Note: Descriptions are shown in the official language in which they were submitted.
CA 02305224 2002-09-05
A Detergent Composition
Technical Field
The present invention relates to detergent compositions comprising anionic mid-
branched surfactant compounds and a bleaching system comprising a hydrophobic
and a hydrophilic bleach precursor. The compositions are particularly useful
as solid
laundry detergent compositions.
Background to the Invention
Recently, a certain new type of anionic mid-chain branched surfactants has
been
developed. These surfactants are described in Canadian Application
Nos. 2,252,435; 2,252,362; 2,252,436; 2,252,424 and 2,252,437.
It has been determined that these mid-chain branched surfactants are excellent
surfactants, in particular for use in laundry products, especially under cool
or cold
water washing conditions even as low as 20°C-5°C. It has also
been found that
combination of two or more of these mid-chain branched surfactants can provide
a
surfactant mixture that is even higher in surfactancy and has better low
temperature
water solubility.
A component traditionally present in most detergents is a bleach. Various
bleaching
systems have been developed over the past decades, such as bleaching systems,
based on organic peroxyacids. The organic peroxyacids are often obtained by
the in
situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach
activators).
However, it is generally known that a variety of other detergent ingredients,
commonly used in detergent, are not always (fully) bleach compatible, for
example
certain surfactants, perfumes, enzymes. These ingredient can react with the
bleach,
which results in a reduction of the performance of both the bleach and these
CA 02305224 2002-09-05
ingredients. It is thus desirable to formulate detergents which comprise as
little
bleach as necessary to obtain a excellent bleaching performance, and to
formulate the
detergents with bleach compatible ingredients
It has now been found these mid-chain branched surfactants are very bleach
compatible. Furthermore, it has been found that detergent compositions
comprising
these mid-chain branched surfactants and a mixed bleaching system, comprising
hydrophobic and hydrophilic bleach precursors, an excellent bleaching and
cleaning
performance is achieved, even when low amounts of bleach are used. It has
surprisingly been found that both hydrophilic and hydrophobic, bleachable and
non-
bleachable stains and soils are more effectively removed. Without being bound
by
theory, it is believed that this is due to the excellent stain and soil
removal by the
mid-chain branched surfactant, which facilitates the access to the remaining
bleachable stains and soils by the hydrophobic and hydrophilic bleaches and
allows
these bleaches to bleach very effectively these remaining bleachable stains.
Another additional benefit is that by the reduction of the amount of bleach
which is
required for a good bleaching performance, the ease of formulation can be
improved
and the formulation costs can be reduced.
Summary of the invention
The invention relates to detergent compositions comprising
a) at least 0.5%, preferably at least 5%, more preferably at least 10% by
weight of
the composition a surfactant system, comprising one or more longer alkyl
chain,
mid-chain branched surfactant compounds of the formula:
Ab-X-B
wherein:
(I) Ab is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to
22 carbons in the moiety,.preferably from 12 to about 18, having: (1) a
longest linear
carbon chain attached to the - X - B moiety in the range of from 8 to 21
carbon
atoms; (2) one or more C 1 - C3 alkyl moieties branching from this longest
linear
carbon chain; (3) at least one of the branching alkyl moieties is attached
directly to a
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WO 99/19429 PCTNS97/18842
carbon of the longest linear carbon chain at a position within the range of
the
position 2 carbon, counting from position 1 carbon (# 1 ) which is attached to
the - X
- B moiety, to the position of the terminal carbon minus 2 carbons, (the (w -
2)
carbon); and (4) when more than one of these compounds is present, the average
total number of carbon atoms in the Ab-X moieties in the above formula is
within
the range of greater than 14.5 to about 18, preferably from about 15 to about
17;
(II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine
oxides, polyoxyalkyiene, preferably polyoxyethylene and polyoxypropylene,
alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol
sulfonates,
polygluconates, polyphosphate esters, phosphonates, sulfosuccinates,
sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates,
sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides,
monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol
esters,
glycerol ester sulfates, glycerol ethers, glycerol ether sulfates,
polyglycerol ethers,
polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters,
ammonioalkanesulfonates, amidopropyl betaines, alkylated goats,
alkyated/polyhydroxyalkylated goats, alkylated goats,
alkylated/polyhydroxylated
oxypropyl goats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and
sulfonated fatty acids; and
(III) X is selected from -CH2- and -C(O)-; and
b) at least 0.5% by weight of the composition a bleaching system comprising
(I) a hydrophobic bleach precursor; and
(II) a hydrophilic bleach precursor.
Detailed description of the invention
Mid-chain branched surfactant compounds-containing surfactant system
The detergent compositions of the invention comprise at least 0.5%, preferably
at
least 5%, more preferably at least 10% by weight of the composition of a
surfactant
system, comprising longer alkyl chain, mid-chain branched surfactant
compounds,
selected from the group consisting of surfactant compounds having the formula
as
defined above.
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4
Preferred surfactant systems herein comprise longer alkyl chain, mid-chain
branched
surfactant compounds of the above formula wherein the Ab moiety is a branched
primary alkyl moiety having the formula:
R R1 R2
CH3CH2(CH2)r,~,CH(CH2}xCH(CH2~CH(CH2)z-
wherein the total number of carbon atoms in the branched primary alkyl moiety
of
this formula (including the R, R1, and R2 branching) is from 13 to 19; R, R1,
and
R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably
methyl), provided R, R1, and R2 are not all hydrogen and, when z is 0, at
least R or
R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to
13; y is an
integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from
7 to 13.
In general, for the mid-chain branched surfactant compounds of the surfactant
system, certain points of branching (e.g., the location along the chain of the
R, R1,
andlor R2 moieties in the above formula) are preferred over other points of
branching along the backbone of the surfactant. The formula below illustrates
the
mid-chain branching range (i.e., where points of branching occur), preferred
mid-
chain branching range, and more preferred mid-chain branching range for mono-
methyl branched alkyl Ab moieties useful according to the present invention.
CH3CH2CH2CH2CH2CH2(CH2)1_~CH2CH2CH2CH2CH2
more referred ran
p g
preferred range
mid-chain branching ran
It should be noted that for the mono-methyl substituted surfactants these
ranges
exclude the two terminal carbon atoms of the chain and the carbon atom
immediately adjacent to the -X - B group.
The formula below illustrates the mid-chain branching range, preferred mid-
chain
branching range, and more preferred mid-chain branching range for di-methyl
substituted alkyl Ab moieties useful according to the present invention.
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5
CH3CH2CH~CHZCH,CH2(CH2)o-6CH~CH~CH~CHZCH~ -
more preferred rang
preferred range
mid-chain branching range
Preferred are surfactant compounds wherein in the above formula the Ab moiety
does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms
directly
attached to one carbon atom).
The most preferred mid-chain branched surfactants compounds for use in the
detergent compositions herein are mid-chain branched primary alkyl sulfonate
and,
even more preferably, sulfate surfactants. It should be understood that for
the
purpose of the invention, it may be preferred that the surfactant system
comprises a
mixture of two or more mid-chain branched primary alkyl sulfate or sulphonate
surfactants.
Preferred mid-chain branched primary alkyl sulfate surfactants are of the
formula
R R1 R2
CH3CH2(CH2h,"CH(CH2~CH(CH2}yCH(CH2)ZOS03M
These surfactants have a linear primary alkyl sulfate chain backbone (i.e.,
the longest
linear carbon chain which includes the sulfated carbon atom) which preferably
comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties
comprise preferably a total of at least 14 and preferably no more than 20,
carbon
atoms. In the surfactant system comprising more than one of these sulfate
surfactants, the average total number of carbon atoms for the branched primary
alkyl
moieties is preferably within the range of from greater than 14.5 to about
17.5.
Thus, the surfactant system preferably comprises at least one branched primary
alkyl
sulfate surfactant compound having a longest linear carbon chain of not less
than 12
carbon atoms or not more than 19 carbon atoms, and the total number of carbon
atoms including branching must be at least 14, and further the average total
number
of carbon atoms for the branched primary alkyl moiety is within the range of
greater
than 14.5 to about 17.5.
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6
R, R1, and R2 are each independently selected from hydrogen and Cl-C; alkyl
group (preferably hydrogen or C 1-C2 alkyl, more preferably hydrogen or
methyl,
and most preferably methyl), provided R, R1, and R2 are not all hydrogen.
Further,
when z is 1, at least R or R1 is not hydrogen.
M is hydrogen or a salt forming cation depending upon the method of synthesis.
Examples of salt forming cations are lithium, sodium, potassium, calcium,
magnesium, quaternary alkyl amines having the formula
R3
R6-N-R4
RS
wherein R3, R4, RS and R6 are independently hydrogen, C 1-C22 alkylene, C4-C22
branched alkylene, Cl-C6 alkanol, Cl-C22 alkenylene, C4-C22 branched
alkenylene, and mixtures thereof. Preferred cations are ammonium (R3, R4, RS
and.
R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium,
and .
mixtures thereof. The monoalkanol ammonium compounds of the present invention
have R3 equal to C 1-C6 alkanol, R4, RS and R6 equal to hydrogen; dialkanol
ammonium compounds of the present invention have R3 and R4 equal to C 1-C6
alkanol, RS and R6 equal to hydrogen; trialkanol ammonium compounds of the
present invention have R3, R4 and RS equal to Cl-C6 alkanol, R6 equal to
hydrogen. Preferred alkanol ammonium salts of the present invention are the
mono-,
di- and tri- quaternary ammonium compounds having the formulas:
H3N+CH2CH20H, H2N+(CH2CH20H)2, HN+(CH2CH20H)3.
Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed
above;
most preferred is sodium.
Further regarding the above formula, w is an integer from 0 to 13; x is an
integer
from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and
w + x + y
+ z is an integer from 8 to 14.
A preferred mid-chain branched primary alkyl sulfate surfactant is, a C 16
total
carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone
and
having l, 2, or 3 branching units (i.e., R, R1 and/or R2) of in total 3 carbon
atoms,
CA 02305224 2003-07-28
(whereby thus; the total number of carbon atoms is at least 16). Preferred
branching
units can be one propyl branching unit or three methyl branching units.
Another preferred surfactant :system of the pre;sent invention have one or
more
branched primary alkyl sulfates having the fomrrula
R1 1~2
I f
CH3CH~(CHZ)xCH(CHZ)y(~,H(CHz)zOSOaM
wherein the total number of carbon atoms. including branching, is from 15 to
18,
and when more than one of these sulfates is present, the average total number
of
carbon atoms in the branched primary alkyl moieties having the above formula
is
within the range of greater than 14.5 to about 17.x; R1 and R2 are each
independently hydrogen or C1-C3 alkyl; M is a water soluble canon; x is from 0
to
I 1; y is from 0 to 11; z is at least 2; and x -+- y + z is liom 9 to 13;
provided R1 and
R2 are not both hydrogen.
Preferably, the surfactant system comprises at least 20% by weight of the
system,
more preferably at least 60°,~° by weight , even mare preferably
at least 90% by
weight of the ;system, of a mid chain branched primary alkyl sulfates,
preferably
having R1 and R2 independently hydrogen or methyl, provided RI and R2 are not
both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the
average
total number of carbon atoms in these sulfate surfactants is preferably from I
S to 17,
more preferably from 16-I i .
Furthermore, !referred surfactant systems are those, which comprise at least
about'
20%, more pr~:ferably at least fi0%, even more preferably at least 95% by
weight of
the system, of one or more mid-chain branched alkyl sulfates having the
formula:
CHI
(1) t:H3 (CHz)aCH (CHZ~CHZ OS03M or
CH3 CH3
CH3 (CH~)dCH (C'.Hz)e CHCH~ OSQ3M
(!I)
or mixtures thereof; wherein M represents one or mare canons; a, b, d, and a
are
integers, a+b is from 10 to l Cr, d+e is from 8 to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8;
when a + b -- 11, a is an integer from 2 to l 0 and b is an integer from 1 to
9:
when a + b = 12, a is an integer from 2 to i 1 .arrd b is an integer from I to
10;
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8
when a + b = 13, a is an integer from 2 to 12 and b is an integer from I to
11;
when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to
12;
when a + b = 15, a is an integer from 2 to 14 and b is an integer from I to
13;
when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to
14;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
when d + a = 9, d is an integer from 2 to 8 and a is an integer from 1 to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from 1 to 8;
when d + a = 11, d is an integer from 2 to 10 and a is an integer from 1 to 9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
when d + a = 13, d is an integer from 2 to 12 and a is an integer from 1 to
11;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12;
whereby, when more than one of these sulfate surfactants is present in the
surfactant
system, the average total number of carbon atoms in the branched primary alkyl
moieties having the above formulas is within the range of greater than 14.5 to
about
I7.5.
Preferred mono-methyl branched primary alkyl sulfates are selected from the
group
consisting of 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-
methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl
pentadecanol
sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-
methyl
pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol
sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-
methyl
hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol
sulfate, 7-
methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol
sulfate, 10-methyl hexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-
methyl
hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol
sulfate;
and mixtures thereof.
Preferred di-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol
sulfate, 2,5-
methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl
tetradecanol
sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate,
2,I0-methyl
tetradecanol sulfate, 2,i 1-methyl tetradecanol sulfate, 2,12-methyl
tetradecanol
sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-
methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl
pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol
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9
sulfate, 2,10-methyl pentadecanol sulfate, 2,11-methyl pentadecanol sulfate,
2,12-
methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixtures
thereof.
The following branched primary alkyl sulfates comprising 16 carbon atoms and
having one branching unit are examples of preferred branched surfactants
useful in
the present invention compositions:
5-methylpentadecylsulfate having the formula:
OS03M
CH3
6-methylpentadecylsulfate having the formula
CH3
OS03M
7-methylpentadecylsulfate having the formula
OS03M
CH3
8-methylpentadecylsulfate having the formula
H3
OS03M
9-methylpentadecylsulfate having the formula
OS03M
CH3
10-methylpentadecylsulfate having the fonmula
CH3
OS03M
wherein M is preferably sodium.
The following branched primary alkyl sulfates comprising 17 carbon atoms
and having two branching units are examples of preferred branched surfactants
according to the present invention:
2,5-dimethylpentadecylsulfate having the formula:
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10
CH3
OS03M
CH3
2,6-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,7-dimethylpentadecylsulfate having the formula
H3
OS03M
CH3
2,8-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,9-dimethylpentadecylsulfate having the formula
CH3
OS03M
CH3
2,10-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
wherein M is preferably sodium.
Bleaching system
The bleaching system of the invention comprises a hydrophobic and a
hydrophilic
bleach precursor.
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11
The bleaching system is present at a level of at least 0.5% by weight of the
composition, preferably from 0.5% to 45% by weight, more preferably from 1% to
30% by weight, most preferably from 1.5% to 25% by weight of the detergent
compositions.
Preferably, the bleach precursors are peroxyacid bleach precursors which may
be
represented as
X-C-L
where L is a leaving group and X is essentially any functionality, which
determines
for the present invention whether the precursor is hydrophobic or hydrophilic,
and
which is such that on perhydroloysis the structure of the peroxyacid produced
is
O
X-C-OOH
The hydrophobic bleach of the present invention comprises a group X which
contain
at least 6 carbon atoms. The hydrophilic bleach of the present invention
comprises a
group X which contain less than 6 carbon atoms.
Preferably, the bleaching system of the invention contains a hydrogen peroxide
source and a hydrophilic and hydrophobic (organic peroxyacid) bleach precursor
compound. The production of the organic peroxyacid occurs by an in situ
reaction of
the precursors with a source of hydrogen peroxide. Preferred sources of
hydrogen
peroxide include inorganic perhydrate bleaches. Preferred perhydrate bleaches
are
metal perborates, metal percarbonates, particularly the sodium salts.
Perborate can
be mono or tetra hydrated. Sodium percarbonate has the formula corresponding
to
2Na2C03.3H202, and is available commercially as a crystalline solid. Potassium
or
sodium peroxymonopersulfate is another optional inorganic perhydrate salt of
use in
the detergent compositions herein.
The inorganic perhydrate bleaches are preferably present at a level of from 1
% to
40% by weight, more preferably from 3% to 35% by weight, most preferably from
5% to 20% by weight of the detergent composition.
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12
Leavine nrouQs
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis 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.
Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ , -O ~ Y , and -O
O
-N-C-R -N N , -N-C-CH-R4 ,
R3 Y
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O C H _O Y O
-O-C-R' -N~ ~NR4 , -Nw /NR4
C C
0 0
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from
1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4
is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be
substituted by essentially any functional group including, for example alkyl,
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WO 99119429 PCT/US97118842
13
hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammmonium groups.
The preferred solubilizing groups are -S03 M+, -C02-M+, -S04-M+, -N+(R3)4X
and O<--N(R3)3 and most preferably -S03 M+ and -C02-M+ wherein R' is an
alkyl chain containing from 1 to 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.
Preferred hydrophilic and hydrophobic precursors
Suitable 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, lactams and acylated derivatives of imidazoles and
oximes. 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.
Alk~Qercarboxvlic acid bleach precursors
Alkyl percarboxylic acid bleach precursors are preferred precursors for use
herein.
They form percarboxylic acids on perhydrolysis. Preferred precursors of this
type
provide peracetic acid on perhydrolysis.
Preferred can be phenyl esters of C ~4_zz - alkanoic or alkenoic acids, esters
of
hydroxylamine, geminal diesters of lower alkanoic acids and gem-idols, such as
those described in EP-A-0125781 especiallyl,l,5-triacetoxypent-4-ene and
1,1,5,5-
tetraacetoxypentane and the corresponding butene and butane compounds,
ethylidene benzoate acetate and bis(ethylidene acetate) adipate and enol
esters, for
instance as described in EP-A-0140648 and EP-A-0092932.
Preferred alkyl percarboxylic precursor compounds of the imide type include
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
CA 02305224 2002-09-05
14
contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED, being a
hydrophilic precursor) is particularly preferred.
Other highly preferred alkyl percarboxylic acid precursors include sodium
acetoxybenzene sulfonate (ABS) and pentaacetyl glucose, dodecanolyloxy -
benzenesulphonate sodium salt, decanoyloxy - benzenesulphonate sodium salt
(DOBS) , benzoyloxy - benzenesulphonate sodium salt (BOBS), more preferred
sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS) and even more
preferred sodium nonanoyloxybenzene sulfonate (HOBS), (being hydrophobic
precursors).
Amide substituted alkyl neroxyacid precursors
Amide substituted alkyl peroxyacid precursors are preferred precursors herein.
They
include those of the following general formulae:
R~--C-N-R2-C-L R~-N-C-R2--C-L
R5 O~ or R5 O[
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group containing from 1 to 14 carbon atoms, and RS is H or an alkyl group
containing 1 to 10 carbon atoms and L can be essentially any leaving group.
Amide
substituted bleach activator compounds of this type are described in EP-A-O i
70386.
Perbenzoic acid precursor
Perbenzoic acid precursors are other preferred precursors herein. They provide
perbenzoic acid on perhydrolysis. Suitable 0-acylated perbenzoic acid
precursor
compounds include the substituted and unsubstituted benzoyl oxybenzene
sulfonates, and the benzoylation products of sorbitol, glucose, and all
saccharides
with benzoylating agents, and those of the imide type including N-benzoyl
succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted
areas.
Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole
and
N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
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15
Highly preferred hydrophobic precursors are (6-octanamido-
caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, (6-
nonanamidocaproyl)oxy benzene sulfonate, decanoyloxy - benzenesulphonate
sodium salt and benzoyloxy - benzenesulphonate sodium salt.
Benzoxazin organic peroxyacid precursors
Also suitable are precursors of the benzoxazin-type, as disclosed for example
in EP-
A-332,294 and EP-A-482,807, particularly those having the formula:
O
II
CEO
\.J , C-Rt
'N
wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.
Additional deter~yent 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 composition, and
the
precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional
detergent components selected from additional surfactants, additional
bleaches,
bleach catalysts, alkalinity systems, builders, organic polymeric compounds,
additional enzymes, suds suppressors, lime soap dispersants, soil suspension
and
anti-redeposition agents and corrosion inhibitors.
Additional surfactant
The detergent compositions of the invention preferably contain an additional
surfactant selected from additional anionic, nonionic, cationic, ampholytic,
amphoteric and zwitterionic surfactants and mixtures thereof.
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16
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.
Anionic surfactant
The detergent compositions of the present invention preferably comprise an
additional anionic surfactant. Essentially any anionic surfactants useful for
detersive
purposes can be comprised in the detergent composition. 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. Anionic sulfate surfactants are
preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-
acyl taurates, fatty acid amides of methyl tauride, alkyl succinate~ and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated
C 12-C 18 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 and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 17 acyl-N-(C 1-
C4
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).
CA 02305224 2002-09-05
17
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary C I p-C I g alkyl sulfates, more preferably the C I I -C 15 branched
chain alkyl
sulfates and the C I2-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C I 0-C I g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles
of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant
is a C I I -C I g, most preferably C I I -C I S alkyl sulfate which has been
ethoxylated
with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per
molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred
alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been
disclosed
in PCT Patent Publication No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 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
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the
alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl
carboxyls'),
especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to CIg 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 20 % and M is a cation. Suitable alkyl polyethoxy
polycarboxylate
surfactants include those having the formula RO-(CHRI-CHR2-O)-R3 wherein R is
a C6 to C I g alkyl group, x is from I to 25, RI and R2 are selected from the
group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic
acid radical, and mixtures thereof, and R3 is selected from the group
consisting of
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WO 99/19429 PCTIUS97/18842
18
hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8
carbon
atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. 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.
Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (R1 ) CH2 COOM, wherein R is a CS-C 1 ~ linear or branched alkyl or
alkenyl
group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred
examples
are the myristyl and_oleoyl methyl sarcosinates in the form of their sodium
salts.
Alkoxvlated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated
and propoxylated nonionic surfactants are preferred.
The nonionic surfactant is preferably present at a ratio to the surfactant
system a0,
comprising the rnid-branched surfactants of the invention, of from 10:1 to
1;10,
more preferably from 5:1 to 1:10, even more preferably from 1:1 to 1:10.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates with propylene glycol, and the nonionic ethoxylate condensation
products with propylene oxide/ethylene diamine adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
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WO 99/19429 PCT/US97118842
19
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, more preferably form 9 to 15 carbon atoms, with from 3 to 12
moles of ethylene oxide per mole of alcohol.
Nonionic nolyhydroxv fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1-C4
alkyl, more
preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2
is a CS-
C31 hydrocarbyl, preferably straight-chain CS-C 19 alkyl or alkenyI, more
preferably
straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain C 11-C
17
alkyl or aIkenyl, 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.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include 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 -(C2H4O)xH, where x is in the range of
from
1 to 3.
Nonionic alkvlpolysaccharide 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 6
to
30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
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WO 99/19429 PCTIUS97/18842
20
wherein R2 is selected from the group consisting of alkyl, alkyiphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is
from 1.3
to 8. The glycosyl is preferably derived from glucose.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants
and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8 to
26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2
to 3
carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3;
and each
RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene
oxide
group containing from l to 3 ethylene oxide groups. Preferred are C 10-C 1 g
alkyl
dimethylamine oxide, and C10_18 acylamido alkyl dimethyiamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol{TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
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.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R is a C6-Clg hydrocarbyl group, each R1 is typically C1-C3 alkyl, and
R2
is a C 1-C~ hydrocarbyl group. Preferred betaines are C 12_1 g dimethyl-
ammonio
hexanoate and the C 1 U-18 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
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WO 99/19429 PCT/US97/18842
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Cationic surfactants
Additional cationic surfactants can also be used in the detergent compositions
herein. Suitable cationic surfactants include the quaternary ammonium
surfactants
selected from mono C6-C I 6, preferably C6-C I O N-alkyl or alkenyl ammonium
surfactants wherein the remaining N positions are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Alkalinity
In the detergent compositions of the present invention preferably an
alkalinity
system is present to achieve optimal cationic ester surfactant performance.
The
alkalinity system comprises components capable of providing alkalinity species
in
solution. By alkalinity. species it is meant herein: carbonate, bicarbonate,
hydroxide,
the various silicate anions, percarbonate, perborates, perphosphates,
persulfate and
persilicate.
Such alkalinity species can be formed for example, when alkaline salts
selected from
alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate,
including
crystalline layered silicate, salts and percarbonate, perborates,
perphosphates,
persulfate and persilicate salts, as described above, and any mixtures
thereof, are
dissolved in water.
Examples of carbonates are the alkaline earth and alkali metal carbonates,
including
sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine
calcium carbonate such as are disclosed in German Patent Application No.
2,321,001 published on November 15, 1973.
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.O 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.
Preferred crystalline layered silicates for use herein have the general
formula
NaMSix02x+1 ~YH20
CA 02305224 2002-09-05
23
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-3 742043. Herein, x in the general formula above preferably 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-6 TM
Water-soluble builder compound
The detergent compositions of the present invention preferably contain a water-
soluble 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% by
weight of the composition.
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, borates,
phosphates, 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
aminosuccintates 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.
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WO 99/19429 PCT/US97/18842
24
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylafes, 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.
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 are useful water-
soluble
builders herein.
Suitable 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.
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 largely water insoluble builders include the sodium
aluminosilicates.
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 276, more preferably from 10 to 264. The
aluminosilicate material are in hydrated form and are preferably crystalline,
CA 02305224 2002-09-05
25
containing from I 0% to 28%, more preferably from 18% to 22% water in bound
form.
The aluminositicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosiiicate ion exchange
materials
are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite
X,
Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 (A102) 12 (Si02)12J. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)86(Si02)106~. 276 H20.
Preformed orsanic peroxyacid
The detergent compositions or the bleaching system may contain, in addition to
the
bleach precursors, a preformed organic peroxyacid, typically at a level of
from 1% 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
O R5 O
R~ -N-C-R2-C-OOH
or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is
an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon
atoms,
and RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon
atoms.
Amide substituted organic peroxyacid compounds of this type are described in
EP-
A-0170386.
CA 02305224 2002-09-05
26
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable
herein.
Other suitable organic peroxyacids include diperoxyalkanedioc acids having
more
than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA),
diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and
diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid (PAP), nonanoylamido peroxo-adipic acid
(NAPAA) decanoyl- or dodecanoylamidoperoxy acids and hexane sulphenoyl
peroxypropionic acid and are also suitable herein.
Other suitable organic peroxyacids include diamino peroxyacids, which are
disclosed in WO 95/ 03275, with the following general formula:
MO~R-(R~N)ri C (NR2)n' -R3-~R2N)~,~--C (NR~)m-RCOOM
wherein:
R is selected from the group consisting of C1-C12 alkylene, CS-C12
cycloalkytene, C6-C12 arylene and radical combinations thereof;
R1 and R2 are independently selected from the group consisting of H, C1-C16
alkyl and C6-C12 aryl radicals and a radical that can form a C3-C12 ring
together
with R3 and both nitrogens; R3 is selected from the group consisting of C1-
C12'
alkylene, CS-C 12 cycloalkylene and C6-C 12 arylene ~ radicals; n and n' each
are an
integer chosen such that the sum thereof is 1; m and m' each are an integer
chosen
such that the sum thereof is 1; and
M is selected from the group consisting of H, alkali metal, alkaline earth
metal,
ammonium, alkanolammonium cations and radicals and combinations thereof.
Other suitable organic peroxyacids are include the amido peroxyacids which are
disclosed in WO 95I 16673, with the following general structure:
X-Ar-CO-NY-R(Z)-CO-OOH
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WO 99119429 PCT/US97118842
27
in which X represents hydrogen or a compatible substituent, Ar is an aryl
group,
R represents (CH2)n in which n = 2 or 3, and Y and Z each represent
independently a substituent selected from hydrogen or an alkyl or aryl or
alkaryl
group or an aryl group substituted by a compatible substituent provided that
at
least one of Y and Z is not hydrogen if n = 3. The substituent X on the'
benzene
nucleus is preferably a hydrogen or a meta or para substituent, selected from
the
group comprising halogen, typically chlorine atom, or some other non-released
non-interfering species such as an alkyl group, conveniently up tv C6 for
example
a methyl, ethyl or propyl group. Alternatively, X can represent a second amido-
percarboxylic acid substituent of formula:-
-CO-NY-R(Z)-CO-OOH
in which R, Y, Z and n are as defined above.
MOOC-R1C0-NR2-R3-NR4-CO-RSCOOOM
wherein Rlis selected from the group consisting of C1-C12 alkylene, CS-CI2
cycloalkylene, C6-C12 arylene and radical combinations thereof; R
It may be found to be particularly useful to mix the pre-formed peracid and
cationic surfactant together prior to incorporation with any other components
of
the detergent composition.
Cationic peroxyacid~recursors
Cationic peroxyacid precursors can be suitable additional components of the
detergent compositions or bleaching systems herein. They produce cationic
peroxyacids on perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid
part of a suitable peroxyacid precursor compound with a positively charged
functional group, such as an ammonium or alkyl ammmonium group, preferably an
ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically
present in the solid detergent compositions as a sait with a suitable anion,
such as a
halide ion.
CA 02305224 2002-09-05
28
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter.
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
WO 95/29160 and US Patent Nos. 5,686,015; 5,460,747; 5,578,136
and 5,584,888.
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. Preferred
cationic peroxyacid precursors of the N-acylated caprolactam class include the
trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium
methylene alkyl caprolactams.
Bleach catalyst
The compositions optionally contain a transition metal containing bleach
catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a heavy
metal
cation of defined bleach catalytic activity, such as copper, iron or manganese
cations, an auxiliary metal cation having little or no bleach catalytic
activity, such as
zinc or aluminum cations, and a sequestrant having defined stability constants
for
the catalytic and auxiliary metal cations, particularly
ethylenediaminetetraacetic
acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
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 MnIV2(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, MnIV4(u-
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WO 99/19429 PCT/US97/18842
29
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.
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
(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 (III), and/or (IV) with a ligand which is a non-
carboxylate polyhydroxy compound having at least three consecutive C-OH
groups.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate ligands, including N4MnIII(u_O)2MnIVN4)+and [Bipy2MnIII{u-
O)2MnIVbiPY2~-(C104)3
Further suitable bleach catalysts are described, for example, in European
patent
application 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 cations and non-catalytic metal cations), and U.S. 4,728,455
(manganese
gluconate catalysts).
Heaw metal ion sequestrant
The detergent compositions of the invention preferably contain as an 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.
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WO 99119429 PCTIUS97/18842
30
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to
20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most
preferably from 0.5% to 5% by weight of the compositions.
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.
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
~i-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.
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), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
CA 02305224 2002-09-05
31
Enzyme
Another preferred ingredient useful in the detergent compositions is one or
more
additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
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 % to 4% 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.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001% to 2% by weight, preferably 0.001% 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., Thermomyces sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali enes or Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein. A
preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is
described
in Granted European Patent, EP-B-0218272.
CA 02305224 2002-09-05
32
Another preferred lipase herein is obtained by cloning the gene from Humicola
lams ig'nosa and expressing the gene in Aspergillus orvza, 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.
Organic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent
compositions in accord with the invention, and are preferably present as
components
of any particulate components where they may act such as to bind the
particulate
component together. By organic polymeric compound it is meant herein
essentially
any polymeric organic compound commonly used as dispersants, and anti-
redeposition and soil suspension agents in detergent compositions, including
any of
the high molecular weight organic polymeric compounds described as clay
flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent
compositions
of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%,
most
preferably from 1 % to I 0% 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 MWt 2000-5000 and their copolymers
with malefic anhydride, such copolymers having a molecular weight of from
20,000
to 100,000, especially 40,000 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.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
CA 02305224 2000-04-04
WO 99119429 PCT/US97118842
33
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose 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.
Suds suppressinyystem
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% to 15%, preferably from 0.05% to 10%, most preferably from
0.1 % to 5% 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
and 2-alkyl 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
24
carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali
CA 02305224 2002-09-05
34
metal salts such as sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty esters (e.g. fatty acid triglycerides), fatty acid esters of rnonovalent
alcohols,
aliphatic C 1 g-C4p ketones (e.g. stearone) N-alkylated amino triazines such
as tri- to
hexa-alkyimelamines 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.
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 SO% 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;
wherein said silica/silicone antifoam compound is incorporated at a level of
from S%
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 under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to 15, at a level of from S% to 80%, preferably 10% to 70%, by weight;
CA 02305224 2000-04-04
WO 99/19429 PCTNS97118842
35
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 I2 to 20 carbon
atoms,
or a mixture thereof, with a melting point of from 45°C to 80°C.
Clay softenin, s~ystem
The detergent compositions may contain a clay softening system comprising a
clay
mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite
clays
are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and
4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of
the Procter and Gamble Company describe suitable organic polymeric clay
flocculating agents.
Polymeric dye transfer inhibiting;.
The detergent compositions herein may also comprise from O.OI% to IO %,
preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting
agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
CA 02305224 2002-09-05
36
P
(I)
R
wherein P is a polymerisable unit, and
II
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or
any combination thereof whereto the nitrogen of the N-O group can be attached
or
wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general
structures
O
1
(R1) x-N-(R2)Y t
(R3)z or N_(R1 )x
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group
forms part of these groups. The N-O group can be part of the polymerisable
unit (P)
or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said
polyamine N-
oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-
O
group forms part of the R-group. Preferred polyamine N-oxides are those
wherein R
CA 02305224 2002-09-05
37
is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine,
quinoline, acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group
is attached to the polymerisable unit. A preferred class of these polyamine N-
oxides
comprises the polyamine N-oxides having the general formula (I) wherein R is
an
aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O
functional
group is part of said R group. Examples of these classes are polyamine oxides
wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and
derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the material has the
desired
water-solubility and dye-suspending power. Typically, the aveFage molecular
weight
is within the range of 500 to 1000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having
an average molecular weight range of from 5,000 to 50,000. The preferred
copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1
to
0.2.
c Polyvinylnyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP")
having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York,
NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular
weight of 10,000), FVP K-30 (average molecular weight of 40,000), PVP K-60
(average molecular weight of 160,000), and PVP K-90 (average molecular weight
of
360,000). PVP K-15 is also available from ISP Corporation. Other suitable
polyvinylpyrroTM ones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
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sa
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric
dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an
average
molecular weight of from 2,500 to 400,000.
Optical bri htg ener
The detergent compositions herein also optionally contain from about 0.005% to
5%
by weight of certain types of hydrophilic optical brighteners:
Hydrophilic optical brighteners useful herein include those having the
structural
formula:
Rl R2
N H H N
N N C C N N
~N H H N
R2/ S03M S03M Rt
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, R1 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-LJNPA-GX by Ciba-Geigy Corporation. Tinopal-LJNPA-GX is the
preferred hydrophilic optical brightener useful in the detergent compositions
herein.
CA 02305224 2002-09-05
39
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-
6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially
marketed
under the trademark Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species
is commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy
Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions in
accordance with the present invention. Suitable cationic fabric softening
agents
include the water insoluble tertiary amines or dilong chain amide materials as
disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from
0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention
include colours and filler salts, with sodium sulfate being a preferred filler
salt.
QH of the compositions
The present compositions preferably have a pH measured as a 1 % solution in
distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably
from 9.5
to 11Ø
Form of the compositions
CA 02305224 2002-09-05
40
The compositions in accordance with the invention can take a variety of
physical
preferably solid forms including granular, tablet, bar forms.
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.
The mid-chain branched surfactant system herein, preferably with additional
surfactants, is preferably present in granular compositions in the form of
surfactant
agglomerate particles, preferably not comprising the bleach precursors, which
may
take the form of flakes, prills, marumes, noodles, ribbons, but preferably
take the
form of granules. The most preferred way to process the particles is by
agglomerating powders (e.g. aluminosilicate, carbonate) with high active
surfactant
pastes and to control the particle size of the resultant agglomerates within
specified
limits. Such a process involves mixing an effective amount of powder with a
high
active surfactant paste in one or more agglomerators such as a pan
agglomerator, a
Z-blade mixer or more preferably an in-line mixer such as those manufactured
by
Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and
Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn l, Elsenerstrasse 7-9,
Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a
Lodige CB (Trade Mark).
A high active surfactant paste comprising from 50% by weight to 95% by weight,
preferably 70% by weight to 85% by weight of the surfactants, including the
mid-
chain branched surfactants, is typically used. The paste may be pumped into
the
agglomerator at a temperature high enough to maintain a pumpable viscosity,
but
low enough to avoid degradation of the anionic surfactants used. An operating
temperature of the paste of 50°C to 80°C is typical.
The bleach precursors of the invention are preferably dry-added to the
detergent base
or the agglomerates.
The mean particle size of the components of granular compositions in
accordance
with the invention should preferably be such that no more that 5% of particles
are
greater than 1.7mm in diameter and not more than 5% of particles are less than
0.1 Smm in diameter.
CA 02305224 2000-04-04
WO 99/19429 PCTIUS97118842
41
The term mean particle size as defined herein is calculated by sieving a
sample of
the composition into a number of fractions (typically 5 fractions) on a series
of Tyler
sieves. The weight fractions thereby obtained are plotted against the aperture
size of
the sieves. The mean particle size is taken to be the aperture size through
which 50%
by weight of the sample would pass.
The bulk density of granular detergent compositions in accordance with the
present
invention typically have a bulk density of at least 300 g/litre, more
preferably from
330 gllitre to 1200 g/litre, more preferably from 380g/litre to 850 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
cylindrical cup disposed below the funnel. The funnel is 130 mm high and has
internal diameters of 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 eg; a knife, across its upper edge. The filled cup is
then
weighed and the value obtained for the weight of powder doubled to provide a
bulk
density in g/litre. Replicate measurements are made as required.
The compositions in accord with the present invention can also be used in or
in
combination with bleach additive compositions, for example comprising chlorine
bleach, as mentioned above.
However, since preferred detergent compositions of the invention are solid,
most
liquid chlorine-based bleaching will not be suitable for these detergent
compositions
and only granular or powder chlorine-based bleaches will be suitable.
Alternatively, the detergent compositions can be formulated such that they are
chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach
can be
added to the detergent composition by the user at the beginning or during the
washing process.
CA 02305224 2002-09-05
42
The chlorine-based bleach is such that a hypochlorite species is formed in
aqueous
solution. 'The hypochlorite ion is chemically represented by the formula OCh.
Those bleaching agents which yield a hypochlorite species in aqueous solution
include alkali metal and alkaline earth metal hypochlorites, hyposchlorite
addition
products, chloramines, chlorimines, chloramides, and chlorimides. Specific
examples of compounds of this type include sodium hypochlorite, potassium
hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite,
chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate,
sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate,
trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide,
Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred
bleaching agent for use in the compositions of the instant invention is sodium
hypochlorite, potassium hypochlorite, or a mixture thereof.. A preferred
chlorine-
based bleach can be Triclosan (Trade Mark).
Most of the above-described hypochlorite-yielding bleaching agents are
available in
solid or concentrated form and are dissolved in water during preparation of
the
compositions of the instant invention. Some of the above materials are
available as
aqueous solutions.
Laundry washing method
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein
an effective amount of a machine laundry detergent composition in accord with
the
invention. By an effective amount of the detergent composition it is meant
from 40g
to 300g of product dissolved or dispersed in a wash solution of volume from 5
to 65
litres, as are typical product dosages and wash solution volumes commonly
employed in conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method.
The dispensing device is charged with the detergent product, and is used to
introduce
the product directly into the drum of the washing machine before the
commencement of the wash cycle. The volume capacity should be such as to be
able
CA 02305224 2002-09-05
43
to contain sufficient detergent product as would normally be used in the
washing
method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement
of the wash cycle of the washing machine water is introduced into the drum and
the
drum periodically rotates. The design of the dispensing device should be such
that it
permits containment of the dry detergent product but then allows release of
this
product during the wash cycle in response to its agitation as the drum rotates
and
also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may
possess
a number of openings through which the product may pass. Alternatively, the
device may be made of a material which is permeable to liquid but impermeable
to
the solid product, which will allow release of dissolved product. Preferably,
the
detergent product will be rapidly released at the start of the wash cycle
thereby
providing transient localised high concentrations of product in the drum of
the
washing machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container integrity is maintained in both the dry state and during the wash
cycle.
Especially preferred dispensing devices for use with the composition of the
invention have been described in the following patents; GB-B-2, 157, 717, GB-B-
2,
157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland
published in Manufacturing Chemist, November 1989, pages 41-46 also describes
especially preferred dispensing devices for use with granular laundry products
which-
are of a type commonly know as the "granulette". Another preferred dispensing
device for use with the compositions of this invention is disclosed in PCT
Patent
Publication No. WO 94/11562.
Especially preferred dispensing devices are disclosed in European Patent
Application Publication Nos. 0343069 & 0343070. The latter Application
discloses
a device comprising a flexible sheath in the form of a bag extending from a
support
ring defining an orifice, the orifice being adapted to admit to the bag
sufficient
product for one washing cycle in a washing process. A portion of the washing
medium flows through the orifice into the bag, dissolves the product, and the
solution then passes outwardly through the orifice into the washing medium.
The
i
CA 02305224 2002-09-05
44
support ring is provided with a masking arrangemnt to prevent egress of
wetted,
undissolved, product, this arrangement typically comprising radially extending
walls
extending from a central boss in a spoked wheel configuration, or a similar
structure
in which the walls have a helical form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or
pouch. The bag may be of fibrous construction coated with a water impermeable
protective material so as to retain the contents, such as is disclosed in
European
published Patent Application No. 0018678. Alternatively it may be formed of a
water-insoluble synthetic polymeric material provided with an edge seal or
closure
designed to rupture in aqueous media as disclosed in European published Patent
Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of
water frangible closure comprises a water soluble adhesive disposed along and
sealing one edge of a pouch formed of a water impermeable polymeric film such
as
polyethylene or polypropylene.
Packa~imP for the compositions
Commercially marketed executions of the bleaching compositions can be packaged
in any suitable container including those constructed from paper, cardboard,
plastic
materials and any suitable laminates.
Abbreviations used in Examples
In the detergent compositions,, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS . Sodium C14-C15 linear alkyl sulfate
MES ~ : -sulpho methylester of C1g fatty acid
CxyEzS : Sodium C 1 x-C 1 y branched alkyl sulfate
condensed
with z moles of ethylene oxide
MBASx, y . Sodium mid-chain branched alkyl sulfate
having an
average of x carbon atoms, whereof an
average of y
carbon atoms are comprised in (a) branching)
units)
CA 02305224 2002-09-05
45
C.~g SAS : Sodium C,.~-C,g secondary alcohol sulfate
SADE2S : Sodium C,4-Czz alkyl disulfate of formula 2-(R).C4 H~-
1,4-(S04-)z where R = C,oOC,g, condensed with z
moles of ethylene oxide
C45E7 : A C14-15 Predominantly linear primary alcohol
condensed with an average of 7 moles of ethylene
oxide
CxyEz : A C 1 x-1 y branched primary alcohol condensed with an
average of z moles of ethylene oxide
QAS II . R2.N'~'(CH3)2(C2H40H) with R2 = 50%-60% Cg;
40%-SO% C 11
QAS IV : RI.N+(CH3)(C2H40H)2 with RI = C12-C14
QAS V . R20(C2H40)x(giycosyl)2, wherein R2 is a Cg-C10
alkyl group ; t is from 2 to 8
Soap . Sodium linear alkyl carboxylate derived from an 80/20
mixture of tallow and coconut oils.
TFAA : C 16-C 1 g alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 27H20 having a primary
particle
size in the range from 0.1 to 10 micrometers
NaSKS-6 : Crystalline layered silicate of formula
8 -Na2Si205
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle
size
between 200~m and 900pm
Bicarbonate : Anhydrous sodium bicarbonate with a
particle size
distribution between 400pm and 1200p,m
Silicate : Amorphous Sodium Silicate (Si02:Na20;
2.0 ratio)
Sodium sulfate : Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425pm
and q 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average
molecular weight about 70,000
CMC . Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g
sold by
NOVO Industries A/S under the ~'ademark
Savinase
i
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46
Alcalase : Proteolytic enzyme of activity 3AU/g
sold by NOVO
Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g
sold by
NOVO Industries A/S under the trademark
Carezyme
Amylase . Amylolytic enzyme of activity 60KNU/g
sold by
NOVO Industries A/S under the trademark
Termamyl
60T
Lipase : Lipolytic enzyme of activity I OOkLU/g
sold by NOVO
Industries A/S under the trademark Lipolase
Endolase : Endoglunase enzyme of activity 3000
CEVU/g sold by
NOVO Industries A/S
PB4 . Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
PB 1 . Anhydrous sodium perborate bleach of
nominal
formula NaB02.H202
Percarbonate . Sodium Percarbonate of nominal formula
2Na2C03.3H202
NAC-OBS . (Nonanamido caproyl) oxybenzene sulfonate
in the
form of the sodium salt.
NOBS . Nonanoyl oxybenzene sulfonate in the
form of the
sodium salt
LOBS . Dodecanoyl oxybenzene sulfonate iri
the form of the
sodium salt
DOBS . Decanoyl oxybenzene sulfonate in the
form of the
sodium salt
DPDA . Diperoxydodecanedioic acid
PAP . N-phthaloylamidoperoxicaproic acid
NAPAA . Nonanoylamido peroxo-adipic acid
NACA . 6 nonylamino - 6 oxo - capronic acid.
TAED . Tetraacetylethylenediamine
DTPMP . Diethylene triamine penta (methylene
phosphonate),
marketed by Monsanto under the Trade mark
bequest
2060
Phvtoactivated : Sulfonated Zinc or aluminium Phthlocyanine
encapsulated .
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
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Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
QEA : bis ({C2H50)(C2H4~)n) (CH3) -N+-C6H12-N+_
(CH3) bis ((C2HS0)-(C2H40)n), wherein
n=from 20
to 30
SRP 1 : Sulfobenzoyl end capped esters with
oxyethylene oxy
and terephtaloyl backbone
SRP 2 . Diethoxylated poly (1, 2 propylene terephtalate)
short
block polymer
Silicone antifoam. Polydimethylsiloxane foam controller
with siloxane-
oxyalkylene copolymer as dispersing agent
with a ratio
of said foam controller to said dispersing
agent of 10:1'
to 100:1.
In the following Examples all levels are quoted as parts per weight of the
composition or % by weight of the composition, as indicated:
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48
Example 1
The following high density granular laundry detergent compositions A to F of
particular utility under European machine wash conditions were prepared in
accord
with the invention:
A B C D E F
LAS 8.0 8.0 - 2.0 8.0 6.0
MES - - 5.0 - - 6.0
TAS - 0.5 - 0.5 1.00 1.5
C25E3 3.4 - - 3.4 5.4 2.4
C25E7 - 3.0 4.5 - - -
C46AS 2.0 2.0 2.5 - - -
C24AS - - - 7.0 4.0 5.0
SADS - - - - 1.0 -
MBAS 165, 1.8 6.0 - 8.0 10 - 5.0
.
MBAS 16.5, 2.8 - 7.0 - - 8.0 5.0
QASII - - - -
0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Citric acid 2.0 1.0 - - - -
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
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Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
PB4 9.0 9.0 ' 9.0 - - -
Percarbonate - - - 18.0 15.0 20.0
TAED 0.5 1.0 4.0 1.5 1.0 1.0
NAC-OBS 4.0 2.5 0.5 1.0 2.0 5.0
DTPMP 0.25 0.25 0.25 0.25 0.25 0.25
EDDS - - 0.25 0.4 - -
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
QEA 0.5 1.0 - - 0.5 -
Protease 0.26 0.26 0.26 0.26 0.26 0.26
Amylase 0.1 0.1 0.1 0.1 0.1 0.1
Photoactivated 15 ppm 1 S 15 ppm 15 ppm 15 ppm 15 ppm
bleach (ppm) ppm
Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
~
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam0.5 0.5 0.5 0.5 0.5 0.5
Density in g/litre850 850 850 850 850 850
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Example 2
The following granular laundry detergent compositions G to I of bulk density
750
g/litre are compositions according to the invention:
G H I
LAS 12.0 10.0 7.0
TAS 1.25 2.86 1.57
C45AS 3.5 3.24 2.0
C25AE3S - 0.76 1.0
C45E7 3.25 - -
C25E3 - 3.5 . 3.5
QAS I 0.8 2.0 -
MBAS 17, 1.7 7.0 - 5.0
MBAS 17, 2.5 - 2.0 -
STPP 19.7 - -
Zeolite A - 19.5 19.5
NaSKS-6/silicate (79:21 10.6 10.6
)
Citric acid/citrate 2.0 4.0 1.0
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
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Silicate 6.8 - -
Sodium sulfate 39.8 - 7.0
PB4 5.0 12.7 -
Percarbonate - - 16.0
TAED 0.5 0.7 2.0
NAC OBS 1.0 2.2 2.0
DTPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Protease 0.26 0.8 5 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
PVP - 0.8
Photoactivated bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 ~ 0.19
Brightener 2 - 0.04 0.04
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Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minorslmisc to 100% n.a. n.a.
Example 3
The following are detergent formulations, according to the present invention
where J
is a phosphorus-containing detergent composition, K is a zeolite-containing
detergent composition and L is a compact detergent composition:
J K L M
Blown Powder - _ ,
STPP 24.0 - 24.0 -
Zeolite A - 24.0 - 24.0
C45AS 9.0 - 4.0 13.0
___-QAS I - 1.0 - _
MBAS 17, 1.7 4.0 - 10.0 6.0
MBAS 17, 3.5 2.0 11.0 - -
SADS 2.0 - - -
C25AE3S - 1.0 - 1.0
_ _~~~ 2.0 4.0 2.0 4.0
LAS 6.0 12.0 13.0 5
TAS - 1.0 2.0 -
Silicate 7.0 3.0 3.0 3.0
CMC 1.0 I.0 0.5 1.0
Brightener 2 0.2 0.2 0.2 0.2
Soap 1.0 - - 1.0
DTPMP 0.4 0.4 0.2 0.4
Spray On
C45E7 - 2.5 - -
C25E3 2.5 - - 1.5
Silicone antifoam 0.3 0.3 0.3 0.3
Perfume 0.3 0.3 0.3 0.3
Dry additives
QEA - 0.5 1.0 -
Carbonate 6.0 13.0 15.0 13.0
PB4 18.0 1$.0 5.0 -
PB1 4.0 - - 14.0
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53
NOBS 3.0 4.2 - 6.0
TAED I.0 1.0 5.0 1.0
LOBS - - 2.0 -
Photoactivated bleach 0.02 0.02 0.02 0.02
Manganese catalyst - - 0.5 -
Protease '1.0 1.0 1.0 1.0
Lipase 0.4 0.4 0.4 0.4
Amylase 0.25 0.30 0.15 0.3
Dry mixed sodium sulfate3.0 3.0 5.0 3.0
Balance (Moisture & 100.0 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 6?0 670
Examgle 4
The following are detergent formulations according to the present invention:
N O P Q
LAS 20.0 14.0 13.0 20.0
.
_
TAS - 1.0 4.0 _
MBAS 16.5, 2.0 10.0 2.0 8.0
1.9
C45AS 4.0 4.0 6.0 6.0
MES 3.0 - -
QAS II - 0.4 1.0 -
TFAA - 1.0 - -
C25ESIC45E7/C2- 2.0 - 1.0
5E3
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - -
DTPMP 0.7 1.0 -
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated70ppm 45ppm - lOppm
bleach (ppm)
Brightener 0.2 0.2 0.08 0.2
1
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54
PB 1 6.0 ~~ 2.0 -
Percarbonate - - 12.0 15.0
NACA - - - 3.0
NAC OBS 2.0 - - 3.1
TAED 2.0 4.0 2.0 1.0
DOBS - - 2.0 -
LOBS - 3.0 - -
Balance (Moisture100 100 100 100
and
Miscellaneous)
Example 5
The following are detergent formulations according to the present invention:
R S T
Blown Powder
MBAS 16.5,1.7 6.0 10.0 -
MBAS 17.5, 3.0 - - 12.0
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 3.0 9.0 3.5
C45AS 5.0 4.0 7.0
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
Spray On
C45E5 1.0 1.0 -
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
TAED 6.4 2.0 2.0
NOBS - 6.1 -
NAC OBS - - 4.5
Percarbonate - - 16.0
PB1 - 10.0 -
PB4 8.0 - -
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Sodium sulfate - 6.0
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 6
The following are high density and bleach-containing detergent formulations
according to the present invention:
U V W _.__
Blown Powder _
Zeolite A 1 S.0 1 S.0 1 S.0
Sodium sulfate 0.0 S.0 0.0
LAS 3.0 - 3.0
C4SAS 3.0 2.0 4.0
QAS - - 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 6.0 4.0 1.0
MBAS 16.5, 1.6 2.0 S.0 10.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Encapsulated Perfume 0.3 0.3 0.3
C2SE3 2.0 -
Dry additives
QEA - - O.S
Citrate S.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 1 S.0 10.0
TAED 1.0 O.S 3.0
NACAOBS 6.0 - S.0
LOBS/ DOBS - I .0 -
Manganese catalyst - - 0.3
NOBS - 2.0
PBI 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
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56
Citric acid - - 0.5
~
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
Example 7
The following are high density detergent formulations according to the present
invention:
X Y
Agglomerate
MES ~ - 8.0
LAS 12.0
TAS - 2.0
C45AS 6.0 4.0
MBAS 17.5, 1.6 4.0 3.0
MBAS 17.5, 2.8 4.0 -
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
M~~ 4 0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E3 1.0 1.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate - 1.0
Citric acid 2.0 -
NAC OBS 4.1 -
LOBS - 3.0
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57
TAED 0.8 2.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
QEA 1.0 -
Silicone antifoam S.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Density (g/litre) 850 850
Examgle 8
The following granular detergent formulations are examples of the present
invention.
AH AI AJ
Blown powder
MES - 6.0 -
LAS 12.0 - 13.0
C45AS - 4.0 -
C46AS 4.0 - -
C45AE35 2.0 5.0 3.0
MBAS 17, 2.2 5.0 - 2-
Zeolite A 16.0 19.0 16.0
MA/AA 3.0 - -
AA 3.0 2.0 3.0
Sodium sulfate 3.3 24.0 13.3
Silicate 1.0 2.0 1.0
Carbonate 9.0 25.7 8.0
QEA 0.4 - 0.5
PEG 4000 - 1.0 1.5
Brightener 0.3 0.3 0.3
Spray on
C25E5 0.5 1.0 -
Perfume 0.3 1.0 0.3
Agglomerates
C45AS 5.0 2.0 5.0
LAS 1.0 1.0 2.0
MBAS 17, 1.6 - 4.0 5.0
Zeolite A 7.5 - 7.5
HEDP 1.0 - 2.0
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Carbonate 4.0 - 4.0
PEG 4000 O.S - O.S
Misc (water etc) 2.0 - 2.0
Dry additives
LOBS/DOBS/NOBS 4.0 4.0 -
TAED ' - - 2.0
NACA-OBS - - 3.0
PB4 14.0 - 2.0
PB 1 - 7.0 -
Carbonate S.3 - 2.S
Cumeme sulfonic acid 2.0 - 2.0
Lipase 0.4 0.1 O.OS
Cellulase 0.2 - 0.2
Amylase 0.3 - -
Protease 1.6 - 1.6
PVPVI O.S - -
PVNO O.S - -
SRP1 O.S - -
Silicone antifoam 0.2 - 0.2
Example 9
AK AL AM AN AO AP
C4SAS 11.0 S.1 4.0 8.S 4.1 9.8
C2SAES 1.3 1.0 - 1.3 1.0 -
LAS 9.4 6.6 20.5 3.7 1.7 4.0
C2SE3/ C2SES 1.S 4.7 3.3 I.S 4.7 3.30
MBAS I6.S, 1.7 10.0 5.0 3.0 i2.2 S.9 14.1
QAS - I .1 0.4 - 1.7
S
Zeolite A 27.0 16.7 11.2 27.0 16.7 11.2
SKS-6 - 9.0 7.S - 9.0 7.S
Citric acid - 1.S - - I.S -
MA/AA - 0.6 - - 0.6 -
MAIAA 3 - - 7.0 - - 7.0
AA 2.2 - - 2.2 - -
EDDS - 0.3 - - 0.3 -
HEDP - O.S - - O.S -
Carbonate 26.0 12.5 14.9 26.5 I2.S 14.9
Silicate O.S 0.8 I2 O.S 0.8 12
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PB1 11.0 - 3.9 7.0 - 3.9
NOBS 3.0 2.7 4.0 - - 4.0
NACA-OBS - 2.7 - 4.0 2.75 -
PC - 17.3 - - 17.3 -
TAED 5.0 3.5 2.0 1.0 3.5 4.0
Protease 0.26 0.3 0.2 0.2 0.3 0.2
Lipase - - - - - -
Carezyme IT 0.33 0.26 - 0.33 0.26 -
Termamy1120T - 0.36 - - 0.36 -
Brightener 0.17 0.06 0.30 0.17 0.06 0.30
SRP1 0.4 0.2 0.5 0.4 0.2 0.5
PEG 1.6 - 0.19 1.6 - 0.19
Sulfate 5.3 6.4 3.4 5.3 6.4 3.4
CMC - 0.5 - - 0.5 -
MgS04 - 0.13 - - 0.13 -
Photobleach - 0.0026 - - 0.0026-
Silicone anti-foam - 0.21 0.17 0.02 0.21 0.17
Perfume 0.42 0.55 0.25 0.42 0.55 0.25
Example 10
The following laundry detergent compositions AQ to AT are prepared in accord
with
the invention:
AQ AR AS AT
MBAS 16.5, 1.8 22 16.5 11 5.5
C45 AS 8 10 I 1 4
C45E1S 4 3 - 1
LAS 8 14 - 4
C16 SAS - - 3 -
MES - - 12 -
C23E6.5 1.5 1.5 1.5 1.5
Zeolite A 17.8 20.8 20.8 27.8
AA 2.3 2.3 2.3 2.3
Carbonate 27.3 27.3 27.3 27.3
Silicate 0.6 0.6 0.6 0.6
Perborate 1.0 1.0 1.0 1.0
Protease 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3
SRP1 0.4 0.4 0.4 0.4
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Brightener 0.2 0.2 0.2 0.2
PEG 1.6 I .6 1.6 1.6
PB1 16.0 6.0
NOBS 2.4 4.5 0.8 3.5
PC 8.0 15.0
Sulfate 5.5 5.5 5.5 5.5
Silicone Antifoam0.42 0.42 0.42 0.42
TAED 0.5 4.5 8.0 2.0
Moisture & Minors---Balance---
Density (g/L) 660 660 660 660
Example 11
The following laundry detergent compositions AU to AY are prepared in accord
with the invention:
AU AV AW AX AY
MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1
C45 AS 5 7 6 4 12
C45E3S 2 - 4 - 5
LAS 14 8 - 18 5
C 16 SAS - - 1 - 1
MES - - 10 - -
TFAA 1.6 0 0 0 0
C24E3 4.9 4.9 4.9 4.9 4.9
Zeolite A I5 15 15 15 15
QAS 1.0 1.5 - - 1.0
NaSKS-6 11 11 11 11 11
Citratelcitric 1.0 2.0 3 3 -
MAIAA 4.8 4.8 4.8 4.8 4.8
HEDP 0.5 0.5 0.5 0.5 0.5
Carbonate 8.5 8.5 8.5 8.5 8.5
Protease 0.9 0.9 0.9 0.9 0.9
Lipase 0.15 0.15 0.15 0.15 0.15
Cellulase 0.26 0.26 0.26 0.26 0.26
Amylase 0.36 0.36 0.36 0.36 0.36
NOBS - - - 4.0 5.0
NACA-OBS 4.0 2.0 6.0 - -
TAED 4.0 5.0 2.0 1.0 0.5
PB1 - - 14.0 - 8.0
Percarbonate 20.0 14.0 - 22.0 -
SRPI 0.2 0.2 0.2 0.2 0.2
QEA1 1.0 1.5 - -
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61
Brightener _ 0.2 0.2 0.2 0.2 0.2
~
Sulfate 2.3 2.3 2.3 2.3 2.3
~
Silicone Antifoam0.4 0.4 0.4 0.4 0.4
Moisture & Minors ---Balance---
Density (g/L) 850 850 850 850
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Example 12
The following laundry detergent compositions AZ to Ee are prepared in accord
with
the invention:
AZ Aa Bb Cc Dd Ee
MBAS 16.5, 1.7 32 32 24 16 16 8
C45 AS 5 - 6 12 2
C45E1S 1 - - 1 5 2
LAS - 20 8 23 12 16
C16 SAS 1 4 - - - -
MES 14 - - - - -
C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6
QAS - 0.5 - - 0.5 -
Zeolite A 9.0 9.0 9.0 9.0 9.0 9.0
Polycarboxylate 7.0 7.0 7.0 7.0 7.0 7.0
Carbonate 18.4 18.4 18.4 18.4 18.4 18.4
Silicate 11.3 11.3 11.3 11.3 11.3 11.3
PB 1 - - 3.9 10.0 3.9 15.0
TAED 2.0 5.0 1.0 0.5 6.0 2.0
Percarbonate 7.0 7.0 - - - -
N()B S 4.1 4.1 4.1 4.1 4.1 4.1
Protease 0.9 0.9 0.9 0.9 0.9 0.9
SRP1 0.5 0.5 0.5 0.5 0.5 0.5
Brightener 0.3 0.3 0.3 0.3 0.3 0.3
PEG 0.2 0.2 0.2 0.2 0.2 0.2
Sulfate 5.1 5.1 5.1 5.1 5.1 5.1
Silicone Antifoam0.2 0.2 0.2 0.2 0.2 0.2
Moisture & Minors---Balance---
Density (g/L) 810 810 810 810 810 810
