Note: Descriptions are shown in the official language in which they were submitted.
CA 02256703 2002-02-11
Detergent Composition
Technical field
The present invention relates to detergent compositions containing a cationic
surfactant and a hydrophobic organic peroxyacid bleaching system, which are
suitable for use in laundry and dishwashing methods.
Back,~,_round to the invention
The satisfactory removal of greasy soils/stains, that is soils/stains having a
high
proportion of triglycerides or fatty acids, is a challenge faced by the
formulator of
detergent compositions for use in laundry and dish washing methods. Surfactant
components have traditionally been employed in detergent products to
facilitate the
removal of such greasy soils/stains. In particular, surfactant systems
comprising
cationic esters have been described for use in greasy soil/stain removal.
A particular challenge to the formulator of detergent compositions for use in
a
laundry washing method is the satisfactory removal of bleachable soils/stains
such
as tea, fruit juice and coloured vegetable soils from stained fabrics.. It is
known that
stained fabrics have a tendency to present a ' dingy' appearance after
frequent
washing. Bleaches are traditionally employed in detergents to remove the
bleachable stains or soils, and also those responsible for the 'dingy'
appearance of
the fabric. It is well established that peroxygen bleaches and bleaching
systetris,
based on organic peroxyacids can provide stain and/or soil removal from
fabrics.
The organic peroxyacids are often obtained by the in situ perhydrolysis of
organic
peroxyacid bleach precursor compounds (bleach activators). To remove greasy
stainsl soils, which are of hydrophobic nature, hydrophobic organic
peroxyacids
CA 02256703 2002-02-11
2
can be employed in detergent products. Such organic peroxyacids generally
comprise long chain ( > 7 carbon atoms) alkyl moieties. Hydrophobic bleaches
are
known to have a tendency to migrate rapidly to the surface of fabrics under
wash
conditions.
Bleaches which may be hydrophobic are disclosed for example in EP-A-0170386.
It is stated that these bleaches may be used in compositions which incorporate
different types of surfactant materials. Anionic, nonionic, zwitterionic and
amphoteric surfactants are disclosed. Hydrophobic bleaching agents are also
described in W095/3226 as useful suds suppressants in detergent compositions
containing high levels of surfactant.
Quaternary ammonium compounds are known cationic surfactants. For example in
GB-A-2040990 alkoxylated nonionic and cationic surfactants and anic>nic
surfactants are used in combination to produce detergents for fabric washing.
It has now been found that a problem with hydrophobic bleaches is that despite
their tendency to migrate to the fabric surface, they do not necessarily
interact fully
with the stain or soil components. It has been found that the hydrophobic
bleaches
can be prevented from migration onto the greasy stainslsoils by deposited
'lime
soaps' (formed by alkaline earth ions with fatty acids, present in the vvash
solution)
on the fabric. Thereby, their bleaching performance can be diminished. This
result
in a lessening of the dingy soil cleaning performance of the hydrophobic
bleach.
The Applicants have found that this problem can be ameliorated by use of a
particular combination of cationic surfactant and bleach resulting in a
surprising
enhancement of the bleach e~cacy of the hydrophobic organic peroxyacid
bleaching system. Thereby, the overall cleaning performance of the detergent
are
improved.
Three mechanisms are believed to be responsible for this unexpected benefit.
First,
the cationic surfactant is capable of reducing 'lime soap' deposition on the
fabric
surface, thereby facilitating the partition of the hydrophobic organic
bleaches into
the greasy stains/soils. Secondly, the cationic surfactant reduces the surface
tension between the fabric and the wash solution. Thereby, the interaction
with the
greasy stains/ soils on the fabric by the hydrophobic organic bleach agent
will be
Ci1 02236703 2002-02-il
3
facilitated. Thirdly, the cationic surfactant and the negatively charged
hydrophobic
organic peroxyacids, formed in the wash, can form a non-polar associated
couple, which
wiU partition rapidly into hydrophobic, greasy stains/soils on the fabric.
Sp~~r of thg Invention
A detergent composition according to a first aspect of the present invention
comprises
(a) from 0.05% to 4.5%, by weight of the detergent composition, of a
cationic surfactant of the formula
RZ
R1' N~ R4 X'
R3
in which R' is a hydroxyalkyl group having no greater than b c~bo~
atoms; each of Rz and R3 is independently selected from C~.~ alkyl or
alkenyl ; R4 is C»~4 alkyl or alkenyl and X' is an anion selected from the '
group consisting of halide, methyl sulfate, sulfate, and nitrate;
(b) a hydrophobic organic peroxyacid bleaching system, capable of providing
a peroxyaeid compound of the formula:
Rs C-N-R' C-OOH or ~--N-C-R' : C-OOH
O R6 O R6 O O
(II) (~
wherein Rs is an aUryl, aryl or aralkyl group containing from 1 to 14
carbon atoms, R' is an aUcylene, arylene or aUcarylene group containing
from 1 to 14 carbon atoms, and R6 is H or an alkyl, aryl or alkaryl group
containing from 1 to 10 carbon atoms, and
(c ) from 5% to about 40% by weight of sodium sulfate.
said composition having a pH as measured in 1% water solution from 10.0 to
11Ø
CA 02256703 2002-02-11
4
Preferred cationic surfactants of formula I are those in which R1 is -CH2CH20H
or -CH2CH2CH2OH; each of R2 and R3 are, independently, C 1.,4 alkyl; R4 is
C6-11 aryl or alkenyl and X' is an anion.
An essential feature of detergent compositions of the invention is a
hydrophobic
organic peroxyacid bleaching system capable of providing a hydrophobic organic
peroxyacid compound. By hydrophobic organic peroxyacid compound it is meant
herein an organic pemxyacid whose parent carboxylic acid has a critical
micelle
concentration less than 0.5 molesllitre and wherein said critical micelle
concentration is measured in aqueous solution at 20°-50°C.
Preferably, the hydrophobic organic peroxyacid contains at least 7 carbon
atoms,
more preferably at least 9 carbon atoms, most preferably at least 11 carbon
atoms.
In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7
carbon
atoms, more preferably at least 8 carbon atoms, most preferably at learnt 9
carbon
atoms.
A preferred hydrophobic organic peroxyacid bleaching system is capable of
providing a peroxyacid compound of the formula:
RS-C-N R7-C-OOH or RS-N-C R~-C-OOH
I~ I ~~ ~ ii
O R6 O ~6 O
wherein RS is an alkyl, aryl or aralkyl group containing from 1 to 14 ca~rban
atoms, R~ is as alkylene, arylene or alkarylene group containing from 1 to
14 carbon atoms, and R6 is H or an alkyl, aryl or alkaryl group containing
from 1 to 10 carbon atoms.
According to a second aspect of the invention there is provided a detergent
composition comprising
A detergent composition comprising
(a) less than 5 96 by weight of a cationic surfactant of the formula
CA 02256703 2002-02-11
S
R2 +
Rl -N R4 x
i
i
R3
in which R1 is a hydroxyalkyl group having no greater than 6 carbon
atoms; each of RZ and R3 is independently selected from C 1.4 ;alkyl or
alkenyl; R4 is a C12-14 amyl or alkenyl and X' is an anion; an<i...
(b) a hydrophobic organic peroxyacid bleaching system, capable of providing a
peroxyacid compound of the formula:
RS-C-N R~-~C-OOH or RS-N-C R7-C-40H
l
O 1~6 ,O ~6 O
wherein RS is an alkyl, aryl or aralkyl group containing from l to 14 carbon
atoms, R~ is an allcyle~, arylene or alkarylene group containing from 1 to
14 carbon atoms, and R6 is H or an alkyl, aryl or alkaryi group containing
from 1 to 10 carbon atoms.
Particularly preferred cationic surfactants of formula I in which Rl is
HOCH2CH2- or HOCH2CH2CH2-; each of R2 and R3 are, independently, C1~
alkyl; R4 is C12-14 ~yl or alkenyl a~ X' is an anion.
Preferred detergent compositions of the invention additionally comprise a hard
base
polymeric component.
Unless otherwise stated alkyl or alkenyl as used herein may be branched,
linear or
substituted. Substituents may be for example, aromatic groups, heterocyclic
groups containing one or more N, S, or O atoms, or halo substituents.
CA 02256703 2002-02-11
6
Detailed description of the invention
Cationic surfactant
An essential element of the detergent compositions of the invention is a
cationic
quaternary ammonium surfactant. The cationic surfactant unless otherwise
stated
may be present in amounts up to 10.0% by weight of the detergent composition.
However, preferably the maximum amount of the cationic surfactant in the
detergent composition is below 5 % . Most preferably, the cationic surfactant
will
be present in an amount below 4 % or even 4.5 % by weight of the detergent
composition. Generally there will be at least 0.45 % by weight or even at
Least
0.1 % or at least 0.5 % by weight of the cationic surfactant in the
composition.
Preferahiy the --0H group in R1 in formula I is separated from the quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Preferred Rl groups
are --~H2-CH20H, -CH2CHZCH20H, CH2CH2(CH3)OH and --
CH(CH3)CH20H. CH2CH20H and --CH2CH2CH20H are most preferred and
-CH2CHZOH is particularly preferred. Preferably R2 and R3 are each selected
from ethyl and methyl groups and most preferably both R2 and R3 are methyl
groups. Preferred R4 groups have at least 6 or even at least ? carbon atoms.
R4
may have no greater than 9 carbon atoms, or even no greater than 8 or ? carbon
atoms. Preferred R4 groups are Linear alkyl groups. Linear R4 groups having
from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
In accordance with a preferred aspect of the present invention the cationic
surfactant of formula I has a R1 group which is -CH2CH20H. Preferably each of
Ra and R3 are methyl groups.
In a preferred aspect of the invention, R4 is a Linear alkyl group, preferably
a C~
11 Linear alkyl group.
It has been found that mixtures of the cationic surfactants of formula I may
be
particularly effective, for example surfactant mixtures in which R4 may be a
combination of Cg and C10 linear alkyl groups, or Cg and C11 linear alkyl
groups. According to one aspect of the invention a mixture of cationic
surfactants
of formula I is present in the composition, the mixture comprising a shorter
alkyl
CA 02256703 2002-02-11
7
chain surfactant of formula I and a longer alkyl chain surfactant of formula
I. The
longer alkyl chain cationic surfactant is preferably selected from the
surfactants of
formula I where R4 is an alkyl group having n carbon atoms where n is from 8
to
11: the shorter alkyl chain surfactant is preferably selected form those of
formula I
where R4 is an alkyl group having (n-2) carbon atoms. Preferably the detergent
compositions of the invention comprise a combination of cationic surfactants
for
formula I comprising 1 % to 65 % of a shorter alkyl chain length R4 group and
35
to 99% by weight of a longer alkyl chain length. Mixtures comprisiing R4
groups
of Cg and Clp alkyt groups are particularly preferred.
X in formula I may be any counteranion providing electrical neutrality, but is
preferably selected from the group consisting of -halide, methyl sulfate,
sulfate and
nitrate, more preferably being selected from methyl sulfate, chloride;,
bromide or
iodide.
Hydrophobic organic peroxyacid bleaching system
Preferably the hydrophobic organic peroxyacid bleaching system comprises a
hydrogen peroxide source and a hydrophobic organic peroxyacid bleach precursor
compound. The production of the hydrophobic organic peroxyacid occurs by an in
situ reaction of the precursor with a source of hydrogen peroxide. Preferred
sources of hydrogen peroxide include inorganic perhydrate bleaches.. In an
alternative preferred execution the hydrophobic organic peroxyacid bleaching
system comprises a preformed hydrophobic organic peroxyacid, which is
incorporated directly into the composition. Compositions containing mixtures
of a
hydrogen peroxide source and hydrophobic organic peroxyacid precursor in
combination with a preformed hydrophobic organic peroxyacid are also
envisaged.
Inorganic perh~ydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These
salts
are normally incorporated in the form of the alkali metal, preferably sodium
salt at
a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight
and most preferably from 5 % to 25 % by weight of the compositions.
CA 02256703 2002-02-11
Examples of inorganic perhydrate salts include perborate, perearbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts
are
normally the alkali metal salts. The inorganic perhydrate salt may be uncluded
as
the crystalline solid without additional protection. For certain perhydrate
salts
however, the preferred executions of such granular compositions utilize a
coated
form of the material which provides better storage stability for the
perhydrate salt
in the granular product. Suitable coatings comprise inorganic salts such as
alkali
metal silicate, carbonate or borate salts or mixtures thereof, or organic
materials
such as waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the
moriohydrate of nominal formula NaH02H202 or the tetrahydrate
NaB02H202.3H2O.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates herein. Sodium percarbonate is an addition compound having a
formula corresponding to 2Na2C03.3H202, and is available commercially as a
crystalline solid.
Potassium peroxymonopersulfate is another inorganic perhydraie salt of use in
the
detergent compositions herein.
P_eroxvacid bleach ~CUrsor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a per6ydrolysis reaction to produce a peroxyacid. Generally peroxyacid
bleach
precursors may be represented as
O
~I
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydrolysis the structure of the peroxyacid produced is
CA 02256703 2002-02-11
9
O
X-C-QOH
For the purposes of the present invention X will thus contain at least 6
carbon
atoms.
The hydrophobic peroxyacid bleach precursor compounds are preferably
incorporated at a level of from 0.05 % to 20 % by weight, more preferably from
0.190 to 15 % by weight, most preferably from 0.2 % to 10 % by weight of the
detergent compositions.
Suitable hydrophobic peroxyacid bleach precursor compounds 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 usefuhmateriais within these
classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-
836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving groups
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 R3Y
Y , and
O- ' 4
-N-C R -N N -N-C-CH--F~
I ~ , 1 I .
R3 Y
I
Y
CA 02256703 2002-02-11
R3 Y
I f
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O CH _Q Y . O
C-RI -N 2 ~NR4 -N~ /NR4
O- .,'C''~ ' ~'C
II ii
O O
R3 O Y
-O-C=C HR4 , and -N-S-C H-Rd
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 Rl, R3 and R4
may be substituted by essentially any functional group including, for example
alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammonium groups
The preferred solubilizing groups are -S03-M + , -CO~ M + , -S04 M' + ,
-N+(R3)4X- and O<--N(R3)3 and most preferably -S03-M+ and -C02-M+
wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms. M is a canon
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,
arnrnonium or
substituted ammonium cation, with sodium and potassium being most ;preferred,
and X is a halide, hydroxide, methylsulfate or acetate anion.
Amide substituted alkyl ~eroxvacid precursors
The amide substituted alkyl peroxyacid precursors of the second aspect of the
invention are also preferred in the fast aspect of the invention. These
include
compounds of the following general formulae:
CA 02256703 2002-02-11
11
RS-C-N-R7-C-i, or R$-N-C--R7-C--L
jo R6 0~ ~ s to ~o
R
wherein RS is an aryl or alkaryl group with from about 1 to about 14 carbon
atoms, R7 is an alkylene, arylene, and alkarylene group containing from about
1 to
I4 carbon atoms, and R6 is H or an alkyl, aryl, or alkaryl group containing 1
to 10
carbon atoms and L can be essentially any leaving group. R$ preferably
contains
from about 6 to 12 carbon atoms. R? preferably contains from about 4 to 8
carbon
atoms. RS may be straight chain or branched alkyl, substituted aryl or
alkylaryl
containing branching, substitution, or both and may be sourced from either
synthetic sources or natural sources including for example, tallow fat.
Analogous
swctural variations are permissible for R7. R7 can include alkyl, aryl,
wherein
said R7 may also contain halogen, nitrogen, sulphur and other typical
substituent
groups or organic compounds. R~ is preferably H or methyl. RS and R6 should
not contain more than 18 carbon atoms total. Amide substituted bleach
activator
compounds of this type are described in EP-A-0170386.
Preferred examples of bleach precursors of this type include amide substituted
peroxyacid precursor compounds selected from (6-octanamido-
caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and
the highly preferred (6-nonanamidocaproyl}oxy benzene sulfonate, and mixtures
thereof as described in EP-A-01?0386. '
~oxazin organi~pgfoxyacid pr~.cursors
For the first aspect of the invention, also suitable are precursor compounds
of the
benzoxazin-type, as disclosed for example iri EP-A-332,294 and EP-A~482,807,
particularly those having the formula:
O
CEO
C-R~
'N
CA 02256703 2002-02-11
12
wherein Rl is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5
carbon
atoms.
Alkyl vercarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylie acids on
perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide
type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the
alkylene group contains at least 7 carbon atoms.
Other preferred alkyl percarboxylic acid precursors include sodium 3,x,5-tri-
methyl hexanoyloxybenzene sulfonate (iso-NOBS) and sodium
nonanoyloxybenzene sulfonate (HOBS).
N-a~,cvlated lactam precursors
Still another class of hydrophobic bleach activators are the N-acylated
precursor
compounds of the lactam class disclosed generally in GB-A-955735. Preferred
materials of this class comprise the caprolactams.
Suitable caprolactam bleach precursors are of the formula:
0
,I
C C ~ CHZ - CHZ
\cxz
C
CH2 --- ~HZ
wherein Rl is an alkyl, aryl, alkoxyaryl or alkaryl group containing frond 6
to 12
carbon atoms. Preferred hydrophobic N-acyl caprolactam bleach precursor
materials are selected from betuoyl caprolactam, octanoyl caprolactam,
tionanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5-
trimethylhexanoyl caproIactam and mixtures thereof. A most preferred is
nonanoyl
caprolactam.
Suitable valem lactams have the formula:
CA 02256703 2002-02-11
13
0
C C CH2 CH2
g1 C N
CH2 CHI
wherein R1 is an alkyl, aryl, alkoxyaryI or alkaryl group containing f7rom 5
to 12
carbon atoms. More preferably, Rl is selected from phenyl, heptyl, octyl,
nonyl,
2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Mixtures of any of the peroxyacid bleach precursor, herein before described,
may
also be used.
The cationic surfactant and hydrophobic organic peroxyacid precursor are
preferably present in the detergent composition at a ratio of 25:1 to 1:1,
most
preferably at a ratio of 10:1 to 1:1.
Preformed o~ani~ pero~yacid
The organic peroxyacid bleaching system may contain, in addition to., or as an
alternative to, an organic peroxyacid bleach precursor compound, a prefornied
hydrophobic organic peroxyacid , typically al a level of from 0.05 ~o to 209
by
weight, more preferably from 1 % to 109b by weight of the composition.
A preferred class of hydrophobic organic peroxyacid compounds are the anode
substituted compounds of the following general formulae:
R$-C-N R~-C-OOH or RS-N--C----R~-C-OOH
'O ~6 ,O Rb OI O)
wherein R$ is an aryl yr alkaryl group with from about 1 to about 14 carbon
atoms, R? is an alkylene, arylene, and alkarylene group containing from about
1 to
CA 02256703 2002-02-11
14
14 carbon atoms, and R6 is H or an alkyl, aryl, or alkaryi group containing 1
to 10
carbon atoms. R3 preferably contains from about b to 12 carbon atoms. R7
preferably contains from about 4 to 8 carbon atoms. RS may be straight chain
or
branched alkyl, substituted aryl or alkylaryl containing branching,
substitution, or
both and may be sourced from either synthetic sources or natural sources
including
for example, tallow fat. Analogous structural variations are permissible for
R?.
R7 can include alkyl, aryl, wherein said R7 may also contain halogen,
nitrogen,
sulphur and other typical substituent groups or organic compounds. R6 is
preferably H or methyl. RS and R6 should not contain more than 18 carbon atoms
total. Amide substituted bleach activator compounds of this type are descr'bed
in
EP-A-0170386. Suitable examples of this class of agents include (6-octylamino)-
6-
oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-
caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
metachloro perbcnzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
4,483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP O,I70,386. A
preferred hydrophobic prefortned peroxyacid bleach compound for the purpose of
the invention is nonanonylamido peroxycarboxylic acid.
Other suitable organic peroxyacids for the first aspect of the invention
include
diperoxyalkanedioc acids having more than 7 carbon atoms, such as
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc acid.
Other suitable organic peroxyacids include diamino peroxyacids, which are
disclosed in WO 95! 03275, with the following general formula:
O O O O
MOCR~R1 N) -C (NR2)n' - R3 --(R2N)m'-C tNR~ )m-RCOOM
n
wherein:
R is selected froth the group consisting of C 1-C 12 alkylene, CS-C 12
cYcloalkylene,
C6-C 12 arylene and radical combinations thereof;
Rl and R2 are independently selected from the group consisting of H, C1-~Clb
alkyl and C6-C~2 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 Cl,-
C12
CA 02256703 2002-02-11
IS
alkylene, CS-C12 cycloalkylene and C6-C12 arylene radicals; n and n' each are
an
integer chosen such that the sum thereof is l; 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 95/ 16673, with the following general structure:
X -Ar- CO - NY- R(Z) -CO- OOH
in which X represents hydrogen or a compatible substituent, Ar is an aryl
group, R
represents {CHZ)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 to C6 for example a methyl,
ethyl
or propyl group. Alternatively, X can represent a second amido-perrarboxylic
acid
substituent of formula:-
-CO-NY-R(Z)-CO-OOH
in which R, Y, Z and n are as defined above.
MOOC-Rl CO-NR2-R3-NR4-CO-RSCOOOM
wherein Rl is selected from the group consisting of C 1-C 12 alkylene, CS-C 12
cycloalkylene, C6-C12 arylene and radical combinations thereof; R
Preferred detergent compositions according to the present invention
additionally
comprise a hard base organic polymeric component. Preferably the total
cationic
surfactant and hard base polymeric component will be present in the detergent
composition at a weight ratio 10:1 to 1:3, most preferably 5:1 to 1:2.
CA 02256703 2002-02-11
16
The hard base polymeric component preferably comprises a polymer having a
pendant group (that is to say a group which is not a polymeric linkage group,
so
that it does not form part of the polymer backbone) which is a harder base
than a
benzene sulphonate group
/,/'
S03_
''\ ,, / .
,,. ; v _._.
in accordance with Pearson's classification of hard and soft behavior.
Preferably
the polymeric component comprises a polymer having a pendant group which is a
harder base than a sulphonate group such as CH3CH2CH2-S03-. The polymeric
component is generally formed from at least 5 % , preferably at least 25 % by
weight
of monomers which result in such pendant groups. The polymeric component
preferably has a molecular weight of from 1500 to 150000 most preferably from
2000 to 100000, especially 5000 to 80000. Molecular weight measurements are
obtained by GPC using styrene as a standard.
Particularly preferred pendant groups are carboxylic groups (references herein
to
acid groups also include their salts). Acrylic and malefic homopolymers or
copolymers are particularly preferred.
The hard base polymer may be any organic polymeric material having a hard base
group commonly used as dispersants, and anti-redeposition and soil suspension
agents in detergent 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
1500-5000 and their copolymers with malefic anhydt~ide, such copolymers having
a
molecular weight of from 2,000 to 100,000, especially 5,000 to 80,000, or even
10,000 to 50,000.
CA 02256703 2002-02-11
17
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.
The hard base polymeric component is preferably present as components of any
particulate components where they may be beneficial as a binder.
Additional detereent 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 may contain an additional
surfactant
selected from anionic, nonionic, additional cationic, ampholytic, amphoteric
and
zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, amphoiytic, 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.
CA 02256703 2002-02-11
18
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally
used in combination with one or more anionic andlor 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 acyi
isethionates, N-
acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated
C12-C18 monoesters) diesters of sulfosuccinate (especially saturated acrd
unsaturated Cb-C14 diesters), N-aryl 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 ethoxysuIfates, fatty oleoyl
,glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the C$-C1~ acyl-N-(Cl-C4
alkyl) aad -N-(Cl-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the norinonic
nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and bratxhed
primary C1~-Cig alkyl sulfates, more preferably the C11-C1$ branched. chain
alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
CA 02256703 2002-02-11
19
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the Clp-Clg 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 11-C 1 g, most preferably C 11-C 15 alkyl sulfate which has been
ethoxylated
with from 0.5 to ?, preferably from I 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 Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C~-
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 carboxvlate 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
CH2C04-M + wherein R is a C6 to C 1 g alkyl group, x ranges from O to 10, and
the ethoxylate distribution is such that, on a weight basis, the amount of
material
where x is.0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy
polycarboxyIate surfactants include those having the formula RO-(CHR1-CHR2-
O)-R3 wherein R is a C6 to Clg alkyl group, x is from 1 to 25, Rl and R2 are
selected from the group consisting of hydrogen, methyl acid radical, succinic
acid
radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is
selected
from the group consisting of hydrogen, substituted or unsubstituted
hydrocarbon
having between I and 8 carbon atoms, and mixtures thereof.
CA 02256703 2002-02-11
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-C1~ linear or branched alkyl or
alkenyl group, R1 is a C1-Cq, 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. ~'he
ethoxylated and propoxylated nonionic surfactants are preferred.
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 oxidelethylene diamine adducts.
Nonionic alkoxvlated 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 secondary, and generally contains from 6 to 22 carbon
atoms. Particularly preferred are the condensation products of alcohol.s
having an
alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of
ethylene oxide per mole of alcohol.
CA 02256703 2002-02-11
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Nonionic poiyhvdroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1Z wherein : R1 is H. Cl-CQ hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-
C4
alkyl, more preferably C1 or C~ alkyl, most preferably C1 alkyl (i.e.,
methyl); and
R2 is a CS-C31 hydrocarbyl, preferably straight-chain CS-C19 alkyl or alkenyl,
more preferably straight-chain Cg-C17 alkyl or alkenyi, most preferably
straight-
chain C11-C1' alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
(preferably
ethoxylated or propoxyiated) thereof. Z preferably will be derived from a
reducing
sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic fatt~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, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H~,0)xH, where x is in the
range of from 1 to 3.
Nonionic alkvlnoiysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January .2 l , 1986, hay ing a hydrophobic group
containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a
poiyglycoside,
hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl"
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
CA 02256703 2002-02-11
22
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.
Amnhoteric 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(ORa)xN0(R$)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8
to 26 carbon atoms; R'l is an alkylene or hydroxyalkylene group containing
from 2
to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably froth 0
to 3;
and each RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a
polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
Preferred
are C 10-C 1 g alkyl dimethylamine oxide, and C 1 Q_ 18 acylamido alkyl
dimethylamine oxide.
A suitable example of an alkyl aphodicarboxyIic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitteriotuc 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 betames are those compounds having the formula R(R')2N+R2C00-
wherein R is a C6-Clg hydrocarbyl group, each Rl is typically C1-C~ alkyl, and
R2 is a C1-CS hydrocarbyl group. Preferred betaines are C12-18 d~ethyl-
ammotuo hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or
diethyl) heroines. Complex betaine surfactants are also suitable for use
herein.
CA 02256703 2002-02-11
23
Cationic surfactants
Additional cationic surfactants may also be used in the detergent compositions
herein. Suitable cationic surfactants include the ethoxylated quaternary
ammonium
surfactants as described in GB-A-2040990, or ester surfactants. Suitable
cationic
ester surfactants, including choline ester surfactants, have for example been
disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
Alkalinity
In the detergent compositions of the present invention preferably a 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 persiIicate.
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 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 2.0 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
CA 02256703 2002-02-11
24
NaMSix02x+ 1 ~YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed
in EP-
A-0164514 and methods for their preparation are disclosed in DE-A-3417b49 and
DE-A-3742043. 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.
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
golycarboxylates, 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 atxl 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) diacedc acid, malefic acid, diglycolic acid,
tartaric
acid, taruonic acid and fumaric acid, as well as the ether carboxylates and
the
sulfinyl carboxylates. Polycarboxytates 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
CA 02256703 2002-02-11
aminosuccinates described in Canadian Patent No. 973,771, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxyiates containing four carboxy groups include oxydisuccinates
disclosed
in British Patent No. 1,261,829, 1,1.2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxyiates
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 citratelcitric 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 polymetalphosphate in which the degree of polymerization ranges from
about 6 to 21, and salts of phytic acid.
Partiallx 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.
CA 02256703 2002-02-11
26
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(AlO2)z(Si02)y].
xH20 wherein z and y are at least 6; the molar ratio of z to y is frorn 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,
containing From 10 % to 28 % , more preferably from 18 ~ to 22 % water in
bound
form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials
are available under the designations ZeoIite A, Zeolite B, Zeolite P, Zeolite
X,
Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [A102) 12 (Si02) I2] . xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)86(Si02)106]. 276 H20.
Bleach catal rLst
The compositions optionally contain a transition metal containing bleach
catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a heavy
metal
canon of defined bleach catalytic activity, such as copper, iron or manganese
canons, an auxiliary metal canon having little or no bleach catalytic
activity, such
as zinc or aluminum canons, and a sequestrant having defined stability
constants
for the catalytic and auxiliary metal canons, 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 MnN2(u-O)3(1,4,7-trimethyl-1,4,'lI-triazacyclononane~-
(PF6)2,
Mn~(u-O)1 (u-OAc~(1,4,7-trimethyl-1,4, 7-triazacyclononane)2-(C104)2,
MnN4(u-O)6(1,4,7-triazacyclononane)4-(CI04~, Mn~Mn~4(u-O)1(u-OAc)2_
(1,4,7-trimethyl-1,4,7-triazacyclononaney2-(CiO4)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,
CA 02256703 2002-02-11
27
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,?-trimethyl-1,4,7-triazacyclononan~;)(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 (IB), 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 N4Nin~(u-O~MnIVN4)+and [Bipy2Mn~(u-
O)2MnNbipY21-(C104)3.
Further suitable bleach catalysts are described, far example, in European
patent
application No. 408, I3 I (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455 (manganeselmultidentate Iigand 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 (manganeselligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,0I9
(cobalt
chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
4,430,243 (chelants with manganese canons and non-catalytic metal cations),
and
U.S. 4,728,455 (manganese gluconate catalysts).
Heavy 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.
CA 02256703 2002-02-11
28
Heavy metal ion sequestrants are generally present at a Ievel 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 potyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid,
ethylenediamine
diglutaric acid, 2-hydroxypropylenediarriine disuccinic acid or any salts
thereof.
Especially preferred is ethyienediamine-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 inzinodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-31?,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, 1U2 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 also 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 02256703 2002-02-11
29
En~me
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 3,519,5?0
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 mare 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 trademark
Termamyi and BAN by Novo Industries AIS. 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 iipolytic enzyme of from
0.0001 °Y to 2'~ by weight, preferably 0.001 °/ to I % by
weight, most preferably
from 0.001 % to 0.5 % by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a
lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp.
including Pseudomonas gseudoalcali~enes or Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein.
CA 02256703 2002-02-11
A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is
described in Granted European Patent, EF-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanu i~ 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 AlS, Bagsvaerd, Denmark, under the trade mark Lipolase.
This lipase is also described in U.S. Patent 4,810,414, Huge-densen et al,
issued
March 7, 1989. .
Organic polymeric compound
Organic polymeric compounds such as the hard base polymeric components
described above 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 10% 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 of 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.
CA 02256703 2002-02-11
31
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,Q00, are also suitable herein.
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 gl;ycols,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000
and most preferably about 4000.
Suds suppressing system
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
CA 02256703 2002-02-11
32
silicone antifoam compounds are the siloxanes, particularly the
polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxyiic fatty acids and
soluble salts thereof. These materials are described in US Patent 2,954,347,
issued
September 27, 1960 to Wayne St. Jvhn. 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
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 monovafent
alcohols,
aliphatic Clg-C40 ketones (e.g. stearone) N-alkylated amino triazines such as
tri-
to hexa-alkylmelamines or di- to tetra alkyldiamine chlorniazines 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 antifoarn compound, most
preferably a silicone antifoam compound comprising in combination
(t) polydimethyl siloxane, at a level of from 50% to 99°x,
preferably 75 9~c to 95 9b by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1 % to 50 °l , preferably 5 %a to 25 9o
by
weight of the silicone/silica antifoarn compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
% to 50 % , preferably 10 % to 40 % by weight;
CA 02256703 2002-02-11
33
(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 prefeured silicone
glycol rake copolymer of this type is. DC0544, commercially available
from DOW Corning under the iradename 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 5% to 80~, preferably 10% to 70~,
by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and comprises a silicone antifoam compound and an organic carrier
material having a melting point in the range 50°C to 85°C,
wherein the organic
carrier material comprises a monoester of glycerol and a fatty acid having a
carbon
chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other
preferred particulate suds suppressing systems wherein the organic ,carrier
material
is a fatty acid or alcohol having a carbon chain containing from 12 to 20
carbon
atoms, or a mixture thereof, with a melting point of from 45°C to
80°C.
Clav ssoftening svstern
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. 8mectite
clays
are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,63:2 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 agents
CA 02256703 2002-02-11
34
The detergent compositions herein cnay also comprise from 0.01 % to 10 %,
preferably from 0.05 °l to 0.5 °k by weight of paIymeric 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 nolvmers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
(1)
R
wherein P is a polymerisable unit, and
00 0
Ii !I fi
AisNC,CO,C,-O-,-S-,-N-;xisOo~l;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicycluc
groups
or airy combination thereof whereto the nitrogen of the N-0 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
CA 02256703 2002-02-11
0
0
(R1 ) x _N_(R2)Y 1
(R3)Z or N-(R~ )x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y orland z is 0 or 1 and. wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-0
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
polyatnine
N-oxides comprises the group of polyamine N-oxides wherein the nitmgen of the
N-O group forms part of the R~group. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyrridine, 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 alicyciic 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 tla;reof.
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 average molecular
weight is within the range of 500 to 1000,000.
b) Covolvmgrs ~ N-viny~vvrrolidon~ and N-vinyi_imidazole
CA 02256703 2002-02-11
36
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.
cy PolyvinyIpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP")
having an average molecular weight of from 2,504 to 400,000. Suitable
polyvinylpyrrolidones are commercially available from ISP Corporation, New
York, NY and Montreal, Canada under the product names PVP K-15 (viscosity
molecular weight of 10,(X?(?), PVP 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 360,0()0). PVP K-15 is also available from ISP
Corporation.
Other suitable polyvinylpyrrolidones which are commercially available from
BASF
Corporation include Sokal n HP 165 and Sokaian HP 12.
d~ Polvvinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as
poiymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of from 2,500, to 40(1,000.
a Polyvinyl_imidazole
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~htener
The detergent compositions herein also optionally contain from about 0.005 %
to
~ by weight of certain types of hydrophilic optical brighteners.
CA 02256703 2002-02-11
37
Hydrophilic optical brighteners useful herein include those having the
siructurai
formula:
R2
N H H N
IV N C C N N.
-N H H N-
R2 S03M S~3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and N'H-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-
methylamino, morphilino, chloro and amino; and M is a salt-forming cation such
as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4' ,-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and
disodiuxn salt.
This particular brightener species is commercially marketed under the
trademark
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the detergent compositions
herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bisj(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 SBM-GX by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the trademark Tinopal AMS-GX by Ciba
Geigy Corporation.
Cationic fabric softening agents
CA 02256703 2002-02-11
38
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-I 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 sail.
pH 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.S to 11Ø
Form of the compositions
The compositions in accordance with the invention can take a variety of
physical
forms including granular, tablet, bar and liquid forms. The compositions are
particularly the so-called concentrated granular detergent compositions
adapted to
be added to a washing machine by means of a dispensing device placed in the
machine drum with the soiled fabric load.
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 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
CA 02256703 2002-02-11
39
greater than 1.7mm in diameter and not more than 5 % of particles are less
than
O.lSmm in diameter.
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 600 glliue, more
preferably from
650 g/litre to 1200 gllitre. 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 exuemiry 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 I30 mm and 40 mm at
its
respective upper and lower exuemities. It is mounted so that the lower
exuemiry 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 fimnel 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
suaight 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 gllitre. Replicate measurements are made as required.
Surfactant agglomerate particles
The cationic ester surfactant herein, preferably with additional surfactants,
is
preferably present in granular compositions in the form of surfactant
agglomerate
particles, which may take the fornn of hakes, grills, 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
CA 02256703 2002-02-11
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, Leiystad,
Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1,
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 SORB by weight to 95'~ by
weight,
preferably 70 % by weight to 85 °l~ by weight of surfactant 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.
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. Its volume capacity should be such as to be
able 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 d~vm 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
CA 02256703 2002-02-11
41
product during the wash cycle in response to its agitation as the dmm 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 1?ut
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 Application No. W094111562.
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 support ring is provided with a masking arrangement 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 constncctian coated with a water impermeable
CA 02256703 2002-02-11
42
protective material so as to retain the contents, such as is disclosed its
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. 11011500, 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.
Packaging 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.
CA 02256703 2002-02-11
43
Abbrevi:~tions used in Examples
In the detergent compositions, the abbreviated component identifications have
the
folic ping meanings:
LAS : Sodium linear C~2 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS . Sodium C 14-C 15 linear alkyl sulfate
CxyEzS : Sodium Clx-Cly branched alkyl sulfate
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
C25E3 . A C~2-15 branched primary alcohol condensed
with an average of 3 moles of ethylene
oxide
C25E5 . A C12-15 branched primary alcohol condensed
with an average of 5 moles of ethylene
oxide
CEQ I . R1COOCH2CH2.N"t'(CH3)3 with Rl = C11-C13
CEQ II . R1COOCH2CH2CH2N+(CH3)3 with R1 = Cil-
Ci3
CEQ III . R1COOCH2CH2N~'(CH3)2(CH2CH2OH) with
RI =C11-CI3
CEQ IV : R1COOCH2CH2N~'(CH3CH2~,(CH3) with
Rl _Ci -C 3
QAS I : R2.N'f'(CH3)2(C2H4OH) with R2 = C12
- C14
QAS II RZ.N'i"(CH3)2(C2H40H) with R2 = Cg
R2.N"~'(CH3)2(CZH40H) with R2 = 50% Cg;
509 C11
QAS IV . R2~N'~'(CH3)2(C2H4OH) with R2 = 70~
C10;
309 Cg
Soap . Sodium linear alkyl carboxylate derived
from an
80/20 mixture of tallow and coconut oils.
TFAA . CI6-C18 alkyl N-methyl giucamide
TPKFA . C i2-C 14 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
CA 02256703 2002-02-11
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nai2(A102SiO2)12~ 2~H20 having a primary
particle size in die range from 0.1 to 10
micrometers
NaSKS-6 . Crystalline layered silicate of formula
s -Na2Si205
Citric acid Anhydrous citric acid
.
Carbonate Anhydrous sodium carbonate with a particle
. size
between 200~xm and 900um
Bicarbonate Anhydrous sodium bicarbonate with a
. particle
size distribution between 400pm and
1200~tm
Silicate : Amorphous Sodium Silicate (Si02:Na2O;
2.0
ratio)
Sodium sulfateAnhydrous sodium sulfate
:
Citrate : Tri-sodium citrate dihydrate of activity
86.4Xo
with a particle size distribution between
425Pm
and g 850~m
MAIAA : Copolymer of 1:4 maleiclacrylic acid,
average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Protease . Proteolytic enzyme of activity 4KNPU/g
sold by
NOVO Industries AIS under the trademark
Savinase
Alcalase . Proteolytic enzyme of activity 3AUIg
sold by
NOVO Industries AIS
Cellulase Cellulytic enzyme of activity 1000
: CEVIl/g sold
by NOVO Industries AIS under the trademark
Carezyme
Amylase . Amylolytic enzyme of activity 60KNU/g
sold by
NOVO Industries AlS under the trademark
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLUlg
sold by
NOVO Industries AlS under the trademark
Lipolase
Endolase : Endoglunase enzyme of activity 3000
CE'VUIg
sold by NOVO Industries AIS
CA 02256703 2002-02-11
PB4 : Sodium perborate tetrahydrate of nominal formula
NaBOZ.3H20.H202
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB02. H2O2
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H202
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt
NAC-OBS . (Nonanamido caproyi) oxybenzene sulfonate in
the form of the sodium salt.
NACA : ~ nonylamino - b oxo - capronic acid.
TAED . Tetraacetylethylenediamine
DTPMP . Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto
under the
Trade mark bequest 2060
PhotoactivatedSulfonated Zinc Phthlocyanine encapsulated
. in
bleach dextrin soluble polymer
Brightener Disodium 4,4'-bis{2-sulphostyryl)biphenyl
1 .
Brightener Disodium 4,4'-bis(4-anilino-6-morgholino-I.3.5-
2 .
triaxin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP . 1,1-hydroxyethane diphosphonic acid
PVNO . Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SR.P 1 . Sulfobenzoyl end capped esters with
oxyechylene
oxy and terephthaloyl backbone
SRP 2 . Diethoxylated poly {I, 2 propylene
terephthalate)
short block polymer
Silicone antifoamPolydimethylsiloxane foam controller
: vvith
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 %a by weight of the
composition:
CA 02256703 2002-02-11
46
Example 1
The following laundry detergent compositions A to F are compositions according
to the invention:
A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
CEQ I 0.8 0.8 2.0 2:0 1.0 0.7
CEQ II _ _ . 0.5 - - 0.8
QAS I 0.2 0.5 0.8 - - 0.8
QAS B _-_. _ _ _ - 0.7 2.0 -
Zeoiite A' 18.I 18.1 18.1 18.1 18.:1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sodium sulfate 26.1 26.1 26.I 26.1 26.1 26.1
pgrl 9.0 9.0 9.0 9.0 9.0 9.0
NAC OBS 2.5 1.5 3.0 4.0 3.2 2.2
DETPMP 0.25 0.25 0.25 0.25 0.2 0.25
~
HEDP 0.3 0.3 0.3 0.3 0:3 0.3
CA 02256703 2002-02-11
47
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
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
Photoactivated 15 pp 15 pp 15 pp 15 pp 15 pp 15 pp
bleach (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
Misclminors to
100 ~
Density in g/litre850 850 850 850 850 850
CA 02256703 2002-02-11
48
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 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - ~ 0.76 1.18
C45E7 -_ _____ 3.25 - 5.0
C25E3 - 5.5
QAS II 0.8 2.0 2.0
QAS III 0.4 1.0 0.5
STPP 19.7 - -
Zeolite p _ - 19.5 19.5
NaSKS-6lcitric acid (?9:21)- 10.6 10.b
6.1 21.4 2I .4
Bicarbonate - 2.0 2.0
Silicate 6.8 -
CA 02256703 2002-02-11
49
Sodium sulfate 39.8 - 14.3
PB4 . 5.0 12.7 _
TAED 0.5 0.2 _
NAC OBS 1.0 2.2 1,3
DETPMP 0.25 ' 0.2 0.2
HEDP - 0.3 0.3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0:28 0.28 0:28
Amylase 0.1 0.1 O. I
MAIAA 0.8 1.6 _~.6_
CMC 0.2 ~ 0.4 0.4
Photoactivated bleach 1~ ppm ?7 ppm 27 ppm
(pptn)
Bt~ighte~r 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
CA 02256703 2002-02-11
Example 3
The following are detergent formulations, according to the present invention
where
3 is a phosphorus-containing detergent composition, K is a zeolite-containing
detergent composition and L is a compact detergent composition:
3 K L
Blown Powder
STPP 24.0 - 24.0
Zeolite A _ ___ -
- 24.0
C45AS 9.0 _ 13.0
6.0
.
QAS II - _ _ -
2.0
QAS III - -
2.0
QAS IV 2.0 _ -
_
MA/AA 2.0 - 4.0-__ _
2.0
LAS 6.0 8.0 11.0
TAS 2.0 - -
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
_
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dty additives
Carbonate 6.0 13.0 15.0
PH4 18.0 18.0 10.0
p$1 4.0 4.0 0
NOBS 3.0 4.2 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
Dry mixed sodium sulfate3.0 3.0 5.0
Balance (Moisture & to 100.0 to 100.0 to 100.0
laneous)
iscel
M
_ 630 ~ 670 ~ 670
_
Density (g/litre) ~
CA 02256703 2002-02-11
51
Example 4
The following are detergent formulations according to the present invention:
P Q R S
LAS 20.0 14. D 24.0 22.0
QAS I 0.7 1.0 - 0.7
CEQ Ill 0:4 0.4 2.2 1.5
CEQ IV 1.5 0.4 1.0 1.5
TFAA - 1.0 - -
C25ES/C45E7 - 2.0 - 0.5
C45E3S - 2.5 -
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 - O.I
MAIAA 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. 0.05 - -
15
Photoactivated _ 45ppm - lOppm
bleach (ppm) 70ppm
Hrightener 1 0.2 0.2 0.08 0.2
PB1 -.. (.0 2.0 -
NAC OBS 2.0 1.0 0.9 3.1
-.
Balance 100 100 100 1
(Moisture and
Miscellaneous)
CA 02256703 2002-02-11
52
Exam~e 5
The following are detergent formulations according to the present: invention:
T U V
Blown Powder
QAS IV - 0.4 1.5
QAS II 1.5 1.5 1.5
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
-_ ~~ 3.0 3.0 6.0
LAS 14.0 12.0 22.0
C45AS 8.0 7.0 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
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 O.S
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
NACA 3.4 6.1 4.5
Sodium sulfate - 6.0 -
Balance (Moisture 100 100 100
and
Miscellaneous)
CA 02256703 2002-02-11
53
E~cample 6
The following are high density and bleach-containing detergent formulations
according to the present invention:
W X Y
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodim sulfate 0.0 5.0 0.0
__ _
LAS ___ ~ 3.0 3.0
3.0
QAS I - 1.5 1.5
QAS II 0.9 - -
CEQ II 0.5 0.5 2.7
CEQIII ~ - 1.2
DTPMP 0.4 0.4 0.4
CMC 0.4 O.a o.4
MAIAA 4.0 2.0 2.0
Agglomerates
LAS 5.0 ' S:0 5.0
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
_
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.4
Carbonate 8.0 15.0 10.0
NAC OBS 6.0 2.0 5.0
NACA 2.0 1.8 1.2
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000 _ _
Hentonite clay - - 10.0
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
CA 02256703 2002-02-11
54
Silicone ancifoam 5.0 5.0 5.0
Drv additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/Iitre) 850 850 850
CA 02256703 2002-02-11
SS
Example 7
The following are high density detergent formulations according to the present
invention:
Z ~ .._
Agglomerate
_ _ _ _ _
C45AS 11.0 14.0
_.
QAS II 1.8 2.2
Zeolite A 15.0 ~ 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 I0.0
Citrate 3.0 1.0
NAC OBS 4.1 6.2
TAED 0.8 1.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 O.b
Amylase 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Balance (Moisture and 100 100
Miscellaneous)
Density (gllitre) . 850 850
CA 02256703 2002-02-11
56
Exam
The following are liquid detergent formulations according to the present
invention:
AB AC AD AE AF A.G AH AI
CEQ I 0.4 1.0 - - 2.0 2.5 - -
CEQ II - - 0.7 - 1.2 - _ _
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 I8.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
QAS I - _ _ - 3.0 1.0 - _-__
_
_
QAS III 0.6 1.2 - - 3.5 -
QAS IV _ _ 0:8 0.8 - 3.5
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed fatty acids- - - 5.0 - - 4.0 4.0
Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenylltetradecenyl12.0 10.0 - - 15.0 - -
succinic acid
Oleic acid 4.0 2.0 1.0 - 1.0 - - -
Ethanol ~ 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.4 6.0 8.0 10.0 13.-
Mono Ethanol Amine - - - 5.0 - - 9.0 9.0
Tri Ethanol Amine - w 8 - - - ' -__
NaOH up to pH 8,0 8.0 7.b 7.7 8.0 7.5 8.0 8.2
Ethoxylated tetraethylene0.5 - 0.5 0.2 - - 0.4 0.3
pentamine
NAC OBS 1.0 I.0 0.5 1.0 2.0 1.2 1.0 1.6
NACA 0.7 1.1 I.8 1.5 1.9 2.1 1.4 1.0
pg4 2.0 2.6 3.1 3.0 3.1 3.5 2.9 2.5
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
protease 0.5 0.5 0.4 0.25 - 0.5 0.3 0.6
Alcalase ___ - _ - 1.5 - - -
Lipase - 0.10 - 0.01 - - 0.15 0.15
,~yi~ 0.25 0.25 0.6 0.5 0.25 0.9 0.6 0.6
Cellulase ~ - - - 0.05 - - 0.15 0.15
Endolase - - -.. 0.10 _- - 0.07 -
Horic acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - _- - - -
Ca chloride - 0.015 - 0.01 - - - ~
-
t
CA 02256703 2002-02-11
5l
Bentonite clay - _~ - _ 4.0 4 -
0
Suspending clay SD3 - - - - 0 .
6
. O.s
Balance (Moisture 100 100 100 100 100 100 I00
and
100
Miscellaneous)
