Note: Descriptions are shown in the official language in which they were submitted.
214fi051
CM698M/AA
Bleaching Comuositions
This invention relates to bleaching compositions containing an oxygen
bleach, a transition metal containing bleach catalyst and a corrosion
inhibitor compound preferably selected from benzotriazole and a paraffin
oil.
The satisfactory removal of bleachable soils/stains such as tea, fruit juice
and coloured vegetable soils from soiled/stained substrates is a particular
challenge to the formulator of a detergent composition for use in a
washing method such as a laundry or machine dishwashing method.
Traditionally, the removal of such bleachable soils/stains has been
enabled by the use of bleach components such as oxygen bleaches,
including hydrogen peroxide and organic peroxyacids. The organic
peroxyacids are often obtained by the in situ perhydrolysis reaction
between hydrogen peroxide and an organic peroxyacid bleach precursor.
A problem encountered with the use of peroxyacids in machine
dishwashing methods is the tarnishing/corrosion of any silverware
components of the washload. Oxygen bleaches tend to give rise to the
problem of tarnishing more than chlorine bleaches. The level of
tarnishing observed can range from slight discolouration of the silverware
to the formation of a dense black coating on the surface of the silverware.
The detergent formulator thus faces the dual challenge of formulating a
product which maximises bleachable soil/stain removal but minimises the
occurrence of any unwelcome tarnishing effects of the bleach.
The occurence of any unwelcome tarnishing effects arising from use of
oxygen bleaches in a washing method can be related to the nature of the
oxygen bleach, and also to both the rate of release of the oxygen bleach
and the absolute level of bleach present in the wash solution. A fast rate
of release of the bleach to the wash solution tends to exacerbate tarnishing
problems, as does a high absolute level of the bleach in the wash solution.
2146p5~
2
The Applicants have also found that the occurence of tarnishing is a
particular problem when the composition contains, in addition to the
oxygen bleach, a transition metal containing bleach catalyst, particularly
an Mn(III) or Mn(IV) containing bleach catalyst.
It has been found that enhanced anti-silver tarnishing as well as good
cleaning performance can be achieved through the combined use, as a
corrosion inhibitor compound, of a paraffin oil, which acts as a silver
coating agent, and preferably careful control of oxygen-bleaching power
and control of the rate of release of the oxygen bleach.
The rate of release of oxygen bleach should be rapid enough to provide
satisfactory cleaning, but not so rapid that tarnishing is enabled. It is the
Applicant's belief that a sufficient time interval, prior to release of the
oxygen bleach, is preferable to allow for an effective coating on the
silverware to form. This coating protects the silver surface from the
potential tarnishing effect of the oxygen bleach species.
It has also been found that enhanced anti-silver tarnishing as well as good
cleaning performance can be achieved through the use of other corrosion
inhibitor compounds, particularly benzotriazole in combination with an
oxygen bleach.
The use of paraffin oil as a coating agent component of a silver tarnish
inhibiting system for use in a machine dishwashing method has been
described in WO 95/01416 published January 12, 1995, none of which
disclose transition metal containing bleach catalysts.
European Patent Application EP-A-0 530 870 in the name of Unilever
discloses machine dishwashing compositions containing a dinuclear
manganese complex in which the manganese is in the III or IV oxidation
state. No recognition is provided therein of the use of corrosion inhibitor
compounds to inhibit silver tarnishing.
Summar~r of the Invention
A
2146051
According to one preferred embodiment of the present invention there is
provided a bleaching composition containing
(a) a transition metal containing bleach catalyst wherein said bleach
catalyst is not an Mn(I>7 compound;
(b) an oxygen bleach; and
(c) a corrosion inhibitor compound selected from a paraffin oil,
benzotriazole any derivatives thereof, and preferably any mixtures
thereof.
Preferably, a means is provided for controlling the rate of release of
available oxygen such that, when using the method described in the
present description, the available oxygen is completely released from the
composition in a time interval of from 3.5 minutes to 10.0 minutes.
Preferably, the level of available oxygen in the present compositions,
measured in units of 9~ available oxygen by weight of the composition,
should be from 0.3 °l6 to 1.7 % measured according to the method
described herein.
The transition metal bleach catalyst is preferably selected from the group
consisting of 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-tri-methyl-1,4,7-
triazacyclononane)2-(C104)2; Mn~4(u-O)6(1,4,7-triazacyclononane)4-
(C104)2; Mn~Mn~4(u-O)1(u-OAc~ (1,4,7-tri-methyl-1,4,7-
triazacyclononane)2-(C104)3; Mn(1,4,7-trimethyl-1,4,7-triaza-
cyclononane(OCH3)3_(PF6); Co(2,2'-bispyridyl-amine)C12~; Di-(isothio-
cyanato)bispyridylamine-cobalt (II]; trisdipyridylamine-cobalt (I~ per-
chlorate; Co(2,2-bispyridylamine)2- 02C104; Bis-(2,2'-bispyridylamine)
copper(I>7 per-chlorate; tris(di-2-pyridylamine) iron (Il] perchlorate;
Mn~(CF3S03)2; Co(NH3)SCI; binuclear Mn complexed with tetra-N-
dentate and bi-N-dentate ligands, including N4MnBI(u-
B
2146051
O)ZMnI~N4)+ and [Bipy2Mn"'(u-O)2Mn'~blpy2]-(C1O4)3 and mixtures thereof.
In a further preferred embodiment there is provided a bleaching composition
containing: (a) a transition metal containing bleach catalyst wherein said
bleach catalyst is not an Mn(II) compound; (b) a particulate oxygen bleach;
(c)
a coating material; and (d) a corrosion inhibitor compound selected from a
paraffin oil, benzotriazole and derivatives thereof, and any mixtures thereof;
wherein the oxygen bleach is substantially coated with the coating material so
as to control the release of available oxygen from the oxygen bleach.
~ygen bleach
The detergent compositions of the invention contain as an essential component
an oxygen bleach. The oxygen bleach may be hydrogen peroxide or a source
thereof, an organic peroxyacid or a source thereof, such as a peroxyacid
bleach
precursor compound.
Where the organic peroxyacid source is a peroxyacid bleach precursor
compound, the production of the peroxyacid occurs by an in situ reaction of
the precursor with a source of hydrogen peroxide. Suitable sources of hydrogen
peroxide include inorganic perhydrate bleaches.
Peroxyacid bleach precursors
Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid
sources herein. Peroxyacid bleach precursors are normally incorporated at a
level of from 1% to 20% by weight, more preferably from 2% to 5% by
weight, most preferably from 3% to 10% by weight of the compositions.
g
2146p5~
4a
Suitable peroxyacid bleach precursors typically contain one or more N- or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides and acylated derivatives
of
imidazoles and oximes, and examples of useful materials within these classes
are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and
EP-A-0170386. The acylation products of sorbitol, glucose and all saccharides
with benzoylating agents and acetylating agents are also suitable.
Specific O-acylated precursor compounds include 2,3,3-tri-methyl hexanoyl
oxybenzene sulfonates, benzoyl oxybenzene sulfonates, nonanoyl-6-amino
caproyl oxybenzene sulfonates, monobenzoyltetraacetyl
B
z14sp51
glucose, benzoyl peroxide and cationic derivatives of any of the above,
including the alkyl ammonium derivatives and pentaacetyl glucose.
Phthalic anhydride is a suitable anhydride type precursor.
Specific cationic derivatives of the O-acyl precursor compounds include
2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate
chloride, and any of the alkyl ammonium derivatives of the benzoyl
oxybenzene sulfonates including the 4-(trimethyl ammonium) methyl
derivative.
Useful N-acyl compounds are disclosed in GB-A-855735, 907356 and
GB-A-124.6338.
Preferred precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas
and the N-,N,N1N1 tetra acetylated alkylene diamines wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene diamine (TAED) is particularly preferred.
N-acylated precursor compounds of the lactam class are disclosed
generally in GB-A-855735. Whilst the broadest aspect of the invention
contemplates the use of any lactam useful as a peroxyacid precursor,
preferred materials comprise the caprolactams and valerolactams.
A
X146051
6
Suitable N-acylated lactam precursors have the formula:
O
II
R6-O N-C H2- ~ Fi2
~C H2~C H2 In
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
Suitable caprolactam bleach precursors are of the formula:
0
p C CH2 CH2
\cH
2
R1 C N
CH2 CH2
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing
from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most
preferably Rl is phenyl.
Suitable valero lactams have the formula:
0
C CH2 CH2
R1 C N
CH2 CH2
2L46051
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing
from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In
highly preferred embodiments, R1 is selected from phenyl, heptyl, octyl,
nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
The most preferred materials are those which are normally solid at
< 30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam,
benzoyl caprolactam and their substituted benzoyl analogues such as
chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
Caprolactam and valerolactam precursor materials wherein the R1 moiety
contains at least 6, preferably from 6 to about 12, carbon atoms provide
peroxyacids on perhydrolysis of a hydrophobic character which afford
nucleophilic and body soil clean-up. Precursor compounds wherein R1
comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species
which are particularly efficient for bleaching beverage stains. Mixtures
of ' hydrophobic' and ' hydrophilic' caprolactams and valero lactams,
typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein
for mixed stain removal benefits.
Highly preferred caprolactam and valerolactam precursors include
benzoyl caprolactam, nonanoyl capro-lactam, benzoyl valerolactam,
nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-
trimethylhexanoyl valerolactam, octanoyl capralactam, 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 caprolactam, isopropylbenzoyl valerolactam,
butylbenzoyl caprolactam, butylbenzoyl valerolactam, tent-butylbenzoyl
caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam,
pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl
valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam,
X146051
8
propoxybenzoyl caprolactam, propoxybenzoyl valerolactam,
isopropoxybenzoyl caprolactam, isopropoxybenzoyl valerolactam,
butoxybenzoyl caprolactam, butoxybenzoyl valerolactam, tert-
butoxybenzoyl caprolactam, tert-butoxybenzoyl valerolactam,
pentoxybenzoyl caprolactam, pentoxybenzoyl valerolactam,
hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam, 2,4,6-
trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam,
pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-
chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam,
terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam,
pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam,
dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam, 2,4-
dichlororbenzoyl valerolactam, terephthaloyl divalerolactam, 4-
nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, and mixtures
thereof.
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl
benzimidazole and other useful N-acyl group-containing peroxyacid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
Another preferred class of peroxyacid bleach activator compounds are the
amide substituted compounds of the following general formulae:
R~ -C-N-R2-C-L R~ -N-C-R2-C-L
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to about 14
carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing
from about 1 to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl
group containing 1 to 10 carbon atoms and L can be essentially any
leaving group. R1 preferably contains from about 6 to 12 carbon atoms.
R2 preferably contains from about 4 to 8 carbon atoms. R1 may be
straight chain or branched alkyl, substituted aryl or alkylaryl containing
branching, substitution, or both and may be sourced from either synthetic
~14fi0~1
9
sources or natural sources including for example, tallow fat. Analogous
structural variations are permissible for R2. The substitution can include
alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups
or organic compounds. RS is preferably H or methyl. R1 and RS should
not contain more than 18 carbon atoms in total. Amide substituted bleach
activator compounds of this type are described in EP-A-0170386.
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.
Preferred bleach precursors are those wherein R1, R2 and RS are as
defined for the amide substituted compounds and L is selected from the
group consisting of:
Y R3 RaY
-O ~ , -O ~ Y , and
0 ~ 0
-N-C-R -N N -N-C-CH-R
R3 ~ , R3 Y ,
I
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
21~f 051
io
O H -~ Y O
II ~ -N C 2 NR4 _N~ jNR4
-O-C-R wC~ C
O , O
R3 O Y
-O-C=C HR4 , and -N-S-C H-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, o3alkaryl group
containing from about 1 to about 14 carbon atoms, R is an alkyl chain
containing from 1 to about 8 carbon atoms, R4 is H or R3, and Y is H or
a solubilizing group.
Th+pre3ferred solubilizing g3 ups are -S03-M+, -C02 M+,~S04 M+,
-N (R ) X- and O < --N(R )3 and most preferably -S03 M and
-C02 M ~ 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 preferred, 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 well dispersed in the bleaching solution in
order to assist in their dissolution.
Preferred examples of bleach activators of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl)oxybenzenesulfo-nate, (6-
decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
.-..
zl4so~1
Other preferred precursor compounds include those of the benzoxazin-
type, having the formula:
O
II
~~0
o ,,~-R,
'N
including the substituted benzoxazins of the type
O
~O
C-R
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, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino,
COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
0
II
~~0
~C
'N
(''at;n,~ic pe_rox~racid precursors
Cationic peroxyacid precursor compounds are also suitable herein.
Typically such cationic peroxyacid precursors are formed by substituting
the peroxyacid part with an ammonium or alkyl ammmonium group,
preferably an ethyl or methyl ammonium group.
2~'~6~51
12
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in
JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in
CA 2,197,443, CA 2,197,445, CA 2,196,703 and CA 2,154,704.
Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-
acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl
peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl ammonium) methyl derivative of benzoyl oxybenzene
sulfonate:
0
~O~S03
~+
A preferred cationically substituted alkyl oxybenzene sulfonate is the
methyl ammonium derivative of 2,3,3-tri-methyl hexanoyloxybenzene
sulfonate.
Preferred cationic peroxyacid precursors of the N-acylated caprolactam
class include the trialkyl ammonium methylene benzoyl caprolactams,
particularly trimethyl ammonium methylene benzoyl caprolactam:
A
,,..,.
2146051
13
O O
v O ,N
~N
/+
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Also preferred is trimethyl ammonium methylene meta chloro xylenol:
CH3
CI
0
~ CI ~ ' 0 CH3
N
/+
Betaine ester trimethyl ammonium meta chloro xylenol is also preferred:
CH3
CI
'~° o
/N~O CH
3
Organic.~eroxXacids
The detergent compositions may also contain organic peroxyacids
typically at a level of from 0.5 °~o to 15 % by weight, more preferably
from
1 % to 10 % by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide
substituted compounds of the following general formulae:
R~ -C-N-R2-C-OOH R~ -N-C-R2-C-OOH
O R5 O or R5 O O
2146051
14
wherein R1 is an aryl or alkaryl group with from about 1 to about 14
carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing
from about 1 to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl
group containing 1 to 10 carbon atoms. R1 preferably contains from
about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8
carbon atoms. R1 may be straight chain or branched alkyl, substituted
aryl or alkylaryl containing branching, substitution, or both and may be
sourced from either synthetic sources or natural sources including for
example, tallow fat. Analogous structural variations are permissible for
R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur
and other typical substituent groups or organic compounds. RS is
preferably H or methyl. R1 and RS should not contain more than 18
carbon atoms in total. Amide substituted organic peroxyacid compounds
of this type are described in EP-A-0170386.
Other organic peroxyacids include diperoxy dodecanedioc acid, diperoxy
tetra decanedioc acid, diperoxyhexadecanedioc acid, mono- and
diperazelaic acid, mono- and diperbrassylic acid, monoperoxy phthalic
acid, perbenzoic acid, and their salts as disclosed in, for example, EP-A-
0341 947.
Inorganic nerhvdrate bleaches
The compositions in accord with the invention preferably include, as a
hydrogen peroxide source, an inorganic perhydrate salt, most especially
when the organic peroxyacid source is a peroxyacid bleach precursor
compound.
The inorganic perhydrate salts are normally incorporated in the form of
the sodium salt at a level of from 1 % to 40 ~ by weight, more preferably
from 2 % to 30 ~ by weight and most preferably from 5 °.~ to 25 % by
weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate
salts are normally the alkali metal salts. The inorganic perhydrate salt
zl4so~1
may be included as the crystalline solid without additional protection. For
certain perhydrate salts however, the preferred executions of such
granular compositions utilize a coated form of the material which
provides better storage stability for the perhydrate salt in the granular
product.
Sodium perborate can be in the form of the monohydrate of nominal
formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Sodium percarbonate, which is a preferred perhydrate for inclusion in
detergent compositions in accordance with the invention, is an addition
compound having a formula typically corresponding to 2Na2C03.3H202,
and is available commercially as a crystalline solid. The percarbonate is
most preferably incorporated into such compositions in a coated form
which provides in product stability.
A suitable coating material providing in product stability comprises mixed
salt of a water soluble alkali metal sulphate and carbonate. Such coatings
together with coating processes have previously been described in GB-
1,466,799, granted to Interox on 9th March 1977. The weight ratio of
the mixed salt coating material to percarbonate lies in the range from 1
200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably
from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate
and sodium' carbonate which has the general formula Na2S04.n.Na2C03
wherein n is form 0.1 to 3, preferably n is from 0.3 to 1.0 and most
preferably n is from 0.2 to 0.5.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of
use in the detergent compositions herein.
The compositions contain a transition metal containing bleach catalyst.
Herein, the term transition metal bleach catalyst, henceforth 'bleach
catalyst', excludes Mn(IZ) compounds, such as Mn(In salts and
2146051
16
complexes, certain of which have been shown to lead to a reduction in the
propensity to cause silver tarnishing.
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 sufficient, under whatever comparative test
conditions are employed, to enhance bleaching and removal of the stain or
stains of interest from the target substrate. 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. Some users elect to use very hot water; others use
warm or even cold water in machine dishwashing 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 1 ppm to about
200 ppm of the catalyst species in the wash 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 perborate and a bleach
precursor (e.g., benzoyl caprolactam). An increase in concentration of 3-
fold may be required under U.S. conditions to achieve the same results.
Conversely, use of a bleach precusor 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.
The bleach catalyst material herein can comprise the free acid or be in the
form of any suitable salts.
One type of bleach catalyst is a catalyst system comprising a heavy metal
cation of defined bleach catalytic activity, such as copper, iron or
manganese III or IV cations, an auxiliary metal cation having little or no
bleach catalytic activity, such as zinc or aluminum cations, and a
r-,
2146051
sequestrant having defined stability constants for the catalytic and
auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof.
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, MnIII2(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-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(C104)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 the compositions herein may also be
selected as appropriate for the present invention. For examples of
suitable bleach catalysts see U.S. Pat. 5,227,084. See also U.S. Pat.
5,194,416 which teaches mononuclear manganese (IV) complexes such as
Mn(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 (IIn, and/or (IV) 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-erythritol, 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 ligands are of the formula:
2146051
R2 R3
R~ -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 R1-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, NR~ and C=O, wherein R5,
R6, and R~ can each be H, alkyl, or aryl groups, including substituted or
unsubstituted groups. Preferred ligands include pyridine, pyridazine,
pyrimidine, pyrazine, imidazole, 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. Highly preferred
catalysts include Co(2,2'-bispyridylamine)C12,
Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-
cobalt(In perchlorate, Co(2,2-bispyridylamine)202C104, Bis-(2,2'-
bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(In
perchlorate, and mixtures thereof.
Other examples include binuclear Mn complexed with tetra-N-dentate and
bi-N-dentate ligands, including N4MnIII(u_O)2Mn~N4)'~'and
[Bipy2MnIII(u-O)2Mn~bipy2]-(CIOq,)3.
Corrosion inhibitor
The compositions contain a corrosion inhibitor which is preferably
incorporated at a level ~of from 0.05 % to 10 % , preferably from 0.1 % to
% by weight of the total composition.
A preferred corrosion inhibitor herein is benzotriazole and any derivatives
thereof.
Another highly preferred corrosion inhibitor is a paraffin oil, typically a
predominantly branched aliphatic hydrocarbon having a number of carbon
atoms in the range of from 20 to 50; preferred paraffin oil selected from
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19
predominantly branched C25-45 species with a ratio of cyclic to noncyclic
hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1. A paraffin
oil meeting these characteristics, having a ratio of cyclic to noncyclic
hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen,
Germany, under the trade mark WINOG 70.
In a highly preferred aspect, the corrosion inhibitor comprises a mixture
of a paraffin oil and benzotriazole.
Other suitable corrosion inhibitor compounds include, mercaptans and
diols, especially mercaptans with 4 to 20 carbon atoms including lauryl
mercaptan, thiophenol, thionapthol, thionalide and thioanthranol.
Phosphonated octa-decane and other anti-oxidants such as
betahydroxytoluene (BHT) are also suitable. Nitrogen-containing
compounds such as amines, especially distearylamine and ammonium
compounds such as ammonium chloride, ammonium bromide, ammonium
sulphate or diammonium hydrogen citrate are also suitable.
Total Available Oxy(Av0) Level
Preferably, the level of available oxygen in the present compositions,
measured in units of 3~o available oxygen by weight of the composition,
should be carefully controlled; the level of available oxygen should thus
preferably be in the range 0.3 36 to 2 .5 ~ , preferably 0.5 % to 1.5 % , more
preferably 0.6 % to 1.2 °~ , measured according to the method described
hereunder.
The rate of release of available oxygen is preferably also controlled; the
rate of release of available oxygen from the compositions herein should
preferably be such that, when using the method described hereinafter, the
available oxygen is not completely released from the composition until
after 3.5 minutes, preferably the available oxygen is released in a time
interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0
minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.
A
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Controlled rate of release - means
The means may provide for controlled release of available oxygen to the
wash solution. Such means could, for example, include delaying release
of the hydrogen peroxide source to the wash solution, by for example,
delaying release of any inorganic perhydrate salt, acting as a hydrogen
peroxide source, to the wash solution.
The controlled release means can include coating any suitable component
with a coating designed to provide the controlled release. The coating
may therefore, for example, comprise a poorly water soluble material, or
be a coating of su~cient thickness that the kinetics of dissolution of the
thick coating provide the controlled rate of release.
The coating material may be applied using various methods. Any coating
material is typically present at a weight ratio of coating material to bleach
of from 1:99 to 1:2, preferably from 1:49 to 1:9.
Suitable coating materials can comprise the alkali and alkaline earth metal
sulphates, silicates and carbonates, including calcium carbonate.
A preferred coating material is sodium silicate of Si02 : Na20 ratio from
1.6 : 1 to 3 .4 : 1, preferably 2. 8 : 1, applied as an aqueous solution to
give a level of from 2 % to 10 l , (normally from 3 °6 to 5 % ) of
silicate
solids by weight of the oxygen bleaching species. Magnesium silicate can
also be included in the coating.
One method for applying the coating material involves agglomeration.
Preferred agglomeration processes include the use of an organic binder
material. Any conventional agglomerator/mixer may be used including,
but not limted to pan, rotary drum and vertical blender types. Molten
coating compositions may also be applied either by being poured onto, or
spray atomized onto a moving bed of bleaching agent.
Other means of providing the required controlled release include
mechanical means for altering the physical characteristics of the bleach to
control its solubility and rate of release. Suitable protocols could include
,.-.
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21
compaction, mechanical injection, manual injection, and adjustment of the
solubility of the bleach compound by selection of particle size of any
particulate component.
Whilst the choice of particle size will depend both on the composition of
the particulate component, and the desire to meet the desired controlled
release kinetics, it is desirable that the particle size should be more than
500 micrometers, preferably having an average particle diameter of from
800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include
the suitable choice of any other components of the detergent composition
matrix such that when the composition is introduced to the wash solution
the ionic strength environment therein provided enables the required
controlled release kinetics to be achieved.
controlled rate of release- test method
The rate of release of Av0 can be measured according to the method now
described:
1. A beaker of water (typically 2 litre) is placed on a stirrer Hotplate,
and the stirrer speed is selected to ensure that the product is evenly
dispersed through the solution.
2. The detergent composition (typically 8g of product which has been
sampled down from a bulk supply using a Pascal sampler), is added
and simultaneously a stop clock is started.
3. The temperature control should be adjusted so as to maintain a
constant temperature of 20°C throughout the experiment.
4. Samples are taken from the detergent solution at 2 minute time
intervals for 20 mins, starting after 1 minute, and are titrated by the
"titration procedure" described below to determine the level of
available oxygen at each point.
~msom
22
Titration Procedure
1. An aliquot from the detergent solution (above) and 2m1 sulphuric acid
are added into a stirred beaker
2. Approximately 0.2g ammonium molybdate catalyst (tetra hydrate
form) are added
3. 3mls of 10% sodium iodide solution are added
4. Titration with sodium thiosulphate is conducted until the end point.
The end point can be seen using either of two procedures. First
procedure consists simply in seeing the yellow iodine colour fading to
clear. The second and preferred procedure consists of adding soluble
starch when the yellow colour is becoming faint, turning the solution
blue. More thiosulphate is added until the end point is reached (blue
starch complex is decolourised).
The level of AvO, measured in units of % available oxygen by weight,
for the sample at each time interval corresponds to the amount of titre
according to the following equation
VoIS203(ml) x Molarity (S203) x 8
Sample mass (g)
Av0 level is plotted graphically versus time to enable the maximum level
of Av0 and the time to achieve that maximum level to be determined.
Additional detergent components
The detergent compositions of the invention may also contain additional
detergent components. The precise nature of these additional components,
and levels of incorporation thereof will depend on the physical form of the
.-.
z1460~i
23
composition, and the nature of the cleaning operation for which it is to be
used.
When formulated as compositions suitable for use in a machine washing
method, eg: machine dishwashing methods, the compositions of the
invention preferably contain one or more additional detergent components
selected from surfactants, water-insoluble builders, organic polymeric
compounds, additional enzymes, suds suppressors, lime soap dispersants,
soil suspension and anti-redeposition agents and corrosion inhibitors.
rf tant
The detergent compositions of the invention may contain as an additional
detergent component a surfactant selected from anionic, cationic, nonionic
ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1 % to 60 % by
weight. More preferred levels of incorporation of surfactant are from 1 %
to 35 % by weight, most preferably from 1 % to 20 rb by weight.
The surfactant is preferably formulated to be compatible with any enzyme
components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at least
does not degrade, the stability of any enzyme in these compositions.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic
classes, and species of these surfactants, is given in U.S.P. 3,929,678
issued to Laughlin and Heuring on December 30, 1975. Further examples
are given in "Surface Active Agents and Detergents" (Vol. I and II by
Schwartz, Perry and Berch). A list of suitable cationic surfactants is given
in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in combination with one or more anionic and/or nonionic
surfactants .
,....
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24
Anionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in the compositions. These can include salts (including, for
example, sodium, potassium, ammonium, and substituted ammonium salts
such as mono-, di- and triethanolamine salts) of the anionic sulfate,
sulfonate, carboxylate and sarcosinate surfactants.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C 12-C 1 g monoesters) diesters of sulfosuccinate
(especially saturated and unsaturated C6-C 14 diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable,
such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin
acids present in or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 1? acyl-N-
(C1-Cq, alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and
sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C6-C 1 g alkyl sulfates which have been ethoxylated with
from about 0.5 to about 20 moles of ethylene oxide per molecule. More
preferably, the alkyl ethoxysulfate surfactant is a C6-C 1 g alkyl sulfate
which has been ethoxylated with from about 0.5 to about 20, preferably
from about 0.5 to about 5, moles of ethylene oxide per molecule.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of
CS-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22
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primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
Anionic carboxylate surfactant
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and
the soaps ('alkyl carboxyls'), especially certain secondary soaps as
described herein.
Preferred alkyl ethoxy carboxylates for use herein include those with the
formula RO(CH2CH20)x CH2C00-M + wherein R is a C6 to C 1 g alkyl
group, x ranges from O to 10, and the ethoxylate distribution is such that,
on a weight basis, the amount of material where x is 0 is less than about
20 % , and the amount of material where x is greater than 7, is less than
about 25 % , the average x is from about 2 to 4 when the average R is
C 13 or less, and the average x is from about 3 to 10 when the average R
is greater than C 13, and M is a cation, preferably chosen from alkali
metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-
ammonium, most preferably from sodium, potassium, ammonium and
mixtures thereof with magnesium ions. The preferred alkyl ethoxy
carboxylates are those where R is a C 12 to C 1 g alkyl group.
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein
include those having the formula
RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group, x is
from 1 to 25, Rl and R2 are selected from the group consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and mixtures thereof, wherein at least one R1 or R2 is a succinic
acid radical or hydroxysuccinic acid radical, and R3 is selected from the
group consisting of hydrogen, substituted or unsubstituted hydrocarbon
having between 1 and 8 carbon atoms, and mixtures thereof.
,~..
'~14~051
26
Anionic secondarX soau surfactant
Preferred soap surfactants are secondary soap surfactants which contain a
carboxyl unit connected to a secondary carbon. The secondary carbon can
be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted cyclohexyl carboxylates. The secondary soap surfactants
should preferably contain no ether linkages, no ester linkages and no
hydroxyl groups. There should preferably be no nitrogen atoms in the
head-group (amphiphilic portion). The secondary soap surfactants usually
contain 11-15 total carbon atoms, although slightly more (e.g., up to 16)
can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
secondary soap surfactants:
A. A highly preferred class of secondary soaps comprises the
secondary carboxyl materials of the formula R3 CH(R4)COOM,
wherein R3 is CH3(CH2)x and R4 is CH3(CHZ)y, wherein y can be
O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum
of (x + y) is 6-10, preferably 7-9, most preferably 8.
B. Another preferred class of secondary soaps comprises those
carboxyl compounds wherein the carboxyl substituent is on a ring
hydrocarbyl unit, i.e., secondary soaps of the formula RS-R6-
COOM, wherein RS is C~-C10, preferably C8-C9, alkyl or alkenyl
and R6 is a ring structure, such as benzene, cyclopentane and
cyclohexane. (Note: RS can be in the ortho, meta or para position
relative to the carboxyl on the ring.)
C. Still another preferred class of secondary soaps comprises
secondary carboxyl compounds of the formula CH3(CHR)k-
(CH2)m-(CHR)n-CH(COOM)(CHR)o-(CH2)p-(CHR)q-CH3,
wherein each R is C 1-C4 alkyl, wherein k, n, o, q are integers in
the range of 0-8, provided that the total number of carbon atoms
(including the carboxylate) is in the range of 10 to 18.
2146051
27
In each of the above formulas A, B and C, the species M can be any
suitable, especially water-solubilizing, counterion.
Especially preferred secondary soap surfactants for use herein are water-
soluble members selected from the group consisting of the water-soluble
salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (Rl) CH2 LOOM, wherein R is a CS-C1~ linear or
branched alkyl or alkenyl group, R1 is a Cl-C4 alkyl group and M is an
alkali metal ion. Preferred examples are the myristyl and oleyl methyl
sarcosinates in the form of their sodium salts.
Nonionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in the compositions. Exemplary, non-limiting classes of useful
nonionic surfactants are listed below.
Nonionic po~hvdrox3r f_ attv acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1 Z wherein : Rl is H, C 1-C4 hydrocarbyl, 2-
hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C 1-C4
alkyl, more preferably C1 or CZ alkyl, most preferably C1 alkyl (i.e.,
methyl); and R2 is a CS-C31 hydrocarbyl, preferably straight-chain CS-
C 19 alkyl or alkenyl, more preferably straight-chain C9-C 1 ~ alkyl or
alkenyl, most preferably straight-chain C 11-C 1 ~ alkyl or alkenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing
sugar in a reductive amination reaction; more preferably Z is a glycityl.
2146051
28
Nonionic condensates of alkyl henols
The polyethylene, polypropylene, and polybutylene oxide condensates of
alkyl phenols are suitable for use herein. In general, the polyethylene
oxide condensates are preferred. These compounds include the
condensation products of alkyl phenols having an alkyl group containing
from about 6 to about 18 carbon atoms in either a straight chain or
branched chain configuration with the alkylene oxide.
Nonionic ethoxvlated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use
herein. The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secondary, and generally contains from 6 to 22
carbon atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from 8 to 20 carbon atoms with
from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Nonionic ethox, laY ted/prc,~oxylated fatty alcohol surfactant
The ethoxylated C6-C 1 g fatty alcohols and C(-C 1 g mixed
ethoxylated/propoxylated fatty alcohols are suitable surfactants for use
herein, particularly where water soluble. Preferably the ethoxylated fatty
alcohols are the C 10-C 1 g ethoxylated fatty alcohols with a degree of
ethoxylation of from 3 to 50, most preferably these are the C 12-C 18
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the mixed ethoxylated/propoxylated fatty alcohols have an
alkyl chain length of from 10 to 18 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to
10.
Nonionic EO/PO condensates with~roovlene glycol
The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol are
suitable for use herein. The hydrophobic portion of these compounds
,,-
2146051
29
preferably has a molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. Examples of compounds of this type include
certain of the commercially-available PluronicTM surfactants, marketed
by BASF.
Nonionic EO condensation products with ~p3rlene oxide/ethvlene
diamine adducts
The condensation products of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylenediamine are suitable for
use herein. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
Nonionic alkvhol~saccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic
group containing from about 6 to about 30 carbon atoms, preferably from
about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group containing from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide containing 5 or 6
carbon atoms can be used, e.g., glucose, galactose and galactosyl
moieties can be substituted for the glucosyl moieties. (Optionally the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or galactose as opposed to a glucoside or galactoside.) The
intersaccharide bonds can be, e.g., between the one position of the
additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the
preceding saccharide units.
~1460~1
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the
alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon
atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8,
preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is
preferably derived from glucose.
Nonionic fatty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those having the
formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to
21, preferably from 9 to 17 carbon atoms and each R7 is selected from
the group consisting of hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and
-(C2H40)xH, where x is in the range of from 1 to 3.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the alkyl amphocarboxylic acids.
A suitable example of an alkyl aphodicarboxylic acid for use herein is
Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful herein include those compounds having the formula
R3(OR4)xN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing
from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an
alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms,
preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 5,
preferably from 0 to 3; and each RS is an alkyl or hydyroxyalkyl group
containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a
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31
polyethylene oxide group containing from 1 to 3, preferable 1, ethylene
oxide groups. The RS groups can be attached to each other, e.g., through
an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C 1 p-C 1 g alkyl
dimethyl amine oxides and Cg-C 1 g alkoxy ethyl dihydroxyethyl amine
oxides. Examples of such materials include dimethyloctylamine oxide,
diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
dimethyldodecylamine oxide, dipropyltetradecylamine oxide,
methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine
oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow
dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide.
Preferred are C lp-C 1 g alkyl dimethylamine oxide, and C 10-18 acylamido
alkyl dimethylamine oxide.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions hereof. These surfactants can be broadly described as
derivatives of secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary ammonium,
quaternary phosphonium or tertiary sulfonium compounds. Betaine and
sultaine surfactants are exemplary zwitterionic surfactants for use herein.
~etaine surfactant
The betaines useful herein are those compounds having the formula
R(R' )2N '~ R2C00- wherein R is a C6-C 1 g hydrocarbyl group,
preferably a C lp-C 16 alkyl group or C 10-16 acylamido alkyl group, each
R1 is typically C1-C3 alkyl, preferably methyl,m and R2 is a C1-CS
hydrocarbyl group, preferably a C 1-C3 alkylene group, more preferably a
C 1-C2 alkylene group. Examples of suitable betaines include coconut
acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14
acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl betaine; 4[C1~16
acylmethylamidodiethylammonio]-1-carboxybutane; C1~18
acylamidodimethylbetaine; C 12-16 acylamidopentanediethyl-betaine;
[C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18
2146051
32
dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or
ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are
also suitable for use herein.
Sultaine surfactant
The sultaines useful herein are those compounds having the formula
(R(Rl )2N +R2S03- wherein R is a C6-C 1 g hydrocarbyl group,
preferably a C 10-C 16 alkyl group, more preferably a C 12-C 13 alkyl
group, each R1 is typically C1-C3 alkyl, preferably methyl, and R2 is a
C 1-C6 hydrocarbyl group, preferably a C 1-C3 alkylene or, preferably,
hydroxyalkylene group.
Amphol3itic surfactant
Ampholytic surfactants can be incorporated into the detergent
compositions herein. These surfactants can be broadly described as
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which the
aliphatic radical can be straight chain or branched.
Cationic surfactants
Cationic surfactants can also be used in the detergent compositions herein.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected from mono C6-C 16, preferably C(-C 10 N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted
by methyl, hydroxyethyl or hydroxypropyl groups.
Water-soluble builder compound
The detergent compositions of the present invention may contain as a
highly preferred component a water-soluble builder compound, typically
present at a level of from 1 °~o to 80 % by weight, preferably from 10
% to
70 % by weight, most preferably from 20 °b to 60 % by weight of the
composition.
33 21 4 6 0 5 1
Suitable water-soluble builder compounds include the water soluble
monomeric polycarboxylates, or their acid forms, homo or copolymeric
polycarboxylic acids or their salts in which the polycarboxylic acid
comprises at least two carboxylic radicals separated from each other by
not more that two carbon atoms, carbonates, bicarbonates, borates,
phosphates, silicates and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic
acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well
as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates
containing three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates described in British Patent No. 1,389,732,
and aminosuccinates described in Canadian Patent No. 973,771, and
the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates,
2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-
tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran -
A
2146051
34
tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol,
mannitol and xylitol. Aromatic polycarboxylates include mellitic acid,
pyromellitic acid and the phthalic acid derivatives disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly
citrates.
The parent acids of the monomeric or oligomeric polycarboxylate
chelating agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid mixtures are also contemplated as useful builder
components.
Borate builders, as well as builders containing borate-forming materials
that can produce borate under detergent storage or wash conditions can
also be used but are not preferred at wash conditions less that about
50°C, especially less than about 40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates, including sodium carbonate and sesqui-carbonate and
mixtures thereof with ultra-fine calcium carbonate as disclosed in German
Patent Application No. 2,321,001 published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta/phosphate in which the
degree of polymerization ranges from about 6 to 21, and salts of phytic
acid.
Suitable silicates include the water soluble sodium silicates with an Si02:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being
preferred, and 2.0 ratio being most preferred. The silicates may be in the
form of either the anhydrous salt or a hydrated salt. Sodium silicate with
an Si02: Na20 ratio of 2.0 is the most preferred silicate.
35 2 t 4 6 0 5
Silicates are preferably present in the detergent compositions in accord
with the invention at a level of from 5 % to 50% by weight of the
composition, more preferably from 10 % to 40 % by weight.
Partially soluble or insoluble builder compound
The detergent compositions of the present invention may contain a
partially soluble or insoluble builder compound, typically present at a
level of from 1 % to 80 % by weight, preferably from 10 % to 70 % by
weight, most preferably from 20% to 60% weight of the composition.
Examples of partially water soluble builders include the crystalline
layered silicates. Examples of largely water insoluble builders include the
sodium aluminosilicates.
Crystalline layered sodium silicates have the general formula
NaMSix02x+ l.yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a
number from 0 to 20. Crystalline layered sodium silicates of this type are
disclosed in EP-A-0164514 and methods for their preparation are
disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the
present invention, x in the general formula above has a value of 2, 3 or 4
and is preferably 2. The most preferred material is 8-Na2Si205,
available from Hoechst AG as NaSKS-6TM.
The crystalline layered sodium silicate material is preferably present in
granular detergent compositions as a particulate in intimate admixture
with a solid, water-soluble ionisable material. The solid, water-soluble
ionisable material is selected from organic acids, organic and inorganic
acid salts and mixtures thereof.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. XH20 wherein z and y are at least 6; the molar
ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to
A
,,.-.
z14so51
36
276, more preferably from 10 to 264. The aluminosilicate material are in
hydrated form and are preferably crystalline, containing from 10% to
28 % , more preferably from 18 % to 22 % water in bound form.
The aluminosilicate ion exchange materials can be naturally occurring
materials, but are preferably synthetically derived. Synthetic crystalline
aluminosilicate ion exchange materials are available under the
designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP,
Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [A102) 12 (Si02) 12] . xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula
Nag6 [(A102)86(Si02)1061. 276 H20.
Heavx metal ion seauestran
The detergent compositions of the invention may contain as a preferred
optional component a heavy metal ion sequestrant. By heavy metal ion
sequestrant it is meant herein components which act to sequester (chelate)
heavy metal ions. These components may also have calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are preferably present at a level of from
0.005 % to 20 % , more preferably from 0.1 % to 10 % , most preferably
from 0.5 % to 5 % by weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for
example phosphonic acid or carboxylic acid functionalities, may be
present either in their acid form or as a complex/salt with a suitable
counter cation such as an alkali or alkaline metal ion, ammonium, or
substituted ammonium ion, or any mixtures thereof. Preferably any
salts/complexes are water soluble. The molar ratio of said counter cation
to the heavy metal ion sequestrant is preferably at least 1:1.
216051
37
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene
phosphonates.
Preferred among the above species are diethylene triamine penta
(methylene phosphonate), ethylene diamine tri (methylene phosphonate)
hexamethylene diamine tetra (methylene phosphonate) and hydroxy-
ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,
ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or
the alkali metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or magnesium salt or
complex thereof. Examples of such preferred sodium salts of EDDS
include Na2EDDS and Na3EDDS. Examples of such preferred
magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
Other suitable heavy metal ion sequestrants for use herein are
iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or
glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-
399,133.
The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid
N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants
described in EP-A-516,102 are also suitable herein. The ~3-alanine-N,N'-
diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic
acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are
also suitable.
,~--
2146p5~
EP-A-476,257 describes suitable amino based sequestrants. EP-A-
510,331 describes suitable sequestrants derived from collagen, keratin or
casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid
sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic
acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS) is also
suitable.
Another optional ingredient useful in the detergent compositions is one or
more additional enzymes.
Preferred additional enzymatic materials include the commercially
available lipases, amylases, neutral and alkaline proteases, esterases,
cellulases, pectinases, lactases and peroxidases conventionally
incorporated into detergent compositions. Suitable enzymes are discussed
in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold
under the trademarks Alcalase, Savinase, Primase, Durazym, and
Esperase by Novo Industries A/S (Denmark), those sold under the
trademarks Maxatase, Maxacal and Maxapem by Gist-Brocades, those
sold by Genencor International, and those sold under the trademarks
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
incorporated into the compositions in accordance with the invention at a
level of from 0.0001 °X~ to 4 ~b active enzyme by weight of the
composition.
Preferred amylases include, for example, a-amylases obtained from a
special strain of B licheniformis, described in more detail in GB-
1,269,839 (Novo). Preferred commercially available amylases include
for example, those sold under the trademark Rapidase by Gist-Brocades,
and those sold under the trademarks Termamyl and BAN by Novo
Industries A/S. Amylase enzyme may be incorporated into the
composition in accordance with the invention at a level of from 0.0001
to 2 % active enzyme by weight of the composition.
A
39 21 4 6 0 5
Lipolytic enzyme (lipase) may be present at levels of active lipolytic
enzyme of from 0.0001 % to 2 % by weight, preferably 0.001 °6 to 1
°~ by
weight, most preferably from 0.001 % to 0.5 % by weight of the
compositions.
The lipase may be fungal or bacterial in origin being obtained, for
example, from a lipase producing strain of Humicola sp., Thermomvces
sp. or Pseudomonas sp. including Pseudomonas ,pseudoalcaligenes or
Pseudomas fluorescens. Lipase from chemically or genetically modified
mutants of these strains are also useful herein.
A preferred lipase is derived from Pseudomonas nseudoalcalig~nes, which
is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from
Humicola lanu~inosa and expressing the gene in Aspergillus , as
host, as described in European Patent Application, EP-A-0258 068, which
is commercially available from Novo Industri A/S, Bagsvaerd, Denmark,
under the trade mark Lipolase. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Where the enzyme is a protease, the ultimate amount in a typical wash
solution is from 0.1 to 100 KNPU, but preferably is from 0.5 to 50
KNPU, more preferably from 3 to 30 KNPU.
Where the enzyme is an amylase, the ultimate amount in a typkical wash
solution is from 1 to 1500 KNU, but preferably is from 5 to 1200 KNU,
more preferably from 30 to 450 KNU.
Where the enzyme is a lipase, the ultimate amount in a typical wash
solution is from 1 to 300 KLU, but preferably is from 10 to 200 KLU,
more preferably from 10 to 100 KLU.
Where the enzyme is a cellulase, the ultimate amount in the wash is
typically from 10 to 1200 CEVU, but preferably is from 50 to 1000
CEVU, more preferably from 80 to 500 CEVU.
A
2146051
Enzvme Stabilizing SXstem
Preferred enzyme-containing compositions herein may comprise from
about 0.001 % to about 10 % , preferably from about 0.005 % to about
8 % , most preferably from about 0.01 % to about 6 % , by weight of an
enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing system which is compatible with the detersive enzyme. Such
stabilizing systems can comprise calcium ion, boric acid, propylene
glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
Such stabilizing systems can also comprise reversible enzyme inhibitors,
such as reversible protease inhibitors.
The compositions herein may further comprise from 0 to about 10 % ,
preferably from about 0.01 % to about 6% by weight, of chlorine bleach
scavengers, added to prevent chlorine bleach species present in many
water supplies from attacking and inactivating the enzymes, especially
under alkaline conditions. While chlorine levels in water may be small,
typically in the range from about 0.5 ppm to about 1.75 ppm, the
available chlorine in the total volume of water that comes in contact with
the enzyme during washing is usually large; accordingly, enzyme stability
in-use can be problematic.
Suitable chlorine scavenger anions are widely available, and are
illustrated by salts containing ammonium cations or sulfite, bisulfate,
thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate,
ascorbate, etc., organic amines such as ethylenediaminetetracetic acid
(EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and
mixtures thereof can likewise be used. Other conventional scavengers
such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as
sodium perborate tetrahydrate, sodium perborate monohydrate and
sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and
mixtures thereof can be used if desired.
Organic,.polxmeric com on and
Organic polymeric compounds are particularly preferred components of
the detergent compositions in accord with the invention. By organic
polymeric compound it is meant essentially any polymeric organic
compound commonly used as dispersants, and anti-redeposition and soil
suspension agents in detergent compositions.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level of from 0.1 ~b to 30°l ,
preferably
from 0.5 % to 15 ~ , most preferably from 19~ to 10 g6 by weight of the
compositions.
Examples of organic polymeric compounds include the water
soluble organic homo- or co-polymeric polycarboxylic acids or their
salts in which the polycarboxylic acid comprises at least two
carboxyl radicals separated from each other by not more than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-
1,596,756. Examples of such salts are polyacrylates of molecular
weight 2000-5000 and their copolymers with any suitable other
monomer units including modified acrylic, fumaric, malefic,
itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid
or their salts, malefic anhydride, acrylamide, alkylene, vinylmethyl
ether, styrene and any mixtures thereof. Preferred are the
copolymers of acrylic acid and malefic anhydride having a molecular
weight of from 20,000 to 100,000.
Preferred commercially available acrylic acid containing polymers
having a molecular weight below 15,000 include those sold under
the trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan
CP10 by BASF GmbH, and those sold under the trademark Acusol
45N by Rohm and Haas.
Preferred acrylic acid containing copolymers include those which contain
as monomer units: a) from 90 °/ to 10 q6 , preferably from 80 to to 20
% by
weight acrylic acid or its salts and b) from 10°7 to 90°0,
preferably from
20% to 80% by weight of a substituted acrylic monomer or its salts
having the general formula -[CR2-CR1(CO-O-R3)]- wherein at least one
of the substituents R1, R2 or R3, preferably Rl or R2 is a 1 to 4 carbon
A
,,..,..
X146051
42
alkyl or hydroxyalkyl group, R1 or R2 can be a hydrogen and R3 can be
a hydrogen or alkali metal salt. Most preferred is a substituted acrylic
monomer wherein R1 is methyl, R2 is hydrogen (i.e. a methacrylic acid
monomer). The most preferred copolymer of this type has a molecular
weight of 3500 and contains 60 % to 80 % by weight of acrylic acid and
40% to 20% by weight of methacrylic acid.
Other suitable polyacrylate/modified polyacrylate copolymers include
those copolymers of unsaturated aliphatic carboxylic acids disclosed in
U.S. Patents No.s 4,530,766, and 5,084,535 which have a molecular
weight of less than 15,000.
Other suitable organic polymeric compounds include the polymers of
acrylamide and acrylate having a molecular weight of from 3,000 to
100,000, and the acrylate/fumarate copolymers having a molecular weight
of from 2,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-351629.
Other organic polymeric compounds suitable for incorporation in the
detergent compositions herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols,
particularly those of molecular weight 1000-10000, more particularly
2000 to 8000 and most preferably about 4000.
Lime soap dispersant com op and
The compositions of the invention may contain a lime soap dispersant
compound, which has a lime soap dispersing power (LSDP), as defined
hereinafter of no more than 8, preferably no more than 7, most preferably
no more than 6. The lime soap dispersant compound is preferably present
at a level of from 0.1 % to 40 % by weight, more preferably 1 % to 20 %
43 2 1 4 6 0 5 1
by weight, most preferably from 2 % to 10 % by weight of the
compositions.
A lime soap dispersant is a material that prevents the precipitation of
alkali metal, ammonium or amine salts of fatty acids by calcium or
magnesium ions. A numerical measure of the effectiveness of a lime soap
dispersant is given by the lime soap dispersing power (LSDP) which is
determined using the lime soap dispersion test as described in an article
by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume
27, pages 88-90, (1950). This lime soap dispersion test method is widely
used by practitioners in this art field being referred to , for example, in
the following review articles; W.N. Linfield, Surfactant Science Series,
Volume ?, p3; W.N. Linfield, Tenside Surf. Det. , Volume 27,
pages159-161, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and
Toiletries, Volume 104, pages 71-73, (1989). The LSDP is the ~o weight
ratio of dispersing agent to sodium oleate required to disperse the lime
soap deposits formed by 0.025g of sodium oleate in 30m1 of water of
333ppm CaC03 (Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap dispersant capability will include
certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and
ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord
with the invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5,
particularly C 12-C 15 alkyl ethoxysulfate surfactant with a degree of
ethoxylation of about 3 (LSDP =4), and the C 13-C 15 ethoxylated alcohols
with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold
under the trade marks Lutensol A012 and Lutensol A030 respectively, by
BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in
the article by M.K. Nagarajan and W.F. Masler, to be found in
Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). Examples of
such polymeric lime soap dispersants include certain water-soluble salts
of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and
A
21~~6051
44
an acrylamide or substituted acrylamide, where such polymers typically
have a molecular weight of from 5,000 to 20,000.
Suds supnressing_~ystem
The detergent compositions of the invention, when formulated for use in
machine washing compositions, preferably comprise a suds suppressing
system present at a level of from 0.01 °6 to 15 °k , preferably
from 0.05
to 10 °b , most preferably from 0.1 l to 5 °b by weight of the
composition.
Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds, 2-alkyl and alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of
compounds which act such as to depress the foaming or sudsing produced
by a solution of a detergent composition, particularly in the presence of
agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone
antifoam compounds defined herein as any antifoam compound including
a silicone component. Such silicone antifoam compounds also typically
contain a silica component. The term "silicone" as used herein, and in
general throughout the industry, encompasses a variety of relatively high
molecular weight polymers containing siloxane units and hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end
blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty
acids and soluble salts thereof. These materials are described in US
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids, and salts thereof, for use 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.
X146051
Other suitable antifoam compounds include, for example, high molecular
weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of
monovalent alcohols, aliphatic C 1 g-C4p ketones (e.g. stearone) 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, bis stearic acid amide and monostearyl
di-alkali metal (e.g. sodium, potassium, lithium) phosphates and
phosphate esters.
Copolymers of ethylene oxide and propylene oxide, particularly the mixed
ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from
10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a
degree of propoxylation of from 1 to 10, are also suitable antifoam
compounds for use herein.
Suitable 2-alley-alcanols antifoam compounds for use herein have been
described in DE 40 21 265. The 2-alkyl-alcanols suitable for use herein
consist of a C6 to C 16 alkyl chain carrying a terminal hydroxy group, and
said alkyl chain is substituted in the a position by a C 1 to C 10 alkyl
chain.
Mixtures of 2-alkyl-alcanols can be used in the compositions according to
the present invention.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most
preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50 % to 99 % ,
preferably 75 % to 95 % by weight of the silicone
antifoam compound; and
(ii) silica, at a level of from 1 % to 50 % , preferably 5 % to 25 %
by weight of the silicone/silica antifoam compound;
46 , 21 4 6 0 5 1
wherein said silica/silicone antifoam compound is incorporated at a level
of from 5 % to 50 % , preferably 10 % to 40 % by weight;
(b) a dispersant compound, most preferably comprising a silicone
glycol rake copolymer with a polyoxyalkylene content of 72-78 %
and an ethylene oxide to propylene oxide ratio of from 1:0.9 to
1:1.1, at a level of from 0.5 % to 10 % , preferably 1 % to 10 % by
weight; a particularly preferred silicone glycol rake copolymer of
this type is DC0544, commercially available from DOW Corning.
(c) an inert carrier fluid compound, most preferably comprising a C 16-
C 1 g ethoxylated alcohol with a degree of ethoxylation of from 5 to
50, preferably 8 to 15, at a level of from 5 % to 80 % , preferably
% to 70 % , by weight;
A preferred particulate suds suppressor system useful herein comprises a
mixture of an alkylated siloxane of the type hereinabove disclosed and
solid silica.
The solid silica can be a fumed silica, a precipitated silica or a silica made
by the gel formation technique. The silica particles suitable have an
average particle size of from 0.1 to 50 micrometers, preferably from 1 to
micrometers and a surface area of at least SOm2/g. These silica
particles can be rendered hydrophobic by treating them with dialkylsilyl
groups and/or trialkylsilyl groups either bonded directly onto the silica or
by means of a silicone resin. It is preferred to employ a silica the
particles of which have been rendered hydrophobic with dimethyl and/or
trimethyl silyl groups. A preferred particulate antifoam compound for
inclusion in the detergent compositions in accordance with the invention
suitably contain an amount of silica such that the weight ratio of silica to
silicone lies in the range from 1:100 to 3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds suppressing system is represented by a
hydrophobic silanated (most preferably trimethyl-silanated) silica having a
particle size in the range from 10 nanometers to 20 nanometers and a
specific surface area above SOm2/g, intimately admixed with dimethyl
A
4, 2146051
silicone fluid having a molecular weight in the range from about 500 to
about 200,000 at a weight ratio of silicone to silanated silica of from
about 1:1 to about 1:2.
A highly preferred particulate suds suppressing system is described in EP-
A-0210731 and comprises a silicone antifoam compound and an organic
carrier material having a melting point in the range 50°C to
85°C,
wherein the organic carrier material comprises a monoester of glycerol
and a fatty acid having a carbon chain containing from 12 to 20 carbon
atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing systems wherein the organic carrier material is a fatty acid or
alcohol having a carbon chain containing from 12 to 20 carbon atoms, or
a mixture thereof, with a melting point of from 45 ° C to 80 ° C
.
Other highly preferred particulate suds suppressing systems are described
in copending Canadian Application 2,099,129 in the name of the
Procter and Gamble Company which systems comprise silicone antifoam
compound, a carrier material, an organic coating material and glycerol at
a weight ratio of glycerol : silicone antifoam compound of 1:2 to 3:1.
EP 461, 699 published December 18, 1991 also discloses highly
preferred particulate suds suppressing systems comprising silicone
antifoam compound, a carrier material, an organic coating material and
crystalline or amorphous aluminosilicate at a weight ratio of
aluminosilicate : silicone antifoam compound of 1:3 to 3:1. The preferred
carrier material in both of the above described highly preferred granular
suds controlling agents is starch.
An exemplary particulate suds suppressing system for use herein is a
particulate agglomerate component, made by an agglomeration process,
comprising in combination
(i) from S g6 to 30 ~o , preferably from 8 °~ to 15 °l~ by
weight of the
component of silicone antifoam compound, preferably comprising
in combination polydimethyl siloxane and silica;
(ii) from 50 ~ to 90 % , preferably from 60 9b to 80 °Y by weight of
the
component, of carrier material, preferably starch;
A
2146051
48
(iii) from 5 % to 30 % , preferably from 10 % to 20 % by weight of the
component of agglomerate binder compound, where herein such
compound can be any compound, or mixtures thereof typically
employed as binders for agglomerates, most preferably said
agglomerate binder compound comprises a C 16-C 1 g ethoxylated
alcohol with a degree of ethoxylation of from 50 to 100; and
(iv) from 2 % to 15 % , preferably from 3 °~ to 10 °k , by
weight of C 12-
C22 hydrogenated fatty acid.
Form of the corr~ositions
The detergent compositions of the invention can be formulated in any
desirable form such as powders, granulates, pastes, liquids, tablets and
gels.
quid compositions
The detergent compositions of the present invention may be formulated as
liquid detergent compositions. Such liquid detergent compositions
typically comprise from 94 % to 35 % by weight, preferably from 90 % to
40 % by weight, most preferably from 80 % to 50 % by weight of a liquid
carrier, e.g., water, preferably a mixture of water and organic solvent.
Gel com,~ositions
The detergent compositions of the present invention may also be in the
form of gels. Such compositions are typically formulated with
polyalkenyl polyether having a molecular weight of from about 750,000
to about 4,000,000.
Solid compositions
The detergent compositions of the invention are preferably in the form of
solids, such as powders and granules.
214601
49
The particle size of the components of granular compositions in
accordance with the invention should preferably be such that no more that
% of particles are greater than 1.4mm in diameter and not more than 5 %
of particles are less than O.lSmm in diameter.
The bulk density of granular detergent compositions in accordance with
the present invention typically have a bulk density of at least 450 g/litre,
more usually at least 600 g/litre and more preferably from 650 g/litre to
1200 g/litre.
Bulk density is measured by means of a simple funnel and cup device
consisting of a conical funnel moulded rigidly on a base and provided
with a flap valve at its lower extremity to allow the contents of the funnel
to be emptied into an axially aligned cylindrial cup disposed below the
funnel. The funnel is 130 mm and 40 mm at its respective upper and
lower extremities. It is mounted so that the lower extremity is 140 mm
above the upper surface of the base. The cup has an overall height of 90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its
nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed
from the cup by passing a straight edged implement e.g. a knife, across
its upper edge. The filled cup is then weighed and the value obtained for
the weight of powder doubled to provide the bulk density in g/litre.
Replicate measurements are made as required.
Making,~nrocesses - granular compositions
In general, granular detergent compositions in accordance with the
present invention can be made via a variety of methods including dry
mixing, spray drying, agglomeration and granulation.
Washing methods
2~~so5~
Sa
The compositions of the invention may be used in essentially any washing
or cleaning method, including machine dishwashing methods.
Machine dishwashine method
A preferred machine dishwashing method comprises treating soiled
articles selected from crockery, glassware, hollowware and cutlery and
mixtures thereof, with an aqueous liquid having dissolved or dispensed
therein an effective amount of a machine dishwashing composition in
accord with the inevntion. By as effective amount of the machine
dishwashing composition it is meant from 8g to 60g of product dissolved
or dispersed in a wash solution of volume from 3 to 10 litres, as are
typical product dosages and wash solution volumes commonly employed
in conventional machine dishwashing methods.
In the detergent compositions, the abbreviated component identifications
have the following meanings:
XYEZS . C lX - C ly sodium alkyl sulfate condensed
with an average of Z moles of ethylene oxide
per mole
Nonionic - . C 13-C 15 ~~ e~oxylated/propoxylated fatty
alcohol with an average degree of ethoxylation
of 3.8 and an average degree of propoxylation
of 4.5 sold under the trademark Plurafac
LF404 by BASF Gmbh
Silicate . Amorphous Sodium Silicate (SiO2:Na20 ratio
= 2.0)
Carbonate . Anhydrous sodium carbonate
Phosphate . Sodium tripolyphosphate
A
51 2146051
MA/AA . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
Mn catalyst Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(PF~2
Citrate . Tri-sodium citrate dihydrate
pg4 , Anhydrous sodium perborate tetrahydrate in
compacted form such that the available oxygen
is released in a 5 minute interval when
incorporated into the compositions of the
Examples and employing the test method
described herein.
Percarbonate . Anhydrous sodium percarbonate bleach of
empirical formula 2Na2C03.3FI202 coated
with a. mixed salt of formula
Na2S04.n.Na2C03 where n is 0.29 and where
the weight ratio of percarbonate to mixed salt
is 39:1
TAED . Tetraacetyl ethylene diamine
Paraffin . Paraffin oil sold under the trademark Winog 70
by Wintershall.
Protease . Proteolytic enzyme sold under the trademark
Savinase by Novo Industries A/S (approx 2 °l~
enzyme activity).
Amylase . Amylolytic enzyme sold under the trademark
Termamyl 60T by Novo Industries A/S
(approx 0.9 °~o enzyme activity)
A
214~G05~
52
Lipase . Lipolytic enzyme sold under the trademark
Lipolase by Novo Industries A/S (approx 2 %
enzyme activity)
DETPMP . Diethylene triamine penta (methylene
phosphoric acid), marketed by Monsanto under
the trade mark bequest 2060
Granular Suds . 12 ~o Silicone/silica, 18 °Xo stearyl alcoho1,70
Suppressor starch in granular form
Sulphate . Anhydrous sodium sulphate.
In the following examples all levels of enzyme quoted are expressed as 9~
active enzyme by weight of the composition.
A
2~4som
53
Example 1
The following machine dishwashing detergent compositions were
prepared (parts by weight). Composition A is a prior art composition,
compositions B to F are in accord with the invention.
A B C D E F
Citrate 15.0 15.0 - 24.0 24.0 29.0
Phosphate - - 46.0 - - -
MA/AA 6.0 6.0 - 6.0 6.0 -
Silicate 9.0 9.0 33.0 27.5 27.5 25.7
Carbonate 20.0 20.0 - 12.5 12.5 -
Percarbonate 9.1 9.1 10.4 10.4 10.4 -
PB4 - - - - - 10.6
TAED 2.2 2.2 3.0 3.0 3.0 4.4
Benzotriazole - 0.4 0.6 - 0.5 0.3
Paraffin - 0.5 - 0.6 0.5 0.5
Mn catalyst 0.03 0.03 0.03 0.03 0.03 0.03
Protease 0.04 0.04 0.03 0.04 0.04 0.04
Amylase 0.02 0.02 0.01 0.02 0.01 0.01
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54
Lipase - - 0.03 0.03 0.03 -
DETPMP - - - - - 0.5
Nonionic 1.7 1.7 1.5 1.5 1.5 1.5
Sulphate 1.4 1.4 2.4 12.1 12.1 3.0
35AE3S - - S.0 - 5.0 -
Granular Suds - - 1.0 - 1.0 -
Su ressor
misc/moisture
to balance
The compositions provide good soil removal when used in a machine
dishwashing process.
Comparative testing 1
The following comparative testing was conducted; composition B of
Example I was compared for anti-silver tarnishing performance, to a
reference composition (composition A of Example I) containing no
benzotriazole or paraffin oil.
The testing involved machine testing, using a Bosch Siemens dishwasher,
20g product dosage, 65 °C economy cycles, and 10 cycles.
Performance was graded by 4 expert panellists through visual inspection
according to the following scale
where 0 = no tarnish (shiny silver)
1 = very slight tarnish
2' = tarnish
3 = very tarnished
4 = severe tarnish (black coverage)
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Results were as follows : (average of the 4 gradings from the panellists)
Com osition A __ Com osition B
3.0 0.5
Composition B shows a reduced level of silver tarnishing in accord with
the invention.
