Note: Descriptions are shown in the official language in which they were submitted.
WO 95/28473 PCT/US95/04209
DETERGENTS CONTAINING A SURFACTANT AND A DELAYED RELEASE PEROXYACID
BLEACH SOURCE
This invention relates to detergent compositions containing a surfactant and a
source of peroxyacid bleach, wherein a means is provided for delaying the
release
to the wash solution of said peroxyacid bleach relative to the release of said
surfactant.
The satisfactory removal of greasy, coloured soils/stains such as foodstuffs,
cosmetics, leather polishes and body soils 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.
Traditionally, the removal of such this type of soils/stains has been enabled
by the
use of surface active ingredients and bleach components such as oxygen
bleaches,
including hydrogen peroxide and organic peroxyacids. The organic peroxyacids
are often obtained by the in situ perhydrolysis reaction between hydrogen
peroxide
and an organic peroxyacid bleach precursor.
A problem encountered with the use of certain organic peroxyacid bleaches in
laundry washing methods is a tendency for these organic peroxyacid bleaches to
affect the colour stability of the fabrics being washed. Effects on fabric
colour
stability can include fading of coloured dyes on the fabrics or localised
areas of
"patchy" bleaching.
The detergent formulator thus faces the dual challenge of formulating a
product
which maximises bleachable soil/stain removal but minimises the occurrence of
any unwelcome fabric colour stability effects of the bleach.
The Applicants have found that the occurrence of any unwelcome fabric colour
stability effects arising from the use of organic peroxyacid bleaches in a
washing
method can be related to the nature of the organic peroxyacid, and also to
both the
sate of release of the peroxyacid bleach to the wash solution and the absolute
level
of peroxyacid present in the wash solution.
R'O 95!28473 PCTlUS95/04209
A fast rate of release of the peroxyacid bleach to the wash solution tends to
heighten the probability that unwelcome fabric colour stability effects will
be
observed, .as does a high absolute level of the bleach in the wash solution.
Whilst reducing either the rate of release of the peroxyacid bleach, or the
absolute
level of the bleach employed in the wash tends to ameliorate this problem,
this can
be accompanied by a negative effect on the bleachable stainlsoil removal
ability.
The Applicants have now however f~~lnd that where a composition containing
both
a surfactant and a peroxyacid bleach source is employed, and wherein a means
is
provided for delaying the release tc a wash solution of the peroxyacid bleach
relative to the release of the surfactant enhanced bleachable stain/soil
removal may
be obtained.
Additionally, where the composition is used in a laundry washing method a
reduction in fabric colour stability problems is also obtained.
The Applicants have in addition found that bleachable stainlsoil removal
benefits
may be obtained when a soiled substrate is pretreated with a solution
containing a
suzfactant, prior to being washed in a method using a bleach containing
detergent
product.
It is therefore an object of the preseri~ invention to provide compositions
suitable
for use in laundry and machine dishwashing methods having enhanced bleachable
stain removal.
It is also an object of the present invention to provide compositions for use
in a
laundry washing method wherein said compositions show less propensity to cause
negative fabric colour stability effects.
It is a related object of the present invention to provide a stain/soil
pretreatment
method involving pretreating the soiled substrate with a solution containing a
surfactant, prior to washing with a bleach-containing detergent product.
~a~m~rv of the Invention
O 95/28473 PCTIUS95/04209
3
According to the present invention there is provided a detergent composition
containing
(a) a surfactant; and
(b) an organic peroxyacid bleach source
wherein a means is provided for delaying the release to a wash solution of
said
peroxyacid bleach relative to the release of said surfactant such that in the
T50 test
method herein described the time to achieve a concentration that is 50 k of
the
ultimate concentration of said surfactant is less than 120 seconds and the
time to
achieve a concentration that is 50 °b of the ultimate concentration of
said
peroxyacid bleach is more than 180 seconds.
According to the present invention there is provided a detergent composition
containing
(a) a surfactant; and
(b) an organic peroxyacid bleach source
wherein a means is provided for delaying the release to a wash solution of
said
peroxyacid bleach relative to the release of said surfactant such that in the
T50 test
method herein described the time to achieve a concentration that is 50 ~ of
the
ultimate concentration of said surfactant is at least 100 seconds, preferably
at least
120 seconds, more preferably at least 150 seconds less than the time to
achieve a
concentration that is 50% of the ultimate concentration of said peroxyacid
bleach.
Said organic peroxyacid bleach source preferably
comprises in combination
(i) a hydrogen peroxide source; and
(ii) a peroxyacid bleach precursor compound
According to another aspect of the present invention there is provided a
washing
' method comprising the steps of:
(1) applying a bleach-free solution of a composition containing a surfactant
to
a soiled substrate;
W0 95128473 PCTlUS95/04209
i. 4
(2) allowing said solution to remain in contact with said soiled substrate for
an
effective time interval;
(3) washing said soiled substrate using a washing method involving use of a
bleach-containing detergent composition.
The detergent compositions of the invention contain as an essential detergent
component a surfactant selected from anionic, cationic, nonionic, ampholytic,
amphoteric and zwitterionic surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1 °k to 6096
by weight.
More preferred levels of incorporation of surfactant are from 1 ~ to 35 96 by
weight, most preferably from 196 to 20°k 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, amphulytic, and zwitterionic classes,
and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Iaughlin
and
Hearing on December 30, 1975. Further examples are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Petry 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
- WO 95/28473 PCT/U595104209
21$'436
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate
surfactants.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-
acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
' sulfosuccinates, monoesters of sulfosuccinate (especially saturated and
unsaturated
CIZ C18 monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6 C14 diesters), N-acyl sarcosinates. Resin acids and
hydrogenated
resin acids are also suitable, such as rosin, hydrogenated rosin, and resin
acids and
hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates,
alkyl
phenol ethylene oxide ether sulfates, the CS-Cl~ acyl-N-(Cl-C4 alkyl) and -N-
(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of allrylpolysaccharides
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 C6-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 ethoxyLited
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 CS-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or
secondary allcane suifonates, C6-C24 olefin sulfonates, sulfonated
polycarboxylic
acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol
sulfonates, and any mixtures thereof.
Anionic carboxvlate surfactant
218'~4~6
W095I28473 PCTIUS95104209
s ~ . w, ~' ;
6
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy
cartioxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps
('alkyl carboxyls'), especially certain secondary soaps as described herein.
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 Clg or less, and the average x is from
about 3
to 10 when the average R is greater than C13, and M is a ration, preferably
chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-
ethanol-ammonium, most preferably from sodium, potassium, ammonium and
mixtures thereof with magnesium ions. The preferred 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 formuia
RO-(CHRI-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.
15128473 ~ pCT/US95104209 ' -
~~8T~~~
Anionic secondary coa~o surfactant
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., =~-"-'$ '---T
l. i. - t:
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
CHg(CH~x and R4 is CH3(CH~y, wherein y can be O or an integer from 1 to
4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-
9, most preferably 8.
B. Another prefermd class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit,
i.e., secondary soaps of the formula RS-R6-COOM, wherein RS is C~-
C1~, 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,
mesa 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-(CHZ)m (CHR)n
CH(COOM)(CHR)o (CH2)P (CHR)q CHg, wherein each R is CI-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
to 18.
In each of the above formulas A, B and C, the species M can be any suitable,
especially water-solubilizing, counterion.
~1~8'~436
W0 95128473 PCTIUS95/04209
8
Especially preferred secondary soap surfactants for use herein are
water=soiuble
members selected from the group consisting of the water-soluble salts of 2-
methyl-
I-undecanoic acid. 2-ethyl-1-decanoic acid, 2-propyl-I-nonanoic acid, 2-butyl-
1-
octanoic acid and 2-pentyl-1-heptanoic acid.
Alkaii metal cafCOSinate surfactant -_ _
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (RI) CH2 COOM, whereinrR is a Cg-C1~ linear or branched alkyl or
alkenyl group, Rl is a CI-Cq 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.
Nonionic surfactant _ . _ _ __ _ __.
Essentially any anionic surfactants useful for detersive purposes can be
included in
the compositions. Exemplary, non-limiting classes of useful nonionic
surfactants
are listed below.
Nonionic ~lvhvdroxy fatt r~acid amide surfactant
Polyhydroxy fatty acid amides suitabie for use herein are those having the
structural formula RZCONR1Z wherein : RI is H, Cl-C4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more
preferably C1 or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and RZ is
a
Cg-Cgl hydrncarbyl, preferably straight-chain Cg-Clg aikyl or alkenyl, more
preferably straight-chain Cg-CIA alkyl or alkenyt, most preferably straight-
chain
C11-C1~ alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected
to
the chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated)
thereof. Z preferably will be derived from a reducing sugar in a reductive
amination reaction; more preferably Z is a glycityl.
jyoninnic ~nn~lPn~atrc of alkyl hp enols
-VVO 95128473 PCT'IUS95/04209
2187436
Thespolyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use herein. In general, the polyethylene oxide
condensares
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.
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about l
to a~out 25 moles of ethylene oxide are suitable for use herein. The alkyl
chain of
the aliphatic alcohol can either be rt'aight or branched, primary or
secondary, and
generally contains from 6 to 22 carton atoms. Particularly preferred are the
condensation products of alcohols having an alkyl group containing from 8 to
20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
Nonionic ethoxylatedlz?ronoxvlated fattv ai_cohol cnrFartant
The ethoxylated C6-Clg fatty alcohols and C6-Clg mixed
ethoxylatedlpropoxylated fatty alcohols are suitable surfactants for use
herein,
particularly where water soluble. Preferably the ethoxylated fatty alcohols
are the
Clp-Clg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to
50,
most preferably these are the C12-Cy8 ethoxylated fatty alcohols with a degree
of
erhoxylation from 3 to 40. Freferatty 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.
No~otic BO/PO condencates with ~Rylene gl_vr~1
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol are suitable for use
herein. The hydrophobic portion of these compounds preferably has a molecular
weight of from about 1500 to about 1800 and exhibits water insolubility.
Examples of compounds of this type include certain of the commercially-
available
PiuronicTM surfactants, marketed by BASF.
,.r.< r,, .
R'O 95!28473 PCTIU595/04209
~0 2187436
L ~ ,
Nonionic EO condensation products with proRylene oxide/ethvlene diamine
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 TetronicT~'t 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- positions on the preceding
saccharide
units.
The preferred allrylpolyglycosides have the formula
R2O(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 I0, 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.
~O 95128473 PCT/U595I04209
11 218743b
FatEy acid amide surfactants suitable for use herein are those having the
formuta:
R6CON(R~)2 wherein R6 is an alkyl group containing from 7 to 21, preferably
' from 9 to 17 carbon atoms and each R~ is selected from the group consisting
of
hydrogen, C1-C4 alkyl, CI-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the
' range of from 1 to 3.
Amphoteric curfac ant
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
Mirirtol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine oxides useful herein include those compounds having the formula
R3(OR4)xIVO(RS)2 wherein R3 is selected from an allryl, 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 allcyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1
to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable
1,
ethylene oxide groups. The RS groups can be attached to each other, e.g.,
through an oxygen or nitrogen atom, to form a ring structure.
T7tese amine oxide surfactants in particular include C10-Clg alkyl dimethyl
amine
oxides and Cg-Clg allcoxy ethyl dihydroxyethyl 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 dimethylaraine oxide, stearyl
dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-
hydroxyoctadecylamine oxide. Preferred are Cl0-Clg alkyl dimethylamine oxide,
and C10-18 acylamido alkyl dimethylamine oxide.
~~.87~3,6
WO95128473 _ , , 5 ,~ , PCTIU595104209
is
~witterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions
hereof. These surfactants can be broadly described as derivatives of secondary
and tertiary amines, derivatives of heterocyclic secondary and tertiary
amines, or
derivatives of quaternary ammonium, quaternary phosphonium or tertiary
sulfonium compounds. Betaine and sultaine surfactants are exemplary
zwitterionic
surfactants for use herein.
The betaines useful herein are those compounds having the formula
R(R')2N+RZCOO- wherein R is a C6-Cig hydrocarbyl group, preferably a CIO-
C16 alkyl group or Cip-16 acylamido alkyl group, each Rl is typically Cl-C3
alkyl, preferably methyl,m and RZ is a CI-CS hydrocarbyl group, preferably a
C1-C3 alkylene group, more preferably a Cl-CZ alkylene group. Examples of
suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl
dimethyl betaine; Cl2-14 acylamidopropylbetaine; Cg_l4 acylamidohexyldiethyl
betaine; 4(C14-16 acylmethylamidodiethylammonio]-1-carboxybutane; C16-18
acytamidodimethylbetaine; C12-16 acylamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine. Preferred betaines are C12_lg dimethyl-
ammonio hexanoate and the CIO-18 acylamidopropane (or ethane) dimethyl (or
diethyl) betaines. Complex betaine surfactants are also suitable for use
herein.
The sultaines useful herein are those compounds having the formula
(R(RI)2N-fR2S03 wherein R is a.C6-Cyg hydrocarbyl group, preferably a C10-
C16 alkyl group, more preferably a C12-C13 alkyl group, each RI is typically
Cl-
C3 alkyl, preferably methyl, and RZ is a CI-C6 hydrocarbyl group, preferably a
C1-C3 alkylene or, preferably, hydroxyalkylene group. .
Amy, is sub
Ampholytic surfactants can be incorporated into the detergent compositions
herein.
These surfactants can be broadly described as aliphatic derivatives of
secondary or
' ~! ; : .., ,..
~WO 95128473 PCT/US95104209
13 2187436
tertiary amines, or aliphatic derivatives of heterocyclic secondary and
tertiary
amihes in which the aliphatic radical can be straight chain or branched.
Cationic surfactants can also be used in the detergent compositions herein.
Suitable
cationic surfactants include the quaternary ammonium surfactants selected from
mono C6-C16, preferably C6-Clp N-alkyl or alkenyl ammonium surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Bleach
The detergent compositions of the invention contain as an essential 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 bleach 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
perhydtate bleaches.
Peroxvacid bleach nrecursorc
Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid
sources
in accord with the invention. Peroxyacid bleach precursors are normally
incorporated at a level of from 1 ~ to 20 96 by weight, more preferably from 2
~ to
1096 by weight, most preferably from 3 96 to 5 96 by weight of the
compositions.
Suitable peroxyacid bleach precursors typically contain one or more N- or O-
acyl
groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides and acylated derivatives of
imidawles
and oximes, and examples of useful materials within these classes are
disclosed in
GB-A-1586789.
WO 95/28473 - PCTIUS95104209
1 '~ ., . 14-
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-
A-0'170386. The acylation products of sorbitol, glucose and all saccharides
with
benzoylating agents and acetylating agents are also suitable.
Specific O-acylated precursor compounds include 2,3,3-tri-methyl hexanoyl
oxybenzene sulfonates, benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl
oxybenzene sulfonates, monobenzoyltettaacetyl 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
succittimide,
tetrnbenzoyl ethylene diamine, N-benzoyl substituted areas and the N-,N,NINI
tetra acetyLued alkylene diamines wherein the alkylene group contains from 1
to 6
carbon atoms, particularly those compounds in which the allcylene group
contains
1, 2 and 6 carbon atoms. Tettaacetyl 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-acyLited lactam precursors have the formula:
0
II
R6-O N-C H2-C Hz
~C Hz-EC HZ ]~
CA 02187436 1999-09-17
15
wherein n is from 0 to about 8, preferably from 0 to 2, and R6 is H, an alkyl.
aryl, alkoxyaryl or alkaryl group containing from 1 to l2 carbons, or a
substituted
phenyl group containing from 6 to l8 carbon atoms
Suitable caprolactam bleach precursors are of the formula:
0
0 C CH2 CH2
CH
Rl C N
CH2 CH2
wherein R1 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.
CA 02187436 1999-09-17
16
Suitable valero lactams have the formula:
0
0 C CH2 CH2
R1 C N
CH2 CH
2
wherein R1 is H or an alkyl, ary l, 3llcoxyaryl or alkaryl group containing
from 1
to 12 carbon atoms, preferably from. 6 to 12 capon atoms. In highly preferred
embodiments, Rl 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, ber~oyl
caprolactam
and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl,
aryl
and alkoxy 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 of a hydrophobic character which afford nucleophilic and body
soil
clean-up. Precursor compo~irds 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 1:5 to 5:1, preferably 1:1, can
be used
hetzin for mixod stain removal benefits.
Highly preferred caprolactam and valerolactam precursors include benzoyl
caprolactam, nonanoyl capro-lactam, benzoyl valerolactam, nonanoyl
valerolactarrl, 3,5,5-trimethylhexanoyl 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
21$7136
0 95/28473 . PCT/US95104209
17
substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl
valeuolaciam, ethylbenzoyl caprolactam, ethylbenzoyl valeroIactam,
propylbenzoyl
caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam,
isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl
valerolactam, tert-butylbenzoyl caprolactam, ten-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, tent-butoxybenzoyl
caprolactam, ten-butoxybenzoyl valerolactam, pentoxybenzoyl caprolactam,
pentoxybenzoyl valerolactam, hexoxybenzoyl caprolactam, hexoxybenzoyl
valerolactam, 2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl
valerolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-chIorobenzoyl
caprolactam, 2,4-dichlororbenzoyl caprolactam, terephthaloyl dicaprolactam,
pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl
valerolactam, 2,4-dichlororbenzoyl valerolactam, terephthaloyl divalerolactam,
4-
nitrobenzoyl caprolactam, 4-nitrobenzoyl valero)actam, and mixtures thereof.
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-RZ-C-L R~-N-C-R2-C-L
~i ~ ~~ ~ ~~ i~
0 R5 0 or RS O 0
wherein Rl is an aryl or allcaryl group with from 1 to 14 carbon atoms, RZ is
an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and
RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms
and L
can be essentially any leaving group. Rl preferably contains from 6 to 12
carbon
atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be straight
r
R'O 95!28473 PCTIUS95104209
2187436 18
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. R~ 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 I I and most
preferably from 8 to 11.
Preferred bleach precursors are those wherein Rl, RZ and RS are as defined for
the amide substituted compounds and L is selected from the group consisting
of:
Y ~R3 -~R3Y
-0~ , - -O-( ( ) r-Y , and p~ -~~)
O O
-N-C-R~ -N N -N-C-CH-R4
R3 Y ,
-I
Y
3
-0-CH=C-CH=CH2 -O-CH=C-CH=CH2
- W O 95!28473 PCTlUS95/04209
2187436 i9
0
0 C HZ-C
_O-C-R~. , -N\C/NRa
II
0
R3 0 Y
-0-C=CHRa , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein RI is an alkyl, aryl, or a(karyl group
containing
from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4 is H-or R3, and Y is H or a solubilizing group.
The preferred solubiIizing groups are -S03 M+, -C02 M+, -S04 M+,
-N+(R3) X and O <--N(R3)3 and most preferably -S03 M+ and -COZ M+
wherein R~ is an allryl chain containing from 1 to 4 carbon atoms, M is a
ration
which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M 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.
Preferred examples of bleach activators of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (Crnonanamidocaproyl)oxybenzenesulfo-
nate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other preferred precursor compounds include those of the benzoxazin-type,
having
the formula:
~' $ w ~. .
2I8'~~3~
W0 95/28473 ' PCT1US95104209
. 2 4 -.. .'
including the substituted benzoxazins of the type
-R~
wherein Rl is H,-alkyl, alkaryL, aryl, aryIdlkyl, and wherein R2, R3, R4, and
RS
may be the same or different substiments 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 especially preferred precursor of the benzoxazin-type is:
The detergent compositions may also contain organic peroxyacids typically at a
level of from 1 °S to 15 96 by weight, more preferably from 19& to 10
Y6 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
I I
i~
O R5 0 or
R~ -N-C-R2-C-OOH
ii '
R5 O O
"WO 95128473 PCT/US95/04209
2187436 Z1
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
alkylene, arytene, and alkarylene group containing from 1 to 14 carbon atoms,
and
' RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
R1
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4
to
' 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl
or
allcylaryl 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. Rl 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 diperazelaic acid,
mono- and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic acid, and
their salts as disclosed in, for example, HP-A-0341 947.
Ino~anic perhydrate bleaches
The compositions in accord with the invention preferably include, as a
hydrogen
peroxide source, an inorganic perhydrate salt, most especially when the
organic
peroxyacid source is a peroxyacid bleach precursor compound.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium
salt at a level of from 19~ to 40 ~ by weight, more preferably from 2 ~ to 30
~ by
weight and most preferably from 5 96 to 25 ~b by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persiHcate salts. The inorganic perhydrnte salts
are
normally the alkali metal salts. The inorganic perhydrate salt may be included
as
the crystalline solid without additional protection. For certain perhydtate
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.
218°~~3~
WO 95/28473 PCTIUS95/04209
~2
s a
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydtate 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 1 : 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.
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
, d '
'WO 95128473 PCTIU595104209
23 2187436
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
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.
One type of bleach catalyst is a catalyst system comprising a heavy metal
ration of
defined bleach catalytic activity, such as cppper, 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.
Othertypes of bleach catalysts include the manganese-based complexes disclosed
in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these
catalysts include Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyciononane)2-(PF6)2,
Mn~2(u-O) 1 (u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CL04)2,
Mn~4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, Mn~Mn~4(u-O)1(u-OAc)2_
w0 95128473 PCTIUS95104209
. ,, as
(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)g, 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-
triazacycIododecane,
2-methyl-1,4,7-triazacyclorionane, 2-methyl-1,4,7-triaiacyclononane, 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)(OCHg)g_(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a
water-soluble complex of manganese ()n, ()II), and/or (I~ 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. 5,114,61 I teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands are of the formula:
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 Rl-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. CR5R6, NR7-and C=O, wherein R5, R6, and R7 can each be
H,-alkyl, or aryl groups, including substituted or unsubstituted groups.
Preferred
Iigands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole,
pyrazole,
and triazole rings. Optionally, said rings may be substituted with
substituents such
as alkyl, aryl, alkoxy, halide, and vitro. Particularly preferred is the
ligand 2,2'-
bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-
bispyridyhnethane and -bispyridylamine complexes. Highly preferred catalysts
~O 95128473 PCT/U595I04209
25 2187436
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(II),~ trisdipyridylamine-cobalt()T) perchlorate, Co(2.2-
bispyridylamine)202C104,
Bis-(2.2'-bispyridylamine) copper(11) perchlorate, tris(di-2-pyridylamine)
iron()?)
perchlorate, and mixtures thereof.
Other examples include Mn gluconate, Mn(CFgSOg)2, Co(NHg)gCl, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate Ligands,
including
N4Mn~(u-O)2Mn~N4)~and [Bipy2Mn~(u-O)2Mn~bipy2]-(CL04)3.
The bleach catalysts of the present invention 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 (Il), (Iln, (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 allcaline pH. - The water may first be de-oxygenated by
boiling
and cooled by sparging with nitrogen. The resulting solution is evaporated
(under
N2, if desired) and the resulting solids are used in the bleaching and
detergent
compositions herein without further purification.
In an alternate mode, 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 ptvcess,
it is
convenient to use a considerable molar excess of the ligand 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
WO 95/28473 PCTlU595104209
26
interaction of f(~e carboxyl and nitrogen atoms of the ligand with the
manganese
ration. Likewise, the oxidation state of the manganese ration during the
catalytic
process is nobknown with certainty, and may be the (+II), (+I!1), (+IV) or
(+~ valence state. Due to the ligands' possible six points of attachment to
the
manganese ration, it may be reasonably speculated that multi-nuclear species
and/or "cage" structures may exist in the aqueous bleaching media. Whatever
the
form of the active Mnligand 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-potphyrin catalysts), U.S.
4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and
European patent application, publication no. 224,952, (absorbed manganese on
aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with
manganese
and zinc or magnesium salt), U.S. 4,626,373 (manganese/Iigand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019
(cobalt
chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
4,430,243 (chelants with manganese rations and non-catalytic metal rations),
and
U.S. 4,728,455 (manganese gluconate catalysts).
Relative release kinetics
In an essential aspect of the invention a means is provided for delaying the
release
to a wash solution of the peroxyacid bleach relative to the release of the
surfactant.
Said means may comprise a means for delaying the release of the peroxyacid
bleach to the wash solution.
Alternatively said means may comprise a means for enhancing the rate of
release
of the surfactant to the solution.
The means may provide for delayed release of the peroxyacid bleach source
itself
to the wash solution. Alternatively, where the peroxyacid source is a
peroxyacid
'W095128473 ~~~.~'~-4~.3~' PCT/US95/04209
27
precursor compound the delayed release means may comprise a means of
inhibiting, or preventing the in situ perhydrolysis reaction which releases
the
peroxyacid into the solution. Such means could, for example, include delaying
release of the hydrogen peroxide source to the wash solution, by for example,
delaying release of any inorganic perhydrate salt, acting as a hydrogen
peroxide
' source, to the wash solution.
The delayed release means can include coating any suitable component with a
coating 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 disso:ution 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 soaiem 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
296 to 10~, (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 tray be combined with organic binder
materials to provie composite inorganic salt/orgattic binder coatings.
Suitable
binders include the C 10-C20 alcohol ethoxylates contacting from 5 - 100 moles
of
ethylene oxide per mole of alcohol and more preferably the C15-C20 P~~1'
alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole
of
alcohol.
~18'~436
WO 95/28473 PCT/US95104209
28
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones 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 peroent 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 Cl0-C20 alcohol ethoxylates
containing
from S - 100 moles of ethylene oxide per mole. Further examples of binders
include the Cl0-C,20 mono- and diglycerol ethers and also the C10-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 agglomeratorlmixer 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 the bleach 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 sizeFshould be more than 500 micrometers,
preferably having an average particle diameter of from 800 to 1200 micrometers
Additional protocols for providing the means of delayed release include the
suitable choice of any other components of the detergent composition matrix
such
~ t
-'W O 95128473 PCT/US95/04209
29 2187436
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
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 surfactant 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.
The release of the peroxyacid bleach component from the peroxyacid bleach
source relative to that of the surfactant component is such that in the T50
test
method herein described the time to achieve a concentration that is 50 % of
the
ultimate concentration of said surfactant is less than 120 seconds, preferably
less
than 90 seconds, more preferably less than 60 seconds, and the time to achieve
a
CA 02187436 1999-09-17
30
concentration that is 50~ of the ultimate concentration of said peroxyacid
bleach
is more than 180 seconds, preferably from 180 to 180 seconds, more preferably
from 240 to 360 seconds.
In a highly preferred aspect of the invention the release of bleach is such
that in
the T50 test method herein described the time to achieve a level of total
available
oxygen (AVO) that is 50°~ of the ultimate level is more than 180
seconds,
preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds. A
method for determining AVO levels is disclosed in Wp 94/16047.
In another preferred aspect of the invention, where the peroxyacid bleach
source is
a peroxyacid bleach precursor, employed in combination with a hydrogen
peroxide
source the kinetics of release to the wash solution of the hydrogen peroxide
relative to those of the surfactant component is such that in the T50 test
method
herein described the time to achieve a concentration that is 50 % of the
ultimate
concentration of said surfactant is less than 120 seconds, preferably less
than 90
seconds, more preferably less than 60 seconds, and the time to achieve a
concentration that is 50 % of the ultimate concentration of said hydrogen
peroxide
is more that 180 seconds, preferably from 180 to 480 seconds, more preferably
240 to 360 seconds.
The ultimate wash concentration of the 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 any inorganic perhydrate bleach is
typically
from 0.005 96 to 0.25 % by weight, but preferably is more than 0.05 % , more
preferably more than 0.075 % .
The ultimate wash concentration of any peroxyacid precursor is typically 0.001
%
to 0.08 % by weio~t, but preferably is from 0.005 % to 0.05 %, most preferably
from 0.015 % to 0. OS % .
layed release - test metho~
The delayed release kinetics herein are defined with respect to a 'TA test
method'
which measures the time to achieve A°,b of the ultimate
concentration/level of that
~O 95128473 PCT/US95/04209
X187436 31
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 IOg 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 attained 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 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.
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.
~ -,. . :. , ='v S .~ .
W0 95!28473 y PCTIUS95/04209
32
TheJcompositions 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, heavy metal ion sequestrants, organic polymeric compounds,
additional enzymes, suds suppressors, lime soap dispersants, soil suspension
and
anti-redeposition agents and corrosion inhibitors. laundry compositions can
also
contain, as additional detergent components, softening agents.
Water-soluble builder comuound
The detergent compositions of the present invention contain as a preferred
optional
component a water-soluble builder compound, typically present at a level of
from
196 to 8096 by weight, preferably from 10°6 to 70% by weight, most
preferably
from 20~ to 6096 by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids
or their salts in which the polycarboxylic acid comprises at least two
carboxylic
radicals separated from each other by not more that two carbon atoms,
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, digiycolic acid,
tartaric
acid, tatuonic acid and fumaric acid, as well as the ether carboxylates and
the
sulfinyl carboxylates. Polycarboxylates containing three carboxy groups
include,
CA 02187436 1999-09-17
33
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 Canadian Patent No. 973,771.
and the oxypolycarboxylate materials such as 2-oxa-1,1, 3-propane
tricarboxylates
described in British Patent No. 1,387,447.
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, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran -
cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates,
2,2,5.5-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing
up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxytate chelating
agents
or mixturrs thertof 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 caa 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 cart~onate and sesqui-carbonate and mixtures thereof with
uttra-
W095128473 PCT/US95/04209
34
fme calcium carbonate as disclosed in German Patent Application No. 2.321,001
published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate.
sodium polymetalphosphate 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 S6 to 50~ by weight of the composition, more
preferably from 10~ to 40~ by weight.
P~ Tally soluble or insoluble builder com~und
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
809& by
weight, preferably from 10~ to 70°~ by weight, most preferabiy from 20~
to
6096 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.
~O 95128473 ~ 18'~ ~ 3 6 ; ,
PCT/US95/04209
Crystalline layered sodium silicates have the general formula
NaMSix02x+ I ~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)y1.
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 109& to 28 ~, more preferably from 18 ~ to 22 9ii 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)121. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(~02)86(Si02)1061. 276 H20.
Heavy metal ion cea ~ c ran
.., Y~ .~ i, r:
WO 95128473 ; . PCTlUS95/04209
36
The detergent compositions of the invention may contain as a preferred
optional
component a heavy metal ion sequestrant. By heavy metal ion sequesttant 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 0.1 % to 103b, most preferably from 0.59& to 5~ by
weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphoric acid or carboxylic acid functionalities, may be present either in
their
acid form or as a complexlsalt with a suitable counter canon 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 cation to the heavy metal ion sequestrant is preferably at least 1: I.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates,
such as the amino alkylene poly (allcylene phosphonates), alkali metal ethane
I-
hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic
acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid,
ethylenediamine
diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts
thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alltali
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 NagEDDS. Examples of such
preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
CA 02187436 1999-09-17
37
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid.
described in EP-A-317,542 and EP-A-399,133.
The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-
carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in
Ep_A_
516,102 are also suitable herein. The ~-al~,e-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 arse alos suitable. Glycinamide-
N,N'-disuccinic acid (GADS) is also suitable.
Another optional ingredient useful in the detergent compositions is one or
more
additional enzymes.
Preferred additional eazymatic materials include the commercially available
lipases, amylases, neutral and alkaline proteaxs, esterises, cellulases,
pectinases,
Lactases and peroxidases conventionally incorporated into detergent
compositions.
Suitable enzymes arse discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
trademarks ply, Savinase, Pi-im~, Du~ym, ~d ~~ by Novo
Industries A/S (Denmark), those sold under the trademarks ~~~ ~o~ ~d
Maxapem by Gist-Brocades, those sold by Genencor International, and those sold
under the trademarks Opticl~ ~d pp~~ by Solvay Enzymes. Protease
enzyme may be incorporated into the compositions in accordance with the
invention at a level of from 0.0001 ~ to 4 ~ active enzyme by weight of the
composition.
CA 02187436 1999-09-17
38
Preferred amylases include, for example. u-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 °b to 2 ~O 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 Hu- sp., Thermomv r sp, or Pseudomonas sp.
including ~rdomonas Qseudoalc li~~r'c or Pseudoma fi o nc. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein.
A preferred lipase is derived from Pseudomonac Dseudo is rig ~Pc, which is
described in Granted European patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humic~
lanu-nosy and expressing the gene in g~ ~~ ~ host, as described in
European Patent Application, EP-A-0258 068, which is commet~cially available
from Novo Industri A/S, Bagsvaerd, Denmark, under the trade mark Lipolase.
~s lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al,
issued
March 7, 1989.
Preferred enzyme-containing compositions herein may comprise from about
0.001 ~ to about 10 ~ , preferably from about 0.005' to about 8 ~ , most
preferably from about 0.01 °~ to about 6~, by weight of an enzyme
stabilizing
system. The enzyme stabilizing system can be any stabilizing system which is
compatible with the detersive enzyme. Such stabilizing systems can comprise
calcium ion, boric acid, propylene glycol, short chain carboxylic acid,
boronic
acid, and mixtures thereof. Such stabilizing systems can also comprise
reversible
enzyme inhibitors, such as reversible protease inhibitors.
~0 95128473 21$'~ 4 ~ ~ ' PCfIUS95104209
39
The compositions herein may further comprise from 0 to about 10%, preferably
from about O.D1 % to about 6% by weight, of chlorine bleach scavengers, added
to
prevent chlorine bleach species present in many water supplies from attacking
and
inactivating the enzymes, especially under alkaline conditions. While chlorine
levels in water may be small, typically in the range from about 0.5 ppm to
about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact
with the enzyme during washing is usually large; accordingly, enzyme stability
in-
use can be problematic.
Suitable chlorine scavenger anions are widely available, and are illustrated
by salts
containing ammonium cations or sulfite, bisulfate, thiosulfite, thiosulfate,
iodide,
etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other
conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perborate tetrahydrate, sodium perborate monohydtate
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.
~ea_nsC polymeric compound
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
0.5 % to 15 9b , most preferably from 1 % to 10 % by weight of the
compositions.
Examples of organic polymeric compounds include the water soluble organic
homo- or co-polymeric polycarboxylic acids or their salts in which the
polycarboxylic acid comprises at least two carboxyl radicals separated from
each
other by not more than two carbon atoms. Polymers of the latter type are
~is~~~s
WO 95128473 ~ ' ' PCTIUS95104209
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.
v
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
acrylatelfumarate copolymers having a molecular weight of from 2,000 to
80x000.
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 glycols,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000 and most preferably about 4000.
lie soap disoersant com oo and
The compositions of the invention may contain a lime soap dispersant compound,
which has a lime soap dispersing power (ISDP), 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 196 to 20~ by weight, most preferably from 2~ to
10°6
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 (ISDP) which is determined using the lime soap
dispersion test as described in an article by H.C. Borghetty and C.A. Bergman,
J.
Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap
dispersibn 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. ,
CA 02187436 1999-09-17
41
Volume '?7, pages159-161. ( 1990): and M.K. Nagarajan. W.F. Masler, Cosmetics
and Toiletries. Volume 104. pages 71-73, (1989). The LSDP is the % 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.
Surfactants having good lime soap dispersant capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates
with an average degree of ethoxyla~ion of from 1-5, particularly C12-C15 ~Y1
ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4),
and
the C 13-C 15 ethoxylated alcohols with an average degree of ethoxylation of
either
12 (I,SDP=6) or 30, sold under the trademarks 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.
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 0.0196 to 15 % , preferably from 0.05 ~ to 10 ~ , most
preferably
from 0.1 °~b to 5 % by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known antifoam compound, including, for example silicone antifoam compounds.
2-alkyl and alcanol antifoam compounds.
By aatifoam compound it is meant herein any compound or mixtures of
compounds which act such as to depress the foaming or sudsing produced by a
21~f'~~3.~~ .
;: ~ ;
W0 95128473 PCTIUS95/04209
42
solution of a detergent composition, particularly in the presence of agitation
of that
solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component. Such silicone antifoam compounds also typically contain a silica
component. The term "silicone" as, used herein, and in general throughout the
industry, encompasses a variety of relatively high molecular weight polymers
containing siloxane units and hydrocarbyl group of various types. Preferred
silicone antifoam compounds are the siloxanes, particularly the
polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble salts thereof. These materials are described in US Patent 2,954,347,
issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids,
and salts thereof, for use as suds suppressor typically have hydrocarbyl
chains of
to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts
include the alkali metal salts such as sodium, potassium, and lithium salts,
and
ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols,
aliphatic Clg-C4p ketones (e.g. stearone) N-alkylated amino triazines such as
tri-
to hexa-alkylmelamines or di- to tetra alkyidiamine 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, Hthium) phosphates
and
phosphate esters.
Copolymers of ethylene oxide and propylene oxide, particularly the mixed
ethoxylatedlpropoxyLUed 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-alley-alcanols antifoam compounds for use herein have been
described in
DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to
C l6
CA 02187436 1999-09-17
43
alkyl chain carrying a terminal hydroxy group, and said alkyl chain is subst~
Muted
in the a position by a C 1 to C 10 alley! chain. Mixtures of 2-alkyl-alcanols
c
an 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
(i) polydimethyl siloxane, at a level of from 50 % to 99 % , prefersbl
Y
75 °.& to 95 % by weight of the silicone antifoam compound; and
(u) silica, at a level of from 1 % to 50 %, preferably 5 % to 25 ~ by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from 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 DC054.4, commercially
available from DOW Corning under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C
18
ethoxylated alcohol with a degree of ethoxylation of fmm 5 to 50,
preferably 8 to 15, at a level of from 5 % to 80 % , preferably 10 % 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 p~ioles can be rendered hydrophobic by
CA 02187436 1999-09-17
WO 95/28473 PCT/US95I04209
44
treating them with dialkylsilyl groups andior trialkylsilyl groups either
bonded
directly onto the silica or by means of a silicone resin. It is preferred to
employ a
silica the particles of which have been rendered hydrophobic with dimethyl
andlor
trimethyl silyl groups. A preferred particulate antifoam compound for
inclusion in
the detergent compositions in accordance with the invention suitably contain
an
amount of silica such that the weight ratio of silica to silicone lies in the
range
from 1:100 to 3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds suppressing system is represented by a
hydrophobic silanated (most preferably trimethyl-silanated) silica having a
particle
size in the range from 10 nanometprs to 20 manometers and a specific surface
area
above SOm2/g, intimately adrnix~ 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: ! to about 1:2.
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and comprises a silicone antifoam compound and an organic carrier
material having a melting point in the range 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 ZO
carbon
atoms, or a mixture thereof, with a melting point of from 45°C to
80°C.
Other highly preferred particulate suds suppressing systems are described in
CA 2099129 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. European publication 461699 also discloses
highly
preferred particulate suds suppressing systems comprising silicone antifoam
compound, a carrier material, an organic coating material and crystalline or
amorphous aluminosilicate at a weight ratio of aluminosilicate : silicone
andfoam
compound of 1:3 to 3:1. The preferred carrier material in both of the above
described highly preferred granular suds controlling .agents is starch.
x ~. _ , ,
R'O 95!28473 PCT/US95/04209
45 2181436
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 60 % to 80 % by weight of the
component, of carrier material, preferably starch;
(iii) from S % 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% to 15%, preferably from 3% to 10%, by weight of ClZ-C22
hydrogenated fatty acid.
Polymeric dve transfer iunh;biting agen c
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, polyvinylpyrrotidonepolymers or combinations thereof.
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
WO 95/28473 ~ _ _ ' . PCT/US95104209
q6
P
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached to,
or
wherein the R-N-O group forms part of the polymerisable unit or a combination
of
both.
O O 0
~I ;
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic,heterocyclic or alicyclic
groups
or any combination thereof whereto the nitrogen of the N-O group can be
attached
or wherein the nitrogen of the N-O group is part of these groups.
O 95128473 PCl'/US95/04209
47
2187436
The N-O group can be represented by the following general
structures
O
1
0
(R1 ) x _N-(R2)y 1
(R3)z or =N-(R1)x
wherein RI , R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y orland z is 0 or 1 and wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups. The N-O group can be part of the
polymerisabIe
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 (n 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 heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
WO 95/28473
218' ~'3
PCTYUS95/04209
. . 4s
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.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are polyviny!s, polyalkylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylat~s 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 1:1000000. 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 obta:~ted in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the material has the
desired
water-solubility and dye-suspending power. Typically, the average molecular
weight is within the range of 500 to 1000,000; preferably from 1,000 to
50,000,
more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
b~on.~lvmers of N-vipylnvrrolidone and N-vinvlimidazole
Preferred polymers for use herein may comprise a polymer selected from N-
vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000 more preferably from 8,000
to 30,000, most preferably from 10,000 to 20,000. The preferred N-
vinylimidazole N-vinylpyrrolidone copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8
to
0.3, most preferably from 0.6 to 0.4 .
CA 02187436 1999-09-17
49
c) Polyvinyloyrrolidone
The detergent compositions herein rnay also utilize polyvinylpyrro[ido
having an average molecular
ne ( pVp
weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, mor
a
preferably from 5,000 to 50,000, and most preferably from 5,000 to I5.
000.
Suitable polyvinylpyrrolidones are commercially vailable from ISP Co
rporation.
New York, NY and Montreal, Canada under the product names PVp K_
15
(viscosity molecular weight of 10,000), pVp K_30 (average molecular wei
ght of
40,000), PVp K_60 (average molecular weight of 160,000), and PVp K-9
0
(average molecular weight of 360,000). pVp K-15 is also available from
ISP
Corporation. Other suitable polyvinylpy~lidones which are commercial)
Y
available from BASF Cooperation include Sokalan"~' Hp 165 and Sokalan >EIP 12.
Polyvinylpyrroiidone may be incorporated in the detergent compositions h
erein at
a level of from O.OI 9i; to 5 ~ by weight of the detergent, preferably from 0.
05 ~
to 3 ~ by weight, and more preferably from 0.1 ~ to 2 ~ by weight. The
amount
of polyvinylpy~lidone delivery in the wash elution is preferabl from 0.
to 250 y 5 ppm
PPm~ preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to
100 ppm.
dl Polvv'nvi~~~
The detergent compositions heron may a1~ u~ polyvinyloxazoiidones as
polymeric dye transfer inhibiting agents. paid polyvinylo~olidones have an
average molecular weight of from 2,500 to 400,000 preferably from 5,000 to
2~,~, mon preferably from 5,000 to 50,000, and most preferably from 5
to 15,000.
,000
The amount of polyvinyloxazolidone incorporated in the detergent com sitions
Po
may be from 0.019b to 5 ~b by weight, preferably from 0.05 ~b to 3 ~ by wei
ht,
g
and more preferably from 0.19b to 2 % by weight. The amount of
P°lY"~Ylo~cazoGdone delivery in the wash solution is typic~y from
0.5 m to
PP
250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 m to
100 ppm. PP
el PolWenvlimir~a~~t~
Y
_~: ,rv ~. -
t i ~. ~ 1 ' :; ~ ..
W0 95128473 .:PCTIUS95/04209
2187436
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 400000, more preferably from
5,000 to, 50,000, and most preferably from S,OOO to 15,000.
The amount of polyvinylimidazole incorpoarted in the detergent compositions
may
be from 0.01 % to 596 by weight, preferably from 0.05 % to 3Wo by weight, and
more preferably from 0.1 ~ to 296 by weight. The amount of polyvinylimidazole
delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5
ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
tical bri htg ener
The detergent compositions herein may also optionally contain from about 0.005
~
to 5 3b 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 0.0136 to 19b by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
Rz
RtON N H H N N
N ~O.~H O C C-~-H~O
Ra S03M S~sM O i
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-
methylamino, morphilino, chloro and amino; and M is a salt-forming ration such
as sodium or potassium.
When in the above formula, Rl 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
CA 02187436 1999-09-17
51
salt. This particular brightener species is commercially marketed under the
trademark Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred, hydrophilic optical brightener useful in the detergent
compositions
herein.
When in the above formula, R1 is aniline, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-2-hydroxyethyl-N-methylamino)_s-triazine_2-yl)amino]2,2'-
stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the Trademark Tinopal SBM-GX by Ciba-Geigy
Corporation.
When in the above formula. R1 is aniline, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-aniline-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the trademark Tinopal AMS-GX by Ciba
Geigy Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used
in combination with the selected polymeric dye transfer inhibiting agents
hereinbefore described. The combination of such selexted polymeric materials
(e.g., PVNO and/or PVPVn with such selected optical brighteners (e.g., Tinopal
LTNPA-GX, Tinopal SBM-GX ,utd: or Tinopal AMS-GX) provides significantly
better dye transfer inhibition :n aq;reous wash solutions than does either of
these
two detergent composition compcments when used alone. Without being bound by
theory, it is believed that such bcighteners 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 oa 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 courx, it will be appreciated that other, conventional optical brightener
types
of compounds can optionally be used in the present compositions to provide
218'7436
WO 95128473 8 r PCTIUS95104209
~~' ~a ~~' ~ 52
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
Fabric softening agents can also be incorporated into laundry detergent
compositions in accordance with the present invention. These agents may be
inorganic or organic in type. Inorganic softening agents are exemplified by
the
smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents
include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and
EP-B-0 011 340.
Levels of smectite clay are normally in the range from 5 °~ to IS %
, more
preferably from 8~ to 1236 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 water-insoluble tertiary amines or dilong chain amide
materials
are incorporated at levels of from 0.5 ~ to 596 by weight, normally from I
°k 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
°.6 to 2°a,
normally from 0. I S % to 1.5 96 by weight.
Other optional ingredients suitable for inclusion in the compositions of the
invention include perfumes, colours and filler salts, with sodium sulfate
being a
preferred filler salt.
The detergent compositions of the invention can be formulated in any desirable
form such as powders, granulates, pastes, liquids, tablets and gels.
Liauid com sno irions
The detergent compositions of the present invention may be formulated as
liquid
detergent compositions. Such liquid detergent compositions typically comprise
from 9496 to 3596 by weight,preferably from 9096 to 4096 by weight, most
~WO 95/28473 PCTIUS95104209
53
preferably from 80~ to 50% by weight of a Liquid carrier, e.g., water,
preferably
a mixture of water and organic solvent.
Gel compositions
The detergent compositions of the present invention may also be in the form of
gels. Such compositions are typically formulated with polyakenyl polyether
having a molecular weight of from about 750,000 to about 4,000,000.
WO 95128473 ' PC'T/US95/04209
54
218743b
Solid compositions
The detergent compositions of the invention are preferably in the form of
solids.
such as powders and granules.
The particle size of the components of granular compositions in accordance
with
the invention should preferably be such that no more that 5 k of particles are
greater than I .4mm in diameter and not more than S ~6 of particles are less
than
O.lSmm in diameter.
The bulk density of granular detergent compositions in accordance with the
present
invention typically have a bulk density of at least 450 gllitre, more usually
at least
600 gllitre and more preferably from 650 gllitre 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 inm, an internal height of 87 mm and an internal diameter of 84
mm.
Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring,
the
flap valve is opened and powder allowed to overfill the cup. The filled cup is
removed from the frame and excess powder removed from the cup by passing a
straight edged implement e.g. a knife, across its upper edge. The filled cup
is
then weighed and the value obtained for the weight of powder doubled to
provide
the bulk density in gllitre. Replicate measurements are made as required.
T~aki processes - ~nular com ~i~tion~
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.
'WO95128473 ' a
PCT/US95/04209
Washine methods
The compositions of the invention may be used in essentially any washing or
cleaning method, including machine laundry and dishwashing methods.
Machine dishwashing method
A preferred machine dishwashing method comprises treating soiled articles
selected from crockery, glassware, hollowware and cutlery and mixtures
thereof,
with an aqueous liquid having dissolved or dispensed therein an effective
amount
of a machine dishwashing composition in accord with the inevntion. By an
effective amount of the machine dishwashing composition it is 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 laundry methods herein comprise treating soiled laundry with an
aqueous
wash solution in a washing machine having dissolved or dispensed therein an
effective amount of a machine laundry detergent composition in accord with the
invention. The detergent can be added to the wash solution either via the
dispenser
drawer of the washing machine or by a dispensing device. By an effective
amount
of the detergent composition ~t is -.o: ant from 40g to 300g of product
dissolved or
dispersed in a wash solution o.' 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
defiver 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.
218'43:6, ,
°.3..,.:~; ~I
WU 95128473 PCT/US95104209
56
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement
of the wash cycle of the washing machine water is introduced into the drum and
the drum periodically rotates. The design of the dispensing device should be
such
that it permits containment of the dry detergent product but then allows
release of
this product during the wash cycle in response to its agitation as the drum
rotates
and also as a result of its immersion in the wash water.
To allow for release of the detergent product during the wash the device may
possess a number of openings through which the product may pass.
Alternatively.
the device may be made of a material which is permeable to liquid but
impermeable to the solid product, which will allow release of dissolved
product.
Preferably, the detergent product will be rapidly released 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 J.Bland
published in Manufactutirtg 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 defusing 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 atiartgement 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.
218"7~3~6' ,~ -.
-WO 95!28473 PCTlUS95J04209
57
In a pretreatment wash method aspect of the invention a soiled/stained
substrate is
treated with an effective amount of a pretreatment solution containing a
surfactant.
but no bleach components. The solution might optionally contain other non-
bleach
detergent components such as builders, heavy metal ion sequesttants, enzymes
and
detergent polymers.
The level of the surfactant 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 a
bleach-containing detergent product is employed. The washing method may for
example, be any of the machine dishwashing or machine laundry washing methods
described herein.
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
RYAS . Sodium ClX - Cly allryl sulfate
25EY . A C12-15 P~o~tly linen' 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 , . CIX - Cly sodium allcyl sulfate condensed with an
' average of Z moles of ethylene oxide per mole
~?~.~, .',_.
W0 95/28473 PCT/US95104209
58
TFAA C16-C18 alkyl N-methyl glucamide.
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula b-Na2Si205
Carbonate . Anhydrous sodium carbonate
Polycarboxylate . Copolymer ~f 1:4 maleiclacrylic acid, average
molecula~ v: eight about 80,000
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20 having a primary particle
size in the range from I to 10 micrometers
Citrate . Tri-sodium citrate dihydrate
Percarbonate (fast release . Anhydrous sodium percarbonate bleach of empirical
particle) formula ZNa2C03.3H202 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 perrarbonate bleach coated with
a
particle) coat;.-tg of odium silicate (Si20:Na20 ratio = 2:1) at
a weight ratio of percarbonate to sodium silicate of
39:1
T,~ . Tettaacetyl ethylene diamine
TAED (slow release . Particle formed by agglomerating TAED with citric
particle) acid and polyethylene glycol (PEG) of Mw=4,000
with a weight ratio of components of TAED:citric
acid:PEG of 75:10:15, coated with an external coating
of citiic acid at a weight ratio of agglomerate: citric
acid coating of 95:5.
CA 02187436 1999-09-17
59
Benzoyl Caprolactam (slow : Particle formed by agglomerating benzoyl
caprolactam
release particle) (BzCI) with citric acid and polyethylene eiycol (PEG)
of Mw=4,Opp, with a weight ratio of components of
BzCl:citric acid:PEG of 63:2(:16, coated with an
external coating of citric acid at a weight ratio of
agglomerate:citric acid coating of 95:5
TAED (fast release : Particle formed by agglomerating TAED with partially
particle) neutralised polycarboxylate at a ratio of
TAED:polycarboxylate of 93:7, coated with an
external coating of polycarboxylate at a weight ratio of
agglomerate:coating of 96:4
EDDS (fast release : Particle formed by spray-drying EDDS with MgS04 at
particle) a weight ratio of 26:74
Protease : Proteolytic enzyme sold under the trademark Savinase
by Novo Industries A/S with an activity of 13
KNPU/g.
~Y~ . Amylolytic enryme sold under the trademark
Termamyl 60T by Novo Industries A/S with an activity
of 300 KNU/g
Cellulase : Cellulosic enzyme sold by Novo Industries A/S with an
activity of 2000 CEW/g
~p~ : Lipolytic enzyme sold under the trademark Lipolase by
Novo Industries A/S with an activity of 165 KLU/g
CMC : Sodium carboxytnethyl cellulose
1,1-hydroxyethane diphosphonic acid
EDDS : Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer
in the form of the sodium salt.
W0 95/28473 PCTIUS95104209
6D
PVNO Poly (4-vinyipyridine)-N-oxide copoiymer of
vinylimidaxole and vinylpyrrolidone
Granular Suds Suppressor . 12 ~ Siliconelsilica, 18 36 stearyl alcoho1,70 %
starch in
granularform
21~'~436
WO 95/28473 PCT/US95/04209
61
Exam~ile 1
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
45AS/25AS (3:1) 9.1 9.1 9.1 9.1
35AE3S 2.3 2.3 2.3 2.3
24FS 4.5 4.5 4.5 4.5
TF~ 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 particle)6.3 - - -
TAED (slow release particle)- 5.0 - 2.3
Benzoyl Caprolactam - - 5.0 2.7
(slow
release particle)
Percarbonate (fast release22.5 - - 22.5
particle)
Percarbonate (slow release- 22.5 22.5 -
particle)
WO 95128473 PCTIUS95104209
62
DETPMP 0.5 0.8 -
EDDS (fast release particle)- - 0.3 0.75
Protease 0.55 1.27 0.55 1.27
Lipase 0.15 0.15 0.15 0.15
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
Grenular suds su ressor1.5 1.5 1.5 1.5
Minorslmisc to 1006
The following T50 values (in seconds) were obtained for each of products A to
D:
T50 A B C D
Peroxyacid 130 190 205 240
AVO 95 225 230 115
Surfactant 90 90 90 60
(45ASI25AS
and 35AE35)
