Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT COMPOSITIONS COMPRISING
POLYAMINE SCAVENGER AGENl'S AND ENZYMES
FELD OF T~IE INVENTION
10The present invention relates to detergent compositions which employ
polyamine scavenger agents and enzymes to boost cleaning, especially greasy stain and
body soil removal, perforrnance. Fabric laundering and hard-surface cle~nine
compositions with improved body soil and greasy stain removal properties are
provided.
15BACKGROUND OF THE ~NVENTION
Detergent for nulators are faced with the task of devising products to remove a
broad spectrum of soils and stains from wash surfaces. It is particularly desirable to
remove body soils as well as greasy stains, such as butter, I,.al~a,i,-e, and bacon from
wash surfaces.
20Detergent compositions cont~inirlg enzymes, incln~ling lipase enzymes, are well
known. Detergent compositions cont~ining lipase enzymes are effective in hydrolyzing
triglycerides in body soils and grease, thereby effectively removing body soils and
grease stains from wash surfaces. Without wishing to be limited by theory, it isbelieved that while lipase enzymes hydrolyzes triglycerides in body oils and grease
25 soils, it is de-activated by coming in contact with chlorine. During the wash process,
the effectiveness of lipase's body and grease soil removal p. upel ly is decleased due to
chlorine in the wash liquor, such as in tap water.
Chlorine scavengers such as sodium sulfite, perborate, and ammonium sulfate
remove or "scavenge" chlorine in wash liquors. However~ during a typical wash
30 process, rnany scavengers only remove the chlorine from the wash liquor through the
initial wash process, and little scavenging benefit is seen during the rinsing stage, when
additional wash liquor, cor.t~ining chlorine, is added.
It has now been discovered that compositions comprising polyamine scavenger
agents can be used to scavenge chlorine in wash liquors. ln addition, the polyamines
35 deposit upon the wash surface, thereby m~int~ining the effectiveness of lipase enzyrnes
in removing greasy stains and body soils through the rinsing stage. While not
intt~n~ing to be limited by theory, the polyamines deposit onto the wash surface during
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the wash stage and remain on the surface during the rinsing stage, thereby effectively
scavenging the chlorine even during the rinsing stage. Detergent compositions
comprising such polyamine scavenger agents thus m~int~in the effectiveness of lipase
enzymes to remove body soils and greasy stains from wash surfaces.
Accordingly, it is an object of the present invention to provide improved body
soil and grease stain removal compositions cont~ining lipase enzymes and polyamine
scavenger agents. These and other objects are secured herein, as will be seen from the
following disclosures.
BACKGROUND ART
The following disclose various polymers or modified polyamines; U.S. Patent
4,548,744, 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,
Gosselinl~ issued May 16,1995; U.S. Patent 4,235,735, Marco, et al., issued
November 25, 1980; WO 95/32272, published November 30, 1995; U.K. Patent
1,537,288, published Dec~n,ber 29, 1978; U.K. Patent 1,498,520, published January
18, 1978; German Patent DE 28 29 022, issued January 10, 1980; Jar~nP~e Kokai JP06313271, published April 27, 1994.
Detergent compositions comprising lipase are reported in the following
patents: U.S. 3,950,277; U.S. 4,011,169; EP 205,208; EP 206,390. EP 214,716 and
EP 258,068 each give det~iled description of lipases.
SUMMARY OF THE INVENTION
The present invention eAco.. ra~ses detergent compositions colllpl;sil-g lipaseer~.... ....cs and polyamine scavenger agents.
Thc present invention is directed to detergent compositions comprising:
A. detersive surfactant;
B. lipase enzymes in an amount of from about 0.004 to about 6 lipolytic
units per milligram of the composition;
C. from about 0.01% to about 15% scavenger agents comprising a
polyamine backbone colTesponding to the formula:
[ H 2N -R ln + ~N -R ]m--IN -R In--N H 2
having a mo-lified polyamine formula V(n+l)wmynz or a polyamine
backbone corresponding to the formula:
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H ¦ ~
~HZN -R]n-k+ r-[N-R]m -[N-R]n t N-R]k-N H2
having a modified polyamine formula V(n-k+l)wmynykz~ 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:
~X- ~
E--~ or E--~+ ~ or E~
ii) W units are backbone units having the forrnula:
~X-
--~ or --~+ n or ~
iii) Y units are branching units having the formu~a:
~X-
--~n or --1~1+ n or r-~
; and
iv) Z units are terminal units having the formula:
EX-
--E or ~E or --~E
;
wherein backbone linking R units are selected from the group
consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12
hydroxyalkylene, C4-C 12 dihydroxy-alkylene, Cg-C12
dialkylarylene, -(R 1 O)XR 1-, -(R 1 O)XRS (OR 1 )x-,
-(CH2CH(OR2)CH20)z(RlO)yRl(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
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hydrogen, -(RIO)xB, and mixtures thereof; R3 is Cl-C1g 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; R5 is Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-
C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -C(O)-, -
C(O)NHR6NHC(O)- -R 1 (OR 1 ), -C(o)(R4)rC(o)-, -
CH2CH(OH)CH2-~
CH2C~I(OH)CH20(RI 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, C 1 ~
C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22
hydroxyalkyl, -(CH2)pCO2M, ~(CH2)qSO3M~ -
CH(CH2C02M)C02M,-(CH2)pPo3M, (Rlo)xB~-c(o)R3
and mixtures thereof; oxide; B is hydrogen, C1-C6 alkyl, -
(cH2)qso3M~ -(CH2)pC02M, -
(CH2)q(CHS03M)CH2S03M~ -(CH2)q-
(CHSO2M)CH2SO3M, -(CH2)pPO3M, -PO3M, and mixtures
thereof; M is hydrogen or a water soluble cation in s~ rient
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. the balance adjunct ingredients.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention it has been found that lipase
cG.~ detergent compositions with excellent greasy and body soil release
pc~o.... "ance can be achieved in such composition con,plising an effective amount of a
polyamine scavenger agent.
All pC~c ~ gec ratios and proportions herein are by weight, unless otherwise
sl,e~,ircd. All te~ al~lres are in degrees Celsius (~C) unless otherwise specified. All
35 doc~ cited are in relevant part, incorporated herein by l efel ence.
Detersive Surf~ct~nts
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The detersive surfactants suitable for use in the present invention are cationic,
anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, fiJrther described
herein below. The laundry detergent composition may be in any suitable form, forexample, high density liquids, light liquids or other pourable forms in addition to
5 granules or laundry bars. The polyamine scavenger agents of the present invention can
be form~ ted into any detersive matrix chosen by the formulator.
The laundry dele.gent compositions according to the present invention may
additionally comprise at least about 0.01%, preferably at least about 0.1%, moreprefelably at least about 1% by weight, of the following detersive surfactants.
10 Nonlimiting examples of surf~ct~nts useful herein typically at levels from about 1% to
about 5~%, by weight, include the conventional C11-C1g alkyl benzene sulfonates
("LAS") and primary, branched-chain and random C1o-C20 alkyl sulfates ("AS"), the
C1o-C1g secondary (2,3) alkyl sulfates ofthe forrnula CH3(CH2)A(CHOS03-M )
CH3 and CH3 (CH2)y(CHOSO3~M ) CH2CH3 where x and (y + 1) are integers of at
15 least about 7, preferably at least about 9, and M is a water-solubilizing cation,
especiqlly sodium, unsaturated sulfates such as oleyl sulfate, the Clo-Clg alkyl alkoxy
sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C1o-C1g alkyl alkoxy
carboAylates (espe~ y the EO 1-5 ethoxycarboAylates), the Clo 18 glycerol ethers,
the Clo-C18 alkyl polyglycosides and their corresponding slllf~ted polyglycosides, and
20 C12-Clg alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surf~ct~ltc such as the C12-C1g alkyl ethoxylates ("AE") includinf~ the so-
called narrow peaked alkyl ethoAylates and C6-C 12 alkyl phenol alkoxylates
(elcperi~lly ethoxylates and mixed ethoxy/propoAy), C 1 2-C 18 betaines and
sulfobetaines ("sl~lt~ines")~ C1o-C1g amine oAides, and the like, can also be included in
25 the overall compo,sitions. The C1o-C1g N-alkyl polyhydroxy fatty acid amides can
also be used. Typical eAan.p'cs include the C12-C1g N-methylgluc~ les. See WO
9,206,154. Other sugar-derived surf~Gt~ntc include the N-alkoxy polyhydroxy fatty
acid amides, such as C 1 o-C 18 N-(3-methoxypropyl) glucamide. The N-propyl
through N-hexyl C12-C1g eluc~,~ides can be used for low suclci~ Clo-C20
30 conventional soaps may also be used. If high sudsing is desired, the blallched-chain
Clo-Cl6 soaps may be used. Mixtures of anionic and nonionic surf~ct~nts are
especi~lly useful. Other conventional useful surfactants are listed in standard texts.
Lipase enzymes
~ Suitable lipase enzymes are those produced by microorganisms of the
35 Pseudomonas group, such as Pseudomonas s~ulzeri ATCC 19.154, as dis~losed in
GB 1,372,034. See also lipases in J~p~n~se Patent Application 53,20487, laid open
Feb. 24, 1978. This lipase is available from Amano Pharmaceutic~l Co. Ltd., Nagoya,
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Japan, under the trade name Lipase P "Amano," or "Amano-P." Other suitable
comrnercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata,
Japan; Chromobac~er viscosum lipases from U.S. Biochemical Corp., U.S.A. and
5 Disoynth Co., The Netherlands. The lipase ex Pseudomonas gladioli. LIPOLASE~
enzyme derived from Humicola lanuginosa and cornmercially available from Novo
Industri A/S, Denmark, see also EP 341,947, is a preferred lipase for use herein.
Mixtures of the above lipases may also be used.
The lipases of the present invention are inch~ded in the detergent composition
10 in such an amount that the final composition has a lipolytic enzyme activity of from
about 0.004 to about 6; preferably about 0.007 to about 3; more preferably about 0.01
to about 1, lipolytic units per milligram (LU/mg) of the composition.
Detergent compositions of the present invention comprises from 0.001% to
about 5%, pref~lably from about 0.0~% to about 2%, more preferably from about
15 0.1%toabout 1%,byweightoflipase.
A Lipolase Unit (LU) is that amount of lipase which produces I rnrnol of
titratable fatty acid per minute in a pH stat, under the following conditions:
t~mpw~ re 30~C; pH = 7.0, substrate is an emulsion of 4.8 wt. % oftributyrine
(Merck art. 1958), 78.5 wt. % of demineralized water, and 16.7 wt. % of
20 emlllcification reagent. The emulsification reagent was prepared from a rnixture of
17 9 g of sodium chloride, 0.41 g of potassium di-hydrogen phosphate (Merck art.4873), 400 mL of dc...;~-P.. ~lized water, 540 mL of glycerol (Merck art. 4094), and 6.0
g of Gum Arabic (Sigma no. G-9752).
Scavenger Agent
The scavenger agent of the present invention relates to modified polyamines.
These poly,u...nes co""~),ise backbones that can be either linear or cyclic. Thepolyamine backbones can also comprise polyamine branching chains to a greater orlesser 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
30 terrns of a unit that is substitllte~1~ quaternized, oxidized, or combh~alions thereof.
For the purposes of the present invention the term "modification" is defined as
le~ ;n9 a backbone -NH hydrogen atom by an E unit (substitution), quaternizing abackbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide
(oxidized). The terrns "modification" and "substitution" are used interch~ng~-ly when
35 ~erel,i,.g to the process of repl~cir~g a hydrogen atom at-~ched to a backbone nitrogen
with an E unit. Quale~ tion or oxidation may take place in some circumct~nces
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without substitution, but substitution is preferably accompanied by oxidation orquaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the scavenger
agents of the present invention have the general formula:
[ H ~1 -R ln + ~N -R ]m--~N -R In~N H 2
said backbones prior to subse~uent modification, comprise primaly, secondary andtertiary amine nitrogens connected by R "linking" units. The cyclic polyamine
backbones comprising the scavenger agents of the present invention have the general
1 0 formula:
H I R
[H2~ -R ]n-k + ~IN ~R]m--lN ~Rln~N -R]k - N H 2
said backbones prior to subsequent modification, co~ "ise primary, secondary andtertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising
the backbone or branching chain once modified are defined as V or Z "terminal" units.
For example, when a primarv amine moiety, located at the end of the main polyamine
backbone or branching chain having the structure
H2N-R]-
is modifi~d accG~ding to the present invention, it is therea~er defined as a V "terminal"
unit, or simply a V unit. However, for the purposes of the present invention, some or
all of the primary amine moieties can remain unrnodified subject to the restrictions
further described herein below. These unmodified primary amine moieties by virtue of
their position in the backbone chain remain "terminal" units. Likewise, when a primary
amine moiety, located at the end of the main polyamine backbone having the structure
-NH2
is modified according to the present invention, it is thereafter defined as a Z '~lell~una
unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions
further described herein below.
In a similar manner, second~ry amine nitrogens co,n~"ising the backbone or
r.~ g chain once modified are defined as W "backbone" units. For example, when
a secondary amine moiety, the major constituent of the backbones and branrhing
chains of the present invention, having the structure
H
~-R}
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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
unrnodified secondary amine moieties by virtue of their position in the backbone chain
5 remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the backbone
or br~nching chain once modified are further referred to as Y "branching" urlits. For
example, when a tertiary amine moiety, which is a chain branch point of either the
polyamine backbone or other branching chains or rings, having the structure
0 --~-R}
is modified according to the present invention, it is thereafter defined as a Y
"branching" unit, or simply a Y unit. However, for the purposes of the present
invention, some or all or the tertiary amine moieties can remain llnmodified. These
llnmo~ified tertiary amine moietiPs by virtue of their position in the backbone chain
remain "br~n~ ing" 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
,re~.e leplesel-led by the general forrnula
V(n~ l )WmYnZ
for linear polyamine polymers and by the general formula
V(n k+l)wmyny kZ
for cyclic polyarnine polyrners. For the case of polyamines cGll.~Jlis;llg rings, a Y' unit
ofthefc"~ la
~ R}
serves as a branch point for a backbone or branch ring. For every Y' unit there is a Y
unit having the forrnula
--~-R~
that will form the coMeclion point of the ring to the main polymer chain or branch. In
the unique case where the backbone is a complete ring, the polyamine backbone has
the forrnula
IH~I ~Rln--IN -R Im--IN -R In--
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therefore comprising no Z terminal unit and having the formula
Vn kWmYnY k
wherein k is the number of ring forming branching units. Preferably the polyamine
5 backbones of the present invention comp. ise no rings.
In the case of non-cyclic polyamines, the ratio of the index n to the index m
relates to the relative degree of branching. A fully non-branched linear modified
polyamine according to the present invention has the forrnula
VWmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the
greater the degree of branching in the molecule. Typically the value for m ranges from
a minim~ 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 prefel I ed.
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 substitllte-l, quaternized or oxidized. Those
polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending
on whether they are primary, secondary or tertiary nitrogens. That is unrnodified
primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are
W units and unmodified tertiary arnine nitrogens are Y units for the purposes of the
present invention.
Modified primary amine moietie~ are defined as V "terminal" units having one
of three forms:
a) simple substituted units having the structure:
b) quaternized units having the structure:
X-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure
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o
E~
Modified secondary amine moieties are defined as W "backbone" units having
one of three forms:
a) simple substituted units having the structure:
b) quaternized units having the structure:
~ X-
~+~
~0 wherein X is a suitable counter ion providing charge bal~nce; and
c) oxidized units having the structure:
Modified tertiary amine moieties are defined as Y "branching" units having one~5 ofthree forms:
a) l~nmo~ified units having the structure:
-~F~
b) quaternized units having the structure:
E X-
--~+~
wherein X is a suitable counter ion providing charge balance; and
c) oxi~i7ed units having the structure:
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Certain modified primary amine moieties are defined as Z "terrninal" units
having one of three forms:
S a) simple substituted units having the structure:
--~E
b) qualtlllized units having the structure:
--~<E
10 wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
--~E
When any position on a nitrogen is unsubstituted of unmodified, it is
15 understood that hydrogen will substit~lte for E. For e~rnrle7 a primary amine unit
comprising one E unit in the form of a hydroxyethyl moiety is a V terrninal unit having
the formula (HOCH2CH2)HN-.
For the y~ uoses of the present invention there are two types of chain
terminating units, the V and Z units. The Z "terminal" unit derives from a terminal
20 primary amino moiety of the structure -NH2. Non-cyclic polyamine backbones
according to the present invention comprise only one Z unit whereas cyclic polyamines
can comprise no Z units. The Z "terminal" unit can be substituted with any of the E
units desc,il,ed 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
2s must be modified and the~ erore E cannot be a hydrogen.
The polyamines of the present invention comprise backbone R "linking" units
that serve to connect the nitrogen atoms of the backbone. R units comprise units that
for the purposes of the present invention are I efe, I ed to as "hydrocarbyl R" units and
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"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 connected to the polyamine backbone
nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any5 two of the carbon atoms of the R unit chain except those carbon atoms directlyconnected to the polyamine backbone nitrogens; Cg-C 12 dialkylarylene which for the
purpose of the present invention are arylene moieties having two alkyl substituent
groups as part of the linking chain. For example, a dialkylarylene unit has the formula
-(a~ ~a~ or lC~)~(C~;~
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substitutedC2-
C12 alkylene, plefel~bly ethylene, 1,2-propylene, and mixtures thereof, more
preferably ethylene. The "oxy" R units comprise -(Rlo)xR5(oRl)x-~ -
CH2CH(OR2)CH2O)z(R 1 O)yR 1 (OCH2CH(OR2)CH2)W-, -CH2CH(OR2)CH2-,
-(RlO)XR1-, and mixtures thereof. Plef~lled R units are C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(RlO)XRl-,
CH2CH(OR2)CH2-,-(CH2CH(OH)CH20)z(RlO)yRl(OCH2CH~(OH)CH2)w~~ -
(R1O)xRS(oRl)x-~ more pler~.~ed R units are C2-C12 alkylene, C3-C12 hydroxy-
alkylene, C4-C12 dihydroxyalkylene, -(R1O)XR~ (R1O)XRS(ORl)x-~ -
(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH-(OH)CH2)W-, and mixtures thereof, even
more piefe.red R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures
thereof, most plefel-ed are C2-C6 alkylene. The most plerel~d backbones ofthe
present invention comprise at least 50% R units that are ethylene.
R1 units are C2-C6 alkylene, and mixtures thereof, prefe~ably ethylene. R2
is hydrogen, and -(R1O)XB, preferably hydrogen.
R3 is C1-Clg alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-
C12 aryl, and mixtures thereof, preferably Cl-C12 alkyl, C7-C12 arylalkylene, more
preferably Cl-C12 alkyl, most pre~l~bly methyl. R3 units serve as part of E units
described herein below.
R4 is Cl-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-Clo
arylene, plefe.~bly Cl-CIo alkylene, Cg-C12 arylalkylene, more p~ere~bly C2-Cg
alkylene, most prc:r~,ably ethylene or butylene.
R5 is Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,
C 8 -C 12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(o)(R4)rC(o)-, -R 1 (OR 1
-CH2CH(OH)CH20(R 1 O)yR I OCH2CH(OH)CH2-, -C(o)(R4)rC(o)-, -
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13
CH2CH(OH)CH2-, R5 is preferably ethylene, -C(O)-, -C(O)N~IR6NHC(O)-, -
R I (OR I )-, -CH2CH(OH)CH2-, -CH2CH(OH)CH20(R 1 O)yR 1 OCH2CH-(OH)CH2-,
more preferably -CH2CH(OH)CH2-.
R6 is C2-C 12 alkylene or C6-C 12 arylene.
The p, efe. . ed "oxy" R units are fiJrther defined in terrns of the Rl, R2, and R5
units. Pl ert;l I cd "oxy" R units comprise the prerel, ed R 1, R2, and RS units. The
p, ere,led scavenger agents of the present invention comprise at least 50% Rl units
that are ethylene. Plefe,led R1, R2, and R5 units are combined with the "oxy" R units
to yield the pl el~,ed "oxy" R units in the following manner.
i) Substit~ltine more prefe"ed R5 into -(CH2CH2O)xR5(OCH2CH2)x-
yields -(CH2CH2O)XCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting prere"ed Rl and R2 into -(CH2CH(OR2)CH20)z-
(R 1 O)yR 1 O(CH2CH(OR2)CH2)W- yields -(CH2CH(OH)CH2O)z~
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)w-,
iii) Substit~ltin.~ prere"ed R2 into -CH2CH(OR2)CH2- yields
-CH2CH(OH)CH2-
E units are s~l~octed from the group consisting of hydrogen, C 1 -C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -
(CH2)qSO3M~ -CH(CH2C02M)C02M, -(CH2)pP03M, -(R 1 O)mB, -C(o)R3,
prcfe,ably hydrogen, C2-C22 hydroxyalkylene, benzyl, Cl-C22 alkylene, -(RlO)mB, -
C(o)R3, -(CH2)pC02M, ~(CH2)qSO3M~ -CH(CH2C02M)C02M, more prefel~bly
C 1 -C22 alkylene, -(R l O)XB, -C(o)R3, -(CH2)pCO2M, ~(CH2)qSO3M~ -
CH(CH2C02M)C02M, most p,ercr~bly Cl-C22 alkylene, -(R10)XB, and -C(o)R3.
When no mo~lifir~tion or substitlltiQn is made on a nitrogen then hydrogen atom will
remain as the moiety .e~,r~ ;ng E
E units do not co,np, ise 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:
- ~R or H--~R or ~H
H H H
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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 the5 structure
O O O
--~R or R~R or ~R3
~0 ~ ~
~3
or combinations thereof.
B is hydrogen, Cl-C6 alkyl, -(CH2)qSO3M~ -(CH2)pCO2M, -(CH2)q-
10 (CHSO3M)CH2SO3M,~(CH2)q(CHSO2M)CH2SO3M,~(CH2)pPO3M.~PO3M7
preferably hydrogen, -(CH2)qSO3M~ ~(CH2)q(cHsO3M)cH2so3M~ -(CH2)~
(CHS02M)CH2S03M, more preferably hydrogen or ~(CH2)qS03M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance. For eY~mrle~ a sodium cation equally s~ticfiec -(CH2)pCO2M, and
(CH2)qSO3Mt thereby rPculting in -(CH2)pCO2Na, and -(CH2)qSO3Na moieties.
More than one monovalent cation, (sodium, potassium, etc.) can be combined to
satisfy the required chemic~l charge bal~nce. However, more than one anionic group
may be charge bal~nce(~ by a divalent cation, or more than one mono-valent cation
may be n~cess~l y to satisfy the charge requil e..le.lt, of a poly-anionic radical. For
example, a -(CH2)pPO3M moiety substituted with sodium atoms has the forrnula -
(CH2)pP03Na3. Divalent cations such as c~ m (Ca2+) or m~nesi\lrn (Mg2+) may
be subctituted for or c~ f~ with other suitable mono-valent water soluble cations.
P-~f~d cations are sodium and pot~Ccillm~ more piefe,.ed is sodium.
X is a water soluble anion such as chlorine (Cl~), bromine (Br~) and iodine
(I-) or X can be any negatively charged radical such as sulfate (S042-) and
m~thoslllf~te (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 1, x has the value
from 1 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 pl efe, re~ scavenger agents of the present invention comprise polyamine
backbones wherein less than about 50% of the R groups comprise "oxy" R units,
CA 022~2883 1998-10-29
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preferably less than about 20%, more preferably less than 5%, most preferably the R
units comprise no "oxy" R units.
The most plefcl,ed scavenger agents which comprise no "oxy" R units
comprise polyamine backbones wherein less than 50% of the R groups comprise more5 than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene
comprise 3 or less carbon atoms and are the prere.,~d "hydrocarbyl" R units. That is
when backbone R units are C2-C12 alkylene, I)refe~led is C2-C3 alkylene, most
p,e~"ed is ethylene.
The scavenger agents of the present invention comprise modified
10 homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of
the -NH units are modified. For the purpose of the present invention the term
"homogeneous polyamine backbone" is defined as a polyamine backbone having R
units that are the same (i.e., all ethylene). However, this s~"çness definition does not
exclude polyamines that comprise other extraneous units comprising the polymer
15 backbone which are present due to an artifact of the chosen method of cl~ic~lsynthesis. For example, it is known to those skilled in the art that ethanolamine may
be used as an "inilialor" in the synthesis of polyethylen~ ee, therefore a sample of
polyethyl~.-P;,..;ne that comprises one hydroxyethyl moiety resulting from the
polyrnerization "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 bl,.llc~ g Y units are present is a
ho,~.o~,c~-~ouc backbone. A polyamine backbone col"p,ising all ethylene R units is a
homogeneous backbone regardless of the degree of branching or the number of cyclic
branches present.
For the purposes of the present invention the term "non-homogeneous polymer
backbone" refers to polyamine backbones that are a composite of various R unit
lengths and R unit types. For ~y~ntple, a non-homogeneous backbone comprises R
units that are a mixture of ethylene and 1,2-propylene units. ~or the purposes of the
present invention a mixture of "hydrocarbyl" and "oxy" R units is not l-ecP,ssa. y to
provide a non-homo~Pneouc backbone. The proper manipulation of these "R unit
chain lengths" provides the forrnulator with the ability to modify the solubility and
fabric subst~ntivity of the scavenger agents of the present invention.
Pl~,f~,.-ed scavenger agent polymers ofthe present invention co.~.p.ise
homogeneous polyamine backbones that are totally or partially substituted by
polyethyleneoxy moieties, totally or partially quaternized an~ines, nitrogens totally or
partially oxidi7ed to N-oxides, and mixtures thereof. However, not all backbone
amine nitrogens must be modified in the same manner, the choice of modification
CA 022~2883 1998-10-29
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16
being left to the specific needs of the formulator. The degree of ethoxylation is also
determined by the specific requirements of the formulator.
The pl ere, red polyamines that comprise the backbone of the compounds of the
present invention are generally polyalkylene~n-ines (PAA's), polyalkyleneimines
5 (PAI's), p~efcldbly polyethylel-P~...ine (PEA's), polyethylençiminps (PEI's), or PEA's or
PEI's connPctçd by moieties having longer R units than the parent PAA's, PAI's, PEA's
or PEI's. A common polyalkyl~neA-..;l~e (PAA) is tetrabutylenep~nt~rnine. PEA's are
obtained by reactions involving ammonia and ethylene dichloride, followed by
fractional di.ctill~tion The common PEA's obtained are triethylenetetramine (TETA)
10 and teraethylenelJ~n~ e (TEPA). Above the penta"~ es, i.e., the he~ es,
hept~ f ~J o~ ..;l-es and possibly nonamines, the cogenerically derived mixture does
not appear to separate by ~i~t~ tion and can include other materials such as cyclic
amines and particularly piperazines. There can also be present cyclic amines with side
chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued
Mayl4,1957,whichdescribestheprcpa,~tionofPEA's.
Prcfc~cd amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethyl~ni.~.;nes (PEI's). P~cfelled PEI's have at
least moderate br~n~hin~, that is the ratio of m to n is less than 4: 1, however PEI's
having a ratio of m to n of about 2: 1 are most plel'c~,ed. Preferred backbones, prior to
modifi~tion have the general formula:
[H2,NCH2~H21n~[NCH2CH2]m--[NcH2cH;~n--NH2
wherein m and n are the same as defined herein above. Prefc" ed PEI's, prior to
mo~ifi~tion, will have a molecular weight greater than about 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the
polyamine ba.,l~one, especially in the case of PEI's, will vary, depe ~ e on themanner of ple"a,~ion. Each hydrogen atom attached to each nitrogen atom of the
polyamine b~n~one chain rep,e3e.,ts a potential site for subsequent substit.ltion,
quaterni7~tion or oX~ tiQn.
These polyamines can be p,e;)d,ed, for example, by poly"l~,.i~ng ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for plepaling
these polyamine backbones are di~closed in U.S. Patent 2,182,306, Ulrich et al., issued
Dec~...he 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S.Patent 2,208,095, F.sselmsnn 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 ~e~rence.
.
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Examples of modified scavenger agent polymers of the present invention
comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a scavenger agent polymer comprising a PEI backbone
wherein all substitutable nitrogens are modified by replacem~.lt of hydrogen with a
5 polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula
cH2~AzN~ a~q7~q2
~NJ HIO~2~7~--N[IC~CH2C~7H]2
ICH2CH2C~7H ~ cH2a7H
n~(c~cH2)7l2N~~ CH2a~7~2
ICH2C~a7H ~7H ~ ~2CH2~7H
[l~~H2c~7]2~ IICH2(1~17H]2
1~, I~ICH2a~0t7H~2
Forrnula I
This is an example of a scavenger agent polymer that is fully modified by one type of
0 moiety.
Formula II depicts a scavenger agent polymer colllpl;~ g a PEI backbone
wherein all substitllt~hle primary amine nitrogens are modified by replncPment of
hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)7H, the molecule is then
modified by subsequent oxidation of all oxidi7~ble primary and secondary nitrogens to
N-oxides, said scavenger agent polymer having the forrnula
~C~ 2cH2~7l2~ ~ICH2CH2a7HJ2 (pa~2 ~
~r~ O~ CH2~71~2
HIOO~ O ~a~C~2qO~ O ~H2~
~~~~(N~~lcH2(~7~l2
a~cH2c~oH ~ ~2aJI
[H a~2CI~I7]2~ ~ ICH2CH20171~2
2a~7~q2
Formula II
Formula III depicts a scavenger agent polymer comprising a PEI backbone
wherein all backbone hydrogen atoms are substituted and some backbone amine units
are quat~.,u~ed. The substituents are polyoxyalkyleneoxy units7 -(CH2CH20)7H7 ormethyl groups. The modified PEI scavenger agent polymer has the formula
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[HlOa 12CH21712~, ~N(cH2cH2q7H CH3
~NJ CH3~N~ll~cH2cH2q7H
[Hloat2c}~ ~N ~--N~~r~N~ I~ICH3)2
Ct CH3 CH3 ~ Cl I~H3
H3 C~
H(OCH2CH2)7]2 N~N~Clt~3
~N(C1~2
Formula III
Formula IV depicts a scavenger agent polymer comprising a PEI backbone
wherein the backbone nitrogens are modified by substitution (i.e. by -(CH2CH20)7H
5 or methyl), quaternized, oxidized to N-oxides or combinations thereof: The res.llting
scavenger agent polymer has the formula
[H~Oa~12),l2N~ ~N+(a 12a~CI7H ~ CH3
~J Cl CH3~ +YCH2CH2cl~7H
H~CXH2CH2)~]~N+~rl~ G r~N~~ 3)2
Ct ~ O ~ ~ Cl
~CH3 C~
lHtOa~C~7l2 N ~N~ 3
~,N(a~2
Formula IV
In the above PY~npl~ s, not all nitrogens of a unit class comprise the same
10 ~ c~ n The present invention allows the forrnulator to have a portion of the
scc4A~ ~ amine n~llu~ ns ethoxylated while having other seCon(~ry amine nitrogens
oxidized to N-oxides. This also applies to the primary amine nitrogens, in that the
form~ tor may choose to modif~r all or a portion of the primary amine nitrogens with
one or more substin~çnts prior to oxidation or quaternization. Any possible
15 co...~ ;on of E groups can be substituted on the primary and secondary amine
r..llogL.ls, except for the restrictions described herein above.
The scavenger agents of the present invention are in~luded in the detergent
co~-.rGs:l;on from about 0.01% to about 15%; preferably about .05% to about 8%;
more pre~,ably about .1% to about 3%.
20 Adjunct Ingredients
Soil Release Agent
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19
Known polymeric soil release agents, hereinaflLer "SRA", can optionally be
employed in the present detergent compositions. If utili7ed SRA's will generallycomprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
s P.efe"t;d SRA's typically have hydrophilic sce."e.. ls to hydrophilize the surface
- of hydrophobic fibers such as polyester and nylon, and hydrophobic seg,.,~.-ts to
deposit upon hydrophobic fibers and remain adhered thereto through completion ofwashing and rinsing cycles, thereby serving as an anchor for the hydrophilic se~mpntc
This can enable stains occurring subsequ~Pnt to ll~.,l,..- .t with the SRA to be more
10 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 Cdppillg moieties which are especially effective in controlling15 molecular weight or altering the physical or surface-active pl ope, lies. Structures and
charge distributions may be tailored for application to di~l enl fiber or textile types
and for varied detergent or detergent additive products.
Plefe"ed SRA's include oligomeric terephth-q-lqlte esters, typically prepared byprocesses involving at least one trancestPrification/oligo,l,e,iGalion, often with a metal
20 catalyst such as a titq~ (IV) all~oYide Such esters may be made using additional
~.~ono...~ ~ capable of being illCOI ~Jol~led into the ester structure through one, two,
three, four or more positio~s~ without, of course, forming a densely crosc1in1~ed overall
structure.
Other SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene
terephthqls~te pol~ei.t~ of U.S. 4,711,730, Dcce,.ll,er 8, 1987 to Gosselink et al., for
e,l ~'e those produced by l~anse~le,;r~cation/oligo".~ alion of poly(ethyleneglycol)
methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other e~ les of SRA's
in~hlde: the partly- and fully- anionic-end-capped oligo",c. ic esters of U.S. 4,721,580,
January 26, 1988 to GossPlinl~ such as oligomers from ethylene glycol ("EG"), PG,
DMT and Na-3,6-dioxa-8-hydroxyoctqnçsulfonate; and the anionic, especiqlly
sulfoaroyl, end-capped tc.~h~ lqte esters of U.S. 4,877,896, October 31, 1989 to-ld~nqdo, the latter being typical of SRA's useful in both laundry and fabric
corl~itiol ;~ products, an PYqmple being an ester composition made from m-
sul~cbc~ 9iC acid monosQdium salt, PG and DMT, optionally but preferably furthercG""";sing added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephth~'-q,te or
propylene terephth~l~te with polyethylene oxide or polypropylene oxide terephthqlqte,
CA 022~2883 1998-10-29
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see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8,
1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as
METHOCEL from Dow; the Cl-C4 alkyl celluloses and C4 hydroAyalkyl celluloses,
see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyi cellulose5 ethers having an average degree of substitution (methyl) per anhydroglucose unit from
about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120
centipoise measured at 20~C as a 2% aqueous solution. Such materials are available
as METOLOSE SM100 and METOLOSE SM200, which are the trade names of
methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KIC.
Suitable SRA's characterised by poly(vinyl ester) hydrophobe segn~Pnts include
graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, plerel~bly poly(vinyl
acetate), grafted onto polyalkylene oxide backbones. See European Patent
Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially
available eAanlples include SOKALAN SRA's such as SOKALAN HP-22, available
15 from BASF, Gea-.~. Other SRA's are polyesters with repeat units cot~il.il~g 10-
15% by weight of ethylene terephtha~Ate together with 80-90% by weight of
polyoxyethylene t~rep~ ql~te derived from a polyoxyethylene glycol of average
molecular weight 300-5,000. Commercial examples include ZELCON 5126 from
Dupont and MlLEASE T from ICI.
Another ~,lef~lled SRA is an oligomer having empirical formula
(CAP)2(EG/PG)s(T)s(S~)l which cG.~ ses terephthaloyl (T), sulfoisophthaloyl
(SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably
terlnin~t~d with end-caps (CAP), pr~f~.~bly modified isethionates, as in an oligomer
CG...~ ;ng one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and OAY-
1,2-propylene~Ay 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)-ethaneslllfi nate. Said
SRA preferably further co...pl;ses from 0.5% to 20%, by weight of the oligomer, of a
crystallinity-reducing st~hi~i7pr~ for eA~Illple an anionic surfactant such as linear
sodium dodecylb~ e, ~lfon~te or a member selected from xylene-, cumene-, and
toluene- sl~lfonqt~s or mixtures thereof, these stiq-hili7~rs 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)-e~l~qnf,~ulfonate, DMT, Na-dimethyl-S-sulfoisophthqlAte, EG and PG.
Additional classes of SRA's include: (I) nonionic tele~htl.AlAtes using
diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and U.S. 4,240,918 T.Ag,qcce et al.; and (II) SRA's with carboxylate
terrninal groups made by adding Llilncll;Lic anhydride to known SRA's to convert
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W O 97/42284 PCT~US96/08511
terminal hydroxyl groups to trim~ t~te esters. With the proper selection of catalyst,
the trimellitic anhydride forms linkages to the terminals of the polymer through an
ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of
the anhydride linkage. Either nonionic or anior~ic SRA's may be used as starting5 materials as lon8 as they have hydroxyl terminal 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 ofthe 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
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 graftin~ 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: (Vl) 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 S~A's plepaled by con-~t?n~ing adipic
acid, caprolact~m, 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, 4,7~7,989 and 4,525,524.
Bleaching Compounds - Bleachin~ Agents and Bleach Activators
The detergent compositions herein may optionally contain bleaçhing agents or
ble~ l~in~ compositions CG~ a bleaching agent and one or more bleach
activators. When present, ble~ching agents will be at levels of from about 0.05% to
about 30%, more preferably from about 1% to about 30%, most prefe~ably from about
5% to about 20%, of the detergent composition, ecpeci~lly 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 blPa~hing composition
COInIJI ;sl~g the bleaching agent-plus-bleach activator.
The b!c~~hine agents used herein can be any ofthe blea~hing agents useful for
de~e.~ compositions in textile cle~nin~ hard surface cle~nin~. or other cle~nin~purposes that are now known or become known. These include oxygen bleaches as
well as other ~leaçhin~ agents. Perborate bleaches, e.g.~ sodium perborate (e.g.,
mono- or tetra-hydrate) can be used herein.
Another category of bl ~ in~e agent that can be used without restriction
encfJ.n?~cses perea~l,o~ylic acid blç chin~e agents and salts thereof. Suitable examples
of this class of agents include ~ f~ m monoperoxyphth~l~te hexahydrate, the
rnagnf~Cillnl salt of metachîoro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid
CA 022~2883 1998-10-29
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and ~lipe.o~-ydodecanedioic acid. Such bleaching agents are disclosed 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. Patent 4,412,934, Chung et al, issued
November 1, 1983. Highly prerél~ed bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987
to Burns et al.
Peroxygen blcaçhing agents can also be used. Suitable peroxygen bleac.h;ng
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleachec, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, nl~nufactl-red commercially by DuPont)can also be used.
A prefelled percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000 micrometers, not
more than about 10% by weight of said particles being smaller than about 200
micrometers and not more than about 10% by weight of said particles being largerthan about 1,250 micrometers. Optionally, the pc;rchlbona~e can be coated with
silicate, borate or water-soluble surf~ct~nts. Percarbonate is available from various
colll..,crcial sources such as ~MC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen ble~hing agents, the perborates, the percarbonates, etc., are
pl efel ably co,llbined with bleach activators, which lead to the in situ production in
aqueous sol~ltiQrl (i.e., during the washing process) of the peroxy acid COII ~,onding
to the bleach activator. Various nonl;...;l;ng examples of activators are disclosed in
U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
The nonanoyloxyl,enLe,-e sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551
for other typical tleach~s and activators useful herein.
Highly pr~féllcd amido-derived bleach activators are those ofthe formulae:
RlN(R5)C(o)R2C(o)L or RlC(o)N(R5)R2C(o)L
whe.~h~ Rl is an alkyl group conla;...l~p from about 6 to about 12 carbon atoms, R2 is
an alkylene conla;l~;ng from I to about 6 carbon atoms, R5 is H or alkyl, aryl, or
alka-yl cG~ g from about I to about 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is ~i~p!~ed from the bleach
35 activator as a con~equPnre of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A pre~.led leaving group is phenyl sulfonate.
CA 022528X3 1998-10-29
WO 97/42284 PCIIUS96/08511
23
~lefe.-ed examples of bleach activators ofthe above formulae include (6-
oct~n~mido-caproyl)oxyben7ene~1fonate, (6-nonanamidocaproyl)oxybenzenesul-
fonate, (6-dec~n~mido-caproyl)oxyben7erlesll1fonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by re~erence.
s Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
mcorporated herein by reference. A highly pl ~fe~ I ed activator of the benzo~ca~in-type
IS:
~ "C~
Still another class of pleÇ~.led bleach activators includes the acyl lactam
activators, eSperi~lly acyl caprolact~m.c and acyl valerclacl~...c ofthe formulae:
Ol Q
O C--CH~CH~ O ~--CH ~CH2
R~ C--N~ ,CH2 R~C~
CH2--CH2 CH2~CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining from I to
about 12 carbon atoms. Highly pl~Çelled lactam activators include benzoyl
15 caprol~ct~m octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolact~m decanoyl caprolact~m, un-lecenoyl caprolactam, benzoyl valerol~ t~m
octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-t".~ hylhexanoyl valerolactam and mixtures thereof. See alsoU.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
20 ,fer~.lce, which rliC~loses acyl caprolact~m~, inclutiin~ benzoyl caprolactam, adsorbed
into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen bl~a~hing agent of particularinterest incllldes phot~a-tivated bl~a 'in~ agents such as the sulronaled zinc and/or
~ll)mimlrn 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 bleaçh~s especially sulfonate zinc
phth~locyanine.
If desired, the ble arhing compounds can be catalyzed by means of a m~ng~rlese
compo~nd Such compounds are well known in the art and include, for exarnple, the
CA 022~2883 1998-10-29
WO 97/42284 PCTrUS96/08511
24
m~ng~n.ose-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; ~le~lled examples ofthese catalysts
include MnIV2(u-O)3 (1,4,7-trimethyl- 1,4,7-triazacyclononane)2(PF6)2, MnIII2(u-O)l (u-OAc)2(1,4,7-1l i"~elhyl-l ,4,7-triazacyclononane)2 (C104)2, MnIV4(u-
O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-O) I (u-OAc)2 (1,4,7-
trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-
triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleachcatalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The
10 use of ~ngP~-ese 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 matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part per ten
million of the active bleach catalyst species in the aqueous washing liquor, and will
plefe,~bly provide from about 0. I 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 dett:- ~t;lll compositions can be
in~h~ded in the co"")o~,lions herein, including other active ingredients, carriers,
hydrollopes, proce~cing aids, dyes or pi~ment~ solvents for liquid formulations, solid
fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the
C1o-C16 alkano!~rnides can be incorporated into the compositions, typically at 1%-
10% levels. The Clo-C14 monoethanol and dietll~nol amides illustrate a typical class
of such suds boosters. Use of such suds boosters with high sudsing adjunct
~w r;~ s such as the amine oxides, bclaines and s~llt~ines noted above is also
ad ,a~ g~rOUS If desired, soluble m~nesi~m 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 p~,.~",lance.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absG,bing said ingled,enls onto a porous hydrophobic
substrate, then coating said substrate with a hydrophobic coating. ~l~fw~bly, the
detersive ,ng~ed;c.,l is admixed with a surfactant before being absorbed into the porous
substrate. In use, the detersive ;ll~ edient is released from the substrate into the
aqueous washing liquor, where it p~.~""s its int~ntled detersive fimctiQI
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPEI~NAT D10, DeGussa) is admixed with a proteolytic enzyme solutionco.. ~ g 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant.
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Typically, the enzyme/surfactant solution is 2.S X the weight of silica. The resulting
powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the
range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or
otherwise added to the final detergent matrix. By this means, ingredients such as the
5 aforementioned enzyrnes, bleaches, bleach activators, bleach catalysts,
photoactivators, dyes, fluorescel s, fabric conditioners and hydrolyzable surfactants can
be "protected" for use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols exemplified by meth~nol,
10 ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are prefelled for
solubilizing surfactant, but polyols such as those contAining from 2 to about 6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol,
glycerin, and 1,2-propanediol) can also be used. The compositions may contain from
5% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will p.efel~bly be formul~ted such that,
during use in aqueous cl~An;ng operations, the wash water will have a pH of between
about 6.5 and about 11, p-efe.ably between about 7.5 and 10.5. Liquid dishwashing
product formulations prere~bly have a pH between about 6.8 and about 9Ø Laundry
products are typically at pH 9-11. Teçllnisl1es for controlling pH at recol.. ended
20 usage levels include the use of buffers, alkalis, acids, etc., and are well known to those
skilled in the art.
Other Enzyrnes
Other enzymes, besides lipase, can also be inchlded in the present detergent
co...pos;lions for a variety of purposes, including removal of protein-based,
25 carbohyd.ale-based stains from surfaces such as textiles or dishes, for the prevention
of refugee dye l,ansÇcr, for example in laundering, and for fabric restoration. Suitable
enzymes include ~uteases~ amylases, ce14~ e~, per~xid~e~, and mixtures thereof of
any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
Plerelle~ selections are influenced by factors such as pH-activity and/or stability
30 optima, thermost~bility~ and stability to active detergents, builders and the like. In this
respect bacterial or fungal enzyrnes are prefe, . ed, such as bacterial amylases and
proteases, and fungal ce~ ses
"Detersive enzyme", as used herein, means any enzyme having a .,JeAn:ng stain
removing or otherwise berlefiri~l effect in a laundry, hard surface cle~ning or personal
35 care detergent cûlllpos;lion. ~I.,f~,.rèd detersive enzymes are hydrolases such as
proteases, and amylases. ~efel.~d enzymes for laundry purposes includç, but are not
limited to, proteases, cçll~ ses, and peroxidases. Highly p~e~er-ed for automatic
. . .
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dishwashing are amylases and/or proteases, includin~ both current cornmercially
available types and improved types which, though more and more bleach compatiblethough s-~cces~ive improvements, have a re.~ainh1g degree of bleach deactivationsusceptibility.
Enzyrnes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount". The term
"cle~nin~ 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 terrns for current
co~lullt:lc;al prepal~lions, 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 othenvise, the compositions herein will typically comprise from 0.001% to 5%,
prererably 0.01%-1% by weight of a COl~u~ cial enzyme pre~al~lion. Protease
enzyrnes are usually present in such conune~ cial preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For
certain deterg~..ls, such as in automatic dishwashing, it may be desirable to increase
the active enzyme content ofthe col,ull~cial plel)ard~ion in order to ..-.--;-..;7e the total
amount of non-catalytically active materials and thereby improve ,polli..g/filrning or
other end-results. Higher active levels may also be desirable in highly conce..~l~ted
20 d~te.ge.l formulations.
Suitable e,.al..?les of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. Iich~r~O~ is. One suitable protease is obtained
from a strain of ~ , having m~rim~lm activity throughout the pH range of 8- 12,
developed and sold as ESPERASE~\ by Novo Industries A/S of Den~"al 1., hereinafter
"Novo". The p,~ lion ofthis enzyme and analogous enzymes is desclil,ed in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and
SAVINASE~ from Novo and MAXATASE~ from International Bio-Synthefics, Inc.,
The ~_thc~lands; as well as ~ol.,ase A as disclosed in EP 130,756 A, January 9, 1985
and ~ut~se B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A,
January 9, 1985. See also a high p~ protease from Bacillus sp. NCIMB 40338
described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, oneor more other enzymes, and a reversible protease inhibitor are described in WO
9203529 A to Novo. Other p. ~,f~, l ed proteases include those of WO 9510591 A to
Procter & Gamble . When desired, a protease having decreased adsorption and
i.,c~ .,ased hydrolysis is available as desc~ ibed in WO 9507791 to Procter & Gamble. A
ecolllbil1a.lt trypsin-like protease for detergents suitable herein is described in WO
9425583 to Novo.
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27
In more detail, an especially preferred protease, referred to as "Protease D" is a
carbonyl hydrolase variant having an amino acid sequence not found in nature, which
is denved from a precursor carbonyl hydrolase by substituting a different amino acid
for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent
5 to position +76, preferably also in combination with one or more amino acid residue
positions equivalent to those selected from the group consisting of+99, +101, +103,
+104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197,
+204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to
the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent
10 applications of A. Baeck, et al, entitled "Protease-Cont~ining Cleaning Compositions"
having US Serial No. 08/322,676, and C. Ghosh, et al, "Bleaclling Compositions
Co~"pli~ing ~lotease Enzymes" having US Serial No. 08/322,677, both filed October
13, 1994.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing purposes, include, for example, -amylases des.,,ibcd in GB 1,296,839 to
Novo; RAPIDASE~)~ International Bio-Syntheticc, Inc. and TERMAMYL~), Novo.
FIJNGAMYL~ from Novo is especially useful. F.n~in~ering of enzymes for improved
stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985, pp 6518-6521. Certain p,ere"ed embo.liments of the present
compositions can make use of amylases having improved stability in detergents such as
automatic dishwashing types, especially improved oxidative stability as measuredagainst a refel ~nce-point of TERMAMYL~ in commercial use in 1993. These
pr~fe,lcd amylases herein share the characteristic of being "stability-enh~nced"amylases, characterized, at a min;~num~ by a measurable improvement in one or more
2s of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenpdi~nline in
buffered sD! ~tion at pH 9-10; thermal stability, e.g., at co"u~-on wash t~llpclalLues
such as about 60~C; or alkaline stability, e.g., at a pH from about 8 to about 11,
measured versus the above-id~ntified refer~ nce-point amylase. Stability can be
measured using any ofthe art-disclosed technical tests. See, for c ,~al"ple, references
disclosed in WO 9402597. Stability-enh~nced amylases can be obtained from Novo or
from Genencor International. One class of highly p, ~re" ed amylases herein have the
co"l.,.ollality of being derived using site-directed mutagenesis from one or more of the
R<~ci/l.~ amylases, especialy the R~rill1~ -amylases, regardless of whether one, two
or mllltiple amylase strains are the ;.~....c l;~te precursors. Oxidative stability-~nh~nced
35 amylases vs. the above-iflentified rerelence amylase are l)le~..ed for use, ~pecially in
bleaching more preferably oxygen ble~c.hin~ as distinct from chlorine ble~ci~ g
detergent compositions herein. Such prere, red amylases include (a) an amylase
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28
accor~ing 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, ofthe methionine residue located in position 197 of
the B.lich~r~ ".is alpha-amylase, known as TERMAMYL~), or the homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis,
or B.stearothermophilus; (b) stability-çnh~ced amylases as described by GenencorInternational in a paper entitled "Oxidatively Reeict~nt alpha-Amylases" presented at
the 207th American Chemical Society National Meeting, March 13- 17 1994, by C.
~;lcl~ .con Therein it was noted that bleaches in automatic dishwashing detergents
10 inactivate alpha-amylases but that improved oxidative stability amylases have been
made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was idçntified
as the most likely residue to be modifie~ Met was substit~lte(l/ 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
15 eA~ ,ssed variant. Stability was measured in CASCADE~ and SUNLIGHT~); (c)
particularly plere--t;d amylases herein include amylase variants having additional
mo~ifi-~fltion in the imme(li~te parent as described in WO 9510603 A and are available
from the ~ cç, Novo, as DURAMYL~. Other particularly plef~l-ed oxidative
stability e-~h~-ced amylase include those described in WO 9418314 to Genencor
20 International and WO 9402597 to Novo. Any other oxidative stability-enhanced
amylase can be used, for example as derived by site-directed mutagenesis from known
chimeric, hybrid or simple mutant parent fonns of available amylases. Other p. ~el .ed
enzyme modifications are ~cG~cc;l-le. See WO 9509909 A to Novo. The amylase
enzyme should be at a conc~ ation offrom about 0.0018% to about 0.06% pure
25 enzyme by weight of the total cG,.,posilion, preferably from about 0.00024% to about
0.048% pure enzyme by weight ofthe total composition.
Ce~ lqeçs usable herein include both bacterial and fungal types, preferably
having a pH oplin..~ between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March6, 1984, .l;c. losPe s~it,a~Jle fungal cellnl~ ees from H1~micol~ insolens or Humicola
strain DSM1800 or a cellul~ce 212-producing fungus belonging to the genus
Aeromonas, and cÇll~ ce extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricula Solander. S~it~ble cell~ cec are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~) (Novo) is
especially useful. See also WO 9117243 to Novo.
Cutin~ce enzymes suitable for use herein are described in WO 8809367 A to
~'~PnPnCOr.
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Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention of transfer of dyes or pigments removed from substrates during the wash to
other substrates present in the wash solution. Known peroxidases include horseradish
5 peroxi~ e, ligni~$e, and haloperoxidases such as chloro- or bromo-peroxidase.
Peroxidase-co~ n;nf~ detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. En_yme materials
useful for liquid dele.~,en~ formulations, and their incorporation into such
formulations, are ~ closed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes
15 for use in detergents can be stabilized by various techniques. ~nzyme stabili~tion
technigues 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 stabili7~tion
systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp.
AC13 giving proteases, Yylanases and cçllul~ecJ is described in WO 9401532 A to
20 Novo.
Enzyme Slab,l;~;"g System
Enzyme-co~ in~hlding but not limited to, liquid compositiQnS herein
may co-"~"ise 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
25 st~ ; ;n~, system. The enzyrne s~abil;~ilg system can be any stabilizing system which
is co,..p ~ le with the detersive enzyme. Such a system may be inhc~ t;nlly provided by
other form~ tion actives, or be added separately, e.g., by the formulator or by a
manufacturer of d- te.g~,"t-ready en_ymes. Such st?~ili7in~ systems can, for eY~mple,
co."~,.;se cslr;um ion, boric acid, propylene glycol, short chain carboxylic acids,
30 boronic acids, and mixtures thereof, and are designed to address diffe~en~ stabilization
problems depen~ling on the type and physical form of the detergent composition.
One st?~ li7in~ approach is the use of water-soluble sources of calcium and/or
~a~,~.r.C;~Jm ions in the finiched compositions which provide such ions to the enzymes.
C~lcium ions are generally more effective than magnesium ions and are plefelled
35 herein if only one type of cation is being used. Typical detergent compositiorls,
espec;~lly liquids, will cG""";se from about I to about 30, pr~f~.~bly from about 2 to
about 20, more prefe. ~bly from about 8 to about 12 millimoles of calcium ion per liter
CA 022~2883 l998-l0-29
PCTrUS96/085
W O97/42284
of finiched detergent composition, though variation is possible depending on factors
inclucling the multiplicity, type and levels of enzymes incorporated. Preferably water-
soluble calcium or m~gneSium salts are employed, including for example calcium
chloride, calcium hydroxide, calcium forrnate, calcium malate, calcium m~le~tç,
5 calcium hydroxide and calcium acetate; more generally, calcium sulfate or m~gnçsium
salts co"esponding to the exemplified calcium salts may be used. Further increased
levels of Calci-lm and/or ~gn~ lm may of course be useful, for example for
promoting the grease-cutting action of certain types of surfactant.
Another st~bili7in~ approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of
the composition though more typically, levels of up to about 3% by weight of boric
acid or other borate compounds such as borax or orthoborate are suitable for liquid
detergent use. Substituted boric acids such as phenylboronic acid, butaneboronic acid,
p-bromophenylboronic acid or the like can be used in place of boric acid and reduced
15 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%, prefe.~bly from about 0.01% to about 6% by weight, of chlorine
bleach scavengers, added to prevent chlorine bleach species present in many water
20 supplies from ~tt~cl~ine 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; accot dillgly, enzyme stability to chlorine in-use is sometimes
25 problematic. Since pc.l,c.~le or perca.l,onale, which have the ability to react with
chlorine bleach, may present in certain of the instant compositions in amounts
~c~o~ for separately from the st~hili7irlg system, the use of additional stabilizers
against chlorine, may, most generally, not be essç ~ l though improved results may
be oblainable from their use. ~ui~le chlorine scavenger anions are widely known and
30 readily available, and, if used, can be salts co~ ammonium cations with sulfite,
bi~ -lfitç, thiosulfite, thios~lf~t~, iodide, etc. Antioxidants such as c&,l,a~.~ate,
ascorbate, etc., organic amines such as ethylel-c.~ -etetracetic acid (EDTA) or
alkali metal salt thereof, monoeth~no!~ ne (MEA), and mixtures thereof can likewise
be used. Likewise, special enzyme inhibition systems can be inco. yo, ated such that
3s di~renl enzymes have maximum compatibility. Other conventional scavengers such
as bi~lf~t~ nitrate, chloride, sources of hydrogen peroxide such as sodium perborate
tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as
CA 02252883 1998-10-29
W O 97t42284 PCT~US96/08511
phosph~t~ con~ nsed phosphate, acetate, bem:oate, citrate, formate, lactate, malate,
tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since
the chlorine scavenger function can be performed by ingredients separately listed under
better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute
5 requirel"c.ll to add a separate chlorine scavenger unless a compound pelro~.l.ing that
function to the desired extent is absent from an enzyme-cont~inin~ embodiment of the
invention; even then, the scavenger is added only for optimum results. Moreover, the
formulator will exercise a chenl.sl's norrnal skill in avoiding the use of any enzyme
scavenger or stabilizer which is majorly incompatible, as formulated, with other10 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. Accordil-~ly, such materials, if present, are desirably
protected in a particle such as that described in US 4,652,392, B~Ein~L-i et al. Builders
De~e~g.,.lt builders can optionally be inclllded in the compositions herein to
assist in controlling mineral hardness. Inorganic as well as organic builders can be
used. Builders are typically used in fabric laundering compositions to assist in the
removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically co,--~"ise 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
dete.~,.,.~l builder. Granular formulations typically comprise from about 10% to about
80%, more typically from about 15% to about 50% by weight, of the delergelll
builder. Lower or higher levels of builder, however, are not meant to be PYcl~ded
Inor~ ic or P-co.~ n;.~g deterg.,.ll builders include, but are not lirnited to, the
alkali metal, ammo~ m and ~ nol~ o- urn salts of polyphosphates (exemplified by
the tripolyphosFh~tes, pyrophosphates, and glassy polymeric meta-phosphates),
pho.~l-hor.~ç~ phytic acid, siliG~tes~ ca-l,onates (inclu~in~ bicarbonates and
sesqui~-l,onales), sulrh~t~c, and ~ mirlosilic~tes However, non-phosphate builders
are ~ u--cd in some locales In.po.l~.llly, the compositions herein function
sul~Jlis;l~glr well even in the prese,lce ofthe so-called "weak" builders (as coll.pa~ed
with phGsl~h~tes) 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 ~ilic~te~s, particularly those
having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered sodium ~ilic~tes des~,.ilJed in U.S. Patent 4,664,839, issued May 12, 1987 to
CA 022~2883 1998-10-29
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32
H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders the NaSKS-6 silicate builder does not contain ahlminum. NaSKS-6 has the delta-Na2SiOs
morphology form of layered silicate. It can be prepared by methods such as thosedescribed in German DE-A-3 417,649 and D3~-A-3,742 043. SKS-6 is a highly
plcfe~led layered silicate for use herein but other such layered silicatec 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, plerclably 2, and y is a number from 0 to 20, preferably 0
can be used herein. Various other layered silir~tes from Hoechst include NaSKS-SNaSKS-7 and NaSKS- I I as the alpha, beta and gamma forms. As noted above, the
delta-Na2SiOs (NaSKS-6 form) is most prcl~l I ed for use herein. Other silicates may
also be useful such as for example rn~gnesillnl silicate which can serve as a crispen,ng
agent in granular formulations as a stabilizing agent for oxygen bleaches and as a
cor-nponc"t of suds control systems.
Exanlples of carbonate builders are the alkaline earth and alkali metal
call,ol1ates as disclosed in Gerrnan Patent Application No. 2,321,001 published on
November 15 1973.
A',um,inosilicate builders are useful in the present invention. A,uminosilicate
builders are of great importance in most currently marketed heavy duty granular
dele.~ l compositions, and can also be a significant builder ingledie.,l in liquid
detergent formulations. A',uminosilicate builders include those having the empirica',
formula:
MZ(zA102)y] xH2o
wherein z and y are il,legcl ~ of at least 6, the molar ratio of z to y is in the range from
1.0 to about 0.5, ar,d x is an integer from about 15 to about 264.
Useful alumino~ cate ion excl,ange materials are collullclc;ally available.
These ~ mi~osi~ tes can be crystalline or all,olphous in structure and can be
natura',ly-occurring al-.minosilicat~ps or synthetically derived. A method for producing
z~lllmino~ilic~te ion eYçh~ e materials is disclosed in U.S. Patent 3 985 669,
Krummel, et al, issued October 12, 1976. Plefclrcd synthetic crystalline
~l~Jmino~ r~te ion exchange materials useful herein are available under the
de~ l;ons Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially
p.ercll~.d embodimPtlt the crystalline ~llmlinosilic~te ion exch~nge material has the
forrnula:
Nal2[(Alo2)l2(sio2)l2] xH2o
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wherein x is from about 20 to about 30, especially about 27. This material is known as
Zeolite A. Dehydrated zeolites (x = O - 10) may also be used herein. ~I~,re~ably, the
urninosilic~te has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
s include, but are not restricted to, a wide variety of polycarboxylate compounds. As
- used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate
groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium, pot~csium,
10 and lithium, or alkanolammonium salts are prel~ed.
Tncluded among the polycarboxylate builders are a variety of categories of
useful materials. One important catego.y of polycarboxylate builders encomp~c~es the
ether polycarboxylates, incl~ in~ oxy~iSuccin~te~ 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 poly~,a.l,oA~lates also include cyclic
compounds, particularly alicyclic compounds, such as those described in U.S. Patents
3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
20 copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
ben~elle-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various
alkali metal, ~...."o~ nn and s~lbstituted a-,u-.olu.lm salts of polyacetic acids such as
ethyle~-e~ ;ne tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates
such as mellitic acid, succiric acid, oxyd~ ccinic acid, polymaleic acid, benzene 1,3,5-
25 tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodiumsalt), are polyca.l,o.~)~late builders of particular i.nl)o, lance for heavy duty liquid
d~t~ t forrn-ll~tionc due to their availability from renewable resources and their
biode~ dakility. Citrates can also be used in granular compositionc~ especially in
30 co.,lbin~.lion with zeolite and/or layered silicate builders. Oxydi~uccin~tes are also
~speci~lly useful in such compositions and co,..binalions.
Also suitable in the deter~elll compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-k~ rdi~a~s and the related compounds ~isclosed in U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
35 include the Cs-C20 alkyl and alkenyl succinic acids and salts thereo~ A particularly
plefe--~d compound ofthis type is dodecenylsuccinic acid. Specific e,~al..ples of
s~lc~in~te builders include: laurylsuccin~te, myristylcuccin~te, palmitylsuccir~te, 2-
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dodecenyl~lcçin~te (plt;re"ed), 2-pent~tlecenylsuccinate~ and the like.
Lauryleuccin~tes are the prefe"ed builders ofthis 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,
Cmt~hfi~ld et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into
the compositions alone, or in co~l~binalion with the aforesaid builders, especially citrate
and/or the succin~te builders, to provide additional builder activity. Such use of fatty
10 acids will generally result in a diminution of sl1~1sin~, which should be taken into
account by the formulator.
In situations where phosphorus-based builders can be used, and especially in theforrnulation of bars used for hand-laundering operations, the various alkali metal
phosphqtçe such as the well-known sodium tripolyphosphates, sodium pyrophosphate15 and sodium orthophosphqte can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphQsphonP~e and other known phosphonates (see, for e Aa",?le, U.S.Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
Chel~tin~ Agents
The detergent co,npos;lions herein may also optionally contain one or more
20 iron and/or nl~n~nese chelating agents. Such chelating agents can be selected from
the group consisting of amino carboxylates, arnino phosphonates, polyfunctionally-
substit..ted aromatic chel~ting agents and rnixtures therein, all as hereinafter d~fined
Without ;..~ n~. to be bound by theory, it is believed that the benefit of thesematerials is due in part to their exceptional ability to remove iron and ~ ng,.ncse ions
25 from ~.. sh;ng sol~tion~ by formation of soluble Ghel~lf-s
Arnino carboxylates useful as optional cl~ ing agents include
clh~lclle~;aminetetracetates,N-hydroxyethylethylencJi~ e~ et~t~, nitrilo-
tat~e, ethylene~ ;ne te~lap.c: p,ionates, triethylenetetra~n inehey~cetates~
diethyl~,n~,tl;~ ..;ne~Denlr--et~te~ diethylent;ll;~ ep~ .llcthyl phosphonic acid, and
30 eth~rlol~i~lycines, alkali metal, ammonium, and substituted a~ o-- ~m salts therein
and mLlctures therein. Also suitable for use as a chelant is methylglycine di-acetic acid
(MGDA).
Amino pho3phonates are also suitable for use as ch~l~ting agents in the
compositions of the invention when at lease low levels of total phosphorus are
35 permitted in d~ compositions, and include ethyl~nedi~...inetetrakis
(methyl~ne~,hGs~,honates) as DEQUEST. Pl ef~. . ed, these amino phosphonates to not
contain alkyl or alkenyl groups with more than about 6 carbon atoms.
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Polyfunctionally-substituted aromatic chelating agents are also usefill in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974? to Connor et
al. Pl cf~.lcd compounds of this type in acid forrn are dihydroxydisulfobe.~enes such
as 1,2-dihydroxy-3,5-disulfobenzene.
A ~J~crelled biodegradable chelator for use herein is ethylenedi~mine
~icucçin~te ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
If utili7ed these ch~l~tin~ agents will generally comprise from about 0.1% to
about 10% by weight of the deterBent compositions herein. More preferably, if
utili7e~l the chel~ agents will comprise from about 0.1% to about 3.0% by weightof such compositionc
Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and antiredeposition proycllies.
Granular deter~cnl compositions which contain these compounds typically contain
from about 0.01% to about 10.0% by weight ofthe water-soluble ethoxylates amines;
liquid de~e.ge.lt compositions typically contain about 0.01% to about 5%.
The most prefclled soil release and anti-redeposition agent is ethoxylated
tetraethylf ncp~ nl~ e Fyçmplqry ethoxylated amines are further described in U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of ~refc.led clay
soil removal-antiredeposition agents are the cationic compounds disclosed in European
Patent AppliC~tion 111,965, Oh and Gosselink, published June 27, 1984. Other clay
soil removal/a.ltilcdeposition agents which can be used include the ethoxylated amine
polyrners dic~losed in European Patent Application 111,984, Gosselink, publishedJune 27, 1984; the zwitterionic polymers ~icçlosed in European Patent Application
112,592, Gosselink, publiched 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 redc~os;tion agents known in the art can also be utilized in the compositions
herein. Another type of ~.ef~.l.,d antiredeposition agent includes the carboxy methyl
cellulose (CMC) materials. These materials are well known in the art.
Polyrneric Dis~e. s."g Agents
Polymeric di~ycr~ing agents can advantageously be utilized at levels from
about 0.1% to about 7%, by weight, in the compositions herein, especially in the~tcsence of zeolite and/or layered silicate builders. Suitable polymeric ~.I;5~JCI ~ing
agents include polymeric polycarboxylates and polyethylene glycols, although others
known in the art can also be used. It is believed, though it is not int~nded to be limited
by theory, that polyrneric d;~ycl ~ing agents enhqnce overall detergent builder
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36
pe~fo"~lance! when used in combination with other builders (including lower molecular
weight polycarboxylates) by crystal growth inhibition, particulate soil release
pepti7~tion, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
5 copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid,
itaconic acid, aconitic acid, mesacor~ic acid, citraconic acid and methylenemalonic acid.
The pr~sence in the polymeric polycarboxylates herein or monomeric Seg~f..llC~
co,~ ;ng no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is
suitable provided that such se~l".,.lls do not conctih~te more than about 40% byweight.
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 prefe,ably ranges from about 2,000 to 10,000, more pler~.ably fromabout 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble
salts of such acrylic acid polymers can include, for example, the alkali metal,
"olu.lm and s~lbstituted ammonium salts. Soluble polymers of this type are knownmaterials. Use of polyacrylates of this type in delelgenl compositions has been
disclosed, for eY~-nplç, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a prert;"ed 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 plt:relably ranges from about 2,000 to 100,000,more preferably ~om about 5,000 to 75,000, most piefelably from about 7,000 to
65,000. The ratio of acrylate to maleate seg.~ c in such copolymers will gem.ally
range from about 30:1 to about 1:1, more p,efe,ably from about 10:1 to 2:1. Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the
alkali metal, a~ m and substituted ammonium salts. Soluble acrylate/maleate
copolymers of this type are known materials which are described in European Patent
Application No. 66915, published Decel,lber 15, 1982, as well as in EP 193,360,
published September 3, 1986, which also describes such polymers CO"I~"iSi"g
hydroxypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, inclu~ling for e~ ple the 45/45/10 terpolymer of acrylic/maleic/vinyl
alcohol.
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Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent perforrnance as well as act as a clay soil
removal-antiredeposition agent. Typical molec.ll~r weight ranges for these purposes
range from about 500 to about 100,000, prerel~bly from about 1,000 to about 50,000,
more preferably from about 1,500 to about 10,000.
Polyaspartate and poly~lut~m~te dispersing agents may also be used, especially
in conjunction with zeolite builders. Dispersing agents such as polyaspartate
p.~lably have a moleclll~r weight (avg.) of about 10,000.
Brightener
Any optical brighteners or other brightening or whitening agents known in the
art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight,
into the detergent compositions herein. Comrnercial optical bnghte~lers which may be
useful in the present invention can be classified into subgroups, which include, but are
not necçss~. ily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic
acid, mPth; ecyanines, dibenzothirhPne-5,5-dioxide, azoles, 5- and 6-~llcu,bered-ring
heterocycles, and other miscell~nçous agents. Fy~mrles of such brighteners are
disclosed in "The Production and Application of Fluorescenl Brigh~ening Agents", M.
Zahradnik, Published by John Wiley & Sons, New Yorlc (1982).
Specific e~a.."~l~s of optical briel.~el-e. a which are useful in the present
compositions are those idçntified in U.S. Patent 4,790,856, issued to Wixon on
Dec~...be. 13, 1988. These b~ighl~ner~ include the PHORW~TE series of
brightPners from Verona. Other briphtençrs ~icclosed in this reference include:
Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-
(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes;
4,4'-bis(stryl)l,isph~ ls; and the aminocoumarins. Specific examples of these
bl;gllt~nf~a include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-vt~.7;...:d~7OI-2-
yl)ethylene; 1,3-diphenyl-phrazolines; 2,S-bis(benzo~azol-2-yl)thiophene; 2-stryl-
napth-[1,2-d]oY~ ; and 2-(stilbene-1 yl)-2H-n~rhtho- [1,2-d]triazole. See also
U. S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brightçnPrs are
pl~,felled herein.
Suds Supl)l essol s
Compounds for reducin~ or suppl e~a;ilg the formation of suds can be
incol ~c-aled into the compositions of the present invention. Suds SUppl ession can be
of particular i"lpol lance in the so-called "high concenl~alion cle~ning process" as
de,_libed in U.S. 4,489,455 and 4,489,574 and in front-loading European-style
washing m~chines
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A wide variety of matelials may be used as suds suppressorst 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 cstegory of suds suppressor of particular interest
S enCon~p~C~s monocarboxylic fatty acid and soluble salts therein. See U.S. Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fattyacids and salts thereof used as suds sup,orc~.sol typically have hydrocarbyl chains of 10
to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali metal salts such as so~ m, pot~c~ m and lithium salts, and ammonium and
10 alkano~mmo~ lm salts.
The detergent compositions herein may also contain non-surfactant suds
su~ esso~s. These in~ d~, for e,~alllple: high moleclllqr weight hydrocarbons such as
paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphqtic Clg-C40 ketones (e.g., stearone), etc. Other suds inhibitors include
15 N-alkylated amino triazines such as tri- to hexa-alkyl.l,çl~...;nçs or di- to tetra-
alkyl.l~ ne chlortri~ines formed as products of cyanuric chloride with two or three
moles of a primary or secont~ry amine co~ g 1 to 24 carbon atoms, propylene
oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and
monostearyl di-alkali metal (e.g., K, Na, and Li) phosphales and phosph~te esters.
20 The hydrocarbons such as paraffin and halopal~ l can be utilized in liquid form. The
liquid hydrocarbons will be liquid at room tc.l,pe~alL~.re and atmospheric pressure, and
wiU have a pour point in the range of about -40~C and about 50~C, and a minim~-mboiling point not less than about 110~C (atmospheric pressure). It is also known to
utilize waxy h~dloc~l,ons, prcf.,.ably having a melting point below about 100~C. The
25 h~dluc~l~ons collctitllte a pr~f~ d category of suds suppi essor for detergent
cQ.-~po~il;Ql~c Hydrocarbon suds su~)lnessors are described, for example, in U.S.
Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus,
include ~ip~qtiC, alicyclic, aromatic, and heterocyclic saturated or unsaturatedhydroc~l,ons having from about 12 to about 70 carbon atoms. The terrn "pararrn," as
30 used in this suds su~.pres.sor ~icc~csion~ is in~ended to include mixtures oftrue
pz.~n~s and cyclic hydrocarbons.
Another ~lefe.red category of non-surfactant suds slJpplessola comprises
silicone suds suppl'ess~,.l a. This cdlegoly includes the use of polyorganosiloxane oils,
such as pol~du~elhylsiloxane, dispersions or çm~ ;onc of polyorganosiloxane oils or
35 resins, and cGn.h .~l;Qrlc of polyorganosiloxane with silica particles wherein the
polyGrg~nos;lox~ne is cl.. .-~icorl.ed 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,
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issued May S, 1981 to Gandolfo et al and European Patent Application No.
89307851 9, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
inco"~ol ~ling therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and sil~n~ted silica are described, for in~t~nce, in GermanPatent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
s~ p. e.,~;ng amount of a suds controlling agent consisting essçnti~lly 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)3SiOI/2 units of SiO2 units in a ratio of from
(CH3)3 SiOI/2 units and to SiO2 units offrom about 0.6:1 to about
1.2:1; and
(iii) from about I to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preft;- l ed silicone suds suppressor used herein, the solvent for a
co~tinUous phase is made up of certain polyethylene glycols or polyethylene-
polypropylene glycol copolymers or mixtures thereof (prefe. . ed), or polypropylene
glycol. The primary silicone suds sul)p.~jsor 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, prefe~àbly
from a~out 0.01 to about 0.7, most pref~.ably from about 0.05 to about 0.5, weight %
of said silicone suds s.~pp-~,ssor, which cG..,p,ises (1) a nonaqueous emulsion of a
p.ima,~ ti~a -. agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous
30 ci10Y ~le 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 Silqnol~tec; (2) at least one nonionic silicone surfactant; and (3)polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room ten,l)e. al~lre of more than about 2 weight %; and without
35 polypropylene glycol. Similar ~mounte can be used in granular compositions, gels, etc.
See also U.S. Patents 4,978,471, Starch, issued Dec~."ber 18, 1990, and 4,983,316,
Starch, issued January 8, 1991, 5,288,431, ~uber et al., issued February 22, 1994, and
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U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through
column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a copolymer of polyethylene glycol/polypropylene glycol, all hav~ng an average
molecular weight of less than about 1,000, ptere. ~bly between about 100 and 800.
The polyethylene glycol and polyethylene/polypropylene copolymers herein have a
solubility in water at room te..,pe~alure of more than about 2 weight %, p-~fe-ably
more than about 5 weight %.
The pl e~e- l ed solvent herein is polyethylene glycol having an average
molecular weight of less than about 1,000, more preferably between about 100 and800, most preferably between 200 and 400, and a copolymer of polyethylene
glycol/polypropylene glycol, preferably PPG 200/PEG 300. P~efe--ed is a weight ratio
of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene
glycol:copolymer of polyethylene-polypropylene glycol.
The p., fel ~~d silicone suds SUppl~i ,so. ~ used herein do not contain
polypropylene glycol, particularly of 4,000 moleclllqr weight. They also preferably do
not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC
L101 .
Other suds supp~ essol ~ useful herein con-y. ise the secondary alcohols (e.g., 2-
alkyl ql~qnol~) and mixtures of such alcohols with silicone oils, such as the silicones
dicrl~sed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secorldq~y alcohols
include the C6-C16 alkyl alcohols having a Cl-C16 chain. A p~efi;lled alcohol is 2-
butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of seCon~ry alcohols are available under the trademark ISALCHEM 123
from F -- ~ rh~m Mixed suds suppressol ~ typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any dele.ge~ll compositions to be used in autoln~qtic laundry washing
machines, suds should not form to the extent that they overflow the washing mq-hine
Suds suppresso~s, when ~tili7~-l, are prefe,hbly present in a "suds suypl~,ss;ng amount.
By "suds suyy~ss;ng amount" is meant that the formulator of the con~pos;lion canselect an amount ofthis suds controlling agent that will sl-ffiriently control the suds to
result in a low-sudsing laundry dele-ge.l~ for use in automatic laundry washing
".~ s,
The compositions herein will generally compl ise from 0% to about 5~/O of suds
s.lpp~ssor. When utilized as suds suppressol ~, monocarboxylic fatty acids, and salts
therein, will be present typically in amo~lnt~ up to about 5%, by weight, of thed~tergenl coll,po~ilion. ~I~,f; .ably, from about 0.5% to about 3% offatty
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monocarboxylate suds suppressor is utilized. Silicone suds supp~esso,~ are typically
utilized in amounts up to about 2.0%, by weight, of the detergent composition,
although higher amounts may be used. This upper limit is practical in nature, due
primarily to concern with keeping costs ~ ed and effectiveness of lower amounts
5 for effectively controlling sudcin_ Preferably from about 0.01% to about 1% ofsilicone suds supp,~Jsor is used, more preferably from about 0.25% to about 0.5%.
As used herein, these weight percentage values include any silica that may be utilized
in co."bil-alion with polyorganosiloxane, as well as any adjunct materials that may be
l~tili7ed Monostearyl phosphate suds su~pl~;.sol~ are generally utilized in amounts
10 ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon
suds suppresso-~ are typically utilized in amounts ranging from about 0.01% to about
5.0%, although higher levels can be used. The alcohol suds suppressors are typically
used at 0.2%-3% by weight of the finished compositions.
Fabric Softeners
Various through-the-wash fabric softeners, especi~lly the impalpable smectite
clays of U.S. Patent 4,062,647, Storm and Nirschl, issued Dece."ber 13, 1977, as well
as other soflençr clays known in the art, can optionally be used typically at levels of
from about 0.5% to about 10% by weight in the present compositions to provide
fabric softener benefits concurrently with fabric cle~ninp. Clay softeners can be used
20 in co",bination with amine and cationic so~eners as disclosed, for example, in U.S.
Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al,
issued Septçmher 22, 1981.
Dye Transfer Inhib;~ g Agents
The co",pos;lions of the present invention may also include one or more materials
25 effective for inhibiting the ~,~;.r~. of dyes from one fabric to another during the
c~ process. Generally, such dye ll~lls~r inhibilh~g agents include polyvinyl
p~ n~ polyrners, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone
and N-vinylimid~olç, ~ n~,~ne~e phthalocyanine, peroxidases, and mixtures thereof.
If used, these agents typically comprise from about 0.01% to about 10% by weight of
30 the co.~rosil;on~ preferably from about 0.01% to about 5%, and more preferably from
about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers p~el~"ed for use herein
contain units having the following structural formula R-AX-P; wherein P is a
pol~",~ able unit to which an N-O group can be att, ~hed or the N-O group can form
35 part of the pol~",.c. i~ble unit or the N-O group can be attached to both units; A is one
of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is
aliphatic, ethoxylated a~iphatics~ arom~ticc heterocyclic or alicyclic groups or any
CA 022s2883 1998-10-29
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42
con.~inaLion thereof to which the nitrogen of the N-O group can be att~cl ed or the N-
O group is part of these groups. Prer~,. I ed polyamine N-oxides are those wherein R is
a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-O group can be represented by the following general structures:
O O
wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or
co.lll,il,ations thereof; x, y and z are 0 or l; and the nitrogen of the N-O group can be
~tt~ched or form part of any of the afol ~ e,,lioned groups. The amine oxide unit of
10 the polyamine N-oxides has a pKa < l O, prefel ~bly 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 pl opc. lies. Exa~plcs of suitable
polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides, polyacrylates and mixtures thereof. These polymers include random or15 block copolymers where one monomer type is an amine N-oxide and the other
mollG"ler type is an N-oxide. The amine N-oxide polymers typically have a ratio of
amine to the amine N-oxide of l O: l to l: l ,000,000. However, the number of amine
oxide groups present in the polyamine oxide polymer can be varied by appl op, iate
copolyll.~ ation or by an app,ul.,iate degree of N-oxidation. The polyamine oxides
20 can be obtained in almost any degree of polylne. ization. Typically, the average
ms~le ;~ r weight is within the range of 500 to l ,000,000; more pl C:I; .led l ,000 to
500,000; most pr~fe...,d 5,000 to lO0,000. This plefel,ed class of materials can be
r~f~,.,d to as "PVNOn.
The most p.~fel.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-vinylpylTolidone and N-vinylimidazole polymers (rerel~ed to
as a class as "PVPVI") are also ,o~fe.,ed for use herein. Plefel~bly the PVPVI has an
average mt)leclll~r weight range from 5,000 to l,000,000, more preferably from 5,000
to 200,000, and most pref~.~bly from lO,000 to 20,000. (The average molecular
weight range is detc. ".Ined by light scattering as described in Barth, et al., Chemical
Analysis, Vol l l 3 . "Modern Methods of Polymer Characterization", the disclosures of
which are incorporated herein by tef~.el1ce.) The PVPVI copolymers typically have a
molar ratio of N-vinylimid~7ole to N-vinylpyrrolidone from l:l to 0.2:1, more
.
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W O 97/42284 PCTrUS96/08511
preferably from 0.8: l to 0.3: l, most preferably from 0.6: l to 0.4: I . 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 S0,000. 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~ ini~g PVP can also contain polyethylene glycol ("PEG") having an
average molecular weight from about 500 to about lO0,000, preferably from about
1,000 to about lO,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash solutions is from about 2: l to about 50: l, and more preferably from about 3: l
to about lO: l .
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also
provide a dye transfer inhibition action. If used, the compositions herein will
preferably co~ ise from about 0.01% to 1% by weight of such optical brightPners.The hydrophilic optical br~ighteners useful in the present invention are those
having the structural formula:
Rt R2
~ 1
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 pot~csiurn
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation such as sodium, the bri&htener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-
s-l.i~.lc-2-yl)arnino]-2,2'-stilbene~ ulfonic acid and disorii~ salt. This particular
briehten~r species is co,-ullercially marketed under the tradename Tinopal-UNPA-GX
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the plc~led hydrophilic optical
bri~ht~ner 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 brightener is 4,4'-bis[(4-anilino-6-
(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino~2,2'-stilbenedisulfonic acid
disodium salt. This particular brigllten~r species is commercially marketed under the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
CA 022~2883 1998-10-29
PCT/U~'V~
W O 97/42284
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'-stilbenedi~ fonic acid, sodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used in
combination with the selected polyrneric dye l- an~r inhibiting agents hereinbefore
described. The con~bi~lalion of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition
in aqueous wash solutions than does either of these two detergent composition
components when used alone. Without being bound by theory, it is believed that such
brighteners work this way because they have high affinity for fabrics in the wash
solution and therefore deposit relatively quick on these fabrics. The extent to which
brigl~tçners deposit on fabrics in the wash solution can be defined by a parameter called
the ''eYh~nstion coefficient". The exhaustion coefficie.lt is in general as the ratio of a)
the brightençr material deposited on fabric to b) the initial brightener concentration in
the wash liquor. 13righ~çn~rs with relatively high exhaustion coefficients are the most
suitable for inhibiting dye h ~n~Çer in the context of the present invention.
Of course, it will be appl ccialed that other, conventional optical briEhtçnPr
types of compounds can optionally be used in the present compositions to provideconventional fabric "brightn~ss" benefits, rather than a true dye transfer inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
The mor~ifiecl polyamines of the present invention useful as scavenger agents
are suitably pl eparcd by the following methods.
EXAMPLE I
P.epa.~ion of PEI 1800 E7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for temperature measurement and control, pressure measurement, vacuum
and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A
~20 Ib. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight
change of the cylinder could be monitored.
A 750 g portion of polyethylen~imine (PEI) (Nippon Shokubai, Epomin SP-
018 having a listed average molecular weight of 1800 equating to about 0.417 moles
of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The
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wo 97/42284 PCT/I~S ~511
autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg
followed by pressurization with nitrogen to 250 psia, then venting to atmospheric
pressure). The autoclave contents are heated to 130~C while applying vacuum. After
about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling
5 the autoclave to about 105~C. Ethylene oxide is then added to the autoclave
incr.oment~lly over time while closely monitoring the autoclave pressure, temperature,
and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is
applied to limit any temperature increase resulting from any reaction exothermic. The
ten.~e.al-lre is rn~int~ined between 100 and 110~C while the total pressure is allowed
10 to gradually increase during the course of the reaction. After a total of 750 grams of
ethylene oxide has been charged to the autoclave (roughly equivalent to one moleethylene oxide per PEI nitrogen function), the telllpc;lalllre is increased to 110~C and
the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied
to remove any residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50
~C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74
moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). Themethoxide solution is sucked into the autoclave under vacuum and then the autoclave
te.~.pe.~l~lre controller setpoint is increased to 130~C. A device is used to monitor the
power consumed by the agitator. The agitator power is monitored along with the
te.npel~L~Ire and pressure. Agitator power and tem~erature values gradually increase
as m~.th~n~l is removed from the autoclave and the viscosity of the mixture increases
and stabilizes in about I hour indicating that most of the methanol has been removed.
The mixture is further heated and ~git~ted under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105~C while it is being
charged with nitrogen to 250 psia and then vented to ~hient ,o~es ,.lre. The autoclave
is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave
inc~ lly as before while closely monitoring the autoclave pressure, temperature,and ethylene oxide flow rate while ~ t~ining the te.,lpe.~ re between 100 and 110~
C and limiting any tt---~,e. ~t-lre increases due to reaction exothermic. APter the
addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide
per mole of PEI nitrogen function) is achieved over several hours, the temperature is
increased to 11 0~C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and eventually
35 llas~ed into a 22 L three neck round bottomed flask equipped with heating andagitation. The strong alkali catalyst is neutralized by adding 167 g meth~neslllfonic
acid (1.74 moles). The reaction rnixture is then deodorized by passing about 100 cu.
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46
ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the
reaction mixture while agitating and heating the mixture to 130~C.
EXAMPLE IA
Quatemization of PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethylen~imine 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, pre~,ared 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 appa, ~ s at approximately 80~C to afford 220
g of the desired partially quaternized material as a dark brown viscous liquid. The
13C-NMR (I)2O) spectrum obtained on a sample ofthe reaction product indic~tes the
absence of a carbon resonance at ~58ppm corresponding to dimethyl sulfate. The lH-
NMR (D2O) spectrum shows a partial shifting ofthe resonance at about 2.5 ppm formethylenes adja~çnt to unquate~,lized nitrogen has shifted to approximately 3.0 ppm.
This is consistent with the desired quaternization of about 38% of the nitrogens
EXAMPLE II
Formation of amine oxide of PEI 1800 E7
To a 500 mL Erle~ cycr flask equipped with a n-~gnetic stirring bar is added
polyethylPn-: ..;ne 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,
pl~pa,~d 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 te-~.pe.~ re overnight. lH-NMR (D2O) spectrum obtained on a
sample of the reaction mixture in-~ic~tes complete conversion. The resonances
ascribed to methylene protons ~ cent to unoxidized nitrogens have shifted from the
original position at ~2.5 ppm to ~3.5 ppm. To the reaction solution is added
applo~nlately 5 g of 0.5% Pd on ~ min~ pellets, and the solution is allowed to stand
at room te."~,e, ~t~lre for approximately 3 days. The solution is tested and found to be
negative for peroxide by indiç~tor paper. The material as obtained is suitably stored as
a 51.1% active solution in water.
EXAMPLE III
Formation of amine oxide of quaternized PEI 1800 E7
CA 022~2883 1998-10-29
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To a 500 mL Erlenmeyer flask e~uipped with a magnetic stirring bar is added
polyethyle.~e;~ e 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 quaternization to approximately 38% with dimethyl
s sulfate (130 g, ~0.20 mol oxidizeable nitrogen, prepared as in Example II), hydrogen
peroxide (48 g of a 30 wt % solution in water, 0.423 mol), and water (~50 g). The
flask is stoppered, and after an initial exotherm the solution is stirred at room
te~ ,e~alure overnight. IH-NMR (D20) spectrum obtained on a sample taken from
the reaction mixture in-~ic~tes 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 chP l~ie~l shift of appro~.-mately 3.7 ppm. To the reaction solution is
added approximately S g of 0.5% Pd on alnm~ pellets, and the solution is allowed to
stand at room te-.~p.,.~lure for approximately 3 days. The solution is tested and found
to be negative for peroxide by indicator paper. The desired material with ~3 8% of the
nitrogens quaternized and 62% of the nitrogens oxidized to amine oxide is obtained
and is suitably stored as a 44.9% active solution in water.
EXAMPLE IV
)a.alion of PEI 1200 E7
The ethoxylation is conducted in a 2 gallon stirred staimess steel autoclave
equipped for te~,~p~alure measurement and control, pressure measurement, vacuum
and inert gac purging, sa,nplillg, and for introduction of ethylene oxide as a liquid. A
~20 Ib. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight
change of the cylinder could be monitored.
A 750 g portion of polyethyl~.ne~ e (PEI) ( having a listed average molecular
weight of 1200 equ~ting to about 0.625 moles of polymer and 17.4 moles of nitrogen
filn~ionc) is added to the autoclave. The autoclave is then sealed and purged of air
(by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 2S0
psia, then venting to atmospheric pressure). The autoclave contents are heated to 130
~C w'nile applying vacuum. After about one hour, the autoclave is charged with
nitrogen to about 250 psia while cooling the autoclave to about 105 ~C. Ethyleneoxide is then added to the autoclave incre.,..o.l~lly over time while closely monitoring
the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide
35 pump is turned offand cooling is applied to limit any te.,lp~ t,lre increase resulting
from any reaction exotherm. The telllpelalure is ~ ;nl~;ned between 100 and 110 ~C
while the total pressure is allowed to gradually increase during the course of the
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48
reaction. A~er a total of 750 grams of ethylene oxide has been charged to the
autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function)
the temperature is increased to 110 ~C and the autoclave is allowed to stir for an
additional hour. At this point, vacuum is applied to remove any residual unreacted
ethylene oxide.
Next vacuum is continlloucly applied while the autoclave is cooled to about 50
~C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74
moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). Themethoxide solution is sucked into the autoclave under vacuum and then the autoclave
te"~l)e~ re controller setpoint is increased to 130 ~C. A device is used to monitor
the power consumed by the agitator. The agitator power is monitored along with the
temperature and pressure. Agitator power and tel"pe,~ re values gradually increase
as methanol is removed from the autoclave and the viscosity of the mixture increases
and stabilizes in about I hour indic~ting that most of the methanol has been removed.
The mixture is further heated and ~git~ted under vacuum for an additional 30 mimltes
Vacuum is removed and the autoclave is cooled to 105 ~C while it is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave
is cl,arged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave
incrementally as before while closely monitoring the autoclave pressure temperature
and ethylene oxide flow rate while ~ the te",l,e,~ re between 100 and 110 ~
C and limiting any ten~pe,dture inc,eases due to reaction exotherm. After the addition
of 4500 g of ethylene oxide (recl.lting in a total of 7 moles of ethylene oxide per mole
of PEI nitrogen fi~nction) is acl i~ ~cd over several hours the te...p~lalllre is increased
to 1 10 ~C and the rnixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged cor.laine. ~ and eventually
tlar~ d into a 22 L three neck round bottomed flask equipped with heating and
~t~tiQn~ The strong alkali catalyst is neutralized by adding 167 g rne~ e,-Jlfonic
acid (1 74 moles). The reaction mixture is then deodorized by passing about 100 cu.
~. of inert gas ~argon or nitrogen) through a gas d;spc~ ~;on frit and through the
reaction mixture while ~g;~ and heating the mixture to 130 ~C.
The final reaction product is cooled slightly and collected in glass con~aine.
purged with nitrogen.
In other pr~pa~alions the neutralization and deodorization is accomplished in
the reactor before dischar~ing the product.
Other p,~f~.~ed examples such as PEI 1200 E15 and PEI 1200 E20 can be
prepa.e~ by the above method by ~ lctirl~ the reaction time and the relative amount
of ethylene oxide used in the reaction.
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49
EXAMPLE V
9.7% Quaternization of PEI 1200 E7
To a 500ml erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4g, 0.707 mol nitrogen,
5 prepared as in Example 5) and acetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich,
8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which is then
stoppered and stirred at room te~pe~alLIre overnight. The acetonitrile is evaporated on
the rotary evaporator at ~60~C, followed by a Kugelrohr appa-~lus (Aldrich) at ~80~C to
afford ~220g ofthe desired material as a dark brown viscous liquid. A 13C-N~ (D20)
10 spectrum shows the absence of a peak at ~58ppm corresponding to dimethyl sulfate. A
lH-NMR (D2O) spectrum shows the partial shifting ofthe peak at 2.5ppm (methylenes
attached to unquaternized nitrogens) to ~3.0ppm.
Laundry Compositions
EXAMPLES VI-IX
High density (above 600g/1) granular detergent compositions are p. ~,pa. ~,d
comprising the following ingredients. ,~
wei~ht %
In~,- edie.. ~ VI V~ vm ~
Sodium Cl l -Cl ~ alkylb~l~enesulfonate 13.3 13.7 10.4 11.1
Sodium C14-Cl ~ alcohol sulfate 3.9 4.0 4.5 11.2
Sodium C14-C1s alcohol ethoxylate 2.0 2.0 0.0 0.0
(0.5) sulfate
Sodium C14-Cl ~ alcohol ethoxylate (6.5) 0.5 0.5 0.5 1.0
Tallow fatty acid 0.0 0.0 0.0 1. I
Sodium tripolyphosphate 0.0 41.0 0.0 0.0
Zeolite A, hydrate (0.1-10 micron size) 26.3 0.0 21.3 28.0
Sodium carbonate 23.9 12.4 25.2 16.1
Sodium Polyacrylate (45%) 3.4 0.0 2.7 3.4
Sodium silicate (1:6 ratio 2.4 6.4 2.1 2.6
NaO/SiO~)(46%)
Sodium sulfate 10.5 10.9 8.2 15.0
Poly(ethyleneglycol), MW~4000 (50%) 1.7 0.4 1.0 1.1
Citric acid 0.0 0.0 3.0 0.0
SUE~STITUTE SHEET (RULE 26)
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WO 97/42284 PCT/US96/08Sll
Nonyl ester of sodium p-hydroxybenzene- 0.0 0.0 5.9 0.0
sulfonate
Lipasel (100LU/mg) 0.3 0 5 0 3 0 5
Scavenger Agent2 (from Example I) 1.5 1.5 2.0 1.0
Soil Release Polymer3 1.5 0.0 0.0 0.0
Moisture and minors4 Balance Balance Balance Balance
1. LIPOLASE~) enzyme from Novo Industri A/S, Denmark.
2. Polyamine scavenger agent according to Example I.
3. Soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., issued
November 6, 1990.
4. Balance to 100% can, for example, include minors like optical br ghtener, perfume,
suds suppresser, soil dispersant, protease, cellulase, chelating agents, dye transfer
inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc.
In testing the grease stain and body soil removal pe,~""ance of the detergent
composition comprising lipase enzymes and scavenger agents, the following test method is
used:
EXAMPLE X
A laundry bar suitable for hand-washing soiled fabrics is prepared by standard
extrusion processes and comprises the following:
Component Weiyht %
C12 linear alkyl benzene sulfonate 30
Phosphate (as sodium tripolyphosphate) 7
Sodium carbonate 25
Sodium pyrophosphate 7
Coconut monoeth~no!~mide 2
Zeolite A (0.1-10 micron) 5
Carboxymethylcellulose 0.5
Polyacrylate (m.w. 1400) 0.2
Polyamine scavenger agent (Example I) 1.0
Lipasel (100 LU/mg) 0.1
Brightener, perfume ~ 0.2
CaS04
MgSO4
Moisture 4
Other minors, including filler2Balance to 100%
SUBSTITUTE SHEET (RULE 26)
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W O 97/42284 PCTnUS96108511
1. LIPOLASE(~ enzyme from Novo Industri A/S, Denmark.
2. Can be selected from convenient materials such as CaCO3, talc, clay, silic~tes, and
the like.
U.S. Patent 3,178,370, Ok~nfilss, issued April 13, 1965, describes laundry
detergent bars and processes for making them. Philippine Patent 13,778, Anderson,
issued September 23, 1980, describes synthetic detergent laundry bars. Methods for
making laundry detergent bars by various extrusion methods are well known in the art.
EXAMPLES XI & XII
Laundry bars suitable for hand-washing soiled fabrics are prepared by standard
extrusion processes and comprise the following:
weig}t %
In~redients XI XII
LAS 12 6
Soap 44 29
Sodium tripolyphosphate 5 5
Sodium Carbonate 4 6
Optical bri~htener 0 03 0
Talc 0 35.5
Perfume 0.45 0
Sodiumsulfate 0.29 0
Bentonite clay 12.81 0
Sodiumchloride 2 2
Soil release polymerl 0.5 0.5
Polyamine scavenger agent (Example I) 0.5 1.0
Lipasc2 (100 LU/mg) 0 05 0.1
Moisture and Minors3 balance balance
1. Soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., issued
November 6, 1990.
15 2. LIPOLASE~ enzyme ~om Novo Industri A/S, Den.n~
3. Can be selected from convenient materials such as Calci~m carbonate, talc, clay,
cilic~e~, and the like.
EXAMPLES XIII-XIV
The following describe liquid detergent compositions according to the present
20 invention:
wei~ht %
Ingredients ¦ xm 1 XIV
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W O 97/42284 PCTrUS96/08511
PolyhydroxyCoco-FattyAcid Amide 3.65 3.50
Cl~-Cl~ Alcohol Ethoxylate Eg 3.65 0.80
Sodium Cl?-Cl ~ Alcohol Sulfate 6.03 2.50
SodiumC12-Cls AlcoholEthoxylateE2 59.29 15.10
Sulfate
Cl~) Amidopropyl Amine 0 1.30
Citric Acid 2.44 3.0
Fatty Acid (Cl?-C14) 4.23 2.00
Ethanol 3.00 2.81
Monoethanolamine 1.50 0.75
Plopanediol 8.00 7.50
Boric Acid 3.50 3.50
Tetraethyl~ne~ q~ e 0 1.18
Sodium Toluene Sulfonate 2.50 2.25
NaOH 2.08 2.43
Minors1 1.60 1.30
Soil Release Polymer2 0.33 0.22
Lipase3 (100 LU/mg) 0.3 0 5
Polyamine scavenger agent4 0.50 0.50
Water balance balance
1. Minors - inchldes optical bri~ht~n~r.
2. Soil Release Polymer ac c ~ ding to U.S. Patent 4 968 451 Scheibel et al.
3. LIPOLASE~ enzyme &om Novo Industri A/S Denmark.
4. Polyamine scavenger agent PEI 1200 E20 p~epal ed according to Example IV.
Dishwashing Compositions
Another aspect of the present invention relates to dishwashing COl. yo;.;lions in
particular ~utomqtic and manual dishwashing co-..pGs;lions especially manual liquid
dishwashing ComroSitiQns.
Liquid dishwashing compos;lions acco,d;ng to the present invention ple~el~bly
col.l~,l;se from at least about 0.1% more preferably from about 0.5% to about 30%
most pl~fc;ldbly &om about 1% to about 15% of the dispc.~il,g agent and &om about
1% to about 99.9% of a detersive surfactant.
Liquid dishwashing compositions n. c~rd;llg to the present invention may
15 co.llp.;se any of the ingl.dienls listed herein above. In addition the dishwashing
coml)os;lions may comprise other ingredients such as bactericides n~ qnte suds
enhqncers opacifiers and calcium and mq.~n~ei~m ions.
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WO 97/42284 PCTNS96/08511
53
EXAMPLE XV
The following liquid compositions of the present invention are prepared by
mixing the listed ingredients in the given amounts.
Composition (by weight %)
Ingredients A B C D E F
Water 28.0 34.0 30.0 41.0 41.0 36.0
Ethanol 13.0 8.0 8.0 8.0 8.0 8.0
Linear dodecylbenzene 9.0 9.0 9.0 9.0 9.0 9.0
sulfonic acid
Sodium cocoyl sulfate 1.0 - 1.0 - - -
Condenc~tion product of 1 7.0 - 7 0
mole of C 1 3-C 15 oxoalcohol
and 7 moles of ethylene oxide
ConA~nc~tion product of 1 - 7.0 7.0 7 0 - 7 0
mole of C13-CIs oxoalcohol and
5 moles of ethylene oxide
C12-C14 (2hydroxyethyl)dimethyl - 0.5 0.5 - 0.5 0.5
ammonium chloride
Dodecenyl succinic acid 12.5 - - 10.0
Dodecenyl-tetradecenyl - - - - 10.0
s~lccinic acid
TMS/TDSl - 12.5 - - - -
Sodium tripolyp~losph~te - - 15.0
Zeolite - - - - - 15.0
Citnc Acid 1.0 3.0 2.8 2.8 3.0 2.8
Oleic Acid 3.0
Diethylene l.;a",.ne penta- 0.7 0.7
methylene phosphonic acid
r"c,thylene ~ tetra - - 0.6 - - 0.7
(methylene phosphonic acid)
Scavenger agent (Ex. I) 0.5 1.5 2.0 0.5 1.0 1.0
Lipase2 100 LU/mg 0.3 0.3 0.5 0 5 0 3 0.3
Protease 8KNPU/g 0.5 - - - - -
- Protease 16 KNPU/g - 0.3 0.3 0.3 0.3 0.3
Amylase 0.2 - - - - 0.2
Sodium follllàle 1.0 - 1.5 1.0
.Soriium acetate - 2.5 2.5
CA 02252883 1998-10-29
W O 97/42284 PCT/U~,''DY~ll
54
Magnesium acetate tetrahydrate 1.7 - 1.7 0.1
~gn~Sill~n chloride hexahydrate - 1.7 0.1 0.7
Sodium hydroxide 5.0 5.0 5 0 5.0 5.0 5 0
Perfume and rninors Balance to 100%
1. (80:20) mixture of tartrate monosucrin~te/tartrate disuccinate
2. LIPOLASE~ enzyme from Novo Industri A/S, Denmark.
EXAMPLE XVI
An automatic dishwashing composition is as follows.
Ingredient % (Wt.)
Tri~odi.-m Citrate 15
Sodium Carbonate 20
Silicatel g
Nonionic Surfactant2 3
Sodium Polyacrylate (m.w. 4000)3 5
Lipase Enyme4 (100 LU/mg) 0.5
Termamyl Enzyme (60T) 1.1
Savinase Enzyme (12T) 3.0
Scavenger Agent (Example I) 1.0
Minors R~l~nce to 100%
1. BRITESIL, PQ Co~olalion
2. Polyethyleneoxide/polypropyleneoxide low sudser
3. ACCUSOL, Rohrn and Haas
25 4. LIPOLASE~ enzyrne from Novo Industri A/S, De~ z.k.
In the above composition, the surfactant may be replaced by an equivalent
amount of any low-fo~ p. nonionic surfactant. Example include low-foaming or
non-fo~ming ethoxylated straight-chain alcohols such as Plurafac~ RA series, supplied
by Eurane Co., ~.ut~n~QI~) LF series, supplied by BASF Co., Triton~ DF series,
30 supplied by Rohm & Haas Co., and S~ )cronic~ LF series, supplied by ICI Co.
Aulo...alic dishwashing compositions may be in granular, tablet, bar, or rinse
aid forrn. Methods of making granules, tablets, bars, or rinse aids are known in the
art. See, for i~ c~, U.S. Pat. Serial Nos. 081106,022, 08/147,222, 081147,224,08/147,219, 081052,860, 071867,941.
