W O 95127773 PCTIU595/03400
BLEACH COMPOSITIONS COMPRISING BLEACH
ACTIVATORS AND BLEACH CATALYSTS
a
TECHNICAL FIFT.n
The present invention relates to cleaning and bleaching compositions which
employ manganese complexes to boost performance. Bleaching, fabric laundering,
automatic dishwashing and sanitizing compositions with improved oxygen bleach
activity are provided.
BACKGROUND OF IN~~TdTT~'"T
It is common practice for formulators of cleaning compositions to include
bleaching agents such as sodium perborate or sodium percarbonate in such
compositions for their bleach effect. Such bleaches are widely recognized for
their
ability to remove various stains and soils from fabrics. In like manner,
formulators of
automatic dishwashing compositions have found that various bleaching agents
can
assist in the removal of tea stains, proteinaceous soils, and the like, from
dishware.
Various fabric bleach and/or pre-soaking compositions also comprise
percarbonate or
perborate bleaches. Sanitizers for toilets, sewers and the like may also
comprise
various bleaches.
Unfortunately, many bleaching agents do not function optimally under all
usage conditions. As a general proposition, perborate and percarbonate
bleaches are
more effective in hot water than in cold. Yet, many consumers now conduct
fabric
laundering and other cleaning operations under moderate-to-cold water
temperatures. To improve the performance of perborate and percarbonate
bleaches,
manufacturers have fumed to the so-called "bleach activators". Such activators
typically comprise organic molecules which interact with perborate or
percarbonate
to release "per-acid" bleaching species. The combination of bleach-plus-
activator
' functions well over a wide range of water temperatures and usage conditions.
It is also known that various transition metal cations, such as manganese,
' have the potential to function as bleach activators or catalysts, presumably
by virtue
of their catalytic interaction with peroxide or per-acid bleaching species.
Unfortunately, many transition metals react so readily with per-compounds that
they
too rapidly destroy the bleaching species under conventional cleaning
conditions.
217176
w0 95!27773 PCT1US95I03400
2
Attempts to catalyze and improve-bleaching with manganese cations have been
especially troublesome, since, if improperly done, the deposition of unsightly
brown
Mn02 stains on the surface being bleached can occur.
Various manganese bleach catalysts have been suggested. U.S. Patent
4,430,243, Bragg, teaches bleach catalysis using various chelants and a
mixture of
manganese cations and non-catalytic metal cations. Manganese gluconate
catalysis is
described in U.S. 4,728,455. Such prior art bleaches have not found commercial
acceptance. More recently, a series of manganese bleach catalysts involving
quite
complex ligands have been reported (citations below).
It has now been discovered that compositions comprising N-acyl lactam
activators or amido-derived activators in combination with bleach catalysts,
especially metal bleach catalysts, can be used to provide effective, improved
bleaching.
Accordingly, it is an object of the present invention to provide improved
cleaning and bleaching compositions using bleach activators and bleach
catalysts. It
is another object herein to provide a means for removing soils and stains from
fabrics
and dishware using the catalyzed bleaching systems of this invention. These
and
other objects are secured herein, as will be seen from the following
disclosures.
BACKGROUND ART
The use of amido-derived bleach activators in laundry detergents is described
in U.S. Patent LT.S. Patent 4,634,551. 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. The use of manganese with various complex ligands to
enhance bleaching is reported in the following United States Patents:
4,430,243;
4,728,455; 5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; 5,227,084; 5,114,606; 5,114,611. See also: EP
549,271 Al; EP 544,490 Al; EP 549,272 Al; and EP 544,440 A2.
SUM14IARY OF THE INVENTION
The present invention encompasses bleach compositions, comprising a
bleaching agent, especially a bleach which is a member selected from the group
consisting of H202, perborate, percarbonate, persulfate and per-acid bleaches,
one
or more selected bleach activators, and a catalytically-effective amount of
one or
more bleach catalysts, especially metal bleach catalysts. Preferred
compositions
comprise a percarbonate or perborate bleach, or mixtures thereof, and a bleach
activator selected from aryl lactam-type activators, amido-derived activators,
benzoaxin-type activators, and mixtures thereof. Additionally, the bleach
compositions of this invention can further comprise a second bleach activator
or per-
CA 02187176 1999-09-07
3
acid selected from tetraacetylethylenediamine (TAIrD), nonanoyloxybenzene
sulfonate (NOHS), and magnesium monoperoxyphthalate.
Preferred bleach activators are selected from the following:
a) an amido-derived bleach activator of the general formula:
O O
O 0
R'~-C-N-RZ-C-L, R~--N-C-RZ-C-L
RS Rs
or mixtures thereof wherein R 1 is an alkyl, aryl, or alkaryl group
containing from about 1 to about 14 carbon atoms, R2 is an alkylene,
arylene or alkarylene group containing from about 1 to about 14
carbon atoms, RS is H or an alkyl, aryl, or alkaryl group containing
from about 1 to about 10 carbon atoms, and L is a leaving group;
b) benzoxazin-type bleach activators of the general formula:
O .
~ C'0
. R4
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3,
R4, and RS may be the same or different substituents selected from H,
halogen, alkyl, alker~yl, aryl, hydroxyl, alkoxyl, amino, alkylamino,
COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions;
c) N-aryl lactam bleach activators of the formula:
0
O C-C iiZ-C HZ
8
R -C-NBC
~h ~ 1~
wherein n is from 0 to about 8, preferably from 0 to about 2, and R6 is
H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12
carbons, or a substituted phenyl group containing from 6 to 18 carbon
atoms (See EP 699,189 and U.S. Patent No. 5,405,413); and
d) mixtures of a), b) and c).
Preferably, the molar ratio of hydrogen peroxide yielded by the peroxygen
bleaching compound to bleach activator is greater than about 1Ø Most
preferably,
the molar ratio of hydrogen peroxide to bleach activator is at least about
1.5.
wo 9s~z7773 218 717 6 p~/I759s103400
4
Preferred bleach activators of type a) are those wherein RI is an alkyl group
containing from about 6 to about 12 carbon atoms, R2 contains from about 1 to
about 8 carbon atoms, and RS is H or methyl. Particuiarly preferred bleach
activators are those of the above general formulas wherein Rl is an alkyl
group
containing from about 7 to about 10 carbon atoms and R2 contains from about 4
to
about 5 carbon atoms. '
Preferred bleach activators of type b) are those wherein R2, R3, R4, and RS
are H and RI is a phenyl group.
The preferred aryl moieties of said N-aryl Iactam bleach activators of type c)
have the formula R6-CO- wherein R6 is H, an alkyl, aryl, alkoxyaryl, or
alkaryl
group containing from about 1 to about 12 carbons, or a substituted phenyl
group
containing from about 6 to about I8 carbons. In highly preferred embodiments,
R6
is a member selected from the group consisting of unsubstituted and
substituted
phenyl, heptyl, octyl, nonyl, 2,4,4-trimtthylpentyl, decenyl and mixtures
thereof.
I~ghly preferred activators include benzoyl caprolactam, nonanoyl capro-
lactam, benzoyl valerolactam, nonanoyl valerolactan~, 3,5,5-trimethylhexanoyl
caprolactam, 3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam,
octanoyl
valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl
caprolactam, undecenoyl valerolactam, (6-octanamidocaproyl)oxybenzene-
sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)-
oxybenzenesulfonate, and mixtures thereof. Examples of highly preferred
substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl
valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam,
propylbenzoyl
caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactan~,
isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl
valerolactam, tart-butylbenzoyl caprolactam, tart-butylbenzoyl valerolactam,
pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl
caprolactam,
hexylbenzoyl valerolactam, ethoxybenzoyl caprolacram, ethoxybenzoyl
valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl valerolactam,
isopropoxybenzoyl caprolactam, isopropoxybenzoyl valerolactam, butoxybenzoyl
caprolactam, butoxybenzoyl valerolactam, tart-butoxybenzoyl caprolactam, tert-
butoxybenzoyl valerolactam, pentoxybenzoyl caprolactam, pentoxybenzoyl
valerolactam, hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam, 2,4,ti-
trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam, pentafluoro-
.
benzoyl caprolactant, pentaffuorobenzoyl valerolactam, dichlorobenzoyl capro-
lactam, dimethoxybenzoyl caprolactam, 4-chlorobenzoyl caprolactam, 2,4-
dichlororbenzoyl caprolactam, terephthaloyl dicaprolactam, pentafluorobenzoyl
,WO 95127773 2 T 8 717 b PCTIUS95103400
caprolactam, pentaffuorobenzoyl valerolactam, dichlorobenzoyl valerolactam,
dimethoxybenzoy( valerolactam, 4-chlorobenzoyl valerolactam, 2,4-dichloro
benzoyl valerolactam,terephthaloyl divalerolactam, 4-nitrobenzoyl caprofactam,
4
nitrobenzoyl valerolactam, dinitrobenzoyl caprolactam, dinitrobenzoyl valero
5 lactam, and mixtures thereof.
' Particularly preferred are bleach activators selected from the group
consisting of benzoyl caprolactam, benzoyl valerolactam, nonanoyl
caprolactaen,
nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl
valerolactam,
octanoyl caprolactam, octanoyl valeroiactam, decanoyl caprolactam, decanoyl
valerolactam, undecanoyl caprotactam, undecanoyl valerolactam, 3,5,5-trimethyl
hexanoyl caprolactam, 3,5,5-trimethythexanoyl valerolactam, dinitrobenzoyl
caprolactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactam, tere
phthaloyl divalerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonan
amidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate,
and mixtures thereof.
Preferred compositions herein are those wherein the bleach catalyst is a
metal-based catalyst.
The invention also encompasses detergent compositions, especially laundry
detergents, comprising otherwise conventional surfactants and other detersive
'20 ingredients and bleach, and a catalytically effective amount of a bleach
catalyst.
Again, in such compositions the bleach preferably comprises a member selected
from
the group consisting of percarbonate, perborate and mixtures thereof with
bleach
activators, especially bleach activators selected from N-aryl caprolactams, N-
acyl
valerolactams, benzoxazin-type activators, amido-derived activators and
mixtures
thereof.
The invention also encompasses detergent or bleach compositions comprising
a bleach, bleach activator, and a catalytically effective amount of a water-
soluble
manganese salt.
The invention also encompasses a method for improving the bleaching
performance of oxygen or per-acid bleach compositions, comprising adding
thereto a
catalytically effective amount of manganese cations in the presence of
selected
ligands. This provides a method for removing stains from fabrics, comparing
contacting said fabrics with an aqueous medium comprising said compositions.
The bleach catalyst is used in a catalytically effective amount in the
compositions and processes herein. By "catalytically effective amount" is
meant an
amount which is su~cient, under whatever comparative test conditions are
employed, to enhance bleaching and removal of the stain or stains of interest
from the
CA 02187176 1999-09-07
6
target substrate. Thus, in a fabric laundering operation, the target substrate
will
typically be a fabric stained with, for example, various food stains. For
automatic
dishwashing, the target substrate may be, for example, a porcelain cup or
plate with
tea stain or a polyethylene plate stained with tomato soup. The test
conditions will
vary, depending on the type of washing appliance used and the habits of the
user.
Thus, front-loading laundry washing machines of the type employed in Europe
generally use less water and higher detergent concentrations than do top-
loading
U.S.-style machines. Some machines have considerably longer wash cycles than
others. Some users elect to use very hot water, others use warm or even cold
water
in fabric laundering operations. Of course, the catalytic performance of the
bleach
catalyst will be affected by such considerations, and the levels of bleach
catalyst used
in Fully-formulated detergent and bleach compositions can be appropriately
adjusted.
~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
preferably
provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm
to
about 500 ppm, of the catalyst species in the laundry liquor. To illustrate
this point
further, on the order of 3 micromolar manganese catalyst is effective at
40°C, pH 10
under European conditions using perbotate and a bleach activator (e.g.,
benzoyl
caprolactam). An increase in concentration of 3-5 fold may be required under
U.S.
conditions to achieve the same results. Conversely, use of a bleach activator
and the
manganese catalyst with perborate may allow the formulator to achieve
equivalent
bleaching at lower perborate usage levels than products without the manganese
catalyst.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified.
DETAn ED DESCRIPTION OF THE INVENTION
Bleach Catalyc~ _
The bleach catalyst material used herein can comprise the free acid form, the
salts, and the like.
One type of bleach catalyst is a catalyst system comprising a heavy metal
ration of defined bleach catalytic activity, such as copper, iron or manganese
rations,
an auxiliary metal ration having little or no bleach catalytic activity, such
as zinc or
aluminum rations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal rations, particularly ethylenediaminetetraacetic
acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof.
Such catalysts are disclosed in U.S. Pat. 4,430,243.
. WO 95127773 218 717 6 PCTIUS95103400
7
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples
of
these catalysts include Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(PF6)2. Mn~2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)2,
Mn~4(u-O)6(1,4,7-triazacyclononane)4(C1O4)4, Mn~Mn~4(u-O)1(u-OAc)2-
(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)3, and mixtures thereof.
Others are
described in European patent application publication no. 549,272. Other
ligands
suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-
methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-
1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful in machine dishwashing compositions and
concentrated powder detergent compositions may also be selected as appropriate
for
the present invention. For examples of suitable bleach catalysts see U.S. Pat.
4,246,612 and U.S. Pat. 5,227,084.
See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (I~
complexes such as MnN(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a
water-soluble complex of manganese (IT), (III), and/or (I~ with a ligand which
is a
non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol,
xylithol, arabitol,
adonitol, meso-er~~thritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic
ligand.
Said 6gands are of the formula:
R2 R3
Rl-N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected
from O, S.
CRSR6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl
groups, including substituted or unsubstituted groups. Preferred ligands
include
pyridine, pyridazine, pyrimidine, pyrazine, intidazole, pyrazole, and triazole
rings.
Optionally, said rings may be substituted with substituents such as alkyl,
aryl, alkoxy,
halide, and vitro. Particularly preferred is the ligand 2,2'-bispyridylamine.
Preferred
bleach catalysts include Co, Cu, Mn, Fe; bispyridylmethane and -
bispyridylamine
complexes. I~ghly preferred catalysts include Co(2,2'-bispyridylamine)CI2,
Di(isothiocyanato)bispyridylamine-cobalt (I)7, trisdipyridylamine-cobalt(I)7
per-
218716
W0 95127773 PCTIUS95/03400
8
chlorate, Co(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridylamine)
copper(11)
perchlorate, tris(di-2-pyridylamine) iron(1T) perchlorate, and mixtures
thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)SCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including
N4Mn~(u-O)2MnNN4)+and [BipY2Mn~(u-O)2Mn~biPY2)-(CI04)3~
The bleach catalysts of the present invention may also be prepared by
combining a water-soluble ligand with a water-soluble manganese salt in
aqueous
media and concentrating the resulting mixture by evaporation. Any convenient
water-soluble salt of manganese can be used herein. Manganese (II), (III), (I~
and/or (~ is readily available on a commercial scale. In some instances,
sulBcient
manganese may be present in the wash liquor, but, in general, it is preferred
to add
Mn cations in the compositions to ensure its presence in catalytically-
effective
amounts. Thus, the sodium salt of the ligand and a member selected from the
group
consisting of MnS04, Mn(C104)2 or MnCl2 (least preferred) are dissolved in
water
I S at molar ratios of ligand:Mn salt in the range of about I :4 to 4:1 at
neutral or slightly
alkaline pH. The water may first be de-oxygenated by boiling and cooled by
sparging
with nitrogen. The resulting solution is evaporated (under N2, if desired) and
the
resulting solids are used in the bleaching and detergent compositions herein
without
further purification.
In an alternate mode, the water-soluble manganese source, such as MnS04, is
added to the bleach/c(eaning composition or to the aqueous bleaching/cleaning
bath
which comprises the ligand. Some type of complex is apparently formed in situ,
and
improved bleach performance is secured. In such an in situ process, it is
convenient
to use a considerable molar excess of the (igand over the manganese, and mole
ratios
of ligand:Mn typically are 3:1 to 15:1. The additional figand also serves to
scavenge
vagrant metal ions such as iron and copper, thereby protecting the bleach from
decomposition. One possible such system is described in European patent
application, publication no. 549,271.
While the structures of the bleach-catalyzing manganese~complexes of the
present invention have not been elucidated, it may be speculated that they
comprise
chelates or other hydrated coordination complexes which result from the
interaction
of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
Likewise, the oxidation state of the manganese ration during the catalytic
process is
not known with certainty, and may be the (+II), (+III), (+1~ or (+~ valence
state.
Due to the figands' possible six points of attachment to the manganese ration,
it may
be reasonably speculated that multi-nuclear species and/or "cage" structures
may
exist in the aqueous bleaching media. Whatever the form of the active
Mn~ligand
CA 02187176 1999-09-07
9
species which actually exists, it functions in an apparently catalytic manner
to provide
improved bleaching performances on stubborn stains such as tea, ketchup,
coffee,
blood, and the like.
Other bleach catalysts are described, for example, in European patent
application, publication no. 408,131 (cobalt complex catalysts), European
patent
applications, publication nos. 384,503, and 306,089 (metallo-porphyrin
catalysts),
U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and
European patent application, publication no. 224,952, (absorbed manganese on
aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with
manganese
and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019
(cobalt
chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
4,430,243 (chelants with manganese rations and non-catalytic metal rations),
and
U.S. 4,728,455 (manganese gluconate catalysts). .
Bleaching Compounds and Bleachin~g~,gents - It is to be appreciated that the
bleach catalyst does not function as a bleach by itself. Rather, it is used as
a catalyst
to enhance the performance of conventional bleaches and, in particular, oxygen
bleaches such as perborate, percarbonate, persulfate, and the like, especially
in the
presence of bleach activators. Accordingly, the compositions herein also
contain
bleaching agents or bleaching mixtures containing a bleaching agent and one or
more
bleach activators, in an amount su~cient to provide bleaching of the stain or
stains of
interest. Bleaching agents will typically be at levels of from about 1% to
about 80~/0,
more typically from about 5% to about 20%, of the detergent composition,
especially
for fabric laundering. Bleach and pre-soak compositions may comprise from 5%
to
99% of the bleaching agent. If present, the amount of bleach activators will
typically
be from about 0.1% to about 60%, more typically from about 0.5% to about 40%
of
the bleaching mixture comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning, hard surface cleaning, or other
cleaning
3 0 purposes that are now known or become known. These include oxygen bleaches
as
well as other bleaching agents. Perborate bleaches, e.g., sodium perborate
(e.g.,
mono- or tetra-hydrate) can be used herein.
Peroxygen bleaching agents are preferably used in the compositions. Suitable
peroxygen bleaching compounds include sodium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
pemxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONET"',
manufactured commercially by DuPont) can also be used.
WO 95/27773 218 717 b p~nJ595/03400 ,
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers,
not more than about 10% by weight of said particles being smaller than about
200
micrometers and not more than about 10% by weight of said particles being
larger
5 than about 1,250 micrometers. Optionally, the percarbonate can be coated
with
silicate, borate or water-soluble surfactants. Percarbonate is available from
various
commercial sources such as FMC, Solvay and Tokai Denka.
The compositions of the present invention also comprise mixtures of
bleaching activators.
10 Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution ~.e., during the washing process) of the peroxy acid
corresponding
to the bleach activator.
A_rr,-;do Derived Bleach Act~~.pt~~~ - Tie bleach activators of type a)
employed in the present invention are amide substituted compounds of the
general
formulas:
R'~-~-N-Rz-O-L, R'~-N-O-R2-C-L
R5 Rs
or mixtures thereof, wherein R1, R2 and RS are as defined above and L can be
essentially any suitable leaving group. A leaving group is any group that is
displaced from the bleaching activator as a consequence of the nucleophilic
attack
on the bleach activator by the perhydroxide anion. This, the perhydrolysis
reaction,
results in the formation of the peroxycarboxylic acid. Generally, for a group
to be
a suitable leaving group it must exert an electron attracting effect. It
should also
form a stable entity so that the rate of the back reaction is negligible. This
facilitates the nucleophilic attack by the perhydroxide anion.
The L group must be sufficiently reactive for the reaction to occur within the
optimum time frame (e.g., a wash cycle). However, if L is too reactive, this
activator will be difficult to stabilize for use in a bleaching composition.
These
characteristics are generally paralleled by the pKa of the conjugate acid of
the
leaving group, although exceptions to this convention are known. Ordinarily,
leaving groups that exhibit such behavior are those in which their conjugate
acid
has a pKa in the range of from about 4 to about 13, preferably from about 6 to
about 11 and most preferably from about 8 to about 11.
WO 95/27773 PCTIUS95103400
11
Preferred bleach activators ark those of the above general formula wherein
Rl, R2 and RS are as defined for the peroxyacid and L is selected from the
group
consisting of
/~( Y /~ R3 RsY
-O-( ( ) ) , -O~Y , and
O
-N-C-Rt -N N -R ~-YH-R4
Y
R3 Y
-O-CH=C-CH=CH2 -O-CH=C-CH=CHz
,
0
-O-C-Rt
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof; wherein Rl is an alkyl, aryl, or alkaryl group
containing from
about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from I to
about
8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
The preferred sotubilizing groups are -S03-M+, -CO -M+, -S04 Iii+,
-N+(R3)4X~ and O<-N(R3)3 and most preferably -SO -M~ and -CO -Ivt+
3 2
wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms,
M is
a cation which provides solubility to the bleach activator and X is an anion
which
provides solubility to the bleach activator. Preferably, M is an alkali metal,
ammonium or substituted ammonium cation, with sodium and potassium being
most prefeaed, and X is a halide, hydroxide, methylsulfate or acetate anion.
It
should be noted that bleach activators with a leaving group that does not
contain a
solubilizing groups should be welt dispersed in the bleaching solution in
order to
assist in their dissolution.
2187176
W0 95127773 PCTIUS95103400
12
Preferred bleach activators are'those of the above general formula wherein L
is selected from the group consisting of
/~ Y R3 R3Y
-0~ , -O~Y , and -O
wherein R3~i~s a/s defined above and Y is -S03~vI~ or -C02-Ivf+ wherein M is
as
defined above.
Preferred examples of bleach activators of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfo-
nate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Another important class of bleach activators, including those of type b) and
type c), provide organic peracids as described herein by ring-opening as a
consequence of the nucleophilic attack on the carbonyl carbon of the cyclic
ring by
the perhydroxide anion. For instance, this ring-opening reaction in type c)
activators involves attack at the lactam ring carbonyl by hydrogen peroxide or
its
anion. Since attack of an acyllactam by hydrogen peroxide or its anion occurs
I S preferably at the exocyclic carbonyl, obtaining a significant fraction of
ring-opening
may require a catalyst. Another example of ring-opening bleach activators can
be
found in type b) activators, such as those disclosed in U.S. Patent 4,966,723,
Hodge et al, issued Oct. 30, 1990.
Such activator compounds disclosed by Hodge include the activators of the
benzoxazin-type, having the formula:
0
including the substituted benzoxazins of the type
-Rt
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
CA 02187176 1999-09-07
13
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl
group) and carbonyl functions.
A preferred activator of the benzoxazin-type is:
1
.nC
, When the activators are used, optimum surface bleaching performance is
obtained with washing solutions wherein the pH of such solution is between
about
8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the
perhydrolysis reaction. Such pH can be obtained with substances commonly
known as buffering agents, which are optional components of the bleaching
systems herein.
Still another class of preferred bleach activators includes the aryl lactam
activators, especially acyl caprolactams and aryl valerolactams of the
formulae:
O
II O
O C-C H2-C HZ ~ C-C H2-C H2
R -C s
~CH2-CH2 CH2 R -C-NCH -
2 H2
wherein R6 is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from
1 to
about 12 carbon atoms, or a substituted phenyl group containing from about 6
to
about 18 carbons. See also EP 699,189 and U.S. Patent No. 5,405,413,
which disclose substituted benzoyl lactams. See also U.S. Patent 4,545,784,
issued
to Sanderson, October 8, 1985, which discloses acyl caprolactams, including
benzoyl caprolactam, adsorbed into sodium perborate.
Additional Bleach Activators - Various nonlimiting examples of additional
activators which may optionally comprise the bleach compositions disclosed
herein
include those in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al,
and U.S.
Patent 4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl
ethylene diamine (TAED) activators are typical, and mixtures thereof can also
be
used. See also U.S. 4,634,551 for other typical bleaches and activators useful
herein.
Bleaching Agsr~ - Another optional, yet preferable, category of bleaching
agent that can be used without restriction encompasses percarboxyiic acid
bleaching
agents and salts thereof. Suitable examples of this class of agents include
magnesium
monoperoxyphthalate hexahydrate (INTEROXT"'), the magnesium salt of metachloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecan~ioic
CA 02187176 1999-09-07 -
14
acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman,
issued
November 20, 1984, U.S. Patent No. 4,634,551, Burns et al, issued January 6,
1987, European Patent Application 0,133,354, Banks et al, published February
20,
1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly
preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid
as
described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
The present invention may further optionally encompass bleaching
compositions comprising an effective amount of a substantiaDy insoluble
organic
peroxyacid having the general formula:
0 O
O O
R~-C-N-RZ-C-OOH , R~--N-C-R2-C-OOH
R5 R5
wherein R1, R2, and RS are as defined for the type a) bleach activator above.
The superior bleachiqg/cleaning action of the present compositions is
achieved with safety to natural rubber machine parts and other natural rubber
articles, including fabrics containing natural rubber and natural rubber
elastic
materials. The bleaching mechanism and, in particular, the surface bleaching
mechanism are not completely understood. However, it is generally believed
that
the bleach activator undergoes nucleophilic attack by a perhydroxide anion,
which
is generated from the hydrogen peroxide evolved by the peroxygen bleach, to
form
a peroxycarboxylic acid. This reaction is commonly referred to as
perhydrolysis.
The amido-derived and lactam bleach activators herein can also be used in
combination with rubber-safe, enzyme-safe, hydrophilic activators such as
TAED,
typically at weight ratios of amido-derived or caprolactam activators:TAED in
the
range of 1:5 to 5:1, preferably about 1:1.
Adjunct Ingredients
The compositions herein can optionally include one or more other detergent
adjunct materials or other materials for assisting or enhancing cleaning
performance,
treatment of the substrate to be cleaned, or to modify the aesthetics of the
detergent
composition (e.g., perfumes, colorants, dyes, etc.). Preferably, ~ the adjunct
ingredients should have good stability with the bleaches employed herein.
Preferably,
the detergent compositions herein should be boron-free and phosphate-free.
Additionally, dishcare formulations are preferably chlorine-free. The
following are
illustrative examples of such adjunct materials.
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as weU as organic
builders
~
WO 95127773 PCTIUS95103400
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
5 typically comprise at least about 1% builder. Liquid formulations typically
comprise
from about S% to about 50%, more typically about 5% to about 30%, by weight,
of
detergent builder. Granular formulations typically comprise from about 10% to
about 80%, more typically from about IS% to about 50% by weight, of the
detergent
builder. Lower or higher levels of builder, however, are not meant to be
excluded.
10 Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12, 1987
to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate
marketed
by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders,
the
15 Na SKS-6 silicate wilder does not contain aluminum. NaSKS-6 has the delta-
Na2SiOg morphology form of layered silicate. It can be prepared by methods
such
as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a
highly preferred layered silicate for use herein, but other such layered
silicates, such
as those having the general formula NaMSixO~+l~yH20 wherein M is sodium or
hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0
to 20,
preferably 0 can be used herein. Various other layered silicates from Hoechst
include
NaSKS-5, NaSKS-7 and NaSKS-I 1, as the alpha, beta and gamma forms. As noted
above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for use herein.
Other
silicates may also be useful such as for example magnesium silicate, which can
serve
as a crispening agent in granular formulations, as a stabilizing agent for
oxygen
bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on
November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical
formula:
Mz(zAIO~,J~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from
1.0 to about 0.5, and x is an integer from about 15 to about 264.
2~g717b -
W095127773 y . _ PC1'IUS95103400
16
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosiiicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline
aluminosilicate ion exchange materials useful herein are available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeoiite X. In an
especially
preferred embodiment, the crystalline aluminosilicate ion exchange material
has the
formula:
to Nal2I(~to2)12(Sio2)121w2o
wherein x is from about 20 to about 30, especially about 27. This material is
known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably,
the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As
used herein, "potycarboxylate" refers to compounds having a plurality of
carboxylate
groups, preferably at least 3 carboxylates. Polycarboxylate builder can
generally be
added to the composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium,
potassium,
and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses
the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg,
U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also
include
cyclic compounds, particularly alicycGc compounds, such as those described in
U.S.
Patents 3,923,679; 3,835,163; 4,158,633; 4,120,874 and 4,102,903.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxylate builders of particular importance for detergent
formulations
due to their availability from renewable resources and their biodegradability.
Citrates
can be used in liquids or in granular compositions, especially in combination
with
aeolite and/or layered silicate builders. Oxydisuccinates are also especially
useful in
such compositions and combinations.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially
citrate and/or the succinate builders, to provide additional builder activity.
Such use
~
WO 95!27773 218 717 6 p~~g95103400
17
of fatty acids will generally result in a diminution of sudsing, which should
be taken
into account by the formulator.
' In situations where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-laundering operations, the various
alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate
and sodium orthophosphate can be used.
h la inQ Agen c - Although builders can be used, the detergent compositions
herein preferably do not contain those manganese chelating agents which
abstract the
manganese from the bleach catalyst complex. In particular, phosphonates,
phosphates, and the aminophosphonate chelating agents such as DEQLTEST are
preferably not used in the compositions. However, nitrogen-based manganese
chelating agents, such as ethylenediamine-N,N-disuccinate (EDDS), are useful.
Detersive Surfact ntc - Nonlimiting examples of surfactants useful herein
typically at levels from about 1% to about 55%, by weight, include the
conventional
IS CII-Clg alkyl benzene sulfonates ("LAS") and primary, branched-chain and
random
C10-C20 FYI sulfates ("AS"), the C10-Clg secondary (2,3) alkyl sulfates of the
formula CH3(CH2~(CHOS03-M+)CH3 and CH3(CH~,(CHOS03ZvI+) CH2CH3
where x and (y + I) are integers of at least about 7, preferably at least
about 9, and
M is a water-solubilizing ration, especially sodium, unsaturated sulfates such
as oleyl
sulfate, the Clp-Clg alkyl alkoxy sulfates ("AEXS'; especially EO I-7 ethoxy
sulfates), Clp-Clg alkyl alkoxy carboxylates (especially the EO I-5
ethoxycarboxylates), the CIO-18 BlYc~l ethers, the Clp-Clg alkyl
polyglycosides
and their corresponding sulfated polyglycosides, and C12-Clg alpha-sulfonated
fatty
acid esters., If desired, the conventional nonionic and amphoteric surfactants
such as
the CI2-Cig alkyl ethoxylates ("AE") including the so-called narrow peaked
alkyl
ethaxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed
ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"), C I O-C
18 amine
oxides, and the like, can also be included in the overall compositions. The
Clp-Cgg
N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include
the Ci2-Clg N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-
Ci8 N_
(3-methoxypropyl) glucamide. The N-propyl through N-hexyl CI2-Clg glucamides
can be used for low sudsing. CIO-C2p conventional soaps may also be used. If
high
sudsing is desired, the branched-chain CIO-Cl6 soaps may be used. Mixtures of
anionic and nonionic surfactants are especially useful. Other conventional
useful
surfactants are listed in standard texts.
WO 95/27773 PCTIUS95/03400
18
Suitable nonionic surfactants particularly suitable for dishcare are the low
foaming or non-foaming ethoxylated straight-chain alcohols such as PlurafacTM
RA
series, supplied by Eurane Co., LutensolTM LF series, supplied by BASF Co.,
TritonTM DF series, supplied by Rohm & Haas Co., and SynperonicTM LF series,
supplied by ICI Co.
Clay Soil Removal_~A~ti-refs~aoaition ent~ - The compositions of the
present invention can also optionally contain water-soluble ethoxylated amines
having clay soil removal and antiredeposition properties. Granular detergent
compositions which contain these compounds typically contain from about 0.01%
to
about 10.0% by weight of the water-soluble ethoxylates amines; liquid
detergent
compositions typicaliy contain about 0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay
soil removal-antiredeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published June 27,
1984.
Other clay soil removal/antiredeposidon agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European
Patent Application 112,592, Gosselink, published July 4, 1984; and the amine
oxides
disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other
clay
soil removal and/or anti redeposition agents known in the art can also be
utilized in
the compositions herein. Another type of preferred antiredeposition agent
includes
the carboxy methyl cellulose (CMC) materials. These materials are well known
in
the art.
Polymeric Dis ersina Agents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1% to about 7%, by weight,
in the
compositions herein, especially in the presence of zeolite and/or layered
silicate
builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates
and polyethylene glycols, although others known in the art can also be used.
It is
believed, though it is not intended to be limited by theory, that polymeric
dispersing
agents enhance overall detergent builder performance, when used in combination
with other builders (including lower molecular weight polycarboxylates) by
crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
WO 95127773 218 71 l 6 PCT/US95103400
19
polycarboxylates include acrylic acid, inaleic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic
acid. The presence in the polymeric polycarboxylates herein or monomeric
segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble
salts of polymerized acrylic acid. The average molecular weight of such
polymers in
the acid form preferably ranges from about 2,000 to 10,000, more preferably
from
about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-
soluble
salts of such acrylic acid polymers can include, for example, the alkali
metal,
ammonium and substituted ammonium salts. Soluble polymers of this type are
known materials. Use of polyacrylates of this type in detergent compositions
has
been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7,
1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-
soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight of
such copolymers in the acid form preferably ranges from about 2,000 to
100,000,
more preferably from about 5,000 to 75,000, most preferably from about 7,000
to
65,000. The ratio of acrylate to maleate segments in such copolym<.rs will
generally
range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for
example, the
alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate
copolymers of this type are known materials which are described in European
Patent
Application No. 66915, published December I5, 1982.
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent performance as well as act as a clay
soil
removal-antiredeposition agent. Typical molecular weight ranges for these
purposes
range from about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
- Enzymes can be included in the formulations herein for a wide
variety of fabric laundering purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, for example, and for the
prevention
CA 02187176 1999-09-07
of refugee dye transfer, and for fabric restoration. The enzymes to be
incorporated
include proteases, amylases, lipases, cellulases, and peroxidases, as well as
mixtures
thereof. Other types of enzymes may also be included. They may be of any
suitable
origin, such as vegetable, animal, bacterial, fungal and yeast origin.
However, their
5 choice is governed by several factors such as pH-activity and/or stability
optima,
thermostability, stability versus active detergents, builders and so on. In
this respect
bacterial or fungal enzymes are preferred, such as bacterial amylases and
proteases,
and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about
10 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active
enzyme per
gram of the composition. Stated otherwise, the compositions herein will
typically
comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a
commercial enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels su~cient to provide from 0.005 to 0.1 Anson
units
15 (AIn of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniforms. Another suitable
protease is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range
of 8-12, developed and sold by Novo Industries A/S under the registered trade
mark
20 ESPERASE. The preparation of this enzyme and analogous enzymes is described
in
British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes
suitable for
removing protein-based stains that are commercially available include those
sold
under the trademarks ALCALASE and SAVINASE by Novo Industries A/S
(Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The
Netherlands). Other protesses include Protease A (see European Patent
Application
130,756, published January 9, 1985) and Protease B (see European Patent
Application Serial No. 251,446, published January 7, 1988, and European Patent
Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, a-amylase3 described in British patent
Specification No. 1,296,839 (Novo), RAPIDASE~, International Bio-Synthetics,
Inc. and TERMAMYLTM, Novo Industries.
The ceUulase usable in the present invention include both bacterial or fungal
ceUulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese
Patent
Application 53,20487, laid open to public inspection on February 24, 1978.
This
CA 02187176 1999-09-07
21
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the
trade mark Lipase P "Amano," hereinafter referred to as "Amano-P." Other
commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from
. 5 Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases
from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The LIPOLASET"' enzyme derived from Humicola lanuginosa
and commercially available from Novo (see also EPO 341,947) is a preferred
lipase
for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching," i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in
PCT
International Application WO 89/099813, published October 19, 1989, by O.
Kirk,
assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139,
issued
January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219,
Hughes,
issued March 26, 1985, both. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to
Gedge, et al, and European Patent Application Publication No. 0 199 405,
published October 29, 1986, Venegas. Enzyme stabilization systems are also
described, for example, in U.S. Patent 3,519,570.
Fr~yrree Stab'1'~~r - The enzymes employed herein may be stabilized by the
presence of water-soluble sources of calcium and/or magnesium ions in the
finished
compositions which provide such ions to the enzymes. (Calcium ions are
generally
somewhat more effective than magnesium ions and are preferred herein if only
one
type of ration is being used.) Additional stability can be provided by the
presence of
various other art-disclosed stabilizers, especially borate species: see
Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from about 1
to
W0 95/27773 2 ~ 8 717 6 pCTIUS95103400
22
about 30, preferably from about 2 to about 20, more preferably from about 5 to
about 15, and most preferably from about 8 to about 12, millimoles of calcium
ion
' per liter of finished composition. This can vary somewhat, depending on the
amount
of enzyme present and its response to the calcium or magnesium ions. The level
of
calcium or magnesium ions should be selected so that there is always some
minimum
level available for the enzyme, after allowing for complexation with builders,
fatty
acids, etc., in the composition. Any water-soluble calcium or magnesium salt
can be
used as the source of calcium or magnesium ions, including, but not limited
to,
calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium
hydroxide, calcium formate, and calcium acetate, and the corresponding
magnesium
salts. A small amount of calcium ion, generally from about 0.05 to about 0.4
millimoles per liter, is often also present in the composition due to calcium
in the
enzyme slurry and formula water. In solid detergent compositions the
formulation
may include a sufficient quantity of a water-soluble calcium ion source to
provide
I S such amounts in the laundry liquor. In the alternative, natural water
hardness may
suffice.
It is to be understood that the foregoing Ievels of calcium and/or magnesium
ions are sufficient to provide enzyme stability. More calcium and/or magnesium
ions
can be added to the compositions to provide an additional measure of grease
removal
performance. Accordingly, as a general proposition the compositions herein
will
typically comprise from about 0.05% to about 2% by weight of a water-soluble
source of calcium or magnesium ions, or both. The amount can vary, of course,
with
the amount and type of enzyme employed in the composition.
The, compositions herein may also optionally, but preferably, contain various
additional stabilizers, especially borate-type stabilizers. Typically, such
stabilizers
will be used at levels in the compositions from about 0.25% to about 10%,
preferably
from about 0.5% to about S%, more preferably from about 0.75% to about 3%, by
weight of boric acid or other borate compound capable of forming boric acid in
the
composition (calculated on the basis of boric acid). Boric acid is preferred,
although
other compounds such as boric oxide, borax and other alkali metal borates
(e.g.,
sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-
bromo
phenylboronic acid) can also be used in place of boric acid.
- Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels=typically from about 0.05% to
about
1.2%, by weight, into the detergent compositions herein. Commercial optical
brighteners which may be useful in the present invention can be classified
into
CA 02187176 1999-09-07
23
subgroups, which include, but are not necessarily limited to, derivatives of
stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-
dioxide,
azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
Examples of such brighteners are disclosed in "The Production and Application
of
Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons,
New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brighteners include .the PHORWHITE~'~'' series of
brighteners from Verona. Other brighteners disclosed in this reference
include:
Tinopal~'~'' UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy;
Antic
White CC and 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)-
stilbenes;
4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venamidazol-2-
yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-
stryl-
napth-[1,2-d]oxazoie; and 2-(stilbene-4-yl~2H-naphtho- [1,2-d]triazole. See
also
U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic
brighteners
are preferred herein.
Suds SunDressors - Compounds for reducing or suppressing the formation of
suds can be incorporated into the compositions of the present invention. Suds
suppression can be of particular importance in the so-called "high
concentration
cleaning proctss" and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430
447 (John Whey & Sons, Inc., 1979). One category of suds suppressor of
particular
interest encompasses monocarboxylic fatty acid and soluble salts therein. See
U.S.
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxyGc fatty acids and salts thereof used as suds suppressor typically
have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium,
potassium, and
lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such
as paraff n, fatty acid esters (e:g., fatty acid triglycerides), fatty acid
esters of
monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other
suds
CA 02187176 1999-09-07
24
inhibitors include N-alkylated amino triazines such as tri- to hexa-
alkylmelamines or
di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric
chloride with
two or three moles of a primary or secondary amine containing 1 to 24 carbon
atoms,
propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate
ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and
phosphate
esters. The hydrocarbons such as paraff n and haloparaffin can be utilized in
liquid
form. The liquid hydrocarbons will be liquid at room temperature and
atmospheric
pressure, and will have a pour point in the range of about -40°C and
about 50°C, and
a minimum boiling point not less than about 110°C (atmospheric
pressure). It is also
known to utilize waxy hydrocarbons, preferably having a melting point below
about
100°C. The hydrocarbons constitute a preferred category of suds
suppressor for
detergent compositions. Hydrocarbon suds suppressors are described, for
example,
in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons,
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated
hydrocarbons having from about 12 to about 70 carbon atoms. The term
"paraffin,"
as used in this suds suppressor discussion, is intended to include mixtures of
true
paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane oils,
such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane
oils or
resins, and combinations of polyorganosiloxane with silica particles wherein
the
polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds
suppressors are well known in the art and are, for example, disclosed in U.S.
Patent
4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent
Application
No. 354,016, published February 7, 1990, by Starch, M.S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating therein small amounts of polydimethylsiloxane fluids.
I~xtures of silicone and silanated silica are described, for instance, in
German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling
agents
in granular detergent compositions are disclosed in U.S. Patent 3,933,672,
Bartolotta
et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of
3 5 (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at 25°C;
.WO 95127773 PCT/US95/03400
(u) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01~ units of Si02 units in a ratio of from
(CH3)3 Si01~2 units and to Si02 units of from about 0.6:1 to about
1.2:1; and
5 (ii) from about 1 to about 20 parts per 100 parts by weight of (i) of a
solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or polyethylene-
polypropylene glycol copolymers of mixtures thereof (preferred), or
polypropylene
10 glycol. The primary silicone suds suppressor is branched/crosslinked and
preferably
not linear.
To illustrate this point further, typical liquid laundry detergent
compositions
with controlled suds will optionally comprise from about 0.001 to about 1,
preferably
from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5,
weight
15 % of said silicone suds suppressor, which comprises (I) a nonaqueous
emulsion of a
primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a
resinous
siloxane or a silicone resin-producing silicone compound, (c) a finely divided
filler
material, and (d) a catalyst to promote the reaction of mixture components
(a), (b)
and (c), to form silanolates; (2) at least one nonionic silicone surfactant;
and (3)
20 polyethylene glycol or a copolymer of polyethylene-polypropylene glycol
having,a
solubility in water at room temperature of more than about 2 weight %; and
without
polypropylene glycol. Similar amounts can be used in granular compositions,
gels,
etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued
February
25 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column
1, line
46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a copolymer of polyethylene glycoUpolypropylene glycol, all having an
average
molecular weight of less than about 1,000, preferably between about 100 and
800.
The polyethylene glycol and polyethylenelpolypropylene copolymers herein have
a
solubility in water at room temperature of more than about 2 weight %,
preferably
more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight of less than about 1,000, more preferably between about 100
and
800, most preferably between 200 and 400, and a copolymer of polyethylene
glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight
CA 02187176 1999-09-07
26
ratio of between about 1:1 and 1: i 0, most preferably between 1:3 and 1:6, of
polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressers used herein do not contain
polypropylene glycol, particularly of 4,000 molecular weight. They also
preferably
do not contain block copolymers of ethylene oxide and propylene oxide, like
PLURONIC'~'''' L 1 Ol .
Other suds suppressers useful herein comprise the secondary alcohols (e.g.,
2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as
the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C 16 alkyl alcohols having a C 1-C 16 chain. A preferred
alcohol is 2-
butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123
from Enichem. Mixed suds suppressers typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine. Suds suppressers, when utilized, are preferably present in a "suds
suppressing amount. By "suds suppressing amount" is meant that the formulator
of
the composition can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry detergent for
use in
automatic laundry washing machines,
The compositions herein will generally comprise from 0% to about 5% of
suds suppresser. When utilized as suds suppressers, monocarboxylic fatty
acids, and
salts thereir~ will be present typically in amounts up to about 5%, by weight,
of the
detergent composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppresser is utilized. Silicone suds suppressers are
typically
utilized in amounts up to about 2.0'/0, by weight, of the detergent
composition,
although higher amounts may be used. This upper limit is practical in nature,
due
primarily to concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about 0.01% to
about
1% of silicone suds suppresser is used, more preferably from about 0.25% to
about
0.5%. As used herein, these weight percentage values include any silica that
may be
utilized in combination, with polyorganosiloxane, as well as any adjunct
materials that
may be utilized. Monostearyl phosphate suds suppressers are generally utilized
in
3 5 amounts ranging from about 0.1 % to about 2%, by weight, of the
composition.
Hydrocarbon suds suppressers are typically utilized in amounts ranging from
about
i WO 95/27773 218 71 7 ~ PCTIU595/03400
27
0.01% to about 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued
December 13, 1977, as well as other softener clays known in the art, can
optionally
be used typically at levels of from about 0.5% to about 10% by weight in the
present
compositions to provide fabric softener benefits concurrently with fabric
cleaning.
Clay softeners can be used in combination with amine and cationic softeners as
disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983
and U.S.
Patent 4,291,071, Harris et al, issued September 22, 1981.
eye Transfer It~h_,'biting~g~ _ The compositions of the present
invention may also include one or more materials effective for inhibiting the
transfer
of dyes from one fabric to another during the cleaning process. Generally,
such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-
oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazote, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
typically
comprise from about 0.01% to about 10% by weight of the composition,
preferably
from about 0.01% to about 5%, and more preferably from about 0.05% to about
2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form part of the polymerizable unit or the N-O group can be attached to both
units; A
is one of the following structures: -NC(0~, -C(O)O-, -S-, -O-, -N=; x is 0 or
1; and
R is aliphatic, ethoxylated aliphatics, aromatics, heterocyctic or alicyclic
groups or
any combination thereof to which the nitrogen of the N-O group can be attached
or
the N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine,
piperidine and derivatives thereof.
The N-0 group can be represented by the following general structures:
(Rt)x-~ (Rz)y = ~-(Rt)x
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 ar 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of
the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa
<6.
CA 02187176 1999-09-07
28
Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples
of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof. These polymers
include
random or block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the
number of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides can be obtained in almost any degree of polymerization.
Typically,
the average molecular weight is within the range of 500 to 1,000,000; more
preferred
1,000 to 500,000; most preferred 5,000 to 100,000.
The most preferred polyamine N-oxide useful in ,the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight
of
about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to
as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has
an average molecular weight range from 5,000 to 1,000,000, more preferably
from
5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average
molecular weight range is determined by light scattering as described in
Barth, et al.,
Chemical An~,vsis. Vol 113. "Modern Met.~ods of Polymer Characterization".)
The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most
preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or
branched.
The present invention compositions also may employ a polyvinylpyrroGdone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000
to about 50,000. PVP's are known to persons skilled in the detergent field;
see, for
example, EP-A-262,897 and EP-A 256,696, incorporated herein by reference.
Compositions containing PVP can also contain polyethylene glycol ("PEG")
having
an average molecular weight from about 500 to about 100,000, preferably from
about
1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis
delivered
in wash solutions is from about 2:1 to about 50:1, and more preferably from
about
3 S 3 :1 to about 10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of ctr<ain types of hydrophilic optical brighteners
which
CA 02187176 1999-09-07
29
also provide a dye transfer inhibition action. If used, the compositions
herein will
preferably comprise from about 0.01% to 1% by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the stnrctural formula:
R~ R2
>--N H H N
N N I
I O C-C O N N
N I
H H N
R2 SO SO
Rt
wherein R1 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 ration such as sodium or
potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M
is a canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl~s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
trademark
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N 2-
methylamino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-
(N-2-hydroxyethyl-N-methylamino}-s-triazine-2-y()amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a ration
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2
y()amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal LTNPA-GX, Tinopal
SBM-GX and/or Tinopal AMS-GX) provides signi5cantly 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
WO 95127773 Y 218 717 6 p~'/~JS95/03400 t
believed that such brighteners work-this way because they have high affinity
for
fabrics in the wash solution and therefore deposit relatively quick on these
fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be
defined
by a parameter called the "exhaustion coefficient". The exhaustion coefficient
is in
5 general as the ratio of a) the brightener material deposited on fabric to b)
the initial
brightener concentration in the wash liquor. Brighteners with relatively high
exhaustion coefficients are the most suitable for inhibiting dye transfer in
the context
of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
10 types of compounds can optionally be used in tie present compositions to
provide
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
Other gredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
15 ingredients, carriers, hydrotropes, processing aids, dyes or pigments,
solvents for
liquid formulations, solid fillers for bar compositions, etc. If high sudsing
is desired,
suds boosters such as the Cl0-C16 alkanolamides can be incorporated into the
compositions, typically at 1%-10% levels. The Cl0-C14 monoethanol and
diethanol
amides illustrate a typical class of such suds boosters. Use of such suds
boosters
20 with high sudsing adjunct surfactants such as the amine oxides, betaines
and sultaines
noted above is also advantageous. If desired, soluble magnesium salts such as
MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to
provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions
25 optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
the substrate into the aqueous washing liquor, where it performs its intended
30 detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D10, Degussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirring in silicone oil (various
silicone oil
viscosities in the range of 500-12,500 can be used). The resulting silicone
oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
.WO 95/27773 PCTIUS95103400
31
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergents, including
liquid
laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers. Low molecular weight primary or secondary alcohols exemplified by
methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols
are
preferred for solubilizing surfactant, but polyols such as those containing
finm 2 to
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-
propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
compositions
may contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between
about 6.5 and about 11, preferably between about 7.5 and 10.5. Automatic
dishwashing product formulations preferably have a pH between about 8 and
about
11. Laundry products are typically at pH 9-11. Techniques for controlling pH
at
recommended usage levels include the use of buffers, alkalis, acids, etc., and
are well
known to those skilled in the art.
The following examples illustrate compositions according to the invention,
but are not intended to be limiting thereof.
E3CAAMPLE I
A dry laundry bleach is as follows:
In edient % . t.l
Sodium Percarbonate 20.0
Benzoyl caprolactam activator 10.0
Mn~catafyst* 0.1
Water-soluble filler** Balance
*MnN2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, as described in
U.S. Pat. Nos. 5,246,621 and 5,244,594.
**Sodium carbonate, sodium silicate mixture (1:1).
In the foregoing composition, the sodium percarbonate can be replaced by an
_ equivalent amount of perborate.
In the foregoing composition, the bleach catalyst can be replaced by an
equivalent amount of the following catalysts:
Mn~2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C1O4)2;
Mn~4(u-O)6(1,4,7-triazacyclononane)4(C104)4: Mn~Mn~4(u-O)1(u-OAc)2
(1,4,7-trimethyl-1,4,7-triazacyclononane)2(Cl04)3; MnN(1,4,7-trimethyl-1,4,7-
tri-
2187176
WO 95!27773 PCTIfJS95103400
32
azacyclononane(OCH3)3(PF6); Co(2;2'-bispyridylamine)C12; Di(isothiocyanato)bis-
pyridylamine-cobalt (II); trisdipyridylamine-cobalt(II) perchlorate; Co(2,2-
bispyridyl-
amine)202C104; Bis-(2,2'-bispyridylamine) copper(II) perchlorate; tris(di-2-
pyridyl-
amine) iron(II) perchlorate; Mn gluconate; Mn(CF3S03)2; Co(NH3~SCI; binuclear
Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn~(u-
O)2MnIVNq)+and [Bipy2MnIII(u_O)2~IVbipy2)_(C104)3 and mixtures thereof.
Additionally, in the foregoing composition, the bleach activator can be
replaced by an equivalent amount of the following activators:
benzoyl valerolactam, nonanoyl caprolactam, nonanoyl valerolactam, 4
nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, octanoyl caprolactam,
octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecanoyl
caprolactam, undecanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam,
3,5,5
trimethylhexanoyl valerolactam, dirutrobenzoyl caprolactam, dinitrobenzoyl
valerolactam, terephthaloyl dicaprolactam, terephthaloyl divalerolactam, (6
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-
fonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixturesthereof
The compositions of Example I can be used per se as a bleach, or can be
added to a pre: soak or surfactant-containing detergent composition to impart
a
bleaching benefit thereto.
In the laundry detergent compositions hereinafter, the abbreviated component
identifications have the following meanings:
LA5 - Sodium C12 alkyl benzene sulfonate
TAS - Sodium tallow alkyl sulfate
TAEn - Tallow alcohol ethoxylated with n moles of ethylene oxide per mole
of alcohol.
25EY - A C12_15 Predominantly linear primary alcohol condensed with an
average of Y moles of ethylene oxide.
TAED - Tetraacetyl ethylene diamine
NOBS - Nonanoyloxybenzenesulfonate
Silicate - Amorphous sodium silicate (Si02:Na20 ratio normally follows)
NaSKS-6 - Crystalline layered silicate
Carbonate - Anhydrous sodium carbonate
CMC - Sodium carboxymethyl cellulose
Zeolite A - Hydrated sodium aluminosilicate having a primary particle size in
the range from 1 to 10 micrometers.
Polyacrylate - Homopolymer of acrylic acid of MWt 4000
Citrate - Tri-sodium citrate dihydrate
WO 95!27773 218 717 6 PCTlU595103400
33
Ma/AA - Copolymer of 1:4 maleiclacrylic acid, average molecular weight
about 80,000.
Enzyme - Mixed proteolytic and amylolytic enzyme
sold by Novo Industries
' AS.
Brightener - Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)
' stilbene-2:2'-disulfonate.
Suds Suppressor - 25% paraffin wax Mpt 50C, 17%
hydrophobic silica,
58% parallin oil.
Sulfate - Anhydrous sodium sulfate
In use for fabric cleaning, the compositions are conventional
employed in
manner and at conventional concentrations. Thus, mode,
in a typical the
compositions are placed in an aqueous liquor at
ievels which may range from about
100 ppm to about 10,000 ppm, depending on soil
load and the stained fabrics are
agitated therewith.
~ E7~AMPLE II
The following detergent compositions are prepared
(parts by weight).
A ~ ~ D E_
LAS 7.71 7.71 7.71 7.71 --
AS __ _ _ __ 6.80
N-Glucosamide -- -- - -- 1.50
TAS 2.43 2.43 2.43 2.43 2.43
TAE11 1.10 1.10 1.10 1.10 1.10
25E3 3.26 3.26 3.26 3.26 3.26
Zeolite A 19.50 19.50 19.50 13.00 13.00
Citrate 6.50 6.50 6.50 -- --
MA/AA 4.25 4.25 4.25 4.25 4.25
NaSKS-6 - -- -- 10.01 10.01
Citric Acid - -- -- 2.73 2.73
TAE50 -- -- --- 0.26 0.26
Carbonate 11.14 11.14 6.00 9.84 4.00
Perborate 16.00 16.00 18.00 16.00 16.00
Benzoylcaprolactam 10.00 3.00 10.00 5.00 15.00
TAED -- -- 0.00 5.00 0.00
NOBS -- 3.00 -- -- -- -
MnCatalyst* 0.50 1.00 0.22 0.02 0.22
CMC 0.48 0.48 0.48 0.48 0.48
Suds Suppressor 0.5 0.5 0.5 0.5 0.5
V4'O 95/27773 218 717 (7 PCT/US95/03400
34
Brightener 0.24 - 0.24 0.24 0.24 0.24
Enryme 1.4 1.4 1.4 1.4 1.4
Silicate (2.0 ratio) 4.38 ~ 4.38 4.38 -- --
MgS04 0.43 0.43 0.43 0.43 0.43
Perfume 0.43 0.43 0.43 0.43 0.43
Sulfate 4.10 4.10 4.10 11.67 11.67
Water and miscellaneous to balance.
*MnN2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2~
The above compositions can be modified by the addition of lipase enzymes.
The above compositions can further be modified by replacing the bleach
catalyst with an equivalent amount of the bleach catalysts identified in
Example I.
The above compositions can also be modified by replacing the benzoyl
caprolactam with an equivalent amount of the bleach activators identified in
Example
I.
The above compositions can also be modified by replacing the TAED with an
equivalent amount of NOBS or by leaving the TAED out of the formulation.
The above compositions can also be modified by replacing the perborate with
an equivalent amount of percarbonate.
E3~AMPLE III -
A laundry bar with bleach is prepared by standard extrusion processes and
comprises: C12-13 LAS (20%); sodium tripolyphosphate (20%); sodium silicate
(7%); sodium perborate monohydrate ( 10%); (6-decanamidocaproyl)oxy-
benzenesulfonate (10%); Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(PF6)2, (1.0%); MgS04 or talc filler; and water (5%).
The above compositions can be modified by the addition of lipase enzymes.
The above compositions can further be modified by replacing the bleach
catalyst with an equivalent amount of the bleach catalysts identified in
Example I.
The above compositions can also be modified by replacing the (6
decanamidocaproyl)oxybenzenesulfonate bleach activator with an equivalent
amount
of the bleach activators identified in Example I.
The above compositions can also be modified by replacing the perborate with
an equivalent amount of percarbonate.
E3~AMPLE IV
An automatic dishwashing composition is as follows.
r i n % (Wt.)
Trisodium Citrate 15
Sodium Carbonate 20
CA 02187176 1999-09-07
Silicatel ~ 9
Nonionic Surfactant2 3
Sodium Polyacrylate (m.w. 4000)3 5
Termamyl Enzyme (60T) 1.1
5 Savinase Enzyme ( 12T) 3.0
Sodium perborate monohydrate 10
Benzoyl caprolactam 2
Mn~catalyst4 0.03
Minors Balance
10 'BRITESILTM, PQ Corporation
2Polyethyleneoxide/polypropyleneoxide tow sudser
3ACCUSOL~'~'', Rohm and Haas
41:1 mole ratio ofMn cation and ligand to form MnIV2(u-O)3(1,4,7-trimethyl-
1,4,7-
triazacyclononane)2(PF6)2, in situ
15 In the above composition, the perborate can be replaced by an equivalent
amount of percarbonate.
In the above composition, the bleach catalyst can be replaced by an equivalent
amount of preformed bleach catalyst, as identified in Example I, or with metal
cations
and ligands to form the bleach catalysts identified in Example I.
20 The above compositions can also be modified by replacing the benzoyl
caprolactam with an equivalent amount of the bleach activators identified in
Example
I.
In the above composition, the surfactant may be replaced by an equivalent
amount of any low-foaming, nonionic surfactant. Example include low-foaming or
25 non-foaming ethoxylated straight-chain alcohols such as PlurafacTM RA
series,
supplied by Eurane Co., LutensolTM LF series, supplied by BASF Co., TritonTM
DF series, supplied by Rohm & Haas Co., and SynperonicTh'I LF series, supplied
by
ICI Co.
Automatic dishwashing compositions may be in granular, tablet, bar, or rinse
aid form.
30 Methods of making granules, tablets, bars, or rinse aids are known in the
art. See, for instance,
EP 713,521 published February 23, 1995; EP 726,937; EP 726,934 and WO 95/12654
all
published May 11, 1995; EP 598,817 published March 4, 1993 and U.S. 5,510,047.
All of the foregoing granular compositions may be provided as spray-dried
granules or high density (above 600 g/1) granules or agglomerates. If desired,
the
35 Mn~catalyst may be adsorbed onto and into water-soluble granules to keep
the
catalyst separate from the balance of the compositions, thus providing
additional
stability on storage. Such granules (which should not contain oxidizable
WO 95127773 218 717 6 pC'1'/U595103400
36
components) can comprise, for example, water-soluble silicates, carbonates and
the
like.
Although the foregoing compositions are typical of those useful herein, it is
most preferred that: (1) the compositions not contain STPP builder; (2) that
the
nonionic:anionic surfactant ratio be greater than 1:1, preferably at least
1.5:1; and (3)
that at least 1% perborate or other chlorine scavenger be present in the
compositions
to minimize formation of Mn02 in use.
While the foregoing examples illustrate the use of the present technology in
cleaning/bleaching compositions designed for use in laundering and dishcare,
it will
be appreciated by those skilled in the art that the catalyzed bleaching
systems herein
can be employed under any circumstance where improved oxygen bleaching is
desired. Thus, the technology of this invention may be used, for example, to
bleach
paper pulp, to bleach hair, to cleanse and sanitize prosthetic devices such as
dentures,
in dentifrice compositions to clean teeth and kill oral bacteria, and in any
other
circumstances where bleaching is advantageous to the user.
WHAT IS CLAIMED IS:
