 3.52 2.88
Protease, Lipase, Arnylase Enzymes 1.25 0.7 1.25 0.7
Soil Release Polymer 0.2 1.18 0.2 1.18
Na Formate 0.093 0.058 0.093 0.058
Boric acid 3.5 2.5 3.5 2.5
Silicone Suds Su~,plessor 0.119 0.085 0.119 0.085
Carezyme (5000CEVU/g) 0.05 -- 1.0
Endolase (5000 CEVU/g) -- 0.2 -- 0.1
PEI 1800 E7l 2.0 2.0 2.0 2.0
Tinopal UNPA-GX BrightPnPr 0.05 -- 0.05 --
Water& minors balance balance balance balance
1 Fabric Surface Modifying Agent
