Note: Descriptions are shown in the official language in which they were submitted.
2176697
WO 95/17495 PCT/US94114294
DETERGENT COMPOSITIONS CONTAINING PERCARHONATE
AND AMYLASE
Technical Field
The present invention relatE~s to detergent compositions
containing percarbonate bleach, and amylase enzyme at narrowly
defined ratios, to provide synergistic stain removal
performance, in particular on specific stains such as starch-
based stains, and blood stains.
Background of the Invention
The inorganic perhydrate bleach most widely used in laundry
detergent compositions is sodium perborate in the form of
either the monohydrate or tetrahydrate. However, concerns
about the impact of boron salts on the environment have led to
an increasing interest in other perhydrate salts, of which
sodium percarbonate is the most readily available.
Detergent compositions containing sodium percarbonate are
known in the art. Sodium percarbonate is an attractive
perhydrate for use in detergent compositions because i~
dissolves readily in water, is weight efficient and, after
giving up its available oxygen, provides a useful source of
carbonate ions for detergency purposes.
2176697
On the other hand, the use of amylase enzymes in detergent
compositions is known, although such use has been mainly
described in perborate-based formulations.
The use c_' enzymes, inclt~di..~.g amylase in percarbonate-based
compositions is known from e.g. JP 5028197; PCT/US93/06302
and PCT/US93/06877.
Although the action of amylase on starch-based stains in
particular, is known, and the action o: percarbonate On
bleacheable stains is also known, it has now been surprisingly
discovered that the combined use of percarbonate and amylase
at specific ratios provides a synergetic effect on the removal
of difficult stains such a~~ starch-based stains and blood
stains, in particular at low temperatures.
In addition such a synergetic removal effect is also seen on
particulate stains such as peat clay, mud, fertilizing soil,
high organic content clay.
It has further been found that the ternary system consisting
of percarbonate/amylase/protease at specific ratios provides
an even better result on they above stains, in particular on
starch-based and blood stains.
Detailed Description of the Invention
The present invention is directed to a granular detergent
composition comprising an alkali metal percarbonate and an
amylase enzyme characterized in that the weight ratio of
percarbonate (expressed as 13.5% AvOx) to amylase (expressed on
an activity of about 60KNU/g) is in the range of from about 1:2
to about 300:1. Methods of treating textiles are also
encompassed.
Percarbonate
The laundry detergent or automatic dishwashing compositions
herein typically contain from. 1to 40'=_, preferably from 3~ to
30? by weight, most preferab~.y from Sx to 25~ by weight of an
alkali metal percarbonate bleach (when expresssed on an AvOx
basis of 13.5=> in the form of particles having a mean size
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.3if O 95/17495 PCT/US94/14294
3
from 25-0 _ t;: 900 micrometers, preferably 500 to 700
micrometers.
Laundry additives typically ccntain from 30°-<, to 80~ cf sa,~d
percarbonate particles.
The alkali metal percarbonate bleach is usually in the form
of the sodium salt. Sodium percarbonate is an addition
compound having a formula corresponding to 2Na2C03 3H202. To
enhance storage stability the percarbonate bleach can be
coated with e.g. a further mixed salt of an alkali metal
sulphate and carbonate. Such coatings together with coating
processes have previously been described in GB-1,466,799,
granted to Interox on 9th March 1977. The weight ratio of the
mixed salt coating material to pE~rcarbonate lies in the range
from 1:2000 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 1.0 and most preferably n is from 0.2 to 0.5.
Other suitable coating materials are sodium silicate, of
Si02:Na20 ratio from 1.6:1 to 2.8:1, and magnesium silicate. .
Commercially available carbonate/sulphate coated
percarbonate bleach may include a low level of a heavy metal
sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic
acid (HEDP) or an aminophosphonate, that is incorporated
during the manufacturing process.
Preferred heavy metal sequestrants for incorporation as
described herein above include the organic phosphonates and
amino alkylene poly(alkylene phosphonates) such as the alkali
metal ethane 1-hydroxy diphosphonates, the nitrilo
trimethylene phsphonates, the ethylene diamine tetra methylene
phosphonates and the diethylene triamine penta methylene
phosphonates.
~- 2176697
Amylase
The compositions herein further comprise as an essential
ingredient an amylase enzyme (ex:pressed on an activity of about
60KNU/g) in a weight ratio with percarbonate expressed on an
activity basis of 13.5% AvOx) of 1:2 to 300:1, preferably 1:2
to 200:1.
An even more preferred ratio is 1:2 to 60:1 while the most
preferred ratio is 20:1 to 40:1.
Preferred amylases include, for example, &-amylases obtained
from a special strain of H. licheniforms, described in more
detail in GB-1, 296, 839 (Novo Nordisk) . Preferred commercially
available amylases include far example, RapidaseT", sold by
International Bio-Synthetics Inc. and TermamylT", sold by Novo
Nordisk A/S.
Optional protease
In a preferred embodiment of the present invention, the
detergent compositions herein also contain a protease enzyme.
(expressed on an activity of about 4KNPU/g) in a weight ratio
of protease to percarbonate (expressed on an activity basis of
13.S~s AvOx) of from 5:1 to 1:60, preferably 2:1 to 1:10.
Preferred commercially available protease enzymes include
those sold under the trade marks Alcalase and Savinase by Novo
Nordisk A/S (Denmark) and Ma~xatase by International Bio-
Synthetics, Inc. (The Netherlands).
In one embodiment of the present invention, the laundry
detergent compositions herein also comprise a surface-active
agent and a builder.
-~ 217661
3~0 95/17495 PCT/US94/14294
SurFace active acent .
Ani onic S;:r sac rants
The detergent compositions of the present invention usually
contain one or more anionic surfactants as described below.
Alkyl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or
acids of the formula ROS03M wherein R preferably is a C10-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-
C2p alkyl component, more preferably a C12-Clg alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
cation (e.g., sodium, potassium, lithium). or ammonium or
substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl
ammonium cations and quaternary ammonium cations, such as
tetramethyl-ammonium and dimetlzyl piperdinium cations and
quarternary ammonium cations derived from alkylamines such as
ethylamine, diethylamine, triethylamine, and mixtures thereof,
and the like). Typically, alkyl chains of C12-16 are
preferred for lower wash temperatures (e. g., below about 50°C)~
and C16-18 alkyl chains are preferred for higher wash
temperatures (e.g., above about .'i0°C) .
Alkyl Alkoxylated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are water
soluble salts or acids of the formula RO(A)mS03M wherein R is
an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a
C10-C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C1~.-C18 alkyl or hydroxyalkyl, A
is an ethoxy or propoxy unit, m is greater than zero,
typically between about 0.5 anal about 6, more preferably
between about 0.5 and about 3, and M is H or a cation which
can be, for example, a metal cation (e. g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-
ammonium cation. Alkyl ethoxylal=ed sulfates as well as alkyl
WO 95/17495 7 0 ~ q PCT/US94114294
J
prcpcxyl~ed sulfates are cc:itempiated herein. Specific
examples o~ su~stitu==d amu:.oniv,~m canons include methyl-,
dimethy~ -, ~_ i~~ethyl-a:rmcnium arid :quaternary ammonium canons,
such as tetramethyl-ammonium, dimethyl piperdinium and cations
derived from alkanolamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like. Exemplary
surfactants are C12-Clg alkyl polyethoxylate (1.0) sulfate,
C12-ClgE(1.0)M), C12-Clg alkyl polyethoxylate (2.25) sulfate,
C12-ClgE(2.25)M), C12-Clg alkyl polyethoxylate (3.0) sulfate
C12-ClgE(3.0), and C12-Clg alkyl polyethoxylate (4.0) sulfate
C12-ClgE(4.0)M), wherein M is conveniently selected from
sodium and potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive purposes can
also be included in the laundry detergent compositions of the
present invention. These can include salts (including, for
example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, di- and triethanolamine salts) of soap,
Cg-C20 linear alkylbenzenesulphonates, Cg-C22 primary or
secondary alkanesulphonates, Cg-C2q olefinsulphonates,.
sulphonated polycarboxylic acids prepared by sulphonation of
the pyrolyzed product of alkaline earth metal citrates, e.g.,
as described in British patent: specification No. 1,082,179,
Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles
of ehtylene oxide): alkyl ester sulfonates such as C14-16
methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isethionates such as
the acyl isethionates, N-acyl taurates, alkyl succinamates
and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C12-Clg monoesters) diesters ef
sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), acyl sarcosinates, sulfates of alkylpolysaccharides
such as the sulfates of alk:ylpolyglucoside (the nonionic
nonsulfated compounds being described below), branched primary
alkyl sulfates, alkyl polyethoxy carboxylates such as those of
_ _..___.~~.~..~....._...____... _._.~ _~~_... ...___.
21 76697
the formula RO (CHZCHzO) kCHzC00-M' wherein R is a Ce-C2z alkyl, k
is an integer from 0 to 10, and M is a soluble salt-forming
cation. Resin acids and hydro<~enated resin acids are also
suitable, such as rosin, hydro<3enated rosin, and resin acids
and hydrogenated resin acids present in or derived From tall
oil. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch).
variety of such surfactants <ire also generally disclosed _n
U.S. Patent 3,929,678, issued December 30, 1975 to Laughli~,
et al. at Column 23, line 58 through Column 29, line 23.
Preferred surfactants for use in the compositions herein are
the alkyl sulfates, alkyl alk:oxylated sulfates, and mixtures
thereof .
When included therein, the laundry detergent compositions of
the present invention typically comprise from about 1 ~ to
about 40 ~, preferably from about 3 ~ to about 20 3 by weight
of such anionic surfactants.
Nonionic Surfactants
The present laundry detergent compositions preferably also
comprise a nonionic surfactant:.
While any nonionic surfact<int may be normally employed in
the present invention, two families of nonionics have been
found to be particularly useful. These are nonionic
surfactants based on alkoxylated (especially ethoxylated)
alcohols, and those nonionic surfactants based on amidation
products of fatty acid ester:; and N-alkyl polyhydroxy amine.
The amidation products of the esters and the amines are
generally referred to herein as polyhydroxy fatty acid amides.
Particularly useful in the present invention are mixtures
comprising two or more nonionic surfactants wherein at lea=.
one nonionic surfactant is selected from each of the groups c.
alkoxylated alcohols and the poiyhydroxy fatty acid amides.
WO 95/17495 fj 1 7 6 G 9 7 PCT/US94/14294 ~_
0
Suitab?.E ~nion~c sur factants inc' ude compounds produced bye
the condensatio:: cr alr:yiene oxide groups (hydrophilic y_.
nature) wit:~. an organic hydrophobic compound, which may be
aliphatic or alkyl aromatic in nature. The length of the
polyoxyalkylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-
soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
Particularly preferred for use' in the present invention are
nonionic surfactants such as the polyethylene oxide
condensates of alkyl phenols, e.,g., the condensation products
of alkyl phenols having an alkyl group containing from about 6
to 16 carbon atoms, in either a straight chain or branched
chain configuration, with from about 9 to 25 moles of ethylene
oxide per mole of alkyl phenol.
Preferred nonionics are the' water-soluble condensation
products of aliphatic alcohols containing from 8 to 22 carbon
atoms, in either straight chain or branched configuration,
with an average of up to 25 moles of ethylene oxide per more
of alcohol. Particularly preferred are the condensation
products of alcohols having an alkyl group containing from
about 9 to 15 carbon atoms with from about 2 to 10 moles of
ethylene oxide per mole of alcohol; and condensation products
of propylene glycol with ethylE~ne oxide. Most preferred are
condensation products of alcohols having an alkyl group
containing from about 12 to 15 carbon atoms with an average of
about 3 moles of ethylene oxide per mole of alcohol.
The nonionic surfactant system herein can also include a
polyhydroxy fatty acid amide component.
Polyhydroxy fatty acid amides may be produced by reacting a
fatty acid ester and an N-alkyl polyhydroxy amine. The
preferred amine for use in the present invention is N-(R1)-
CH2(CH20H)4-CH2-OH and the prefE~rred ester is a C12-C20 fatty
...,..._........~..~.... .._.,.....,-..~,...._.,e %,...»-
,._......e.........,~"._....,~.m..._.......~.._ .... 1
2176697
a
acid methyl ester. Most preferred is the reaction product of
N-methyl glucamine with Clz-Czo fatty acid methyl ester.
L~tethcds ;:= 'l3nu°acturi.~.g oclyhydroxy fatty acid amides have
been descr ibed i.~. WO 92 0073, published on 1 oth April, 199 .
This application describes the preparation of polyhydroxy
fatty acid amides in the presence of solvents. In a highly
preferred embodiment of the invention N-methyl glucamine is
reacted with a C12-C20 methyl ester. It also says that the
formulator of granular detergent compositions may find i=
convenient to run the amidation reaction in the presence of
solvents which comprise alkox;ylated, especially ethoxylated
(EO 3-8) C12-C14 alcohols (page 15, lines 22-27). This
directly yields nonionic surfactant systems which are
preferred in the present invention, such as those comprising
N-methyl glucamide and C12-C14 alcohols with an average of 3
ethoxylate groups per molecule..
Nonionic surfactant systems, and granular detergents made
from such systems have been described in WO 92 6160, published
on 16th April, 1992. This application describes (example 15) a
granular detergent composition prepared by fine dispersion
mixing in an Eirichl'''' RV02 mixer which comprises N-methyl
glucamide (10%), nonionic surfactant (10%).
Both of these patent applications describe nonionic
surfactant systems together with suitable manufacturing
processes for their synthesis, which have been found to be
suitable for use in the present invention.
The polyhydroxy fatty acid amide may be present i.~.
compositions of the present invention at a level of from 0= to
50= by weight of the detergent component or composition,
preferably from 5. to 40~ by weight, even more preferably from
10= to 30'=_ by weight.
2176697
Other Surfactants
The laundry detergent compositions of the present invention
may also cc~tain cationic, ampho'_ytic, zwitterionic, and semt-
polar surfactants, as well as nonionic surfactants other than
those already described herein, including the semi-poia~
nonionic amine oxides described below.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
those having one long-chain hydrocarbyl group. Examples of
such cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those
surfactants having the formula .
(R2 (OR3) y1 ~F~4 (OR3) y] 2R5N+X-
- wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each R3
is selected from the group consisting of
-CH2CH2_, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and
mixtures thereof; each R4 is selected from the group
consisting of C1-Cq alkyl, f1-Cq hydroxyalkyl, benzyl ring
structures formed by joining the two R4 groups,
-CH2COH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R5 i.s the same as R4 or is an alkyl
chain wherein the total number of carbon atoms of R2 plus R5
is not more than about 18; each y is from 0 to about 10 and
the sum of the y values is from 0 to about 15; and X is any
compatible anion.
Other cationic surfactants useful herein are also described
in US Patent 4,228,044, Cambre, issued October 14, 1980.
when included therein, the laundry detergent compositions o.
the present invention typicall~~ comprise from 0 % to about 25
%, preferably from about 3 % to about 15 % by weight of such
cationic surfactants
~.:
2176697
m
Ampholytic surfactants ax-e also suitable for use in the
laundry detergent compositions of the present invention.
These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines ~n
which the aliphatic radical can be straight- or branche~
chain. One of the aliphatic ;substituents contains at least 3
carbon atoms, typically from about 8 to about 18 carbon atoms,
and at least one contains an anionic water-solubilizing group
e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 a~
column 19, lines 18-35 for examples of ampholytic surfactants.
When included therein, the laundry detergent compositions of
the present invention typically comprise form 0 ~ to about 1~
~. preferably from about 1 ~ to about 10 3 by weight of such
ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
laundry detergent compositions. These surfactants can be
broadly described as derivatives of secondary and tertiary
amines, derivates of heterocyclic secondary and tertiary
amines, or derivatives of quaternary ammonium, quarternary
phosphonium or tertiary sulfonium compounds. See U.S. Patent
No. 3. 929, 678 to Laughlin et al., issued December 30, 1975 at
columns 19, line 38 through column 22, line 48 for examples of
zwitterionic surfactants.
When included therein, the laundry detergent compositions cf
the present invention typical:Ly comprise form 0 f to about 1~
3, preferably from about 1 ~ to about 10 = by weight of such
zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about
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WO 95/17495 PCT/US94/14294
12
carbon a~om~ and = :r.cieties selected from the group consisting
of alkyl groups ana hydrocya,~r:yl groups containing corm about
i to about :~ carbon atoms; water-soluble phosphine oxides
containing one alkyl moiety of form about 10 to about 18
carbon atoms and 2 moieties selected form the group consisting
of alkyl groups and hydroxyalkyl groups containing from about
1 to about 3 carbon atoms.
Semi-polar nonionic detergent ~>urfactants include the amine
oxide surfactants having the formula .
0
T
R3(OR4)xN(R5)2
Builder
The compositions herein preferably contain a builder, most
preferably non-phosphate detergent builders. These can
include, but are not restricted to alkali metal carbonates,
bicarbonates, silicates, aluminosilicates, carboxylates and
mixtures of any of the foregoing. The builder system is
present in an amount of from 25~ to 80~ by weight of the.
composition, more preferably from. 30~ to 60~ by weight.
Suitable silicates are those having an Si02 . Na20 ratio in
the range from 1.6 to 3.4, the so-called amorphous silicates
of Si02 . Na20 ratios from 2.0 to 2.8 being preferred.
Within the silicate class, highly preferred materials are
crystalline layered sodium silicates of 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 purposes of the present invention,
____ .- ~ _.__.~_.~.__-___._ _____ .. r
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WO 95/17495 PCT/US94/14294
13
x in the-general formula above has a value of 2,3 or 4 and is
preferably ~ . More preferably M is sodium and y is 0 and a
preferred example cf this formula comprise the form of
Na2Si205. These materials are available from Hoechst AG FRG
as respectively NaSKS-5, NaSKS-~~, NaSKS-11 and NaSKS-6. The
most preferred material is -Na2Si205, NaSKS-6. Crystalline
layered silicates are incorporated either as dry mixed solids,
or as solid components of agglomerates with other components.
Whilst a range of aluminosilicate ion exchange materials can
be used, preferred sodium alum:inosilicate zeolites have the
unit cell formula
Nazf(R102)z~(Si02)y]~xH20
wherein z and y are at least about 6, the molar ratio of z
to y is from about 1.0 to about 0.4 and z is from about 10 to
about 264. Amorphous hydrated aluminosilicate materials
useful herein have the empirical formula
Mz ( zAlO,o ~ ySi02 )
wherein M is sodium, potassium, ammonium or substituted
ammonium, z'is from about 0.5 to about 2 and y is 1, said
material having a magnesium ion exchange capacity of at least
about 50 milligram equivalents of CaC03 hardness per gram of
anhydrous aluminosilicate. Hydrated sodium Zeolite A with a
particle size of from about 1 tc> 10 microns is preferred.
The aluminosilicate ion exchange builder materials herein
are in hydrated form and contain from about 10~ to about 28
of water by weight if crystalline, and potentially even higher
amounts of water if amorphous. Highly preferred crystalline
aluminosilicate ion exchange materials contain from about 18=
to about 22== water in their crystal matrix. The crystalline
aluminosilicate ion exchange materials are further
characterized by a particle size diameter of from about 0.1
micron to about 10 microns. Amorphous materials are often
.__._..~_._. _~._ ___w_ _~_.._~~ __ _. .._ __ _ _.___ _~ _
~. 2176697
smaller, e.g., down to less than. about 0.01 micron. Preferred
ion exchange materials have a particle size diameter of from
about 0.2 micron to about 4 microns. The term ~~particle size
diameter~~ herein represents the average particle size diameter
by weig::t c. a given ion exch<~nge material as determined by
conventional analytical techniques such as, for example,
microscopic determination utilizing a scanning electron
microscope.
Aluminosilicate ion exchange materials useful in the
practice of this invention are commercially available. The
aluminosilicates useful in this invention can be crystalline
or amorphous in structure and can be naturally occurring
aluminosilicates or synthetically derived. A 'method for
producing aluminosilicate ion exchange materials is discussed
in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12,
1976. Preferred synthetic crystalline aluminosilicate ion
exchange materials useful herein are available under the
designations Zeolite A, Zeolite :K, P and MAP, the latter species
being described in EPA 384070. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange material
is a Zeolite A having the formu7La
Nal2((A102)12(Si02)121~xH20
wherein x is from about 20 to about 30, especially about 27
and has a particle size general:Ly less than about 5 microns.
Suitable carboxylate builders containing one carboxy group
include lactic acid, glycollic acid and ether derivatives
thereof as disclosed in Belgian Patent Nos. 831,368, 821,369
and 821,370. Polycarboxylates containing two carboxy groups
include the water-soluble salts of succinic acid, malonic
acid, (ethylenedioxy) diacetic acid, malefic acid, diglycollic
acid, tartaric acid, tartronic acid and fumaric acid, as well
as the ether carboxylat.es described in German
Offenlegenschzift 2,446,686 and 2,446,687 and U.S. Patent No.
2178697
i5
3,935,257 and the sulfinyl carboxylates described in Belgian
- Patent No. 640,623. Polycarlboxylates containing three carboxy
groups include, in particular, water-soluble citrates,
aconitrates and citraconates as well as succinate derivatives
such as the carboxymethylo~s:ysuccinates described in British
Patent No. 1, 379, 241, lacto~s:ysuccinates described in Canadian
Patent No. 973, 771, and the oxypolycarboxylate materials such as
2-oxa-1,1,3-propane tricarbo:~ylates described in British Patent
No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,1,
and the 1,2,2-ethane tetracarboxylates ,1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and
the sulfonated pyrolysed citrates described in British Patent
No. 1,082,179, while polycarboxylates containing phosphone
substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tet:racarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran. - cis,cis,cis-
tetracarboxylates. 2,5-tetrahydrofuran -cis- dicarboxylates,
2,2,5,5,-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-
hexane hexacarboxylates and carbxoymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid, pyromellitic
acid and the phthalic acid derivates disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups peg
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
WO 95/17495 217 6 6 9 7 PCT/US94/14294 .--
~n
are also-con~.tempiate~ as components cf builder systems use~ul
i.~. the prese: = inver.ticn.
Density
The present compositions are preferably in a compact form,
having a bulk density of at least: 650 g/l, but can also be in
a conventional form, with densities in a range of from 200 g/1
to 700 g/1.
In another embodiment of the invention, are provided
Automatic Dishwashing Compositions .
Automatic dishwashing composil_ions typically contain, in
addition to the percarbonate and silica of the inventions, a
builder, such as described above, and a source of alkalinity,
such as silicate or carbonate, those ingredients amounting to
up to 700 of the formulation. Optional ingredients include
polymers and enzymes.
In still another embodiment of the invention, are provided
Laundry Additive Compositions such compositions typically
contain in addition to the percarbonate and silica of the
invention, a builder and a source of alkalinity.
Optional Ingredients
Other ingredients which are known for use in detergent
compositions may also be used a~~ optional ingredients in the
various embodiments of the present invention, such as bleach
activators, other bleaching agents, polymers, other enzymes,
suds suppressing agents, as well as dyes, fillers, optical
brighteners, pH adjusting agents, non builder alkalinity
sources, enzyme stability agents, hydrotopes, perfumes.
Bleach activators
The present compositions, especially the laundry detergent
compositions/additives, preferably contain from 1= to 20~ by
weight of the composition, preferably from 2-_ to 15~ by
2 ~ ~bf~97
-CVO 95/17495 PCT/US94/14294
. 7
weight, -most preferabl_~ ~ro~~ 3 to lu by weight of a
peroxyacid b~~eaci-: activa~,er .
Peroxyacid bleach activators (bleach precursors) as
additional bleaching components in accordance with the
invention can be selected from a. wide range of class and are
preferably those containing one c>r more N-or 0-acyl groups.
Suitable classes include anhydrides, esters, amides, and
acylated derivatives of imidazoles and oximes, and examples of
useful materials within these classes are disclosed in GB-A-
1586789. The most preferred classes are esters such as are
disclosed in GB-A-836 988, 864,798, 1 147 871 and 2 143 231
and amides such as are disclosed in GB-A-855 735 and 1 246
338.
Particularly preferred bleach activator compounds as
additional bleaching components in accordance with the
invention are the N-,N,N'N' tetra acetylated compounds of the
formula
0 0
II II
CH3C CCH3
N-( CH2 ) x-N
CH3C ~ CCH3
0 0
where x can be 0 or an integer between 1 and 6.
Examples include tetra acetyl methylene diamine (TAMD) in
which x=1, tetra acetyl ethylene diamine (TAED) in which x=2
and Tetraacetyl hexylene diamine (TAHD) in which x=6. These
and analogous compounds are described in GB-A-907 356. The
most preferred peroxyacid bleach activator as an additional
bleaching component is TAED.
2176697
WO 95/17495 PCT/US94/14294 r-
lc
AnotheK pie=erred class o~ perox~yacv:~ oleach compounds are
ti:e amide s~,:~stituted compounds of ~.he ~oilowing ger~era~~
zormulae .
R1 - C - N-R2 - C - L or R1 - N - C-R2 - C - L
II I II I II II
0 R5 0 R5 0 0
wherein R1 is an aryl or alkaryl group with from about 1 to
about 14 carbon atoms, R2 is an alkylene, arylene, and
alkarylene group containing from about 1 to about 14 carbon
atoms, and R5 is H or an alkyl, aryl, or alkaryl group
containing 1 to 10 carbon atoms and L can be essentially any
leaving group. R1 preferably contains from about 6 to 12
carbon atoms. R2 preferably contains from about 4 to 8 carbon
atoms. R1 may be straight chain or branched alkyl,
substituted aryl or alkyl.aryl containing branching,
substitution, or both and may be sourced from either synthetic
sources or natural sources including for example, tallow fat.
Analogous structural variation~> are permissible for R2. The
substitution can include alkyl, aryl, halogen, nitrogen,
sulphur and other typical substituent groups or organic
compounds. R5 is preferably H or methyl. R1 and R5 should
not contain more than 18 carbon atoms total. Amide
substituted bleach activator compounds of this type are
described in EP-A-0170386.
Another class of bleach activators to use in combination
with percarbonate comprises Cg, Cg, and/or C10 (6-
octanamidocaproyl) oxybenzer.,esulfonate, 2-phenyl-(4H)3,1
benzoxazin-4-one, benzoyllactam preferably benzoylcaprolactam
and nonanoyl lactam preferably nonanoyl caprolactam.
In addition to percarbonate, the compositions herein may
also contain another bleaching system such as perborate and
activator, or a preformed organic peracid or perimidic acid,
such as N,N phthaloylaminoperoxy caproic acid, 2-carboxy-
phtaloylaminoperoxy caproic acid, N,N phthaloylaminoperoxy
7f~~3~7
~0 95/17495 PCT/US94/14294
19
valeric -acid, Nonyl amide of peroxy adipic acid, 1,12
diperoxydodecanedcic acid, Peroxybenzoic acid and ring
substituted peroxyber.~oic acid, Monoperoxyphtalic acid
(magnesium salt, hexhydrate), Diperoxybrassylic acid.
Polymers
Also useful are various organic: polymers, some of which also
may function as builders to improve detergency. Included
among such polymers may be mentioned sodium carboxy-lower
alkyl celluloses, sodium lower alkyl celluloses and sodium
hydroxy-lower alkyl celluloses, such as sodium carboxymethyl
cellulose, sodium methyl cellulose and sodium hydroxypropyl
cellulose, polyvinyl alcohols (which often also include some
polyvinyl acetate), polyacrylamides, polyacrylates and various
copolymers, such as those of malefic and acrylic acids.
Molecular weights for such polymers vary widely but most are
within the range of 2,000 to 100,000. Also very useful are
terpolymers of maleic/acrylic acid and vinyl alcohol having a
molecular weight ranging from 3.000 to 70.000.
Polymeric polycarboxylate builders are set forth in U.S:
Patent 3,308,067, Diehl, issued Nfarch 7, 1967. Such materials
include the water-soluble salts of homo-and copolymers of
aliphatic carboxylic acids such as malefic acid, itaconic acid,
mesaconic acid, fumaric acid, ac:onitic acid, citraconic acid
and methylenemalonic acid.
Other useful polymers include species known as soil release
polymers, such as described in EPA 185 427 and EPA 311 342.
Still other polymers suitable for use herein include dye
transfer inhibition polymers such as polyvinylpyrrolidone,
polyvinylpyrridine, N-oxide, N-vinylpyrrolidone, N-imidazole,
polyvinyloxozolidone or polyvinylimidazole.
2176687 ,.;
~: 0
Other Enzymes
Er.zynatic -aterials other r':an amylases an~ pro teases ca-: he
incorporate =nto the detergent. compositions herein. Suitable
are aioases, cellulases and mixtures thereon.
A suitable lipase enzyme is manufactured and sold by Novo
Nordisk A/S (Denmark) under the trade mark Lipolase° and
mentioned along with other suitable lipases in EP-A-0258068
(Novo Nordisk A/S).
Suitable cellulases are described in e.g. WO-92/13057
(Novo).
Method of treating textiles
It has been found that the binary and/or ternary mixtures
described above provide unexpe~~tedly good performance, through
a synergistic removal effect on such difficult stains as
starch-based stains and blood stains, even at low
temperatures.
Starch-based stains include chocolate stains, as well as
typical kitchen stains such as mayonnaise, mustard, ice-cream,
dairy products.
Such stains are very difficult to remove at low temperature,
and the present invention provides for a method of treating
textiles at all temperatures. including at low temperature,
wherein a detergent composition according to the above
description is used.
The invention also encompasses a similar method for treating
fabrics to remove blood stains. and fabrics stained with stains
rich in blood.
According to the invention, a synergistic removal effect
of particulate stains is also seen. With "particulate stains"
is meant for instance peat clay, mud, high organic content
clay mainly found in socks, sportswear and the like.
3b~0 95/17495 ~ PCT/US94/14294
Mucin _ cr muci n-pro=ein base srai~:s i.~.clude femaia
secretions and :~andr:erchier stains bro:.c~:iai mucusi .
Such stains are very di~ficult t=o remove at low temperature,
and the present invention provides for a method of treating
textiles at all temperatures, including at low temperature,
wherein a detergent composition according to the above
description is used.
The method for treating fabrics is typically a laundry machine
washing operation, and can be conducted by any method well
known in the art; a particularly preferred method includes the
use of a reusable dispensing device, in which the detergent
composition is put before the washing cycle, and which is
placed in the drum of the washing machine together with the
clothes to be washed, before starting the washing machine.
WO 95/I7495 217 ~ ~ 7 ? PCT/US94/14294 ,.,...
'' 2
L
The followin_~, granular de=eraent comoositicns are prepared:
Composition: I II
45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
Malefic acrylic copolymer 4.0 2.0
CMC 0.5 0.5
*DTPMA 0.4 0.4
AE5 5.0 5.0
Perfume 0.5 0.5
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 7.0 7.0
Percarbonate (14.0 AvOx) 20.0 20.0
Soil release polymer 0.3 0.3
Savinase (4KNPU) 1.4 1.4
Lipolase (100,000LU) 0.4 0.4
Cellulase C' . 6 0 . 6
Termamyl (60KU) 0.6 0.6
Silicone antifoam particle 5.0 5.0
Brightener 0.2 0.2
Density: 850g/L
* DTPMA = Diethylenetriaminepent:amethy lene phosphonic acid.
217~~~97
CVO 95/17495 PCT/US94/14294
23
Comcositic~ III IV V
Zeolite A 15.0 15.0
Na2S04 0.0 5.0
3.0 3.0
DTPMA 0.4 0.5
CMC 0.9 0.4
Malefic acryliccopolymer 4.0 4.0
95AS 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Na2 Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC 0.5
Malefic acryliccopolymer 2.0
Na2 Carbonate 9.0 7.0 7.0
Perfume 0.3 0.3 0.5
AE7 4.0 4.0 4.0
p,E 3 2 . 0 2 . 0 2 .
0
Malefic acryliccopolymer 3.0
SKS 6 12.0
Citrate 10.0 0.0 8.0
Na Bicarbonate 7.0 3.0 5.0
Na2 Carbonate 8.0 5.0 7.0
pVp 0 0.5 0
PVPVI 0.2 C 0.25
7
? ~ ' ~ ~ ~ ~
WO 95117495 PCT/US94114294
.---
24
p'~O ~. 3 0 'J
.
4
Savinase (4.Gi:NPU/gi y.0 1.0 1.30
Lipolase (100.OOOLU/L) 0.4 0.4 0.4
Amylase (Termamyl) 60KNU/g 0.5 0.6 0.6
Carezyme 0.6 0.5 0.6
Silicone antifoam granule 5.0 5.0 5.0
Dry mixe d Na2 Sulfate 0.0 9.0 0.0
Percarbo nate 0.1 - -
Balance (Moisture and Miscellaneous)100.0 100.0 100.0
Density: 700g/L
~~ ~ ~C~~~
-CVO 95117495 PCT/US94/14294
25
- VI VII VIII IX X XI
Compositio:::
Zeolite A i5.0 15.0 15.0 15.0 15.0 15.0
Na2S04 0.0 5.0 0.0 0 0 0
LAS 3.0 3.0 3.0 3 3 3
DTPMA 0.4 0.4 0.4 0.4 0.4 0.4
CMC 0.4 0.4 0.4 0.4 0.3 0.3
Malefic acrylic 4.0 2.0 2.0 0 0 0
copolymer
Polyaspartate 0 0 0 4 4 0
Terpolymer malefic 0 0 0 0 0 4
acid acrylic vinyl
alcohol
LAS 5.0 5.0 5.0 5 5 5
TAS 2.0 2.0 2.0 2 2 2
Na2 Silicate 3.0 3.0 4.0 4 4 4
Zeolite A 8.0 8.0 8 5 6 8
Na2 Carbonate 8.0 8.0 4.0 4 4 4
Perfume 0.3 0.3 0.3 . 0.3 0.3 0.3
p,E ~ 2 . 2 . 0 2 . 2 . 2 2
0 0 0
2.0 2 2 2
Na2 Citrate 5.0 0.0 2.0 5 5 5
Na Bicarbonate 3.0 0.0 0 0 0
Na2 Carbonate 8.0 15.0 10.0 8 8 8
TAED 6.0 2.0 5.0 5 5 5
Percarbonate 14 20.c) 10.0 5 5 5
Polyethylene oxide 0.2 0 0 0
WO 95/17495 ~ ~ 7 ~ ~~ Q 7 PCT/US94/14294 ..,
26
BentonitP 10.0 0 0 0
Savinase (4.0 1.0 1.0 1.0 1.0 1.0 1.0
KNPU/g)
Lipolase (100.000 0.4 0.4 0.4 0.4 0.4 0.4
LU/L)
Amylase (Termamyl) 0.6 0.5 0.6 0.6 0.4 0.4
60KNU/g
Carezyme 0.6 0.6 0.6 0.6 0.3 0.2
Silicone antifoam 3.0 4.0 5 4 5 5
granule
Dry mixed Na2 0.0 3.0 0.0 0 0 0
Sulfate
Balance (Moisture 100.0 100.0 100.0 100.0 100.0 100.0
and Miscellaneous)
Density: 700-850 g/L
..
-~~'O 95/17495 PCT/US94/14294
L
Composit~on~ XII XIII XIV
Zeolite A 30.0 22.0 6.0
Na Sulfate 19.0 10.0 7.0
Malefic acrylic copolymer 3.0 3.0 6.0
LAS 14.0 12.0 22.0
45AS 8.0 7.0 7.0
Na2Silicate 1.0 5.0
Soap
2.0
Brightener 0.2 0.2 0.2
Na2 Carbonate 8.0 16.0 20.0
DTPMA 0.4 0.4
p,E~ 1.0 1.0 1.0
PVPVI 0.25 0 0.1
pip 0.2 0 0.2
pVp 0 0.5 0
Savinase (4.0 KNPU/g) 1.0 , 1.0 1.0
Lipolase (100.000 LU/L) 0.4 0.4 0.4
Amylase (Termamyl) 0.1 0.3 0.5
60KNU/g
NOBS 6.1 4.5
Percarbonate 1.0 3.0 3.0
Dry mixed Na2 Sulfate 6.0
Balance/Miscellaneous 100 100 100
Density: 500-600 g/L
WO 95/17495 ~' ~ ~ ~ 9 7 ~ s PCT/US94/14294
EXA.NiPLES -
Example 1: blood based stain removal
Launderometer test
2g/1 finished product
40°C/8°H water
40 minutes wash cycle
STAIN TYPE PC3 AMYLASE ~ STAIN REMOVAL
Meat Pate 14~ 0.5Q 80~
Meat Pate - 0.5~ 24~
Meat Pate 14=s - 45~-
Example 2: stain removal from chocolate ice cream
Conditions
Washing machine test
40°C/8°H Hard Water
2Kg mixed ballast load
STAIN TYPE PERCARBONATE AMYLASE ~ STAIN REMOVAL
Chocolate ice cream 14.5 - 40
Chocolate ice cream - 0.25v 25
Chocolate ice cream 14.5 0.250 75
Example 3: blood based stain removal
Conditions
Sotax test
40°C/15°H Hard Water
40 minutes wash cycle
No ballast load
STAIN TYPE PERCARBONATE AMYLASE STAIN REMOVAL
Beef stew 18~ - 40=
Beef stew - 0.6~ 20=
Beef stew 18= 0.6. 77
21 766
i7
~O 95/17495 PCT/US94/14294
29
Example 4_:-:chocolate cream stain removal
ice
Conditions
Launderometer
2 g/1 product
40C/8H water
40 min. wash cycle
Stain type ~ Percar- ~ amylase $ stain
bona to removal
Low fat choc ice cream 19 - 35
with choc sauce
Low fat choc ice cream - 0.5 20
with choc sauce
Low fat choc ice cream 19 0.6 70
with choc sauce
Low fat choc ice cream 19 0.3 60
with choc sauce
Low fat choc ice cream - 0.3 15
with choc sauce
Low fat choc ice cream 19 0.03 35
with choc sauce
Low fat choc ice cream - 0.03 -
with choc sauce
Example 5 . particulate
stain rs~moval
Conditions as mentioned 4
under Exaimple
Stain type $ Percar- $ amylase $ stain
bona.te removal
Peat clay 1~ - 25
Peat clay - 0.6 35
Peat clay 19 0.6 75
Peat clay - 0.03 -
Peat clay 19 0.03 25
WO 95/17495 7 ~ ~~ PCT/US94114294
In ail oS the abcve ~es~s the measurements were made using a
colour eye spe~~rcp~:o~cme~er.
The following formula was used to calculate stain removal:
Washed stain - Unwashed stain
x 100 = ~ stain removal
Clean fabric - Unwashed fabric
(The standard LAB calculation; were used in the above
experiment)
The above clearly shows that the combined use of percarbonate
and amylase provides a synergetic effect on the removal of
difficult stains, such as blood stains and starch-based stains
like chocolate and particulate stains like peat clay as well .
2176697
-.WO 95/17495 PCT/US94/14294
31
Example ~ :. chocolate ice cream removal
atain
Conditicns
Launderometer .
amylase present at 0.1=~ in every testing
2 g/1 product
40C/8H water
40 min wash cycle
Stain type ~perc:ar- ~ per- ~ pro- ~ stain
bonate borate tease removal
Full cream ice cream and 20 - - 30
choc sauce
Full cream ice cream and 20 - 20 70
choc sauce
Full cream ice cream and - - 20 20
choc sauce
Full cream ice cream and 20 - 5 55
choc sauce
Full cream ice cream and - - 5 15
choc sauce
Full cream ice cream and 2.5 17.5 20 30
choc sauce
Full cream ice cream and 2.5 17.5 - 10
choc sauce
C__
