Note: Descriptions are shown in the official language in which they were submitted.
,i h ~,
~W~ 95125464 _ z ~ s ~ ~ ~~ . :w , , PCT/US95/04085
DETERGENTS CONTAINING A HEAVY METAL SEQUESTRANT AND A DELAYED
RELEASE PEROXYACID BLEACH SYSTEM
This invention relates to detergent compositions containing a heavy metal ion
sequestrant and an organic peroxyacid bleaching system, wherein a means is
provided for delaying the release to the wash solution of the organic
peroxyacid
bleach relative to the release of the heavy metal ion sequesttant.
The satisfactory removal of bleachable soils/stains such as tea, fruit juice
and
coloured vegetable soils from soiled/staived substrates is a particular
challenge to
the formulator of a detergent composit:un for use fin a washing method such as
a
laundry or machine dishwashing method
Traditionally, the removal of such bleachable soils/stains has been enabled by
the
use of bleach components such as oxygen bleaches, including hydrogen peroxide
and organic peroxyacids. The organic peroxyacids are often obtained by the in
situ
perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid
bleach
precursor.
A problem encountered with the use of certain organic peroxyacid bleaches in
laundry washing methods is a tendency for these organic peroxyacid bleaches to
affect the colour stability of the fabrics in the wash. Types of fabric damage
can
include fading of coloured dyes on the tahrics or localised areas of "patchy"
colour
bleaching.
The detergent formulator thus faces the dual challenge of formulating a
product
which maximises bleachable soillstain removal but minimises the occurrence of
any
unwelcome fabric colour stability effects of the bleach.
The Applicants have found that the occurrence of any unwelcome fabric colour
stability effects arising from the use of organic peroxyacid bleaches in a
washing
method can be related to the rate of release of the peroxyacid bleach to the
wash
solution and also to the absolute level of peroxyacid present in the wash
solution.
A fast rate of release of the peroxyacid bleach to the wash solution tends to
heighten
the probability that unwelcome fabric colour stability effects will be
observed, as
does a high absolute level of the bleach in the wash solution.
CA 02187438 1999-11-10
Whilst reducing either the rate of release of the peroxyacid bleach, or the
absolute level
of the bleach employed in the wash tends to ameliorate this problem, this can
be
accompanied by a negative effect on the bleachable stain/soil removal ability.
The Applicants have now however found that where a composition containing both
a
heavy metal ion sequestrant and a peroxyacid bleach source is employed, and
wherein a
means is provided for delaying the release to a wash solution of the
peroxyacid bleach
relative to the release of the heavy metal ion sequestrant enhanced bleachable
stain/soil
removal may be obtained. Additionally, where the composition is used in a
laundry
washing method a reduction in the propensity for negative fabric colour
stability effects
to be observed is also obtained.
The Applicants have in addition found that bleachable stain/soil removal
benefits may be
obtained when a soiled substrate is pretreated with a solution containing a
heavy metal
ion sequestrant, and optionally a water soluable builder, prior to being
washed in a
method using a bleach containing detergent product.
It is therefore an object of the present invention to provide compositions
suitable for use
in laundry and machine dishwashing methods having enhanced bleachable stain
removal.
It is also an object of the present invention to provide compositions for use
in a laundry
washing method wherein said compositions show less propensity to cause
negative fabric
colour stability effects.
It is a related object of the present invention to provide a stain/soil
pretreatment method
involving pretreating the soiled substrate with a solution containing a heavy
metal ion
sequestrant and optionally a water soluble builder, prior to washing with a
bleach-
containing detergent product.
Summary of the Invention
According to one aspect of the present invention there is provided a detergent
composition comprising: (a) a heavy metal ion sequestrant; (b) an organic
peroxyacid
bleaching system comprising: an inorganic perhydrate salt coated with a
coating
composition comprising an organic binder and an inorganic salt selected from
the group
consisting of sulphates, silicates, carbonates and mixtures thereof; and an
organic
peroxyacid bleach precursor agglomerated with the organic binder; wherein the
organic
binder is selected from the group consisting of Coo-C2o alcohol ethoxylates,
Cep-C20
CA 02187438 1999-11-10
monoglycerol ethers, C,o-C2o diglycerol ethers, Clo-CZo fatty acids,
polyvinylpyrrolidones, polyethylene glycols, copolymers of malefic anhydride
and
ethylene, copolymers of malefic anhydride and methylvinyl ether, copolymers of
malefic
anhydride and methacrylic acid, methylcellulose, carboxymethyl cellulose,
ethylhydroxyethylcellulose, hydroxyethylcellulose, homopolymeric
polycarboxylic acids
and salts thereof, co-polymeric polycarboxylic acids and salts thereof, and
mixtures
thereof; and (c) a fabric softening agent selected from the group consisting
of (i) from
0.5% to 5% by weight of the composition, of water-insoluble tertiary amines;
(ii) from
0.5% to S% by weight of the composition, of di-long chain amides; (iii) from
0.1% to 2%
by weight of the composition, of polyethylene oxides; and (iv) mixtures
thereof; wherein
in the T50 test method the time to achieve a concentration that is 50% of the
ultimate
concentration of the heavy metal ion sequestrant is less than 120 seconds and
the time to
achieve a concentration that is 50% of the ultimate concentration of the
organic
peroxyacid is more than 180 seconds.
According to another aspect of the present invention there is provided a
detergent
composition comprising: (a) a heavy metal ion sequestrant; (b) an organic
peroxyacid
bleaching system; and (c) a polyalkenyl polyether having a molecular weight of
from
about 750,000 to about 4,000,000; wherein a means is provided for delaying the
release
to a wash solution of said organic peroxyacid relative to the release of said
heavy metal
ion sequestrant such that in the T50 test method the time to achieve a
concentration that
is 50% of the ultimate concentration of said heavy metal ion sequestrant is at
least 100
seconds less than the time to achieve a concentration that is 50% of the
ultimate
concentration of said organic peroxyacid; and wherein the composition is in
the form of
a gel.
Said organic peroxyacid bleaching system preferably comprises in combination
(i) a hydrogen peroxide source; and
(ii) an organic peroxyacid bleach precursor compound.
According to a preferred aspect of the present invention said composition
additionally
contains a water soluble builder wherein a means is provided for delaying the
release to a
wash solution of the organic peroxyacid relative to the release of said water
soluble
builder such that in the T50 test method herein described the time to achieve
a
concentration that is 50 % of the ultimate concentration of said water soluble
builder is
less than 120 seconds.
CA 02187438 1999-11-10
4
According to another aspect of the present invention there is provided a
washing
method comprising the steps of:
( 1 ) applying a bleach-free solution of a composition containing a heavy
metal
ion sequestrant to a soiled substrate;
(2) allowing said solution to remain io contact with said soiled substrate for
an
effective time interval;
(3) washing said soiled substrate using a washing method involving use of a
bleach-containing detergent cor.~position.
Heavy metal ion seauestrant
The detergent compositions of the invention contain a heavy metal ion
sequestrant.
By heavy metal ion sequestlant it is meant herein components which act to
sequester
(chelate) heavy metal ions. These components may also have calcium and
magnesium chelation capacity, but pr~efer~entially they show selectivity to
binding
heavy metal ions such as iron, manganese and copper.
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.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphoric acid or carboxylic acid functionalities, may be present either in
their
acid forth or as a complex/salt with a suitable counter ration such as an
alkali or
alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures
thereof. Preferably any salts/complexes are water soluble. The molar ratio of
said
counter ration to the heavy metal ion sequestrant is preferably at least 1:1.
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.
- t>:'~' ~" i.'
WO 95128464 ~ 18 7 4 3 ~ PCT/US95/04085
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
~ tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
~ Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid
and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine ~disuccinic acid,
ethylenediamine
diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts
thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof. Preferred EDDS compounds are the free acid form and the
sodium or magnesium salt or complex thereof. Examples of such preferred sodium
salts of EDDS include Na2EDDS and Na3EDDS. Examples of such preferred
magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133.
The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-
carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-
516,102 are also suitable herein. The (i-alanine-N,N'-diacetic acid, aspartic
acid-
N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid
seiluestrants 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 sequestrent. Dipicolinic acid
and 2-
phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-
disuccinic acid (GADS) is also suitable.
Orgg~'c peroxvacid bleaching system
An essential feature of the invention is an organic peroxyacid bleaching
system. In
one preferred execution the bleaching system contains a hydrogen peroxide
source
R'O 95128464 F~ ~ ~ °~ ~~~ PCTIUS95104085~
6
and an organic peroxyacid bleach precursor compound. The production of the
organic peroxyacid occurs by an in situ reaciion of the precursor with a
source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate bleaches. In an alternative preferred execution a preformed organic
peroxyacid is incorporated directly into the composition. Compositions
containing
mixtures of a hydrogen peroxide source and organic peroxyacid precursor in
combination with a preformed organic peroxyacid are also envisaged.
Inornanic perhvdrate bleaches
Inorganic perhydrate salts are a preferred souroe 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 23b to 30?6 by
weight
and most preferably from 536 to 25 Y& by weight of the compositions.
Examples of suitable inorganic perhydrate salts include perborate,
perrarbonate,
perphosphate, persulfate and persilicate salts and any mixtures thereof. The
inorganic perhydrate salts are normally the alkali metal salts. The inorganic
perhydrate salt may be included as the crystalline solid without additional
protection. For certain perhydrate salts however, the preferred executions of
such
granular compositions utilize a coated form of the material which provides
better
storage stability for the perhydrnte salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaBO2H202 or the tetrahydtate NaB02H202.3H20.
Alkali metal pert;arbonates, particularly sodium perrafironate are preferred
perhydrates for inclusion in compositions in accordance with the invention.
Compositions, containing percarbonate, have been found to have a reduced
tendency
to form undesirable gels in the presence of surfactants and water than similar
compositions which contain perborate. It is believed that this is because
typically
percarbonate has a lower surface area and lower porosity than perborate
monohydrate. This low surface area and low porosity acts to prevent the co-
gelling
with fme particles of surfactant agglomerates and is therefore not detrimental
to
dispensing.
WO 95128464 ~s~:~ ~~ ~ ~y PCTlUS95/04085
(L (~~
7
Sodium percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid. The
percarbonate is most preferably incorporated into such compositions in a
coated
form which provides in product stability.
A suitable coating material providing in product stability comprises mixed
salt of a
water soluble alkali metal smphate and carbonate. Such coatings together with
coating processes have previously been described in GB-1,466,799, granted to
Interox on 9th March 1977. The weight ratio of the mixed salt coating material
to
percarbonate lies in the range from I : 200 to 1 : 4, more preferably from 1 :
99 to
1 : 9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt
is of
sodium sulphate and sodium carbonate which has the general formula
Na2S04.n.Na2C03 wherein n is from 0.1 to 3, preferably n is from 0.3 to I.0
and
most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric
acids or
other inorganics), waxes, oils, fatty soaps can also be used advantageously
within
the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in
the
detergent compositions herein.
pr arm hlearh DteCUtSOn
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in
a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
parhydroloysis the structure of the peroxyacid pnoduced is
O
~I
X-C-OOH
WO 95/28464 PCTlUS95/04085
8
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of
from 0.5 °.b to 20 °b by weight, more preferably from 1
°k to 15 % by weight, most
preferably from 1.5 ~ to 10°k by weight of the detergent compositions.
Suitable 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 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-017C38F.
The Applicants have found that 'patchy' damage can be particularly associated
with
peroxyacid bleach precursor compounds ,vhich on perhydrolysis provides a
peroxyacid which is
ti) a perbenzoic acid, or non-cationic substituted derivative thereof; or
(ii) a cationic peroxyacid.
Benzoxazin precursors have also been found to be particularly susceptible to
the
problem.
Leavine Qrouns
The leaving group, hereinafter L gtnlF, 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 trzctive, this activator will be difficult to stabilize
for use in a
bleaching composition.
Frefermd L groups are selected from the group consisting of:
WO 95/28464 ~ t'~ PCT/US95/04085
Y ~R3 - ~R3Y
-O~Y , and ~!(~'~O
0 O
-N-C-R' -N N -N-C-CH-R4
R3 , ~ , R3 Y
I
Y
R3 Y
-0-CH=C-CH=CH2 -O-CH=C-CH=CH2
O
-O-C-R'
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 0
and mixtures thereof, wherein R1 is an alkyl, aryl, or allcaryl 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 allryl,
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) X and O <-N(R3)3 and most preferably -S03 M~ and -COZ M+
wherein R~ is an alkyl chain containing from 1 to 4 carbon atoms, M is a
ration
which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M as an alkali metal, ammonium
or
WO 95/28464 _ _ ~~,~;~~~ ~~~ PCT1U595104085~
.3 - ,
IO
substituted ammonium canon, with sodium and potassium being most preferred,
and
X is a halide, hydroxide, methylsulfate or acetate anion.
Perbe~~oic acid and derivatives thereof precursors
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted
and unsubstituted benzoyi oxybenzene sulfonates, including for example benzoyl
oxybenzene sulfonate:
O
~ ~S03
Also suitable are the benzoyhition products of sorbitol, glucose, and all
saccharides
with benzoylating agents, including for example:
OAc
Ac0 ~-O
OAc
OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted
ureas.
Suitable imidazole type petbenzoic acid precursors include N-benzoyl imidazole
and
N-beozoyl benzimidazole and other useful N-acyl group-containing perbenzoic
acid
precursors include N-bettzoyl pytrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
w0 95128464 PCT/US95/04085
11
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
- ~ o
o-~
o~cooH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
0
II
R6-0 N-CHz-~ H2
~C HZ-EC HZ ]~
wherein n is from 0 to 8, picferably from 0 to 2, and R6 is an aryl,
alkoxyaryl or
alkaryl group containing from 1 to 12 carbon atoms, or a substituted phenyl
group
containing from 6 to 18 carbon atoms, preferably a benzoyl group.
1?e~enzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of the
herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially any non-positively charged (ie; non-cationic) functional group
including,
for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
CA 02187438 1999-11-10
12
A preferred class of substituted perbenzoic acid precursor compounds are the
amide
substituted compounds of the following general formulae:
R1 C _- N __.___ R2 __.C _ _ ~ R1N C _ R2 C _ ~
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
arylene, or 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 and L can be
essentially any leaving group. R1 preferably contains from 6 to 12 carbon
atoms.
R2 preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted
aryl
or alkylaryl containing branching, substitution, or both and may be sourced
from
either synthetic sources or natural sources including for example, tallow fat.
Analogous structural variations are permissible for R2. The substitution can
include
alkyl, aryl, halogen, nitrogen, sulphur and other typical subsntuent groups or
organic compounds. RS is preferably H or methyl. R1 and RS should not contain
more than 18 carbon atoms in total. Amide substituted bleach activator
compounds
of this type are described in EP-A-0170386.
Cationic neroxyacid precursors
Cationic peroxyacid precursor compounds 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 salt with a suitable anion,
such as a
halide ion.
The peroxyacid precursor compound to be so canonically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percartioxylic acid precursor compound or an amide substituted alkyl
peroxyacid
precursor as described hereinafter
CA 02187438 1999-11-10
13
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.
A preferred canonically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
0
~~ ~S03
~+
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
SO
v + ~ ~ ~~ 3
/N~/~O
Preferned cationic peroxyacid precursors of the N-acylated caprolactam class
include
the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl
ammonium methylene benzoyl caprolactam:
CA 02187438 1999-11-10
14
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl -caprolactams:
O O
I
+~ (CH2)n /
where n is from 0 to 12.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium)
ethyl sodium 4-sulphophenyl carbonate chloride.
Alk~percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form perrarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid 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
from 1 to 6 carbon atoms, particularly those compounds in which the alkylene
group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is
particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkylperoxvacid precursors
CA 02187438 1999-11-10
15
Amide substituted alkyl peroxyacid precursor compounds are also suitable.
including those of the following general formulae:
R1 -_ C__ _N. __R2._ _C_~ R1 -_NC_._R2 C -.~
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
gmup 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. R1
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4
to 8
carbon atoms. Rl may be straight chain or branched alkyl containing branching,
substitution, or both and may be sourced from either synthetic sources or
natural
sources including for example, tallow fat. Analogous structural variations are
permissible for R2. 1fie substitution can include alkyl, halogen, nitrogen,
sulphur
and other typical substituent groups or organic compounds. R5 is preferably H
or
methyl. Rl and RS should not contain more than 18 carbon atoms in total. Amide
substituted bleach activator compounds of this type are described in EP-A-
0170386.
Benzoxazin o is perox av cid precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example in EP-A-332,294 and EP-A-482,807, particularly those having the
formula:
O
I
N ~-R~
CA 02187438 1999-11-10
16
including the substituted benzoxazins of the type
0
R3 ~O
0
R N C _R~
4
Rs
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, allcoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl
group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
0
il
C~0
o
., o
N
Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid , typically at a level of from 1 ~ to 15 °~ by
weight, more
preferably from 1 ~ to 10 °b 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-RZ-C-OOH R~ -N-C-R2-C-OOH
OI R~
or R 0 O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
RZ 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. Rl
2 ~,~ ~ ~.3 $,.:
~W095128464 ~ r s ~: PCT/U595/04085
17
preferably contains from 6 to I2 carbon atoms. RZ prefeiabIy contains from 4
to 8
carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or
alkylaryl containing branching, substitution, or both and may be sourced from
either
' synthetic sources or natural sources including for example, tallow fat.
Analogous
structural variations are permissible for R2. The substitution can include
alkyl,
aryl, halogen, nitrogen, sulphur and other typical substituent groups or
organic
compounds. RS is preferably H or methyl. RI and RS should not contain more
than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds
of
this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetcadecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and dipeiazelaic acid, mono- and
diperbrassyiic acid and N-phthaloylaminoperoxicaproic acid are also suitable
herein.
Chlorine bleach
The compositions herein are preferably free of chlorine bleach.
The invention also encompasses compositions containing a catalytically
effective
amount of a bleach catalyst such as a water-soluble manganese salt.
The bleach catalyst is used in a catatytically effective amount in the
compositions
herein. By "catalytically effective amount" is meant an amount which is
sufficient,
under whatever comparative test conditions are employed, to enhance bleaching
and
removal of the stain or stains of interest from the target substrate. Thus, in
a fabric
Laundering operation, the target substrate will typically be a fabric stained
with, for
example, various food stains. For automatic dishwashing, the target substrate
may
be, for example, a porcelain cup or plate with tea stain or a polyethylene
plate
stained with tomato soup. The test conditions will vary, depending on the type
of
washing appliance used and the habits of the user. Thus, front-loading laundry
washing machines of the type employed in Europe generally use less water and
higher detergent concentrations than do top-loading U.S.-style machines. Some
machines have considerably conger wash cycles than others. Some users elect to
use
very hot water; others use warm or even cold water in fabric laundering
operations.
~: ~: :... ~ E t
R'O 95118464 ~' ,P PCT/US95I04D8~
18
Of course, the catalytic performance of the bleach catalyst will be affected
by such
considerations, and the levels of bleach catalyst used in fully-formulated
detergent
and bleach compositions can be appropriately adjusted. As a practical matter,
and
not by way of limitation, the compositions and processes herein can be
adjusted to
provide on the order of at least one part per ten million of the active bleach
catalyst
species in the aqueous washing liquor, and will preferably provide from about
I
ppm to about 200 ppm of the catalyst species in the laundry liquor. To
illustrate
this point further, on the order of 3 micromolar manganese catalyst is
effective at
40°C, pF3 10 under Eutnpeart conditions using perborate and a bleach
precursor
(e.g., benzoyl caprolactam). An increa~e in concentration of 3-5 fold may be
required under U.S. conditions to achieve the same results. Conversely, use of
a
bleach precusor and the manganese cara~yat with perbotate may allow the
formulator
to achieve equivalent bleaching at lower oerborate usage levels than products
without the manganese catalyst.
The bleach catalyst material herein can comprise the free acid or be in the
form of
any suitable salts.
One type of bleach catalyst is a catalyst system comprising a heavy metal
ration of
defined bleach catalytic activity, such as copper, iron or manganese canons,
an
auxiliary metal ration having little or no bleach catalytic activity, such as
zinc or
aluminum rations, and a sequesttartt having defined stability constants for
the
catalytic and auxiliary metal rations, par.icularly ethylenediaminetetraacetic
acid,
ethylenediaminetetra(methylenephosphooc 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 Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-ttiazacyclononane)2-(PF6)2>
Mn~(u-O) 1 (u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2,
Mn~4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, Mn~Mn~'4(u-O)1(u-OAc)2-
(1,4,7-trimethyl-1,4,7-ttiazacyclononane)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-ttiazacyclododecane, 2-
methyl-
1,4,7-triazacyclononane, 2-methyl-1.4,7-triazacyclonottane, 1,2,4,7-
tettamethyl-
1,4,7-triazacyclononane, and mixtures thereof.
~W095f28464 218 ~ ~ ~ ~ ' ~ '. PCT/US95104085
19
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 (Il], ()II], and/or (IV) with a ligand
which is
a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol,
xylithol,
arabitol, adottitol, meso-erythritol, meso-inositol, lactose, and mixtures
thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic tigand. Said
ligands are of the formula:
R2 R3
R~ -N =C-B-C = N-R4
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each RI-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected
from O,
S. CRSR6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl
groups, including substituted or unsubstituted groups. Preferred ligands
include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pytazole, and triazole
rings.
Optionally, said rings may be substituted with substituents such as alkyl,
aryl,
alkoxy, halide, and vitro. Particularly preferred is the ligand 2,2'-
bispyridylamine.
Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -
bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-
bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt ()n,
ttisdipyridylamine-cobalt(I17 perchlotate, Co(2,2-bispyridylamine)202C104, Bis-
(2,2'-bispyridylamine) copper(f)] perchlorate, ttis(di-2-pyridylamine)
iron()?)
perchlorate, and mixtures thereof.
Other examples include Mn gluconate, Mn(CFgSO3)2, Co(NHg)SCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including
N4Mn~(u-O)2Mn~N4)+and [BipY2Mn~(u-O)2Mn~bipY21-(C104)3.
:. ird~,'~. :~ .4 ~" ti ~. i
WO 95/28464 PCTIUS95104085!
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The bleach catalysts may also be prepared by combining a water-soluble ligand
with
a water-soluble manganese salt in aqueous media and concentrating the
resulting
mixture by evaporation. Any convenient water-soluble salt of manganese can be
used herein. Manganese (II), ()II), (I~ andlor (~ is readily available on a
commercial scale. In some instances, sufficient manganese may be present in
the
wash liquor, but, in general, it is preferred to add Mn rations in the
compositions to
ensure its presence in catalytically-effective amounts. Thus, the sodium salt
of the
ligand and a member selected from the group consisting of MnS04, Mn(C104)2 or
MnCl2 (least preferred) are dissolved in water at molar ratios of Iigand:Mn
salt in
the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water
may first
be de-oxygenated by boiling and cooled by sparging with nitrogen. The
resulting
solution is evaporated (under N2, if desired) and the resulting solids are
used in the
bleaching and detergent compositions herein without further purification.
In an alternate mode, a water-soluble manganese source, such as MnS04, is
added
to the bleach/cleaning composition or to the aqueous bleaching/cleaning bath
which
comprises the ligand. Some type of complex is apparently formed in situ, and
improved bleach performance is secured. In such an in situ process, it is
convenient
to use a considerable molar excess of the ligand over the manganese, and mote
ratios of ligand:Mn typically are 3:1 to 15:1. The additional ligand also
serves to
scavenge vagrant metal ions such as iron and copper, thereby protecting the
bleach
from decomposition. One possible such system is described in European patent
application, publication no. 549,271.
While the structures of some of the bleach-catalyzing manganesecomplexes
described herein have not been elucidated, it may be speculated that they
comprise
chelates or other hydrated coordination complexes which result from the
interaction
of the carboxyl and nitrogen atoms of the ligand with the manganese canon.
T-ikgwise, the oxidation state of the manganese ration during the catalytic
process is
not known with certainty, and may be the (+I)7, (+II>I), (+I~ or (+~ valence
state. Due to the ligands' possible six points of attachment to the manganese
ration,
it may be reasonably speculated that mule-nuclear species andlor "cage"
structures
may exist in the aqueous bleaching media. Whatever the form of the active
Mnligand species which actually exists, it functions in an apparenny catalytic
manner to provide improved bleaching performances on stubborn stains such as
tea,
ketchup, coffee, blood, and the like.
T t7 i-
218.7438
W095I28464 ,Y ~ ~ >. f, PCT/US95/04085
s. 'x. ~ , ~ g .
21
Other bleach catalysts are described. for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-potphyrin catalysts), U.S.
4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and
European
patent application, publication no. 224,952, (absorbed manganese on
aluminosilicate
catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or
magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557
(ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant
catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243
(chelants with manganese rations and non-catalytic metal rations), and U.S.
4,728,455 (manganese gluconate cata!~:,ts).
Relative release kinetics
In an essential aspect of the invention a means is provided for delaying the
release
to a wash solution of the organic peroxyacid bleach relative to the release of
the
heavy metal ion sequesttant.
Said means may comprise a means for delaying the release of the organic
peroxyacid bleach to the wash solution.
Alternatively said means may comprise a means for enhancing the rate of
release of
the heavy metal ion sequesttant to the s: lotion.
pelayed rate of release - means
The means may provide for delayed release of an organic peroxyacid bleach
source
itself to the wash solution. Alternatively, where the peroxyacid source is an
organic
peroxyacid precursor compound the delayed release means may comprise a means
of inhibiting, or preventing the in situ perhydrolysis reaction which releases
the
organic peroxyacid into the solution. Such means could, for example, include
delaying release of the hydrogen peroxide source to the wash solution, by for
example, delaying release of any inorganic perhydrate salt, acting as a
hydrogen
peroxide source, to the wash solution.
The delayed release means can include coating any suitable component with a
coating or mixture of coatings designed to provide the delayed release. The
coating
2-~:8;~~4i3~a
W 0 95/28464 PCTIUS95/04085~
22
may therefore, for example, comprise a poorly water soluble material, or be a
coating of sufficient thickness that the kinetics of dissolution of the thick
coating
provide the controlled rate of release.
The coating material may be applied using various methods. Any coating
material
is typically present at a weight ratio of coating material to bleach of from I
:99 to
1:2, preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially) hydrogenated
vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides,
microcrystalIine
waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and allcaline earth
metal
sulphates, silicates and carbonates, including calcium carbonate.
Preferred coating material is sodium silicate of Si02 : Na20 ratio from 1.6 :
1 to
3:4 : 1, preferably 2.8 : 1, applied as an aqueous solution to give a level of
from
2~ to 10°.6, (normally from 396 to 596) of silicate solids by weight of
the
percarbonate. Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials
to provide composite inorganic saitlorganic binder coatings. Suitable binders
include the Clp-C2p alcohol ethoxylates containing from 5 - 100 moles of
ethylene
oxide per mole of alcohol and more preferably the Clg-C20 primary alcohol
ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of
alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpytrolidones
with an average molecular weight of from 12,000 to 700,000 and polyethylene
glycols (PEG) with an average molecular weight of from 600 to 10,000 are
examples of such polymeric materials. Copolymers of malefic anhydride with
ethylene, methylvinyl ether or methacrylic acid, the malefic anhydride
constituting at
least 20 mole percent of the polymer are further examples of polymeric
materials
useful as binder agents. These polymeric materials may be used as such or in
combination with solvents such as water, propylene glycol and the above
mentioned
C10'C20 ~~hol ethoxylates containing from 5 - 100 moles of ethylene oxide per
mole. Further examples of binders include the C 10-C20 mono- and diglycerol
ethers and also the C10-C20 fatty acids.
2 I ~'~ ~ i~ $~; ~.
R'O 95128464 PGT/US95/04085
23
Cellulose derivatives such as methylcellulose, carboxymethylcellulose, ethyl
hydroxyethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric
polycarboxylic acids or their salts are other examples of binders suitable for
use
herein.
One method for applying the coating material involves agglomeration. Preferred
agglomeration processes include the use of any of the organic binder materials
described hereinabove. Any conventional agglomerator/mixer may be used
including, but not limted to pan, rotary drum and vertical blender types.
Molten
coating compositions may also be applied either by being poured onto, or splay
atomized onto a moving bed of bleaching agent.
Other means of providing the required delayed release include mechanical means
for
altering the physical characteristics of the bleach to control its solubility
and rate of
release. Suitable protocols could include compacCion, mechanical injection,
manual
injection, and adjustment of the solubility of the bleach compound by
selection of
particle size of any particulate component.
Whilst the choice of particle size will depend both on the composition of the
particulate component, and the desire to meet the desired delayed release
kinetics, it
is desirable that the particle size should be more than 500 micrometers,
preferably
having an average particle diameter of from 800 to 1200 micrometers.
Additional protocols for providing the means of delayed release include the
suitable
choice of any other components of the detergent composition matrix such that
when
the composition is introduced to the wash solution the ionic strength
environment
therein provided enables the required delayed release kinetics to be achieved.
Enhanced rate of release - means
All suitable means for enhancing the rate of release of the heavy metal ion
sequesttant to the solution are envisaged.
The enhanced release means can include coating any suitable component with a
coating designed to provide the enhanced release. The coating may therefore,
for
example, comprise a highly, or even effervescently, water soluble material.
CA 02187438 1999-11-10
24
Other means of providing the required delayed release include mechanical means
for
altering the physical characteristics of the heavy metal ion sequestrant to
enhance its
solubility and rate of release.
A suitable protocol could include deliberate selection of the particle size of
any
heavy metal ion sequestrint containing component. The choice of particle size
will
depend both on the composition of the particulate component, and the desire to
meet
the desired enhanced release kinetics. It is desirable that the particle size
should be
less than 1200 micrometers, preferably having an average panicle diameter of
from
1100 to 500 micrometers.
Additional protocols for providing the means of delayed release include the
suitable
choice of any other components of the detergent composition matrix, or of any
particulate component containing the heavy metal ion sequestrant, such that
when
the composition is introduced to the wash solution the ionic strength
environment
therein provided enables the required enhanced release kinetics to be
achieved.
Relative cafe of release - kinetic parameters
The release of the organic peroxyacid bleach component from the peroxyacid
bleaching system relative to that of the heavy metal ion sequestrant component
is
such that in the T50 test method herein described the difference between the
time to
achieve a concentration that is 50 °b of the ultimate concentration of
said heavy
metal ion sequestrant is less than 120 seconds, preferably less than 90
seconds,
more preferably less than 60 seconds, and the time to achieve a concentration
that is
50~ of the ultimate concentration of said organic peroxyacid bleach is more
than
180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to
360
seconds.
In a highly preferred aspect of the invention the release of bleach is such
that in the
T50 test method herein described the time to achieve a level of total
available
oxygen (Av0) that is 50 ~ of the ultimate level is more than I 80 seconds,
preferably from. 180 to 480 seconds, more preferably from 240 to 360 seconds.
A
method for determining Av0 levels is disclosed in WO 94/16047.
.. ~:.-~- ~, w' ~ ~~' ,
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WO 95128464 PCT/US95/04085
In another preferred aspect of the invention, where the peroxyacid bleach
source is a
peroxyacid bleach precursor, employed in combination with a hydrogen peroxide
source the kinetics of release to the wash solution of the hydrogen peroxide
relative
to those of the heavy metal ion sequesttant component is such that in the T50
test
method herein described the time to achieve a concentration that is 50 % of
the
ultimate concentration of said heavy metal ion sequestrant is less than 120
seconds,
preferably less than 90 seconds, more preferably less than 60 seconds, and the
time
to achieve a concentration that is 50~ of the ultitrnate concentration of said
hydrogen peroxide is more that 180 seconds, preferably from 180 to 480
seconds.
more preferably from 240 to 360 seconds.
The ultimate wash concentration of the heavy metal ion sequesttant is
typically from
0.000196 to 0.059b by weight, but preferably is more than 0.001 °6,
more preferably
more than 0.002.
The ultimate wash concentration of any inorganic perhydrate bleach is
typically
from 0.0059& to 0.259b by weight, but preferably is more than 0.0596, more
preferably more than 0.075 ~.
The ultimate wash concentration of any peroxyacid precursor is typically 0.001
k to
0.089& by weight, but preferably is from 0.00596 to 0.0596, most preferably
from
0.015' to 0.05 96.
Detaved release - test method
The delayed release kinetics herein are defined with respect to a 'TA test
method'
which measures the time to achieve A~ of the ultimate concentrntion/level of
that
component when a composition containing the component is dissolved according
to
the standard conditions now set out.
The standard conditions involve a 1 litre glass beaker filled with 1000 ml of
distilled
water at 20oC, to which lOg of composition is added. The contents of the
beaker
are agitated using a magnetic stirrer set at 100 rpm. The magnetic stirrer is
pea/ovule-shaped having a maximum dimension of l.Scm, and a minimum
dimension of O.Scm. The ultimate concentrationllevel is taken to be the
concentration/level attained 10 minutes after addition of the composition to
the
water-filled beaker.
W095128464 , ' PCl'1US9510408~
.. a~ z ~ ..
26
Suitable analytical methods are chosen to enable a reliable determination of
the
incidental, and ultimate in solution concentrations of the component of
concern.
subsequent to the addition of the composition to the water in the beaker.
Such analytical methods can include those involving a continuous monitoring of
the
level of concentration of the component, including for example photometric and
conductimetric methods.
Alternatively, methods involving remov~rg titres from the solution at set time
intervals, stopping the disssolution process by an appropriate means such as
by
rapidly reducing the temperature of the nitre, and then determining the
concentration
of the component in the titre by any means such as chemical titrimetric
methods,
can be employed.
Suitable graphical methods, including curve fitting methods, can be employed,
where appropriate, to enable calculation of the the TA value from raw
analytical
results.
The particular analytical method selected for determining the concentration of
the
component, will depend on the nature of that component, and of the nature of
the
composition containing that component.
Water-soluble builder compound
The detergent compositions of the present invention may contain as a highly
preferred component a water-soluble builder compound, typically present at a
level
of from 196 to 8096 by weight, preferably from 10'~ to 7096 by weight, most
preferably from 2096 to 6096 by weight of the composition.
In a highly preferred aspect of the invention a means is also provided for
delaying
the release to a wash solution of the bleach relative to the release of the
preferred
water soluble builder component. Said means can comprise equivalents of any of
the
delayed release means herein described for achieving the delayed release of
the
bleach components, described hereinbefore.
.
~F~ '~
W O 95/28464 ~' ' 5 ~ ; ' '~ PCTlUS95/04085
27
Said delayed release means is preferably chosen such that in the test method
herein
described the time to achieve a concentration that is 50 % of the ultimate
concentration of said water soluble builder is less than 120 seconds,
preferably less
than 90 seconds, more preferably less than 60 seconds.
The ultimate wash concentration of the water-soluble builder is typically from
0.005 ~ to 0.4 ~ , preferably from 0.05 9b to 0.35 ~, more preferably from 0.1
°k to
0.3 ~ .
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or
their salts in which the polycarboxylic acid comprises at least two carboxylic
radicals separated from each other by not more that two carbon atoms,
carbonates,
bicarbonates, borates, phosphates, silicates and mixtures of any of the
foregoing.
The carboxylate or polycarboxylate builder can be monomeric or ofigomeric 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 cittaconates as well as
succinate
derivatives such as the carboxymethyloxysuccinates described in British Patent
No.
1,379,241, Ltctoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as Z-oxa-1,1,3-propane tricarboxylates
described
in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tettaaarboxyiates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing sulfo substituents include the sulfosuccinate derivatives disclosed
in
~,, ,= 1 ' i ~:
s.j%a'i,:
WO 95/28464 PCT/US95104085~
28
British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448,
and the sulfonated pyrolysed citrates described in British Patent No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
teuacarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuren
-
cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates,
2,2,S,S-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the prefetzed polycarboxylates are hydroxycarboxylates
containing up
to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents
or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are
also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can
produce borate under detergent storage or wash conditions can also be used but
are
not preferred at wash conditions less that about 50°C, especially less
than about
40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with
ultrn-
fme calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from
about 6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an Si02:
Na20 ratio
of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0
ratio
being most preferred. The silicates may be in the form of either the anhydrous
salt
2187438
-WO 95/28464 _ PCTJUS95/04D85
y ~ ~. ~w ~; t. ~.
x .
29
or a hydrated salt. Sodium silicate with an Si02: Na20 ratio of 2.0 is the
most
preferred silicate.
Silicates are preferably present in the detergent compositions in accord with
the
invention at a level of from 59b to 50~ by weight of the composition, more
preferably from 1036 to 40% by weight.
Aririirinnal detergen components
The detergent compositions of the invent;~n may also contain additional
detergent
components. The precise nature of these additional components, and levels of
incorporation thereof will depend on toe physical form of the composition, and
the
nature of the cleaning operation for which it is to be used.
The compositions of the invention may for example, be formulated as hand and
machine laundry detergent compositions, including laundry additive
compositions
and compositions suitable for use in the pretreatment of stained fabrics and
machine
dishwashing compositions.
When formulated as compositions suitable for use in a machine washing method,
eg: machine laundry and machine dishwashing methods, the compositions of the
invention preferably contain one or more additional detergent components
selected
from surfactants, water-insoluble builder', organic polymeric compounds,
additional
enzymes, suds suppressors, lime soap aispersants, soil suspension and anti-
redeposition agents and corrosion ~~thibitors. Laundry compositions can also
contain, as additional detergent components, softening agents.
The detergent compositions of the invention may contain as an additional
detergent
component a surfactant selected from anionic, cationic, nonionic ampholytic,
amphoteric and zwitterionic surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.196 to 6096 by
weight. More
preferred levels of incorporation of surfactant are from 19b to 35 96 by
weight, most
preferably from 1 ~ to 2096 by weight.
-:nar~
a-,
R'O 95128464 ~ -~ PCTlUS95104085.
The surfactant is preferably formulated to be compatible with any enzyme
components present in the composition. In liquid or gel compositions the
surfactant
is most preferably formulated such that it promotes, or at least does not
degrade, the
stability of any enzyme in these compositions.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin
and
Heuring on December 30, 1975. Further examples are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwattz, 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 andlor nonionic surfactants.
Anionic surfactant
Essentially any anionic surfactants uxful for detersive purpoxs can be
included in
the compositions. These can include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate
surfactants.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-
acyl.taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated
C12 C18 monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated
C6-C14 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.
An;o2c sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary allryl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates,
alkyl
phenol ethylene oxide ether sulfates, the CS-C17 acyl-N-(Cl-C4 alkyl) and -N-
(C1-
C2 hydroxyaikyl) glucamine sulfates, and sulfates of aikylpolysaccharides such
as
J .
. W095/28464 ~ PCT/US95104Q85
31
the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C6-CIg alkyl sulfates which have been ethoxylated with from about 0.5 to
about
20 moles of ethylene oxide per molecule. More preferably, the alkyl
ethoxysulfate
surfactant is a C6-CIg alkyl sulfate which has been ethoxylated with from
about 0.5
to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per
molecule.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20
linear alkylbenzene sulfonates, allryl ester sulfonates, C6-C22 primary or
secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty aryl glycerol sulfonates, fatty ofeyl glycerol
sulfonates,
and any mixtures thereof.
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps
('alkyl
carboxyls'), especially certain secondary soaps as described herein.
Preferred alkyl ethoxy carboxylates for uce herein nnclude those with the
formula
RO(CH2CH20)x CH2C00-M'1' wherein R is a C6 to Clg allryl group, x tattges
from O to 10, and the ethoxylate distribution is such that, on a weight basis,
the
amount of material where x is 0 is less than about 20 ~6, and the amount of
material
where x is greater than 7, is less than about 25 ~, the average x is from
about 2 to
4 when the average R is Clg or less, and the average x is from about 3 to 10
when
the average R is greater than C13, and M is a ration, preferably chosen from
alkali
metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium,
most preferably from sodium, potassium, ammonium and mixtures thereof with
magnesium ions. The preferred allryl ethoxy carboxylates are those where R is
a
Cl2 to Clg alkyl group.
! .!
. .~'...' '~l.i['i:~, q.r.
WO 95128464 PCT1US95I04085~
.y~ ~-; a-:
as
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include
those
having the formula
RO-(CI3Rl-CHR2-O)-Rg wherein R is a C6 to Clg alkyl group, x is from 1 to 25.
Rl and R2 are selected from the group consisting of hydrogen, methyl acid
radical.
succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof,
wherein at
least one Rl or R2 is a succinic acid radical or hydroxysuccinic acid radical,
and R3
is selected from the group consisting of hydrogen, substituted or
unsubstituted
hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Anionic secondary soap surfactant . _
Preferred soap surfactants are seconda:y snap surfactants which contain a
carboxyl
unit connected to a secondary carbon. The secondary carbon can be in a ring
structure, e:g. as in p-octyl benzoic acid, or as in alkyl-substituted
cyclohexyl
carboxylates. The secondary soap surfactants should preferably contain no
ether
linkages, no ester linkages and no hydroxyl groups. There should preferably be
no
nitrogen atoms in the head-group (amphiphilic portion). The secondary soap
surfactants usually contain 11-15 total carbon atoms, although slightly more
(e.g.,
up to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
secondary
soap surfactants:
A. A highly preferred class ci secondary soaps comprises the secondary
carboxyl materials of the formula R3 CFI(R4)COOM, wherein R3 is
CHg(CFI2)x and R4 is CHg(CH~y, wherein y can be O or an integer from 1
to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably
7-9,
most preferably 8.
B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit,
i.e., secondary soaps of the formula RS-R6-COOM, wherein RS is C~-C10
preferably C8-C9, allryl or allcenyl and R6 is a ring structure, such as
benzene, cyclopentane and cyciohexane. (Note: RS can be in the ortho,
meta or para position relative to the carboxyl on the ring.)
WO 95128464 2 i 8 7 4 3 8 , PCT~595/04085
33
C. Still another preferred class of secondary soaps comprises secondary
carboxyl compounds of the formula
CH3(C~)I~(CH2)m-(C~)n-CH(COOM)(CHR)o-(CH2)p (CHR)q CH3,
wherein each R is Cl-C4 alkyl, wherein k, n, o, q are integers in the range
of 0-8, provided that the total number of carbon atoms (including the
- carboxylate) is in the range of 10 to 18.
In each of the above formulas A, B and C, the species M can be any suitable,
especially water-solubilizing, counterion.
Especially preferred secondary soap surfactants for use herein are water-
soluble
members selected from the group consisting of the water-soluble salts of 2-
methyl-
1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-I-nonanoic acid. 2-butyl-
1-
octanoic acid and 2-pentyl-I-heptanoic acid.
Alkali metal carcoc'nate ~urfac ant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (RI) CH2 COOM, wherein R is a CS-C17 linear or branched alkyl or alkenyl
group, RI is a Cl-C4 allryl group and M is an allcali metal ion. Preferred
examples
are the myristyi and oleyl methyl sarcosinates in the form of their sodium
salts.
Nonionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in
the compositions. Exemplary, non-limiting classes of useful nonionic
surfactants are
listed below.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula RZCONR1Z wherein : Rl is H, CI-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydmxy propyl, or a mixture thereof, preferable Cl-C4 alkyl, more preferably
C1
or C2 allcyl, most preferably CI alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl, preferably straight-chain CS-CI9 alkyl or alkenyl, more
preferably
straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain Cl1-C17
alkyl or alkenyi, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having
a
~L87438
WO 95/28464 ' PCTIUS95104085,
. ~,ry..,a ,1_.~~'~-
34
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 condensates of alkvlr~henols _ _
The polyethylene, polypropylene, and potybutylene oxide condensates of alkyl
phenols are suitable for use herein. In general, the polyethylene oxide
condensates
are preferred. These compounds include the condensation products of alkyl
phenols
having an allcyl group containing from about 6 to about 18 carbon atoms in
either a
straight chain or branched chain configuration with the alkylene oxide.
Nonionic ethoxvlated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1
to about 25 moles of ethylene oxide are suitable for use herein. The alkyl
chain of
the aliphatic alcohol can either be straight or branched, primary or
secondary, and
generally contains from 6 to 22 carbon atoms. Particularly preferred are the
condensation products of alcohols having an alkyl group containing from 8 to
20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
Nonionic ethoxylatedlpronoxvlated fatty alcohol surfactant
The ethoxylated C6-Clg fatty alcohots and C6-CIg mixed
ethoxylatedlpropoxylated
fatty alcohols are suitable surfactants for use herein, particularly where
water
soluble. Preferably the ethoxylated fatty alcohols are the CIp-CIg ethoxylated
fatty
alcohols with a degree of ethoxylation of from 3 to 50, most preferably these
are the
C12-Clg ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the mixed ethoxylated/ptropoxylated fatty alcohols have an alkyl
chain
length of from IO to 18 carbon atoms, a degree of ethoxylation of from 3 to 30
and
a degree of propoxylation of from 1 to 10.
Nonionic EOIPO condensates with proRylene glycol
e, ,' ,y y t'' i ~:
~W095128464 ~ PCTlUS95l04085
The condensation products of ethylene oxide with a hydrophobic base formed by
the
condensation of propylene oxide with propylene glycol are suitable for use
herein.
The hydrophobic portion of these compounds preferably has a molecular weight
of
from about 1500 to about 1800 and exhibits water insolubility. Examples of
compounds of this type include certain of the commercially-available
PluronicTM
surfactants, marketed by BASF.
Nonionic EO condensation products with nronvlene oxidelethvlene diamin~ a duct
The condensation products of ethylene oxide with ehe product resulting from
the
reaction of propylene oxide and ethylenediamine are suitable for use herein.
The
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight
of from about 2500 to about 3000. Examples of this type of nonionic surfactant
include certain of the commercially available TetronicTM compounds, marketed
by
BASF.
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from
about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon
atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing
from about 1.3 to about 10, preferably from about 1.3 to about 3, most
preferably
from about 1.3 to about 2.7 saccharide units. Any reducing saccharide
containing 5
or 6 carbon atoms can be used, e.g., glucose, gaLtctose and galactosyl
moieties can
be substituted for the glucosyl moieties. (Optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose
as
opposed to a glucoside or galactoside.) The intersaccharide bonds can be,
e.g.,
between the one position of the additional saccharide units and the 2-, 3-, 4-
, and/or
6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the fornrula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyallrylphenyl, and mixtures thereof in which the alkyl
groups
~; ~ r: ., ,,
218 °~ 4~3 $J ~ ~
WO 95128464 PCTIUS95I04085
36
contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t
is
from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3,
most
preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.
~nninnir fatty 3CId amide SUifaCtant
Fatty acid amide surfactants suitable for use herein are those having the
formula:
R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably
from 9 to 17 carbon atoms and each R7 is selected from the group consisting of
hydrogen, C1-C4 alkyl, C1-C4 hydroxyaikyl, and -(C2H40)xH, where x is in the
range of from 1 to 3.
A~gphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants
and the alkyl amphocarboxylic acids.
A suitable example of an allcyl aphodicarboxylic acid for use herein is
Miraa~ol(Tlv))
C2Nt Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful herein include rho~: compounds having the formula
R3(OR4)xlVO(RS)2 wherein R3 i~ selectxi from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl pher:yl groun, or mixtures thereof, containing from
8 to
26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an aikylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon
atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; aird
each RS is
an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable
1,
ethylene oxide groups. The RS groups can be attached to each other, e.g.,
through
an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include Cl0-Clg allryl dimethyl
amine
oxides aird Cg-Clg allcoxy ethyl dihydroxyethyl amine oxides. Examples of such
materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecyiamine oxide, dimethyldodecylamine oxide,
2I8'~438
W095f18464 ~ ~~ ~7 ~~ ~' ": PCTIU595/04085
37
diptnpyltetradecylamine oxide, methylethylhexadecylamine oxide,
dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl
dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-
hydroxyoctadecylamine oxide. Preferred are Clp-C18 a~Yl dimethylamine oxide.
and C10-18 ~Yl~ido alkyl dimethylamine oxide.
Zwitterionic surfactant _ _ .,
Zwitterionic surfactants can also be incorporated into the detergent
compositions
hereof. These surfactants can be broadly described as derivatives of secondary
and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quaternary ammonium, quaternary phosphonium or tertiary
sulfonium
compounds. Betaine and sultaine surfactants are exemplary zwitterionic
surfactants
for use herein.
L'%~f<,~ e~~~'.
s : 1., v. .r r n,
w0 95/28464 ' PCTIUS95/04085~
38
The betaines useful herein are those compounds having the formula
R(R')ZN~'R2C00- wherein R is a C6-Clg hydrocarbyl group, preferably a CIO-
C16 alkyl group or CIO-16 acylamido alkyl group, each RI is typically CI-Cg
alkyl, preferably methyl,m and R2 is a CI-CS hydrocarbyl group, prefetably a
CI-
Cg alkylene group, more preferably a CI-C2 alkylene group. Examples of
suitable
betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl
betaine; C12-14 acylamidopropylbetaine; Cg-14 acylamidohexyldiethyl betaine;
4[C14-16 acylmethylamidodiethylammonioj-I-carboxybutane; C16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine. Preferred betaines are CIZ_Ig dimethyl-ammonio
hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
The sultaines useful herein are those compounds having the formula
(R(RI)2N~-R2S03' wherein R is a C6-Clg hydrocarbyl group, preferably a CIO-
CI6 alkyl group, more preferably a C12-C13 alkyl group, each RI is typically
CI-
Cg alkyl, preferably methyl, and R2 is a CI-C6 hydrocarbyl group, preferably a
CI-C3 alkylene or, preferably, hydroxyalkylene group.
Amnloolvtic surfactant _ _
Ampholytic surfactants can be incorporated into the detergent compositions
herein.
These surfactants can be broadly described as aliphatic derivatives of
secondary or
tertiary amines, or aliphatic derivatives of heterocyclic secondary and
tertiary
amines in which the aliphatic radical can be straight chain or branched.
Cationic surfactants can also be used in the detergent compositions herein.
Suitable
cationic surfactants include the quaternary ammonium surfactants selected from
mono C6-C16, preferably C6-Clp N-alkyl or alkenyl ammonium surfactants
CA 02187438 1999-11-10
39
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Partially soluble or insoluble builder compound
The detergent compositions of the present invention may contain a partially
soluble
or insoluble builder compound, typically present at a level of from 1 % to 80
% by
weight, preferably from 10 % to 70 % by weight, most preferably from 20 % to
60 %
weight of the composition.
Examples of partially water soluble builders include the crystalline layered
silicates.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Crystalline layered sodium silicates have the general formula
NaMSix02x+ 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-3417649 and
DE-A-3742043. For the purpose of the present invention, x in the general
formula
above has a value of 2, 3 or 4 and is preferably 2. The most preferred
material is
8-Na2Si205, available from Hoechst AG as NaSKS-6T"".
The -crystalline layered sodium silicate material is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid.
water-
soluble ionisable material. The solid, water-soluble ionisable material is
selected
from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y].
XH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to
0.5
and x is at least 5, preferably from 7.5 to 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.
CA 02187438 1999-11-10
40
The aluminosilicate ion exchange materials can be naturally occurring
materials, but
are preferably synthetically derived. Synthetic crystalline aluminosilicate
ion
exchange materials are available under the designations Zeolite A, Zeolite B.
Zeolite P. Zeolite X. Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A
has
the formula
Na 12 ~~G2) 12 (Si02)12). X20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)1061. 276 H20.
nz me
Another optional ingredient useful in the detergent compositions is one or
more
additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
amylases, neutral and alkaline proteases, estetases, cellulases, pectinases,
,lactases
and peroxidases conventionally incorporated into detergent compositions.
Suitable
enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
trademarks Alcalase, Savinase, Primase, Dutazym, 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 licheniform.is, 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 trademark
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 °b to 2 ~ active enzyme by weight of the composition.
CA 02187438 1999-11-10
41
Lipolytic enzyme (lipase) 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., Thermomvces sp. or Pseudomonas sp.
including Pseudomonas nseudoalcal~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 pseudoal~as~enes, which is
described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanuginosa 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.
Enzyme Stabilizing System
Preferred enzyme-containing compositions herein may comprise from about 0.001
%
to about 10 % , preferably from about 0.005 % to about 8 % ,most preferably
from
about 0.01 % to about 6 % , by weight of an enzyme stabilizing system. The
enzyme
stabilizing system can be any stabilizing system which is compatible with the
detersive enzyme. Such stabilizing systems can comprise calcium ion, boric
acid,
propylene glycol, short chain carboxylic acid, boronic acid, and mixtures
thereof.
Such stabilizing systems can also comprise reversible enzyme inhibitors, such
as
reversible protease inhibitors.
The compositions herein may further comprise from 0 to about 10%, preferably
from about 0.01 ~ to about 6 % by weight, of chlorine bleach scavengers, added
to
prevent chlorine bleach species present in many water supplies from attacking
and
inactivating the enzymes, especially under alkaline conditions. While chlorine
levels in water may be small, typically in the range from about 0.5 ppm to
about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact
~i~_'~;: a
W0 95/28464 ~ ~~'~ $' - ' PCTIUS95/04085-
as
with the enzyme during washing is usually large; accordingly, enzyme stability
in-
use can be problematic.
Suitable chlorine scavenger anions are widely available, and are illustrated
by salts
containing ammonium cations or sulfite, bisulfate, thiosulfite, thiosulfate,
iodide,
etc. Antioxidants such as caafiamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other
conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perbotate tettahydtate, sodium perborate monohydrate
and
sodium percaafionate, as well as phosphate, condensed phosphate, acetate,
benzoate,
citrate, foamate, lactate, malate, tartrate, salicylate, etc. and mixtures
thereof can be
used if desitrd.
~; ae nic i2o_lvmeric coma o~ and
Organic polymeric compounds are particularly preferred components of the
detergent compositions in accord with the invention. By organic polymeric
compound it is meant essentially any polymeric organic compound commoraly used
as dispersatats, and anti-redeposition and soil suspension agents in detergent
compositions.
Organic polymeaic compound is typically incorporated in the detergent
compositions
of the invention at a level of from 0.196 to 30°6, preferably from
0.59b to 159&,
most preferably from 1 °~6 to 10°,6 by weight of the
compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or co-polymeric polycatiaoxylic acids or their salts in which the
polycarboxytic 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.
FzampleS of such salts ate polyacrylates of MWt 2000-5000 and their copolymers
with naaieic anhydride, such copolymers having a molecular weight of farom
20,000
to 100,000, especially 40,000 to 80,000.
Other suitable organic polymeric compounds include the polymers of acrylamide
and acrylate having a molecular weight of from 3,000 to 100,000, and the
acrylate/fumarate copolymers having a molecular weight of from 2,000 to
80,000.
WO 95128464 ~ ~ ~.r~~~ Y. ~ PCT~S95/04085
43
The polyamino compounds are useful herein including those derived from
aspartic
acid such as those disclosed in F.P-A-305282, EP-A-305283 and F.P-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.
Other organic polymeric compounds suitable for uncorporation in the detergent
compositions herein include cellulose de~vatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycois,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000
and most prefetabty about 4000.
Lime soaR dis~ersant comowund
The compositions of the invention may contain a lime soap dispetsant compound,
which has a lime soap dispersing power (I,SDP), as defined hereinafter of no
more
than 8, preferably no more than 7, most preferably no more than 6. The lime
soap
dispersant compound is preferably present at a level of from 0.196 to 4096 by
weight, more prefetabty 196 to 2096 by ~.veight, most preferably from 2~ to
10°.&
by weight of the compositions.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. A
numerical measure of the effectiveness of a lime soap dispersattt is given by
the
lime soap dispersing power (LSDP) which is determined using the Lime soap
dispersion test as described in an article by H.C. Borghetty and C.A. Bergman,
J.
Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap dispersion
test method is widely used by practitioners in this art field being referred
to , for
example, in the following review articles; RT.N. I~,.infield, Surfactant
Science Series,
Volume 7, p3; W.N. Li~eld, Tenside SurF. Det. , Volume 27, pages159-161,
(1990); and M.K. Nagatajan, W.F. Masler, Cosmetics and Toiletries, Volume 104,
pages 71-73, (1989). The LSDP is the 96 weight ratio of dispersing agent to
sodium oleate required to disperse the Lime soap deposits formed by 0.025g of
CA 02187438 1999-11-10
44
sodium oleate in 30m1 of water of 333ppm CaC03 (Ca:Mg=3:2) equivalent
hardness.
Surfactants having good lime soap dispersant capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates
with an average degree of ethoxylation of from 1-5, particularly C 12-C 15
alkY~
ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4),
and
the C 13-C 15 ethoxylated alcohols with an average degree of ethoxylation of
either
12 (LSDP=6) or 30, sold under the trade marks Lutensol A012 and Lutensol A030
respectively, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the
article
by M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries,
Volume 104, pages 71-73, (1989). Examples of such polymeric lime soap
disper~,ants include certain water-soluble salts of copolymers of acrylic
acid,
methacrylic acid or mixtures thereof, and an acrylamide or substituted
acrylamide,
where such polymers typically have a molecular weight of from 5,000 to 20,000.
Suds suppressing'sy tem
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 ~O to 10 ~ , most
preferably from
0.191; 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.
2-alkyl and alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a
detergent composition, particularly in the presence of agitation of that
solution.
21~.'~~~~
WO 95128464 , . : r a PGT/IJS95/04085
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 trimethylsilyi 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 VJayne St. John. The monocarboxyHc fatty acids, and
salts
thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to
about
24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali
metal salts such as sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols,
aliphatic Clg-C4p ketones (e.g. stearone) N-alkylated amino triazines such as
tri- to
hexa-alkyhnelamines 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
monostearyi di-alkali metal (e.g. sodium, potassium, lithium) phosphates and
phosphate esters.
Copolymers of ethylene oxide and propylene oxide, particularly the mixed
ethoxylatedlpropoxylated fatty alcohols with an alkyl chain length of from 10
to 16
carbon atoms, a degr~ of ethoxylation of from 3 to 30 and a degree of
propoxylation of from 1 to 10, are also suitable antifoam compounds for use
herein.
Suitable 2-alley-alcanols antifoam compounds for use herein have been
described in
DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to
C 16
alkyl chain carrying a terminal hydroxy group, and said alkyl chain is
substituted in
the a position by a CI to Clp alkyl chain. Mixtures of 2-alkyl-alcanols can be
used
in the compositions according to the present invention.
2:~ $'~~,4 3 8. .
WO 95128464 PCTlUS95104085
46
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 5096 to 999b, preferably
7596 to 9596 by weight of the silicone antifoam compound; and
(ii) silica, at a level of from l 96 to 50 ~ , preferably 5 ~ to 25 ~ by
weight of the siliconelsilica antifosrtt compound;
wherein said silica/silicone antioam compound is incorporated at a level of
from 5% to 5096, preferably 10% to 4096 by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-7896 and an ethylene oxide
to propylene oxide ratio of from 1:0.9 to I:1.1, at a level of from 0.596 to
1096, preferably 1 ~ to 1096 by weight; a particularly preferred silicone
glycol rake copolymer of this type is DC0544, commercially available from
DOW Corning under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C18
ethoxylated alcohol with a degree ~f ethoxylation of from 5 to 50, preferably
8 to 15, at a level of from S ~ to 8096, preferably 1096 to 7096, by weight;
A preferred particulate suds suppressor system useful herein comprises a
mixture of
an alkylated siloxane of the type hereinabove disclosed and solid silica.
The solid silica can be a fumed silica, a precipitated silica or a silica,
made by the
gel formation technique. The silica particles suitable have an average
particle size
of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a
surface
area of at least SOm2lg. These silica particles can be rendered hydrophobic by
treating them with dialkylsilyl groups and/or trialkylsilyl groups either
bonded
directly onto the silica or by means of a silicone resin. It is preferred to
employ a
silica the particles of which have been rendered hydrophobic with dimethyl
andlor
trimethyl silyl groups. A preferred particulate antifoam compound for
inclusion in
the detergent compositions in accordance with the invention suitably contain
an
CA 02187438 1999-11-10
47
amount of silica such that the weight ratio of silica to silicone lies in the
range from
1:100 to 3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds suppressing system is represented by a
hydrophobic silanated (most preferably trimethyl-silanated) silica having a
particle
size in the range from 10 nanometers to 20 nanometers and a specific surface
area
above SOm2/g, intimately admixed with dimethyl silicone fluid having a
molecular
weight in the range from about 500 to about 200,000 at a weight ratio of
silicone to
silanated silica of from about 1:1 to about 1:2.
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and comprises a silicone antifoam compound and an organic carrier
material having a melting point in the range SO°C to 85°C,
wherein the organic
carrier material comprises a monoester of glycerol and a fatty acid having a
carbon
chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other
preferred particulate suds suppressing systems wherein the organic carrier
material
is a fatty acid or alcohol having a carbon chain containing from 12 to 20
carbon
atoms, or a mixture thereof, with a melting point of from 45°C to
80°C.
Other highly preferred particulate suds suppressing systems are described in
CA 2099129 in the name of the Procter and Gamble Company which
systems comprise silicone antifoam compound, a carrier material, an
organic coating material and glycerol at a weight ratio of glycerol:
silicone antifoam compound of 1:2 to 3:1. CA 2110409 also discloses
highly preferred particulate suds suppressing systems
comprising silicone antifoam compound, a carrier material, an organic coating
material and crystalline or amorphous aluminosilicaie at a weight ratio of
aluminosilicate : silicone antifoam compound of 1:3 to 3:1. The preferred
carrrier
material in both of the above described highly preferred granular suds
controlling
agents is starch.
An exemplary particulate suds suppressing system for use herein is a
particulate
agglomerate component, made by an agglomeration process, comprising in
combination
~. f5 g.
~' fi
W095/18464 ~ ~.~~i ~ ~~ ~:. PCT/U895104085
~i87438
48
(i) from 5 ~ to 30 °1z, preferably from 8 ~ to 15 k by weight of the
component
of silicone antifoam compound, preferably comprising in combination
polydimethyl siloxane and silica;
(ii) from 50 ~ to 90 % , preferably from 60 °k to 80 ~ by weight of the
component, of carrier material, preferably starch;
(iii) from 5 ~ to 30 ~, preferably from 10 ~ to 20 % by weight of the
component
of agglomerate binder compound, where herein such compound can be any
compound, or mixtures thereof typically employed as binders for
agglomerates, most preferably said agglomerate binder compound comprises
a C16-Clg ethoxylated alcohol with a degree of ethoxylation of from SO to
100; and
(iv) from 2 ~ to 15 30 , preferably from 3 % to 10 Rb , by weight of C 12-C22
hydrogenated fatty acid.
Polymeric dye transfer inhibitsng~YP,~; r~
The detergent compositions herein may also comprise from 0.01 % to 10 ~,
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-vinyIimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
CA 02187438 1999-11-10
49
a) Polyamine N-oxide nol~,mers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
(I)
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached to,
or
wherein the R-N-O group forms part of the polymerisable unit or a combination
of
both.
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O orl;
R are aliphatic, ethoxylated aliphatics, ammatic,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 gencral structures
O
O
(R1 ) x _ ( _~R2)Y
R I
or N-~R1 )x
wherein R1, R2, and R3 ane 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.
WO 95/28464
PC1'/US95104085~
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymetisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicycIic 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 is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine,
piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group
is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having
the
general formula (17 wherein R is an aromatic,hetetocyclic or alicyclic groups
wherein the nitrogen of the N-0 functional group is part of said R group.
Examples
of these classes are polyamine oxides wherein R is a heterocyclic compound
such as
pytridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the
general formula (>7 wherein R are aromatic, heterocyclic or alicyclic groups
wherein
the nitrogen of the N-0 functional group is attached to said R groups.
Examples of
these classes are polyamine oxides wherein R groups can be aromatic such as
phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are polyvinyls, poiyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oiude polymers of the present invention typically have a ratio of
amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of arsine
oxide groups present in the polyamine oxide polymer can be varied by
appropriate
copolymerizaiion or by appropriate degree of N-oxidation. Preferably, the
ratio of
amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present
CA 02187438 1999-11-10
51
invention actually encompass random or block copolymers where one monomer type
is an amine N-oxide and the other monomer type is either an amine N-oxide or
not.
The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa
< 7, more preferred PKa < 6.
The polyamine 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; preferably from 1,000 to 50,000, more
preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
b Copolymers of N-vinylpvrrolidone and N-vinylimidazole
Preferred polymers for use herein may comprise a polymer selected from N-
vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average
molecular weight range from 5,000 to 50,000 more preferably from 8,000 to
30,000, most preferably from 10,000 to 20,000. The preferred N-vinylimidazole
N-vinylpyrrolidone copolymers have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most
preferably
from 0.6 to 0.4 .
cl Polyvinyl-wrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from
5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably
from
5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially vailable from
ISP
Corporation, New York, NY and Montreal, Canada under the product names pVpTM
K-15 (viscosity molecular weight of 10,000), 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 360,000). PVP K-15 is also available from ISP
Corporation. Other suitable polyvinylpyrrolidones which are commercially
available
from BASF Cooperation include SokalanT"" HP 165 and Sokalan HP 12.
Polyvinylpyrrolidone may be incorporated in the detergent compositions herein
at a
level of from 0.01 ~ to 5 ~ by weight of the detergent, preferably from 0.05 ~
to
3 ~O by weight, and more preferably from 0.19 to 2 ~ by weight. The amount of
218'~~4 3 g ~ ~,
WO 95/28464 PCTlU5951040&S/
52
poiyvinylpyrroGdone delivered in the wash solution is preferably from 0.5 ppm
to
250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100
ppm.
dl Pol~vinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of fmm 2,500 to 400,OOD, preferably from 5,000 to
200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000
to
15,000.
The amount of polyvinyloxazolidone incorporated in the detergent compositions
may be from 0.019& to 5 96 by weight, preferably from 0.05 °6 to 3 96
by weight, and
more preferably from 0.19b to 296 by weight. The amount of
polyvinyloxazolidone
delivered in the wash solution is typically from 0.5 ppm to 250 ppm,
preferably
from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
el Polyvinvlimidazole
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, more preferably from 5,000 to
50,000,
and most preferably from 5,000 to 15,000.
The amount of polyvinylimidaaole incorpoarted in the detergent compositions
may
be from 0.0196 to 5 % by weight, preferably from 0.05 9& to 3 96 by weight,
and
more preferably from 0.13b to 296 by weight. The amount of polyvinylimidazole
delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5
ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
The detergent compositions herein may also optionally contain from about 0.005
~
to 5 96 by weight of certain types of hydrophilic optical brighteners which
also
provide a dye transfer inhibition action. If used, the compositions herein
will
prefcrably comprise from about 0.0196 to 196 by weight of such optical
brighteners.
CA 02187438 1999-11-10
53
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
Ri R_,
-V H H
N N C C O N ~O
O N H H 'N
R2 S03M SO~M R~
wherein RI 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 canon such as sodium or
potassium.
When in the above formula, R1 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 disodium
salt.
This particular brightener species is commercially marketed under the
trademark
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the detergent compositions
herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a ration such as sodium, the brightener is 4,4'-bis[(4-
anilino-
6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)aminoJ2,2'-
stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially
marketed
under the trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a ration
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
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.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used
in combination with the selected polymeric dye transfer inhibiting agents
hereinbefore described. The combination of such selected polymeric materials
(e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g.,
Tinopal
f~~.~..;,~,.
218~~38
W095128464 ''. i. < < ' . . PCT/US9510408_~
54
UIVPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly
better dye transfer inhibition in aqueous wash solutions than does either of
these two
detergent composition components when used alone. Without being bound by
theory, it is believed that such brighteners work this way because they have
high
affinity for-fabrics in the wash solution and therefore deposit relatively
quick on
these fabrics. The extent to which brighteners deposit on fabrics in the wash
solution can be defined by a parameter called the "exhaustion coefficient".
The
exhaustion coefficient is in general as the ratio of a) the brightener
material
deposited on fabric to b) the initial brightener concentration in the wash
Liquor.
Btighteners with relatively high exhaus~ion coefficients are the most suitable
for
inhibiting dye transfer in the context cf the present invention.
Of course, it will be appreciated tnat other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
Fabric softening agents can also be incorporated into laundry detergent
compositions
in accordance with the present invention. These agents may be inorganic or
organic
in type. Inorganic softening agents are exemplified by the smectite clays
disclosed
in GB-A-1 400 898. Organic fabric soft°ning agents include the water
insoluble
tertiary amines as disclosed in GB-A-1 .514 276 and EP-B-0 011 340.
Levels of smectite clay are normally in the range from 536 to 1596, more
preferably
from 896 to 1296 by weight, with the material be9ng added as a dry mixed
component to the remainder of the formulation. Organic fabric softening agents
such as the water-insoluble tertiary amines or dilong chain amide materials
are
incorporated at levels of from 0.5 9b to 5 96 by weight, normally from 1 ~O to
3 96 by
weight, whilst the high molecular weight polyethylene oxide materials and the
water
soluble cationic materials are added at levels of from 0.19iO to 29b, normally
from
0.15 96 to 1.5 9b by weight.
~r f i
WO 95128464 PCT/US95/04085
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes, colours and filler salts, with sodium sulfate being a
preferred
filler salt.
Form of the compositions
The detergent compositions of the invention can be formulated in any desirable
form
such as powders, granulates, pastes, liquids and gels.
Liquid compositions
The detergent compositions of the present invention may be formulated as
liquid
detergent compositions. Such liquid detergent compositions typically comprise
from
94 ~6 to 35 Rb by weight, preferably from 90 ~ to 40 ~6 by weight, most
preferably
from 80°b to SOY6 by weight of a liquid carrier, e.g., water,
preferably a mixture of
water and organic solvent.
Gel compositions
The detergent compositions of the present invention may also be in the form of
gels.
Such compositions are typically formulated with polyakenyl polyether having a
molecular weight of from about 750,000 to about 4,000,000.
Solid com sitions
The detergent compositions of the invention are preferably in the form of
solids,
such as powders and granules.
The particle size of the components of granular compositions in accordance
with the
invention should preferably be such that no more that 5 °.6 of
particles are greater
than l.4mm in diameter and not more than 5 R6 of particles are less than 0.
l5mm in
diameter.
The bulk density of granular detergent compositions in accordance with the
present
invention typically have a bulls density of at least 450 gllitre, more usually
at (east
600 g/litre and more preferably from 650 gllitre to 1200 gllitre.
~ t : ] ~~ b \
f, .. n
R'O 95/28464 ''~ ~ ~ ~ 4 3 8 PCT/US95104085*
56
Bulk density is measured by means of a simple funnel and cup device consisting
of a
conical funnel moulded rigidly on a base and provided with a flap valve at its
lower
extremity to allow the contents of the funnel to be emptied into an axially
aligned
cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at
its
respective upper and lower extremities. It is mounted so that the lower
extremity is
140 mm above the upper surface of the base. The cup has an overall height of
90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal
volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring,
the
flap valve is opened and powder allowed to overfill the cup. The filled cup is
removed from the frame and excess powder removed from the cup by passing a
straight edged implement e.g. a knife, across its upper edge. The filled cup
is then
weighed and the value obtained for the weight of powder doubled to provide the
bulk density in gllitre. Replicate measurements are made as required.
Making processes - eranular compositions
In general, granular detergent compositions in accordance with the present
invention
can be made via a variety of methods including dry mixing, spray drying,
agglomeration and granulation.
The compositions of the invention may be used in essentially any washing or
cleaning method, including machine laundry and dishwashing methods.
Machine dishwashine method
A preferred machine dishwashing method comprises treating soiled articles
selected
from crockery, glassware, hollowware and cutlery and mixtures thereof. with an
aqueous liquid having dissolved or dispensed therein an effective amount of a
_
machine dishwashing composition in accord with the inevntion. By an effective
amount of the machine dishwashing composition it is typically meant from 8g to
60g of product dissolved or dispersed in a wash solution of volume from 3 to
10
litres, as are typical product dosages and wash solution volumes commonly
employed in conventional machine dishwashing methods.
218743$
WO 9SI28464 " ~'- ;: -.., _~ PCT/US95/04085
57
~VIachine laundry methods
Machine laundry methods herein 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. The detergent can be added to the wash solution either via the
dispenser
drawer of the washing machine or by a dispensing device. By an effective
amount
of the detergent composition it is typically 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 solurioa volumes commonly employed in
conventional machine laundry methods.
In a preferred washing method herein a dispensing device containing an
effective
amount of detergent product is introdu~ea into the drum of a, preferably front-
loading, washing machine before the commencement of the wash cycle.
The dispensing device is a container for the detergent product which is used
to
deliver the product directly into the drum of the washing machine. Its volume
capacity should be such as to be able to contain sufficient detergent product
a~
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 immersion in 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 atthe start of the wash cycle
thereby
providing transient localised high concentrations of components such as water-
soluble builder and heavy metal ion sequestrarit components in the drum of the
washing machine at this stage of the wash cycle.
r v a .' 7 y.
1 ' x,
2181#~3$~',~ r
WO 95/28464 PCTIUS95104085
58
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 in accord with 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".
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 arrangemnt to prevent egress of
wetted,
undissolved, product, this arrangement typically comprising radially extending
walls
extending from a central boss in a spoked wheel co~guration, or a similar
structure
in which the walls have a helical form.
~~tre~tmern washine method
In a pretreatment wash method aspect of the invention a soiledlstained
substrate is
treated with an effective amount of a pretreatment solution containing a heavy
metal
ion sequestrant, but no bleach components. The solution might optionally
contain
other non-bleach detergent components such as surfactants, builders, enzymes
and
detergent polymers. Preferably the solution also contains water-soluble
builder.
The level of the heavy metal ion sequestrartt in said pretreatment solution is
typically from 0.0005 9& to I °b , and preferably is more than 0.05 96.
The pretreatment solution is allowed to remain in contact with the soiled
substrate
for an effective time interval. Said time interval will typically be from IO
seconds
to 1800 seconds, more preferably from 60 seconds to 600 seconds.
PCTlUS95104085
W O 95128464 ;= ~
",
59
The soiled substrate is then washed using a suitable washing method wherein a
bleach-containing detergent product is employed. The washing method may for
example, be any of the machine dishwashing or machine laundry washing methods
described herein.
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
Xy~ . Sodium C1X - Cly alkyl sulfate
24EY ~ A ~=12-14 P~ominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide
XyEZ . A Clx - Cly predominantly linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
XYEZS ~ C1X - ClY slum alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
~,e,A . Cl6-Clg alkyl N-methyl glucamide.
S~~ : Amorphous Soduum Silicate (Si02:Na20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula 8-Na2Si20g
C~~m . Anhydrous sodium carbonate
PolycarboxyLue . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
Zeolite A . Hydrated Sodium Aluminosilicate of formula
NaI2(A102SiC~l2. 27Fi20 having a primary particle
size in the iattge from 1 to !0 micrometers
R'095/28464 ~:~~~~'~~,v PCTlUS95104085~
so
Citrate . Tri-sodium citrate dihydrate
Petrzrbonate (fast release . Anhydrous sodium percarbonate bleach of empirical
particle) formula 2Na2C03.3H202 coated with a mixed salt of
formula Na2S04.n.Na2C03 where n is 0.29 and
where the weight ratio of percarbonate to mixed salt is
39:1
Per~carbonate (slow release . Anhydrous sodium percarbonate bleach coated with
a
particle) cnatimg ef sodium silicate (Si20:Na20 ratio = 2:1) at
a weight ratio of percarbonate to sodium silicate of
39:1
TAED . Tetraacetylethylenediamine
TAED (slow release . Particle formed by agglomerating TAED with citric
particle) acid and polyethylene glycol (PEG) of Mw=4,000
with a weight ratio of components of TAED:citric
acid:PEG of 75:10:15, coated with an external coating
of citric acid at a weight ratio of agglomerate: citric
acid coating of 95:5.
Benzoyl Caprolactam (slow . Pattecle formed by agglomerating benzoyl
caprolactam
release particle) (BzCrl .v9th citric acid and polyethylene glycol (PEG)
of Mw=4,000, with a weight ratio of components of
BzCl:citric acid:PEG of 63:21:16, coated with an
external coating of citric acid at a weight ratio of
agglometate:citric acid coating of 95:5
TAED (fast release . Particle formed by agglomerating TAED with partially
particle) neutralised polycarboxylate at a ratio of
TAED:polycarboxylate of 93:7, coated with an
external coating of polycarboxylate at a weight ratio of
agglomerate:coating of 96:4
CA 02187438 1999-11-10
61
EDDS (fast release : Particle formed by spray-drying EDDS with MgS04 at
particle) a weight ratio of 26:74
Protease : Proteolytic enzyme sold under the trademark Savinase
by Novo Industries A/S with an activity of 13
KNPU/g.
Amylase : Amylolytic enzyme sold under the trademark
Termamyl 60T by Novo Industries A/S with an activity
of 300 KNU/g
Cellulase : Cellulosic enzyme sold by Novo Industries A/S with an
activity of 1000 CEV'U/g
Lipase : Lipolytic enzyme sold under the 'trademark Lipolase by
Novo Industries A/S with an activity of 165 KLU/g
CMC : Sodium carboxymethyl cellulose
)rlEIDP : 1;1-hydroxyethane diphosphonic acid
EDDS : Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer
in the form of sodium salt.
PVNO : Poly (4-vinylpyridine)-N-oxide copolymer of
vinylimidaxole and vinylpyrrolidone having an average
molecular weight of 10,000.
Granular Suds Suppressor : 12 °.b Siliconelsilica, 18 ~ stearyl
alcoho1.70 ~ starch in
granular form
Nottionic ~ C 13-C 15 ~~ e~oxylated/propoxylated fatty
alcohol with an average degree of ethoxylation of 3.8
and an average degree of propoxylation of 4.5 sold
under the trademark Plurafac LF404 by BASF Gmbh
(low foaming)
CA 02187438 1999-11-10
62
Metasilicate : Sodium metasilicate (Si02:Na~0 ratio = 1.0)
Phosphate : Sodium tripolyphosphate
480N : Random copolymer of 3:7 acrylic/methacrylic acid.
average molecular weight about 3.500
PB 1 : Anydrous sodium perborate monohydrate - in
compacted particulate form to retard release of
hydrogen peroxide
Cationic lactam : Cationic peroxyacid bleach precursor salt of trialkyl
' ammonium methylene CS-alkyl caprolactam with
tosylate
DET'PMP : Diethylene triamine penta (methylene phosphoric
acid), marketed by Monsanto under the trademark
bequest 2060
Bismuth nitrate . Bismuth nitrate salt
Paraffin : Paraffin oil sold under the trademark Winog 70 by
Wintershall.
BSA : Amylolytic enzyme sold under the trademark LE17 by
Novo Industries A/S (approx 1 ~ enzyme activity)
Sulphate : Anhydrous sodium sulphate.
pH : Measured as a 1 ~ solution in distilled water at 20 ° C .
~ ~ s;~~~3~y
WO95128464 f " ~ ~' PCTIUS95/04085
63
The following laundry detergent compositions were prepared values being
expressed
as percentages by weight of the compositions: Composition A is a comparative
composition, compositions B to E are in accord with the invention:
A B C D E
45AS/25AS (3:1) 9.1 9.1 9.1 9.1 7.0
35AE3S 2.3 2.3 2.3 2.3 2.0
24E5 4.5 4.5 4.5 4.5 6.0
'AAA 2.0 2.0 2.0 2.0 -
Zeolite A 13.2 13.2 13.2 13.2 15.0
Na SKS-6lcitric acid 15.6 15.6 15.6 15.6 13.0
(79:21)
Carbonate 7.6 7.6 7.6 7.6 8.0
TAED (fast release particle)6.3 - - - -
TAED (slow release particle)- 5.0 - 2.3 3.5
Benzoyi Caprolactam - - 5.0 2.7 -
(slow
release particle)
Percarbonate (fast release22.5 - - 22.5 -
particle)
Percarbonate (slow release- 22.5 22.5 - -
particle)
318'7 438
WO 95/28464 ;~ i., :: s ': ~- '_ PC1'/US95104085
64
PB1 - - - - 16.0
DETPMP 0.5 - - - 0.3
EDDS (fast release particle)- 0.8 0.3 0.75 -
Protease 0.55 1.27 0.55 1.27 1.5
Lipase 0.15 0.15 0.15 0.15 0.2
Cellulase 0.28 0.28 0.28 0.28 0.4
Amylase 0.27 0.27 0.27 0.27 0.4
Polycarboxylate 5.1 5.1 5.1 5.1 4.0
CMC 0.4 0.4 0.4 0.4 0.4
PVNO 0.03 0.03 0.03 0.03
Granular suds su ressor1.5 1.5 1.5 1.5 1.5
Minorslmisc to 10096 _.
The following T50 values (in sec:ords) were obtained for each of products A to
D:
TSO A B C D
Peroxyacid 130 190 205 240
AVO 95 225 230 115
Builder (citric)90 60 60 60
fr ~,
;: ~ $' i ;~ ~i a
WO 95128464 ~ 1 g 7 4 3 8 PCT/US95104085
fi5
Heavy metal150 30 30 60
ion sequestrant
(DETPMP
or
EDDS)
Comparative testing
Test method - stain removal
Swatch preoaiation
Three white cotton sheets were prewashed in a non-biological bleach-free heavy
duty detergent. Sets of six test swatches of size 6cm x 6cm were cut from each
sheet. Stains were evenly applied onto each swatcfi set (e.g. by painting on).
Additionally, pre-prepared swatches obtained from the EMPA institute were also
employed.
In summary, the following sets of swatches were employed:
Enzymatic stains
Grass;
EMPA Blood;
EMPA Blood Mills and Ink;
C.teacy gtaLna
Dirty Motor Oil;
- Shoe Polish;
The sets of fabric swatches were subjected to one wash cycle in an automatic
washing machine. The swatches were then assessed for removal of the stains by
an
expert panel using a four point Scheffe scale. The combined averaged paired
results
of each of the sets of comparisons are as set out below, with prior art
composition
A being used as the common reference.
CA 02187438 1999-11-10
66
In more detail, a MieleT"" 698 WM automatic washing machine was employed, and
the
40oC short cycle programme selected. Water of 12o German hardness ( Ca : Mg =
3 : I) was used. 75g of detergent. dispensed from a granulette dispensing
device
placed in the middle of the load was employed. One swatch of each type was
washed along with a ballast load of 2. 7 Kg of lightly soiled sheets ( I weeks
domestic usage).
Comparative testing - stain removal
The above stain removal test method was followed in comparing the efficiency
of
Composition B with the reference prior art Composition A in removing different
type
of stains.
The results obtained were as follows:
Stain removal benefit (PSIn
FMPA blood .~ 1.8*
EMPA BMI +0.6
Grass +0.7
Dirt Motor Oil +0.6
Shoe fish +0.7
*significant at 95 ~ confidence limit
WO 95128464 PCT/U595/04085
67
Example 2 _
The following bleach-containing machine dishwashing compositions were prepared
(parts by weight) in accord with the invention.
A B C D E F G
Citrate 15.0 15.0 15.0 15.0 15.0 I5.0 -
480N 6.0 6.0 6.0 6.0 6.0 6.0 -
Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 -
Phosphate - - - - - - 38.0
Silicate (as 8.0 8.0 8.0 8.0 8.0 8.0 14.0
Si
Metasilicate 1.2 1.2 1.2 1.2 1.2 1.2 2.5
(as Si02)
PBl - slow 1.2 1.2 1.5 1.5 1.5 2.2 1.2
release particle
Av0
TAED (slow 2.2 2.2 2.2 3.5 - 2.2 2.2
release article)
Cationic lactam- - - - 3.3 - -
Pataffm 0.5 0.5 0.5 0.5 0.5 0.5 ~ 0.5
Bismuth - 0.2 0.2 0.2 0.3 0.4 0.2
niuate
Protease 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Amylase 1.5 L5 1.5 1.5 1.5 I.5 -
PCTIUS95104085~
WO 95/28464
6B
BSA _ _ _ _ _ - 1.5
DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 -
I~Dp 1.0 1.0 1.0 1.0 1.0 1.0 -
Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5
Sul hate 23.0 22.8 22.4 22.7 22.2 21.5 0.3
misc inc
moisture
to
balance
pH (1 ~ 10.7 10.7 10.7 10.7 10.7 10.7 11.0
solution
W095128464 r: _ ... .,
PCTIUS95/04085
69 ~-, .
iExample 33
The following representative beaker test method was carried out to determine
whether the sequential order of exposure of a stained fabric to heavy metal
ion
sequesttant and hydrogen peroxide bleach solution would give rise to
differences in
the stain removal profile.
Pre-stained cotton swatches were prepared by immersing the swatches in a
concentrated tea solution. Tea stains contain high levels of manganese. and
are
recognised to be difficult to remove from soiled/stained substrates.
Individual 1000 ml beakers were charged with solutions containing individually
0.5~ by weight concentration of EDDS, and a hydrogen peroxide solution
equivalent to 236 AvO. Each of the heavy metal ion sequesttant and bleach
solutions was buffered to a pH of 10.5, which is a typical "in wash" pH
encountered in a laundry washing method.
Sets of the pre-stained swatches were subjected to soaking in either, or
sequentially
both, of the solutions. The soak time in each solution was 20 minutes. Each
soak
was followed by a rinse in dilute NaOH solution.
In detail, the following wash/soak protocols were employed:
Set . Protocol
A Soaking in bleach solution only
Soaking in EDDS solution only
C Soaking in bleach solution followed by
soaking in
EDDS solution
D ~ Soaking in EDDS solution followed by
soaking in
bleach solution
W0951284G4 F ~ ' ,~ ;; " PCT/US95/04085~
t,. ~;, . K ..:~
The stain removal results achieved for each washlsoak protocol were assessed
using
a Macbeth Spectrometer, measuring the yellowness, whiteness and a, b and l
values, by comparison with a clear white cotton swatch.
The following results were obtained:
Stained A ili C D
swatch
Yellowness 55.1 35.7 36.7 29.4 19.3
Whiteness -141.2 -92.1 -94.1 -75.0 -50.1
I -9.7 -5.8 -8.6 -4.5 -3.4
a 3.5 -.3 2.3 0.0 -0.7
b 23.8 16.1 15.5 13.4 8.9
Less positive yellowness, a and b values are desirable. More positive
whiteness and
1 values are desirable.
The stain removal results for the set of swatches D are hence seen to be
better than
those obtained for swatches A - C. The enhanced stain removal performance
obtained for the sequential exposure of a stained fabric to a heavy metal ion
sequesttant containing solution prior to a bleach-containing solution is thus
demonstrated.
W O 95/28464 _ ~ 18 7 4 3 8 ", f . } PCT/US95104085
a ': t : ..
71
ample 4
' The following representative test method demonstrates that significant
bleachable
stain removal performance is obtained when stained swatches are treated with a
' solution containing heavy metal ion sequesttant prior to being washed in a
bleach-
containing detergent product having fast (i.e. uncontrolled rate of release of
bleach).
Pre-stained cotton swatches were prepzmd by immersing the swatches in a
concentrated tea solution. Tea stains contain high levels of manganese, and
are
recognised to be difficult to remove frum soiled/stained substrates.
Individual 1000 ml beakers were charged with solutions containing 0.005 ~ by
weight concentration of EDDS buffered to a pH of 10.5, which is a typical "in
wash" pH encountered in a laundry washing method.
Sets of the pre-stained swatches were subjected to rinsing in the EDDS
solutions
followed by washing in a full scale laundry wash method using a bleach-
containing
detergent product. The rinse time in the EDDS solution was set to be either 2
or 5
minutes. The laundry washing method comprised) a main wash in a Miele washing
machine at 40°C using soft water. The detergent product employed in
this washing
method had fast release of bleach, and had the composition of formulation A of
Example 1.
The effect of the pre-rinsing in the heavy metal ion sequestrant solution
prior to
washing was assessed by reference to sets of the pre-stained swatches
subjected only
to the full scale laundry wash method.
Bleachable stain removal was assessed both visualily using the well known 4 -
point
Scheffe scale utilising panel score units (PSLT), and using the Macbeth
spectometer
to calcuL~tte a ~ stain removal value.
r; t: y, ~.
VVO 95128464 PCTJUS95104085~
72
The following results were obtained:
RinseIWash Protocol %a stain removalPSU (Scheff~)
VS wash onl
Wash onl 87 -
Rinsing for 2 minutes 92 +3*
in EDDS
solution followed by
wash
Rinsing for 5 minutes 97 +3*
in EDDS
solution followed by
wash
* significant at the 95 ~ co~dence level
Marked bleachable stain removal benefits are observed for the swatches exposed
to
the heavy metal ion sequestrutt solution prior to washing in the bleach-
containing
detergent product.
218 4,38 X
W O 95128464 ~~ '~ PCTlUS95/04085
73
The washlrinse protocol of Example 3 was repeated with the following
variations:
1. The 0.0059fi of EDDS solution was replaced by a solution containing
' 0.005 % EDDS and 0.05 % sodium citrate, which was also buffered to pH
10.5.
2. The rinse time was set at 3 minutes.
3. Swatches (cotton) stained individually with the following stains were
employed:
(a) Blood (»IPA)
(b) Coffee
(c) Red wine
(d) Cocoa
(e) Blood, mills and ink (ESA)
The swatches (a) and (e) were obtained from the >~A organization. Swatches (b)
to (d) were obtained by painting the stains onto prewashed 15 cm x 15 cm
samples
of white cotton sheet.
Using this modified test protocol the effect of pre-rinsing the stained
swatches in a
heavy metal ion sequestrant/ builder containing solution prior to washing was
assessed, by comparison with the results obtained for the same stained
swatches
exposed solely to the laundry washing method, without any pre-rinsing step.
The stain removal results were assessed using the Ivlacbeth spectometer to
calculate
a 9~ stain removal value.
~, i. : :- ." t
~ n :,~ ,
i,
WO 95/28464 PCTIUS95104085~
74
The following results were obtained:
RinselWash %a Stain
removal
rotocol
Blood Coffee Red Cocoa BMI
Wine
Wash only 78 ~ 76 100 36 70
Rinsing in 100 78 100 34 78
EDDSlbuilder
solution for
3
minutes prior
to
wash
Enhanced stain removal performance is hence seen to be obtained when the
rinsing
in the builder/heavy metal ion sequestrent solution step was employed prior to
the
wash step.
