Note: Descriptions are shown in the official language in which they were submitted.
WO 95128466 PCT/U59510369Z
DETERGENTS CONTAINING A SURFACTANT AND A DELAYED RELEASE ENZYME
This invention relates to detergent compositions containing a surfactant and
an
enzyme, wherein a means is provided for delaying the release to the wash
solution of
said enzyme relative to the release of said surfactant.
The satisfactory removal of enzyme sensitive soilslstains such as blood, egg,
chocolate and gravy from soiled/stained substrates is a particular challenge
to the
formulator of a detergent composition for use in a washing method such as a
laundry
or machine dishwashing method.
Commonly, the removal of such soils/stains has been enabled by the use of
enzyme
components, proteolytic, amylolytic, cellulolytic and lipolytic enzymes.
The Applicants have now found that where a composition containing both a
surfactant
and an enzyme is employed, and wherein a means is provided for delaying the
release
to a wash solution of the enzyme relative to the release of the surfactant
enhanced
stain/soil removal may be obtained.
The Applicants have in addition found that stain/soil removal benefits may be
obtained when a soiled substrate is pretreated with a solution containing a
surfactant,
and optionally a water soluble builder, prior to being washed in a method
using an
enzyme 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 stain removal.
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
surfactant and optionally a water soluble builder, prior to washing with an
enzyme
containing detergent product.
CA 02187306 1999-07-12
2
Summary of the Invention
According to the present invention there is provided a detergent composition
containing (a) a surfactant; (b) an enzyme; (c) a water soluble builder; and
(d) an organic peroxyacid bleach source; wherein a means is provided for
delaying
the release to a wash solution of said enzyme and said organic peroxyacid
bleach
source relative to the release of said surfactant and said water soluble
builder such
that in the TSO test method herein described, the time to achieve a
concentration that
is 50% of the ultimate concentration of said surfactant is less than 60
seconds; the
time to achieve a concentration that is 50% of the ultimate concentration of
said
enzyme is more than 90 seconds; the time to achieve a concentration that is
50% of
the ultimate concentration of said water soluble builder is less than 60
seconds; the
time to achieve a concentration that is 50% of the ultimate concentration of
the
peroxyacid bleach is more than 180 seconds.
According to another aspect of the present invention there is provided a
washing
method comprising the steps of:
(1) applying an enzyme-free solution of a composition containing a surfactant
to
a soiled substrate;
(2) allowing said solution to remain in contact with said soiled substrate for
an
effective time interval;
WO 95/28466 PGT/U595/03692
3
(3) washing said soiled substrate using a washing method involving use of an
enzyme-containing detergent composition.
The detergent compositions of the invention contain 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 0.13o to 606 by weight.
More
preferred levels of incorporation of surfactant are from 1 ~ to 353'o by
weight, most
preferably from 1 % to 20~ by weight.
The surfactant is preferably formulated to be compatible with any enzyme
components
present in the composition. In liquid or gel compositions the surfactant is
most
preferably formulated such that it promotes, or at least does not degrade, the
stability
of any enzyme in these compositions.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin
and
Heuring on December 30, 1975. Further examples are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of
suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on
March
31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used
in combination with one or more anionic and/or nonionic surfactants.
Essentially any anionic surfactants useful for detersive purposes can be
included in the
compositions. These can include salts (including, for example, sodium,
potassium,
ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine
salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate
surfactants.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
W0 95128466 4 PCT/US95103692
''~18730b ,
4
monoesters of sulfosuccinate (especially safurated and unsaturated C12 C18
monoestersj diesters of sulfosuccinate (especially saturated and unsaturated
C~ 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.
Anionic sulfate surfactants suitable for u:e herein include the linear and
branched
primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates,
alkyl phenol
ethylene oxide ether sulfates, the Cg-C1-r acyl-N-(C1-Cq alkyl) and -N-(C1-C2
hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as
the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein].
. ~,- .- - " ... .. ,., .
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the Cb-Clg 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-Clg 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 surfactants suitable for use herein include the salts of Cg-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C~ primary or
secondary
alkane sulfonates, C6-C2q olefn sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl 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.
W0 95128466 ; PCT/US95/03692
Preferred alkyl ethoxy carboxylates for use herein include those with the
formula
RO(CH2CH20)x CH2C00-M+ wherein R is a C6 to Clg alkyl group, x ranges from
O to 10, and the ethoxylate distribution is such that, on a weight basis, the
amount of
material where x is 0 is less than about 20 % , and the amount of material
where x is
greater than 7, is less than about 25 % , the average x is from about 2 to 4
when the
average R is C13 or less, and the average x is from about 3 to 10 when the
average R
is greater than Clg, and M is a cation, preferably chosen from alkali metal,
alkaline
earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably
from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The
preferred alkyl ethoxy carboxylates are those where R is a C12 to Clg alkyl
group.
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include
those
having the formula RO-(CHRl-CHR2-O)-Rg wherein R is a C6 to Clg alkyl group, x
is from I 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.
Preferred soap surfactants are secondary soap surfactants which contain a
carboxyl
unit connected to a secondary carbon. The secondary carbon can be in a ring
structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted
cyclohexyl
carboxylates. The secondary soap surfactants should preferably contain no
ether
linkages, no ester linkages and no hydroxyl groups. There should preferably be
no
nitrogen atoms in the head-group (amphiphilic portion). The secondary soap
surfactants usually contain 11-15 total carbon atoms, although slightly more
(e.g., up
to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
secondary
soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary
carboxyl
materials of the formula R3 CH(R4)COOM, wherein R3 is CH3(CH~x and
R4 is CHg(CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer
WO 95128466 PCTIItS95103692
..
6
from 4 to 10 and the sum of (x + y) is d-10, preferably 7-9, most preferably
8.
B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl sulistituent is on a ring hydrocarbyl unit,
i.e., secondary soaps of the formula RS-R6-COOM, wherein RS is C~-C10
preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as
benzene,
cyclopentane and cyclohexane. (Note: RS can be in the ortho, meta or para
position relative to the carboxyl on the ring.)
C. Still another preferred class of secondary soaps comprises secondary
carboxyl
compounds of the formula CHg(CHR)k-(CH2)m (CHR)n-
CH(COOM)(CFiR)o-(CH2)p (CHR)Q CH3, wherein each R is C1-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-1-nonanoic acid, 2-butyl-1-
octanoic acid and 2-pentyl-1-heptanoic acid.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(Rl) CH2 COOM, wherein R is a CS-C17 linear or branched alkyl or alkenyl
group,
Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the
myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
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.
a
PCT/ITS95/03692
WO 95128466
7
Nonionic Col hvdroxv fatty acid amide surfactant __
- Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, CI-Cq, hydrocarbyl, 2-hydroxy ethyl, 2-
~ hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more
preferably CI or
C2 alkyl, most preferably CI alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl,
preferably straight-chain CS-C19 alkyl or alkenyl, more preferably straight-
chain C9-
CI~ alkyl or alkenyl, most preferably straight-chain CI I-CIA alkyl or
alkenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from a
reducing sugar in a reductive aminatlon reaction; more preferably Z is a
glycityl.
Nonionic condensates of alkyl_ hn enols
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use herein. In general, the polyethylene oxide
condensates
are preferred. These compounds include the condensation products of alkyl
phenols
having an alkyl group containing from about 6 to about 18 carbon atoms in
either a
straight chain or branched chain configuration with the alkylene oxide.
Nonionic ethoxyiated alcohol surfactant
The alkyl ethoxylate condensation produce 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.
Nnninn;r Pthoxylated/ rn oooxyl to ed fatty alcohol surfactant
The ethoxylated C6-Clg fatty alcohols and C6-Clg mixed
ethoxylated/propoxylated
fatty alcohols are suitable surfactants for use herein, particularly where
water soluble.
Preferably the ethoxylated fatty alcohols are the CIO-Clg ethoxylated fatty
alcohols
with a degree of ethoxylation of from 3 to 50, most preferably these are the
C12-C18
R'O 95/28466 ~ ~ ~ 7.3 a ~ PCTIUS95~~3692
8
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the
mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of
from 10
to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of .
propoxylation of from 1 to 10.
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.
r
'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 nroducts with RroRvlene oxide/ethylene diamine adduc
c
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine are suitable for use herein.
The
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight of
from about 2500 to about 3000. Examples of this type of nonionic surfactant
include
certain of the commercially available TetronicTM compounds, marketed by BASF.
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from
about
6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms
and a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about
1.3 to
about 10, preferably from about 1.3 to about 3, most preferably from about 1.3
to
about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon
atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the
glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-
, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or
galactoside.)
The intersaccharide bonds can be, e.g.,~between the one position of the
additional
saccharide units and the 2-, 3-, 4-, andlor 6-a positions on the preceding
saccharide
units. -
W O 95128466 PCT/US95/03692
i
9
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10
to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10,
preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most
preferably from
1.3 to 2.7. The glycosyl is preferably derived from glucose.
Nonionic fatty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those having the
formula:
R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably
from
9 to 17 carbon atoms and each R7 is selected from the group consisting of
hydrogen,
Cl-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of
from
1 to 3.
Amnhoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxylic acids.
A suitable example of an alkyl aphodicarboxylic acid for use herein is
Miranol(TM)
C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful herein include those compounds having the formula
R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8 to
26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon
atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each
RS is
an alkyl or hydyroxyalkyl group containing from I to 3, preferably from 1 to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable
1,
W0 95128466 PCTIUS95103692
.. ..
1D
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 C10-Clg alkyl dimethyl
amine
oxides and Cg-Clg alkoxy ethyl dihydroxyethyI amine oxides. Examples of such
materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,
dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,
dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl
dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-
hydroxyoctadecylamine oxide. Preferred are Cl0-CIg alkyl dimethylamine oxide,
and
C10-18 acylamido alkyl dimethylamine oxide.
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 surfactanu are exemplary zwitterionic
surfactants for
use herein.
The betaines useful herein are those compounds having the formula
R(R')2N'i'RZCOO- wherein R is a C6-CIg hydrocarbyl group, preferably a C10-C16
alkyl group or C10-16 acylamido alkyl group, each Rl is typically CI-Cg alkyl,
preferably methyl,m and R2 is a C1-CS hydrocarbyl group, preferably a C1-Cg
allryIene group, more preferably a Cl-CZ alkylene group. Examples of suitable
betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl
betaine; C12-14 acylamidopropylbetaine; Cg_14 acyIamidohexyldiethyl betaine;
4[C14_16 acylmethylamidodiethylammonio]-1-carboxybutane; C16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine. Preferred betaines are C12_lg dimethyl-ammonio
hexanoate and the C10-18 acylamidopropane (or ethane) dimethyl (or diethyl]
betaines. Complex betaine surfactants are also suitable for use herein.
CA 02187306 1999-07-12
1:1
Sultaine surfactant
The sultaines useful herein are those compounds having the formula
(R(R1)2N'~R2S03- wherein R is a C6-Clg hydrocarbyl group, preferably a Clp-C16
alkyl group, more preferably a C 12-C 13 alkyl group, each R 1 is typically C
1-C3
alkyl, preferably methyl, and R2 is a C1-CE; hydrocarbyl group, preferably a
CI-C3
alkylene or, preferably, hydroxyalkylene group.
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 CUrfar~tS
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 wherein the
remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups.
The detergent compositions contain an enzyme. Suitable enzymatic materials
include
the commercially available lipases, amylases, neutral and alkaline proteases,
esterases,
cellulases, pectinases, lactases and peroxidases conventionally incorporated
into
detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570
and
3,533,139.
Preferred commercially available protease enzymes include those sold under the
trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries
A/S (Denmark), those sold under the trademarks. Maxatase, Maxacal and Maxapem
by
Gist-Brocades, those sold by Genencor International, and those sold under the
trademarks Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
CA 02187306 1999-07-12
12
incorporated into the compositions in accordance with the invention at a level
of from
0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special
strain of
B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially available amylases include for example, those sold under the
trademark
Rapidase by Gist-Brocades, and those sold under the 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 % to 2 % active
enzyme by
weight of the composition.
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., ThermomX~es sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali~enes or ~seudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein.
A preferred lipase is derived from Pseudomonas Rseudoalcal~enes, which is
described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from mic la
]anugino~ and expressing the gene in i 1 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 trademark Lipolase. This
lipase
is also described in U.S. Patent 4,810,414, kluge-Jensen et al, issued March
7, 1989.
Where the enzyme is a protease; the ultimate amount in a typical wash solution
is
from 0.1 to 100 KNPU, but preferably is from 0.5 to 50 KNPU, more preferably
from 3 to 30 KNPU and most preferably frorn 6 to 30 KNPU.
Where the enzyme is an amylase, the ultimate amount in a typical wash solution
is
from 1 to 200 KNU, but preferably is from 10 to 100 KNU, more preferably from
40
to 80 KNU.
WO 95128466 2 ~ ~ ~ ~ p ~ PCT/US95/03692
13
Where the enzyme is a lipase, the ultimate amount in a typical wash solution,
from 1
to 300 KLU, but preferably is from 10 to 200 KLU, more preferably from 10 to
100
- KLU.
Where the enzyme is a cellulase, the ultimate amount in the wash is typically
from 10
to 1200 CEVU, but preferably is from 50 to 1000 CEVU, more preferably from 80
to
500 CEVU.
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 635, 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 0.0135 to about 61 by weight, of chlorine bleach scavengers, added to
prevent
chlorine bleach species present in many water supplies from attacking and
inactivating
the enzymes, especially under alkaline conditions. While chlorine levels in
water may
be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the
available
chlorine in the total volume of water that comes in contact with the enzyme
during
washing is usually large; accordingly, enzyme stability in-use can be
problematic.
Suitable chlorine scavenger anions are widely available, and are illustrated
by salts
containing ammonium rations or sulfite, bisuIfite, thiosuIfite, thiosulfate,
iodide, etc.
Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine
tMEA), and mixtures thereof can likewise be used. Other conventional
scavengers
such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as
sodium
perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate,
as
well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate,
lactate,
malate, tartrate, salicylate, etc. and mixtures thereof can be used if
desired.
VVO 95128466 v~ ' PCTfUS95103692
14
In an essential aspect of the invention a means is provided for delaying the
release to a '
wash solution of the enzyme relative to the release of the surfactant.
Said means may comprise a means for delaying the release of the enzyme to the
wash
solution.
Alternatively said means may comprise a means for enhancing the rate of
release of
the surfactant to the solution.
~ved rate of release - means _ _
The delayed release means can include coating the enzyme with any suitable
component with a coating designed to provide the delayed release. The coating
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 1:99
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, microcrystalline
waxes,
gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline 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
2fo to
1096, (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 provie composite inorganic saltlorganic binder coatings. Suitable binders
include
W O 95128466 PCT/US95/03692
the CI0-C2p alcohol ethoxylates containing from 5 - 100 moles of ethylene
oxide per
mole of alcohol and more preferably the C IS-C20 Pnm~Y alcohol ethoxylates
containing from 20 - I00 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials.
Polyvinytpyrrolidones
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 CIO-C20 alcohol ethoxylates
containing from 5 - 100 moles of ethylene oxide per mole. Further examples of
binders include the C10-C2p mono- and diglycerol ethers and also the CI0-C20
fatty
acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose 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 spray
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 any enzyme containing particulate to
control its
solubility and rate of release. Suitable protocols could include compaction,
mechanical injection, manual injection, and adjustment of the solubility of
the bleach
compound by selection of particle size of any particulate component.
Whilst the choice of particle size will depend both on the composition of the
particulate component, and the desire to meet the desired 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.
WO 95128466 PCT/US95103692
16
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.
Ettitanaed rate of release - means
All suitable means for enhancing the rate of release of the surfactant 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.
Other means of providing the required delayed release include mechanical means
for
altering the physical characteristics of the water-soluble builder to enhance
its
solubility and rate of release.
A suitable protocol could include deliberate selection of the particle size of
any
surfactant 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 particle 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 surfactant, 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 rate of release - kinetic parameters
The release of the enzyme relative to the surfactants) is such that in the T50
test
method herein described the time to achieve a concentration that is 50~ of the
ultimate concentration of surfactant is less than 60 seconds, preferably less
than 50
R'O 95128466 PC!'1US95/03692
17
seconds, more preferably less than 40 seconds, and the time to achieve a
concentration that is 50% of the ultimate concentration of said enzyme is more
than
90 seconds, preferably more than 120 seconds, more preferably more than 150
seconds.
The ultimate wash concentration of surfactant is typically from 0.005% to
0.4%,
preferably from 0.05 % to 0.35 % , more preferably from 0.1 % to 0.3 % .
The ultimate wash concentration of the en:,yme is typically from 0.000001 % to
0.01 % by weight of active enzyme, b:a preferably is from 0.00001 % to 0.001 %
,
more preferably from 0.00005 % to O.Ov(~5 % .
The delayed release kinetics herein are defined with respectto a 'TA test
method'
which measures the time to achieve A% of the ultimate concentration 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 ultimate
concentration/level is
taken to be the concentration/level =trained 10 minutes after addition of the
composition to the water-filled beaker.
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
conductrimetric methods.
Alternatively, methods involving removing 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 titre, and then determining the concentration
of the
WO 95128466 . PCT/US95103692
18
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.
Additional detergent com o~ nents
The detergent compositions of the invention may also contain additional
detergent
components. The precise nature of these additional components, and levels of
incorporation thereof will depend on the physical form of the composition, and
the
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
builders, organic polymeric compounds, bleaches, suds suppressers, lime soap
dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors.
Laundry compositions can also contain, as additional detergent componenu,
softening
agents.
Water-soluble builder c~m_~und
The detergent compositions of the present invention may contain a water-
soluble
builder compound, typically present at a level of from 1 % to 80% by weight,
preferably from 103'o to 70~ by weight, most preferably from 20% to
60°k by weight
of the composition.
CA 02187306 1999-07-12
19
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo~ or copolymeric polycarboxylic
acids or
their salts in which the polycarboxylic acid comprises at least two carboxylic
radicals
separated from each other by not more that 'two carbon atoms, carbonates,
bicarbonates, borates, phosphates, silicates and mixtures of any of the
foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing
two carboxy groups include the water-soluble salts of succinic acid, malonic
acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid
and fumaric acid, as well as the ether carbox:ylates and the sulfinyl
carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well .as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates
described in CA 973,771, issued September 2, 1075, and the oxypolycarboxylate
materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated
pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyelopentadienide pentacai~boxylates, 2,3,4,5-
tetrahydrofuran - cis,
cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates,
2,2,5,5-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,-'i,6-hexane - hexacarboxylates
and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include rnellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
R'O 95128466 PCT/US95103692
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up
to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can
produce borate under detergent storage or wash conditions can also be used but
are
not preferred at wash conditions less that about 50°C, especially less
than about
40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with
ultra-fine
calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from
about
6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an Si02:
Na20 ratio
of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0
ratio being
most preferred. The silicates may be in the form of either the anhydrous salt
or a
hydrated salt. Sodium silicate with an Si02: Na20 ratio of 2.0 is the most
preferred
silicate.
Silicates are preferably present in the detergent compositions in accord with
the
invention at a level of from 5% to 50~ by weight of the composition, more
preferably from 109 to 40% by weight.
~tially soluble or insoluble builder compound
VV0 95128466 ~ ~~ ~ ~ ~ ~ ~ PCT/US95103692
ai
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-
Na2Si20g, available from Hoechst AG as NaSKS-6.
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)yj.
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°1 to 28'Yo, more preferably from 189& to 22% water
in bound
form.
The aluminosilicate ion exchange materials can be naturally occurring
materials, but
are preferably synthetically derived. Synthetic crystalline aluminosilicate
ion exchange
materials are available under the designations Zeolite A, Zeolite B, Zeolite
P, Zeolite
X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [A102) 12 (Si02)12j. xH20
W 0 95/28466 ' PCTlUS95f03692
22
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
I(A102)86~Si02)1061. 276 H20.
The detergent compositions of the invention contain as a preferred optional
component
an organic peroxyacid bleach source. The peroxyacid bleach source may be the
organic peroxyacid per se, or it may be a peroxyacid bleach precursor
compound.
Where the source is a peroxyacid ble3ct precursor compound, the production of
the
peroxyacid occurs by an in situ reaction of the precursor with a source of
hydrogen
peroxide. Suitable sources of hydrogen peroxide include inorganic perhydrate
bleaches.
The organic peroxyacid bleach source is preferably also provided with means
for
delaying its release to the wash solution, such that in the T50 test, the time
to achieve
a concentration that is 509& of the ultimate concentration of the peroxyacid
bleach is
more than 180 seconds, preferably more than 240 seconds. Any of the means
herein
described for achieving the delayed release can be employed.
P~.vacid bleach precursors _. __
Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid
sources.
Peroxyacid bleach precursors are normaily incorporated at a level of from 1 %
to 20%
by weight, more preferably from 2~ to 5'Yo by weight, most preferably from 396
to
109b by weight of the compositions.
Suitable peroxyacid bleach precursors typically contain one or more N- or O-
acyl
gmups, which precursors can be selected from a wide range of classes. Suitable
classes include anhydrides, esters, imides and acylated derivatives of
imidazoles and
oximes, and examples of useful materials within these classes are disclosed in
GB-A-
1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-
A-
0170386. The acylation products of sorbitol, glucose and all saccharides with
benzoylating agents and acetylating agents are also suitable.
R'O 95!28466 ~ ~ ~. 7 3 0 6 PCT/US95/03692
i
as
Specific O-acylated precursor compounds include 2,3,3-tri-methyl hexanoyl
oxybenzene sulfonates, benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl
oxybenzene sulfonates, monobenzoyltetraacetyl glucose benzoyl peroxide and
cationic
derivatives of any of the above, including the alkyl ammonium derivatives and
pentaacetyl glucose. Phthalic anhydride is a suitable anhydride type
precursor.
Specific cationic derivatives of the O-acyl precursor compounds include 2-
(N,N,N-
trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride, and any of
the
alkyl ammonium derivatives of the benzoyl oxybenzene sulfonates including the
4-
(trimethyl ammonium) methyl derivative.
Useful N-acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-
1246338.
Preferred precursor compounds of the imide type include N-benzoyl succinimide,
tetrabenzoyi ethylene diamine, N-benzoyl substituted ureas and the N-,N,N1N1
tetra
acetylated alkylene diamines wherein the alkylene group contains from 1 to 6
carbon
atoms, particularly those compounds in which the alkylene group contains 1, 2
and 6
carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
N-acylated precursor compounds of the lactam class are disclosed generally in
GB-A-
955735. Whilst the broadest aspect of the invention contemplates the use of
any
lactam useful as a peroxyacid precursor, preferred materials comprise the
caprolactams and valerolactams.
Suitable N-acylated lactam precursors have the formula:
0
II
Rs-0 N-CHa-~ Hz
~CHz-ECHa In
wherein n is from 0 to 8, preferably from 0 to about 2, and R6 is H, an alkyl,
aryl,
alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted
phenyl
group containing from 6 to 18 carbon atoms
W0 95/28466 PCTIUS95103692
24
Suitable caprolactam bleach precursors are of the formula:
0
II
C - CH - CH
!I I
i i ~ CHz
Rl - C -- N
CHZ -=CH2
wherein RI is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
1 to
12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably Rl is
phenyl.
Suitable valero lactams have the formula:
O
o c - cxa - cH2
Rl - C - N
CHZ - CHz
wherein Rl is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
1 to
12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred
embodiments, R1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-
trimethylpentyl,
decenyl and mixtures thereof.
The most preferred materials are those which are normally solid at <
30°C,
particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl
caprolactam
and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl,
aryl and
allcoxy derivatives.
Caprolactam and valerolactam precursor materials wherein the R1 moiety
contains at
least 6, preferably from 6 to 12, carbon atoms provide peroxyacids on
perhydrolysis
W095128466 218 7 3 0 6 pCT~S9~03692
of a hydrophobic character which afford nucleophilic and body soil clean-up.
Precursor compounds wherein R1 comprises from 1 to 6 carbon atoms provide
hydrophilic bleaching species which are particularly efficient For bleaching
beverage
stains. Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero
lactams,
typically at weight ratios of I:5 to 5:1, preferably 1:1, can be used herein
for mixed
stain removal benefits.
Highly preferred caprolactam and valerolactam precursors include benzoyl
caprolactam, nonanoyl capro-lactam, benzoyl valerolactam, nonanoyi
valerolactam,
3,5,5-trimethylhexanoyi caprolactam, 3,5,5-trimethylhexanoyl valerolactam,
octanoyl
caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl
valerolactam,
undecenoyl caprolactam, undecenoyl valerolactam, (6-
octanamidocaproyl)oxybenzene-sulfonate, (6-
nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)-
oxybenzenesulfonate, and mixtures thereof. Examples of highly preferred
substituted
benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam,
ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl
caproIactam,
propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl
valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tent-
butylbenzoyl
caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam,
pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl
valerolactam,
ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl
caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactam,
isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoyl
valerolactam, tert-butoxybenzoyl caprolactam, tent-butoxybenzoyl valerolactam,
pentoxybenzoyl caproIactam, pentoxybenzoyl valerolactam, hexoxybenzoyl
caprolactam, hexoxybenzoyl valerolactam, 2,4,6-trichlorobenzoyl caprolactam,
2,4,6-
trichlorobenzoyl valerolactam, pentafluorobenzoyl caprolactam,
pentafluorobenzoyl
valerolactarn, dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-
chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam, terephthaIoyl
dicaprolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl
vaIerolactam,
dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl
valerolactam, 2,4-dichlororbenzoyi valerolactam, terephthaloyl divaIerolactam,
4-
nitrobenzoyI caprolactam, 4-nitrobenzoyl valerolactam, and mixtures thereof.
R'O 95!28466 PCTIUS95103692
26
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole
and
other useful N-acyl group-containing peroxyacid precursors include N-benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Another preferred class of peroxyacid bleach activator compounds are the amide
substituted compounds of the following general formulae:
R~-C-N-R2-C-L R~-N-C-R2-C-L
0 R5 0 or R' 0 0
wherein RI is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and R5
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L
can be
essentially any leaving group. Rl preferably contains from 6 to 12 carbon
atoms. RZ
preferably contains about 4 to 8 carbon atoms. R1 may be straight chain or
branched
alkyl, substituted aryl or alkylaryl containing branching, substitution, or
both and may
be sourced from either synthetic sources or natural sources including for
example,
tallow fat. Analogous suvctural 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. 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.
The L group must be sufficiently reactive for the reaction to occur within the
optimum
time frame (e.g., a wash cycle). However, if L is too reactive, this activator
will be
difficult to stabilize For use in a bleaching composition. These
characteristics are
generally paralleled by the pKa of the conjugate acid of the leaving group,
although
exceptions to this convention are known. Ordinarily, leaving groups that
exhibit such
behavior are those in which their conjugate acid has a pKa in the range of
from 4 to
13, preferably from 6 to 1 I and most preferably from 8 to 11.
Preferred bleach pr~ursors are those wherein RI, RZ and RS are as defined for
the
amide substituted compounds and L is selected from the group consisting of:
WO 95128466 PGT/US95I03692
i
27
/~( Y /~ R3 R3Y
-0-( ( ) ) , -O-( ( J rY , and -0
O 0
-N-C-R' -N N r -N-C-CH-R4
R3 '
I
Y
R3 Y
I I
-0-C H=C-C H=C H2 -0--C H=C-C H=C HZ
O
-0-C-R~
R3 0 Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1
to 14 carbon atoms, R3 is an alkyl chair. containing from 1 to 8 carbon atoms,
R4 is
H or R3, and Y is H or a solubilizing group.
The preferred solubilizing groups are -803 M+, -C02 M+, -S04 M+,
-N+(R3) X and O <--N(R3)3 and most preferably -S03 M+ and -C02 M+
wherein R~ is an alkyl chain containing from 1 to 4 carbon atoms, M is a
cation
which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M is an alkali metal, ammonium
or
substituted ammonium ration, with sodium and potassium being most preferred,
and
X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted
that
bleach activators with a leaving group that does not contain a solubilizing
groups
should be well dispersed in the bleaching solution in order to assist in their
dissolution.
W O 95128466 - PCTlUS95103692
as
Preferred examples of bleach precursors of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfo-
nate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other preferred precursor compounds include those of the benzoxazin-type,
having
the formula:
0
NrrC-R1
including the substituted benzoxazins of the type
v
R4 II (\~/1 fI N
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl
group) and carbonyl functions.
An especiaily preferred precursor of the benzoxazin-type is:
0
N C
R'O 95128466 2 1 8 7 3 0 6 p~~g95103G92
29
Organic peroxvacids
The detergent compositions may also contain organic peroxyacids typically at a
level
of from 1 % to 15 % by weight, more preferably from 1 % to 10% by weight of
the
composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
R~ -C-N-R2-C-OOH R~ -N-C-R2-C-OOH
0 R5 0 or R5 0 0
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS
is H or an alkyl, aryl, or alkaryl group containing I to 10 carbon atoms. 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, substituted aryl or
alkylaryl containing branching, substitution, or both and may be sourced from
either
synthetic sources or natural sources including for example, tallow fat.
Analogous
structural variations are permissible for R2. The substitution can include
alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds.
RS is preferably H or methyl. R1 and RS should not contain more than 18 carbon
atoms in total. Amide substituted organic peroxyacid compounds of this type
are
described in EP-A-0170386.
Other organic peroxyacids include diperoxy dodecanedioc acid, diperoxy tetra
decanedioc acid, diperoxyhexadecanedioc acid, mono- and dipetazelaic acid,
mono-
and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic acid, and their
salts as
disclosed in, for example, EP-A-0341 947.
The compositions preferably include, as a hydrogen peroxide source, an
inorganic
perhydrate salt, most especially when the organic peroxyacid source is a
peroxyacid
bleach precursor compound.
'r
W0 95128466 PCT/US95f03692
30 -
The inorganic perhydrate salts are normally incorporated in the form of the
sodium
salt at a level of from 1 % to 40% by weight, more preferably from 2~ to 3096
by
weight and most preferably from 5 % to 25 % by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally
the alkali
metal salts. The inorganic perhydrate salt may be included as the crystalline
solid
without additional protection. For certain perhydrate salts however, the
preferred
executions of such granular compositions utilize a coated form of the material
which
provides better storage stability for the perhydrate salt in the granular
product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaB02H202.3H20.
Sodium percarbonate, which is a preferred perhydrate for inclusion in
detergent
compositions in accordance with the invention, is an addition compound having
a
formula corresponding to 2Na2C03.3H202, and is available commercially as a
crystalline solid. The percarbonate is most preferably incorporated into such
compositions in a coated form which provides in product stability.
A suitable coating material providing in product stability comprises mixed
salt of a
water soluble alkali metal sulphate and carbonate. This coating however allows
for
rapid release of the percarbonate bleach to the wash solution and is therefore
not a
suitable means for providing delayed release of the percarbonate bleach into a
wash
solution. 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 form 0.1 to 3, preferably n is
from
0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in
the
detergent compositions herein.
W0 95/28466 PCT1US95/03692
31
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 catalytically effective amount in the
compositions and
processes herein. By "catalytically effective amount" is meant an amount which
is
sufficient, under whatever comparative test conditions are employed, to
enhance
bleaching and removal of the stain or stains of interest from the target
substrate.
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 longer wash cycles than others. Some users elect to
use
very hot water; others use warm or even cold water in fabric laundering
operations.
Of course, the catalytic performance of the bleach catalyst will be affected
by such
considerations, and the levels of bleach catalyst used in fully-formulated
detergent and
bleach compositions can be appropriately adjusted. As a practical matter, and
not by
way of limitation, the compositions and processes herein can be adjusted to
provide
on the order of at least one part per ten million of the active bleach
catalyst species in
the aqueous washing liquor, and will preferably provide from about 1 ppm to
about
200 ppm of the catalyst species in the laundry liquor. To illustrate this
point further,
on the order of 3 micromolar manganese catalyst is effective at 40°C,
pH 10 under
European conditions using perborate and a bleach precursor (e.g., benzoyl
caprolactam). An increase in concentration of 3-5 fold may be required under
U.S.
conditions to achieve the same results. Conversely, use of a bleach precusor
and the
manganese catalyst with perborate may allow the formulator to achieve
equivalent
bleaching at lower perborate usage levels than products without the manganese
catalyst.
The bleach catalyst material herein can comprise the free acid or be in the
form of any
suitable salts.
WO 95128466 ~ ~ g ~ 3 ~ ~ PCT/US95103692
32
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 rations,
an
auxiliary metal ration having little or no bleach catalytic activity, such as
zinc or
aluminum rations, and a sequestrant having defined stability constants for the
catalytic
and auxiliary metal rations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such
catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these
catalysts
include MnTV2(u-O)3(1,4,7-trimeth fl-1.4,7-triazacyclononane)2-(PF6)2,
MnIII2(u-
O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-
0)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u_O)1(u_OAc)2_(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof. Others are
described in European patent application publication no. 549,272. Other
ligands
suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-
methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-
1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as
appropriate for the present invention. For examples of suitable bleach
catalysts see
U.S. Pat. 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 (II), (III), and/or (IV) with a ligand which is a
non-
carboxylate polyhydroxy compound having at least three consecutive C-OH
groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol,
arabitol,
adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
Iigands are of the formula:
WO 95128466 PCTIUS95/03692
33
R2 R3
R~-N=C-B-C=N-R4
wherein RI, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected
from O, S.
CRSR6, NR~ and C=O, wherein R5, R6, and R~ can each be H, alkyl, or aryl
groups, including substituted or unsubstituted groups. Preferred ligands
include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triaaole
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)CI2,
Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II)
perchlorate, Co(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridylamine)
copper(II)
perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures
thereof.
Other examples include Mn gluconate, Mn(CFgS03)2, Co(NH3)SCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including
N4MnIn(u-O)2Mn~N4)-1'and [BipY2MnIII(u_O)2MnIVbipY27-(C104)g.
The bleach catalysts of the presentinvention 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), (Ill], (IV) and/or (V) 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 cations
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
alltaline 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.
WO 95128466 2 ~ 8 7 3 0 b PCT~S95/03692
i
34
In an alternate mode, the 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 Iigand over the manganese, and mole
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 the bleach-catalyzing manganesecomplexes of the
present
invention 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 ration. Likewise,
the
oxidation state of the manganese ration during the catalytic process is not
known with
certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to
the
ligands' possible six points of attachment to the manganese ration, it may be
reasonably speculated that multi-nuclear species andlor "cage" structures may
exist in
the aqueous bleaching media. Whatever the form of the active Mniigand species
which actually exists, it functions in an apparently catalytic manner to
provide
improved bleaching performances on stubborn stains such as tea, ketchup,
coffee,
blood, and the like.
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-porphyrin catalysts), U.S.
4,728,455
(manganeselmultidentate Iigand catalyst), IT.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 (manganeselIigand 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 (cheIants
with
manganese rations and non-catalytic metal rations), and U.S. 4,728,455
(manganese
gluconate catalysts).
l~wy metal ion seguesttant
W 0 95128466 PGT/US95/03692
i
The detergent compositions of the invention may contain a heavy metal ion
sequestrant. By heavy metal ion sequestrant it is meant herein components
which act
to sequester (chelate) heavy metal ions. These components may also have
calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding
heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are preferably present at a level of from 0.005%
to
20%, more preferably from 0.130 to 10%, most preferably from 0.5% to S~ 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
form 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.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
tetra (methyiene 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.
WO 95128466 ' j - - PCTIUS95f03692
36
Other suitable heavy metal ion sequestrants.for use herein are iminddiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133.
The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-
carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-
516,102 are also suitable herein. The /3-alanine-N,N'-diacetic acid, aspartic
acid-
N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid
sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes
suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859
describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid
and 2-
phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-
disuccinic acid (GADS) is also suitable.
Oreanic polymeric com o~ . __ . _ .. _ ____ __
Organic polymeric compounds are particularly preferred components of the
detergent
compositions in accord with the invention. By organic polymeric compound it is
meant essentially any polymeric organic compound commonly used as dispersants,
and anti-redeposition and soil suspension agents in detergent compositions.
Organic polymeric compound is typically incorporated in the detergent
compositions
of the invention at a level of from 0.1 % to 30%, preferably from 0.59'o to
159'0, most
preferably from 1 °/ to 10'Yo by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or co-polymeric polycarboxylic acids or their salts in which the
polycarboxylic acid
comprises at least two carboxyl radicals separated from each other by not mare
than
two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers
with malefic anhydride, such copolymers having a molecular weight of from
20,000 to
100,000, especially 40,000 to 80,000.
R'O 95/28466 ~ ~ ~ ~ ~ ~ ~ PCTIUS95/03692
37
Other suitable organic polymeric compounds include the polymers of acrylamide
and
acrylate having a molecular weight of from 3,000 to 100,000, and the
acrylate/fumarate copolymers having a molecular weight of from 2,000 to
80,000.
The polyamino compounds are useful herein including those derived from
aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycoIs,
particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most
preferably about 4000.
The compositions of the invention may contain a lime soap dispersant compound,
which has a lime soap dispersing power (LSDP), as defined hereinafter of no
more
than 8, preferably no more than 7, most preferably no more than 6. The lime
soap
dispersant compound is preferably present at a level of from 0.1 ~ to 40% by
weight,
more preferably 1 % to 20~ by weight, most preferably from 23o to 103'o by
weight
of the compositions.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. A
numerical
measure of the effectiveness of a lime soap dispersant is given by the lime
soap
dispersing power (LSDP) which is determined using the lime soap dispersion
test as
described in an article by H.C. Borghetty and C.A. Bergman, 1. Am. Oil. Chem.
Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is
widely used by practitioners in this art field being referred to , for
example, in the
following review articles; W.N. Linfield, Surfactant Science Series, Volume 7,
p3;
W.N. Linfield, Tenside_Surf. Det. , Volume 27, pages159-161, (1990); and M.K.
Nagarajan, W:F. Masler, Cosmetics and Toiletries, Volume 104, pages 7I-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 sodium oleate
in
30m1 of water of 333ppm CaC03 (Ca:Mg=3:2) equivalent hardness.
CA 02187306 1999-07-12
3. 8
Surfactants having good lime soap dispersant capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethox;ysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates with
an average degree of ethoxylation of from 1-5, particularly C 12-C 15 alkyl
ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4),
and the
C 13-C 15 e~oxylated alcohols with an average degree of ethoxylation of either
12
(LSDP=6) or 30, sold under the trade marls;s Lutensol A012 and Lutensol A030
respectively, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the
article by
M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries,
Volume
104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants
include
certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or
mixtures
thereof, and an acrylamide or substituted acrylamide, where such polymers
typically
have a molecular weight of from 5,000 to 20,000.
Suds sunnressin cVCtPm
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 0.019 to 15 30 , preferably from 0.05 % to 10 % , most
preferably from
0.1 % to 5 9o by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds, 2-alkyl
and
alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a
detergent composition, particularly in the presence of agitation of that
solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam cornpound including a silicone
component.
Such silicone antifoam compounds also typically contain a silica component.
The
R'O 95!28466 PCT/U595103692
39
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
Lhe
siloxanes, particularly the polydimethylsiIoxanes having trimethylsilyl end
blocking
units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and
salts
thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to
about 24
carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali
metal sale 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-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products
of
cyanuric chloride with two or three moles of a primary or secondary amine
containing
1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl
di-
alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate
esters.
Copolymers of ethylene oxide and propylene oxide, particularly the mixed
ethoxylatedlpropoxylated fatty alcohols with an alkyl chain length of from 10
to 16
carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation
of from 1 to 10, are also suitable antifoam compounds for use herein.
Suitable 2-alky-alcanols antifoam compounds for use herein have been described
in
DE 40 2I 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to
C16
alkyl chain carrying a terminal hydroxy group, and said alkyl chain is
substituted in
the a position by a Cl to C10 alkyl chain. Mixtures of 2-alkyl-alcanols can be
used in
the compositions according to the present invention.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
CA 02187306 1999-07-12
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%
to 95 % by weight of the siliconc: antifoam compound; and
(ii) silica, at a level of from 1 %a to 50 ~ , preferably 5 % to 25 % by
weight
of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from 5 % to 50 % , preferably 10 % to 40 ~ by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available from DOW
Corning under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8
to 15, at a level of from 5 % to 80 % , ;preferably 10 ~O to 70 % , by weight;
A preferred particulate suds suppressor system useful herein comprises a
mixture of
an alkylated siloxane of the type hereinabove disclosed and solid silica.
The solid silica can be a fumed silica, a precipitated silica or a silica,
made by the gel
formation technique. The silica particles suitable have an average particle
size of
from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface
area
of at least SOm2/g. These silica particles can be rendered hydrophobic by
treating
them with dialkylsilyl groups andlor trialkylsilyl groups either bonded
directly onto
the silica or by means of a silicone resin. It is preferred to employ a silica
the
particles of which have been rendered hydrophobic with dimethyl and/or
trimethyl
silyl groups. A preferred particulate antifoam compound for inclusion in the
detergent compositions in accordance with the invention suitably contain an
amount of
silica such that the weight ratio of silica to silicone lies in the range from
1:100 to
3:10, preferably from 1:50 to 1:7.
CA 02187306 1999-07-12
41
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 manometers to 20 manometers 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 ~oripo:rnd and an organic carrier material
having a
melting point in the range 50°C to 85°C, wherein the organic
carrier material
comprises a monoester of glycerol and a fatty acid having a carbon chain
containing
from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate
suds
suppressing systems wherein the organic carrier material is a fatty acid or
alcohol
having a carbon chain containing from 12 to 20 carbon atoms, or a mixture
thereof,
with a melting point of from 45°C to 80°C.
Other highly preferred particulate suds suppressing systems a,re described in
CA 2,099,129, in the name of the Procter anti Gamble
Company which systems comprise silicone antifoam compound, a carrier material,
an
organic coating material and glycerol at a weight ratio of glycerol : silicone
antifoam
compound of 1:2 to 3:1. EP 461,699, published December 18, 1991 also discloses
highly preferred particulate suds suppressing systems comprising silicone
antifoam
compound, a carrier material, an orga,~i~ coating material and crystalline or
amorphous aluminosilicate at a weight r3no of aluminosilicate : silicone
antifoam
compound of 1:3 to 3:1. The preferre3 czrrrier material in both of the above
described highly preferred granular suds controlling agents is starch.
An exemplary particulate suds suppressing system for use herein is a
particulate
agglomerate component, made by an agglomeration process, comprising in
combination
(i) from 5 % to 30 % , preferably from 8 % to 15 % by weight of the component
of
silicone antifoam compound, preferably comprising in combination
polydimethyl siloxane and silica;
(ii) from 50% to 90%, preferably from 6(1% to 80% by weight of the component,
of carrier material, preferably starch;
W095128466 ; , PCT/US95103692
42
(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 50 to 100;
and
(iv) from 2 h to 15S'o, preferably from 3% to 10%, by weight of C12-C22
hydrogenated fatty acid.
W O 95!28466 218 7 3 0 6 PCT/US95/03692
43
Polymeric dye transfer inhibiting a ents
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-vinylimidazole,
polyvinyipyrrolidonepolymers or combinations thereof.
al Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
(i) Ax
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 0 O
A is NC, C0, C, -0-, -S-, -N-; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or
any combination thereof whereto the nitrogen of the N-O group can be attached
or
wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general structures
21~73~~
W0 95128466 PCTIU595/03692
44
O
O
(R1 ) x _ ~ _(R2)Y 1
(R3)Z or =N-(R1)x
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group
forms part of these groups. The N-O group can be part of the polymerisable
unit (P)
or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable
unit comprise polyamine N-oxides wherein R is selected from aliphatic,
aromatic,
alicyclic or heterocyclic groups. One class of said polyamine N-oxides
comprises the
group of polyamine N-oxides wherein the nitrogen of the N-O group forms part
of the
R-group. Preferred polyamine N-oxides are those wherein R 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 (I) wherein R is an aromatic,heterocyclic 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 heterocycIic compound such as
pyrridine,
pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the
general formula (I) 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.
R'O 95!28466 PCT/US95/03692
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting propetties. Examples of suitable
polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio of
amine
to the amine N-oxide of 10:1 to 1:100C000. However the amount of amine oxide
groups present in the polyamine oxide polymer can be varied by appropriate
copolymerization 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
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.
]~~polvmers of N-vinvl~vrrolidoue aid N-vinylimidazole
Preferred polymers for use herein may comprise a polymer selected from N-
vinyIimidazole N-vinylpyrrolidone copolymers wherein said polymer ha$ 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 .
~1 Polyvinvlnvrroiidone
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
CA 02187306 1999-07-12
46
to 200,000, more preferably from 5,000 to 50,OU0, 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 PVP"~ K-
15 (viscosity molecular weight of 10,000), PVI' 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 Sokalan~ HP 165 and Sokalan HP 12.
Polyvinylpyrrolidone may be incorporated in the detergent compositions herein
at a
level of from 0.01 to to 5 % by weigh: c.' the detergent, preferably from 0.05
% to 3 %
by weight, and more preferably from 0.1 % to 2 % by weight. The amount of
polyvinylpyrrolidone 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.
d7 Polyvin~rloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average
molecular weight of from 2,500 to 400,000, 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 ~~co-porated in the detergent compositions
may
be from 0.01 % to 5 ~O by weight, prPferahly from 0.05 % to 3 % by weight, and
more
preferably from 0.1 % to 23o by weigh. ~ ne 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.
gl Pol~nrinylimidazole
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 polyvinylimidazole incorpoarted in the detergent compositions
may be
from 0.01 % to 5 % by weight, preferably from 0.05 % to 3 % by weight, and
more
WO 95128466 PCT/US95/03692
47
preferably from 0. I % to 2% 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.
CA 02187306 1999-07-12
4 Fi
~Dtlcal brlPhtPns.r
The detergent compositions herein may also optionally contain from about 0.005
% to
% by weight of certain types of hydrophilic: optical brighteners which also
provide a
dye transfer inhibition action. If used, the compositions herein will
preferably
comprise from about 0.01 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
Ri RZ
-N H H N
N ~..~N _I
O/ I O C-_C ~) N N
N I
H H N
R2 S03M SO M
Ri
wherein R1 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 ration such as sodium or
potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
ration 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, R 1 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)amino]2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R 1 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'-
CA 02187306 1999-07-12
4 S~
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 brightene:rs (e.g., Tinopal UNPA-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. 'JVithout 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. Brighteners with relatively high
exhaustion coefficients are the most suitable for inhibiting dye transfer in
the context
of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional
fabric "brightness" benefits, rather than a we dye transfer inhibiting effect.
Such
usage is conventional and well-known to detergent formulations.
Softening_agents
Fabric softeriing 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 softening agents include the water insoluble
tertiary
amines as disclosed in GB-A-1 514 276 and F:P-B-0 011 340.
Levels of smectite clay are normally in the range from 5 9o to 15 % , more
preferably
from 8 ~ to 12 9'o by weight, with the material being added as a dry mixed
component
to the remainder of the formulation. Organic fabric softening agents such as
the
PCTIUS95103692
WO 95128466
water-insoluble tertiary amines or dilong chain amide materials are
incorporated at
levels of from 0.5 % to 5% by weight, normally from 1 % to 3% by weight,
whilst the
high molecular weight polyethylene oxide materials and the water soluble
cationic
materials are added at levels of from 0.1 % to 2 % , normally from 0.15 % to I
.5 % by
weight.
O h r optional finer Tents
Other optional ingredients suitable for im;lusion in the compositions of the
invention
include perfumes, colours and filler silts, with sodium sulfate being a
preferred filler
salt.
Form of the comtoositions
The detergent compositions of the invention can be formulated in any desirable
form
such as powders, granulates, pastes, liquids, tablets and gels.
The detergent compositions of the present invention may be formulated as
liquid
detergent compositions. Such liquid detergent compositions typically comprise
from
94~ to 35% by weight, preferably from 90% to 40% by weight, most preferably
from 80% to SO% by weight of a liqu'_d carrier, e.g., water, preferably a
mixture of
water and organic solvent.
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.
The detergent compositions of the invention are preferably in the form of
solids, such
as powders and granules.
WO 95128466 2 ~ ~ 7 3 0 6 PCT/US95/03692
51
The particle size of the components of granular compositions in accordance
with the
invention should preferably be such that no more that 5 R'o of particles are
greater than
l.4mm in diameter and not more than 5%a of particles are less than O.ISmm in
diameter.
The bulk density of granular detergent compositions in accordance with the
present
invention typically have a bulk density of at least 450 g/litre, more usually
at least
600 g/litre and more preferably from 650 g/litre to 1200 gllitre.
Bulk density is measured by means of a simple funnel and cup device consisting
of a
conical funnel moulded rigidly on a base and provided with a flap valve at its
lower
extremity to allow the contents of the funnel to be emptied into an axially
aligned
cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at
its
respective upper and lower extremities. It is mounted so that the lower
extremity is
140 mm above the upper surface of the base. The cup has an overall height of
90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal
volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring,
the
flap valve is opened and powder allowed to overfill the cup. The filled cup is
removed from the frame and excess powder removed from the cup by passing a
straight edged implement e.g. a knife, across its upper edge. The filled cup
is then
weighed and the value obtained for the weight of powder doubled to provide the
bulk
density in g/litre. Replicate measurements are made as required.
M~k;ne Processes - eranula_r 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.
Was ' methods
The compositions of the invention may be used in essentially any washing or
cleaning
method, including machine laundry and dishwashing methods.
Lylachine dishwashing method
WO 95/28466 PC1'IUS95103692
52
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 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.
Machine laundr~methods _
Machine laundry methods herein comprise treating soiled laundry with an
aqueous
wash solution in a washing machine having dissolved or dispensed therein ari
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 meant from 40g to 300g of product dissolved or dispersed in
a wash
solution of volume from 5 to 65 litres, as are typical product dosages and
wash
solution volumes commonly employed in conventional machine laundry methods.
In a preferred washing method herein a dispensing device containing an
effective
amount of detergent product is introduced into the drum of a 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 as would
normally
be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement of
the wash cycle of the washing machine water is introduced into the drum and
the
drum periodically rotates. The design of the dispensing device should be such
that it
permits containment of the dry detergent product but then allows release of
this
product during the wash cycle in response to its agitation as the drum rotates
and also
as a result of its immersion in the wash water.
W O 95/28466 PCTlUS95/03692
53
To allow for release of the detergent product during the wash the device may
possess
' a number of openings through which the product may pass. Alternatively, the
device
may be made of a material which is permeable to liquid but impermeable to the
solid
product, which will allow release of dissolved product. Preferably, the
detergent
product will be rapidly released at the start of the wash cycle thereby
providing
transient localised high concentrations of product in the drum of the washing
machine
at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container integrity is maintained in both the dry state and during the wash
cycle.
Especially preferred dispensing devices for use 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 I.BIand 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 configuration, or a similar structure in which the
walls have a
helical form.
Pretreatment washing 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 water-
soluble
builder, but no enzyme components. The solution might optionally contain other
non-
enzyme detergent components such as surfactants, builders, and detergent
polymers.
Preferably the solution also contains water-soluble builder.
W O 95!28466 ' PC1'IUS95I03692
54
The level of the water-soluble builder in said pretreatment solution is
typically from
0.05 % to 80%, and preferably is more than 1 %.
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 10
seconds to
1800 seconds, more preferably from 60 seconds to 600 seconds.
The soiled substrate is then washed using a suitable washing method wherein an
enzyme-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:
XYAS . Sodium C1X - Cly alkyl sulfate
25EY . A C 12-15 Pr~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 sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
TFAA . C16-Clg alkyl N-methyl glucamide.
Silicate . Amorphous Sodium Silicate (SiO2:Naz0 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula b-Na2Si205
Carbonate . Anhydrous sodium carbonate
W O 95128466 218 7 3 0 6
PCT/US95/03692
Polycarboxylate . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si0~12. 27H2O having a primary particle
size in the range from 1 to 10 micrometers
Citrate . Tri-sodium citrate dihydrate
Percarbonate (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
Percarbonate (slow release . Anhydrous sodium percarbonate bleach coated with
a
particle) coating of sodium silicate (Si20:Na20 ratio = 2:1) at
a weight ratio of percarbonate to sodium silicate of
39:1
TAED . Tetraacetyl ethylene diamine
TAED (slow release . Pxrttol~ formed by agglomerating TAED with citric
particle) acid a.~d 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 : Particle formed by agglomerating benzoyl
caprolactam
release particle) (BzCI) with 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
agglomerate:citric acid coating of 95:5
CA 02187306 1999-07-12
56
TAED (fast release : Particle formed by agglomerating TAED with partially
particle) neutralised polycarboxylate at a ratio of
TAED:polycarboxyiate of 93:7, coated with an
external coating of polycarboxylate at a weight ratio of
agglomerate:coating of 96:4
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
ItPNU/g.
Protease (slow release : An enzyme prill containing proteolytic enzyme sold
particle) under the trademark Savinase by Novo Industries A/S
with an activity of 13 KNPU/g coated with a coating
of sodium silicate (Si02:Na20 ratio = 2:1) at a
coating level of 5 90
Amylase . Amylolytic Enzyme sold under the trademark
Termamyl 6~'T 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/g CEW/g
Lipase . Lipolytic enzyme sold under the trademark Lipolase by
Novo Industries A/S with an activity of 165 ICLU/g
CMC : Sodium carboxymethyl cellulose
HEDP : 1,1-hydroxyethane diphosphonic acid
EDDS ~ ' : Ethylenediamine -N, N'- disuccinic acid, [S,S) isomer
in the form of the sodium salt.
W O 95128466 PCTlUS95/03692
57
PVNO . Poly (4-vinylpyridine)-N-oxide copolymer of
vinylimidaxole and vinylpyrrolidone
Granular Suds Suppressor . 12% Silicone/silica, 18'9 stearyl alcoho1,70%
starch in
granular form
VVO 95128466 ' pCT~1S95103692
2187306
58
The following laundry detergent compositions were prepared, values being
expressed
as percentages by weight of the compositions: Composition A is a prior art
composition, compositions B to D are in accord with the invention:
A B C D
4SAS/2SAS (3:1) 9.1 9.1 9.1 9.1
35AE3S 2.3 2.3 2.3 2.3
24E5 4.5 4.S 4.S 4.5
TFAA 2.0 2.0 2.0 2.0
Zeolite A 13.2 13.2 13.2 13.2
Na SKS-6/citric acid 15.6 15.6 15.6 15.6
(79:21)
Carbonate 7.6 7.6 7.6 7.6
TAED (fast release 6.3 - - -
particle)
TAED (slow release - 5.0 - 2.3
particle)
Benzoyl Caprolactam - - 8.0 2.7
(slow
release particle)
Percarbonate (fast 22.5 - - 22.5
release
particle)
Percarbonate (slow - 22.5 22.5 -
release
particle)
W0 95728466 PCT/US95/03692
59
DETPMP 0.5 0.8 - -
EDDS (fast release particle) - 0.3 0.75
-
Protease 0.55 - - -
Protease (slow release - 01.27 0.55 1.27
particle)
Lipase 0.15 0.15 0.15 O.IS
Cellulase 0.28 0.28 0.28 0.28
Amylase 0.27 0.27 0.27 0.27
Polycarboxylate 5.1 5.1 5.1 5.1
CMC 0.4 0.4 0.4 0.4
PVNO 0.03 0.03 0.03 0.03
Granular suds su ressor 1.5 1.5 1.5 1.5
Minors/misc to 1006
