Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Cationic deter~ent compounds
Technical field
The present invention relates to selected cationic ester surfactants which are
suitable for use in laundry and dish w~hing methods.
Back~round to the invention
The satisfactory removal of greasy soils/stains, that is soils/stains having a
high proportion of triglycerides or fatty acids, is a challenge faced by the
formlll~tQr of detergent compositions for use in machine laundry and
dishw~.~hing methods. Surfactant components have traditionally been
employed in detelgellt products to facilitate the removal of such greasy
soils/stains.
In particular, surf~ct~nt systems comprising cationic ester surf~ct~ntc have
been described for use in greasy soil/stain removal. By cationic ester
surfactants it is meant those compounds having surf~ct~nt properties which
comprise at least one ester (i.e. -COO-) linkage and at least one cationically
charged group. The cationically charged group is often an ammonium or
substituted ammonium group.
For example, EP-B-21,491 discloses delel~,elll compositions cont~ining a
nonionic/cationic surfactant mixture and a builder mixture comprising
aluminosilicate and polycarboxylate buildler. The cationic surfactant may be
a cationic ester. Improved particulate and greasy/oily soil removal is
described.
US-A-4,228,042 discloses biodegradable cationic surf~ct~nt~, including
cationic ester surfactants for use in detergent compositions to provide
greasy/oily soil removal. The combination of these cationic surfactants with
nonionic surf~ct~nt~ in compositions de~ign~l for particulate soil removal is
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also described. Anionic sur~actants are disclosed as optional components of
the compositions, but are present at low levels relative to the cationic
surfactant component.
US-A-4,239,660 discloses laundry detergent compositions cont~inin~
cationic ester surfactant and nonionic surfactant at defined weight ratios and
an ~lk~linity source. The ~lk~linity source enables a wash solution having a
pH of from 8 to 10 to be formed within 3 minlltes of dissolution of the
composition in water at 100~F (37~C) at a solution concentration of
0.15%.
US-A-4,260,529 discloses laundry detergent compositions having a pH of
no greater than 11 cont~inin~ cationic ester surfactant and nonionic
surfactant at defined weight ratios. Anionic surfactants are disclosed as
optional components of the compositions, but are present at low levels
relative to the cationic ester surf~et~nt component.
The Applicants have now found that certain cationic ester surf~t~nt~, in
which the cationically charged group is an amrnonium group substi~lte~l by
at least one hydroxyalkyl group, demonstrate enhanced stain removal
performance under the wash conditions of a typical laundry method,
particularly at low wash temperatures. The enh~n~e~l low wash temperature
performance is believed to be related to the good cold water solubility of
these cationic esters. Additionally, the cationic ester surf~ct~nt~
demonstrate enh~nce ;l perfume robustness, that is to say that fabrics
washed in perfume-cont~ining detergellls cont~inin~ these surfactants have
an improved perfume profile.
The prior art documents cited above include a general description of
cationic ester surf~ct~nts in which it is envisaged that the cationically
charged group is an ammonium substituted optionally by various
substitutuent groups. Choline ester surf~ct~nt.~ having methyl substituerlts
are however, exclusively exemplified. None of the documents provides any
teaching of the enhanced stain removal capability or perfume robustness
exhibited by the present cationic ester surfactants in which the cationically
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charged group is an ammonium group substituted by at least one
hydroxyalkyl group.
All documents cited in the present description are, in relevant part,
incorporated herein by reference.
S~-mm~ of the Invention
According to the present invention there is provided a cationic ester
surfactant comprising at least one ester (i.e. -COO-) linkage and at least
one cationically charged group characterized in that said cationically
charged group is an ammonium group substi~lte~l by at least one
hydroxyalkyl group.
In a preferred aspect, the cationic ester surfactant is selected from those
having the forrnula:
R2
Rs +
R~ (CH)nO b (X)U (C~2)m-(~v-(CH2)t-N-R3 M
-a
R4
wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain
or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from
the group consisting of COO, OCO, O, CO, OCOO, CONH,NHCO,
OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,
OCOO, OCONH or NHCOO group; R2 is a hydroxyalkyl group having
from 1 to 4 carbon atoms; R3, R4, R6, R7, and R8 are independently
selected from the group consisting of alkyl, alkenyl, hydroxyalkyl,
hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
Rs is independently H or a C1-C3 alkyl group; wherein the values of m, n,
s and t independently lie in the range of from 0 to 8, the value of b lies in
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the range from 0 to 20, and the values of a, u and v independently are
either 0 or 1 with the proviso that at least one of u or v must be 1; and
wherein M is a counter anion.
l;)etailed description of the invention
Cationic ester surfactant
The sur~actant of the present invention is a cationic ester surfactant, that is
a compound having surfactant properties comprising at least one ester (ie -
COO-) linkage and at least one cationically charged group.
The cationically charged group is an amrnonium group substituted by at
least one, preferably only one, hydroxyalkyl group. The hydroxyallyl
preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon
atoms, most preferably 2 carbon atoms.
Preferred cationic ester surfactants are those having the formula:
~l-- R5 ~X)u ( C H2 )m (Y)v--(C H2 )t--N--R3 M
b
R4
wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain
or M-. N+(R6R7Rg)(CH2~S; X and Y, independently, are selected from
the group con~i~tin~ of COO, OCO, O, CO, OCOO, CONH, NHCO,
OCONH and NHCOO wherein at least one of X or ~ is a COO, OCO,
OCOO, OCONH or NHCOO group; R2 is a hydroxyalkyl group having
from 1 to 4 carbon atoms; R3, R4, R6, R7, and R8 are independently
selected from the group consisting of alkyl, alkenyl, hydroxyalkyl,
hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
Rs is independently H or a Cl-C3 alkyl group; wherein the values of m, n,
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s and t independently lie in the range of from O to 8, the value of b lies in
~ the range from O to 20, and the values of a, u and v independently are
either O or 1 with the proviso that at least one of u or v must be 1; and
~ wherein M is a counter anion.
Preferably R2 is a -CH2CH20H group and R3 and R4 are both CH3
groups.
Preferably M is selected from the group consisting of halide, methyl
sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,
bromide or iodide.
Preferred water dispersible cationic ester surfactants are the hydroxyethyl
choline esters having the formula:
O CH2CH201 1
R1 C ~--CH2CH2--N~--CH3 M-
CH3
wherein Rl is a Cll-Clg linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl choline
ester quaternary dime~yl(hydroxyethyl)ammonium halides (Rl=C17
alkyl), p~lmitoyl choline ester quaternary
dimethyl(hydroxyethyl~ammonium halides (Rl =Cls alkyl), myristoyl
choline ester quaternary dimethyl(hydro~cyethyl)ammonium halides
(Rl = C 13 alkyl), lauroyl choline ester dimethyl(hydroxyethyl)ammonium
halides (Rl =Cl l alkyl), cocoyl choline ester quaternary
dimethyl(hydroxyethyl)ammonium halides (Rl =Cl l C13 alkyl), tallowyl
choline ester quaternary dimethyl(hydroxyethyl)ammonium halides
(Rl=Cls C17 alkyl), and any mixtures thereof.
The particularly preferred cationic esters, given above, may be synthesized
by the direct ~mid~tion of a fatty acid (RlCOOH), fatty acid ester
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(RlCOORn) or fatty acid halide (R1COOHal) of the desired chain length
with diethanol~mine (a secondary amino alcohol) to form diethanolamide,
preferably in the presence of a catalyst, such as an acid catalyst
methanesulfonic or sulfuric acid or a basic catalyst, such as sodium
methoxide. The reaction product is heated, preferably under acid
conditions, to force the rearrangement of the ethanolamide to the ester
amine, which is then quaternized with a 'quaternizing agent' such as methyl
halide, methyltosylate or dimethylsulfate forming the desired cationic ester.
The quaternization step in the above synthetic route is preferably carried
out in the presence of a solvent such as ethanol, toluene, propylene glycol
or preferably a fatty alcohol ethoxylate such as C1o-C1g fatty alcohol
ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups
per mole. It can be useful to have an anionic surfactant, such as linear alkyl
benzene sulfonate present during the ~uaternization step to disrupt the
formation of any aqueous gel phases.
Analogous synthetic routes may be employed to make other cationic esters
in accord with the invention.
Thus a route involving esterification of an, optionally substi~-te~l,
secondary amino alcohol with a fatty acid, fatty acid ester or fatty acid
halide to form an alkanol~mirle, followed by rearrangement of the amide to
form an ester amine, followed by quaternization of the amine group with
an, optionally substitl~te~l~ alkyl halide to obtain the cationic ester product is
generally envisaged.
Surfactant systems
Surfactant systems herein comprise the cationic ester surfactant in accord
with the present invention in combination with an additional surfactant
selected from nonionic, non-ester cationic, ampholytic, amphoteric and
zwitterionic surf~ct~nt~ and mixtures thereof.
-
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A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and species of these surfactants, is given in U.S.P. 3,929,678 issued to
l_aughlin and EIeuring on December 30, 1975. Further examples are given
in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz,
Perry and Berch). A list of suitable cationic surfactants is given in U.S.P.
4,259,217 issued to Murphy on March 31, 1981.
Surfactant sytems comprising anionic and/or nonionic surfactants in
combination with the cationic ester surfactants of the invention are
preferred herein. Most preferably the surfactant systems comprise both
anionic and nonionic surfactants in combination with the cationic ester
surfactants of the invention.
The weight ratio of anionic surfactant to cationic ester surfactant in the
surfactant system is preferably from 3:1 to 50:1, more preferably from 4:1
to 40:1, most preferably from 5:1 to 20:1.
The weight ratio of nonionic surfactant to cationic ester surf~l~t~nt in the
surfactant system is preferably from 3:1 to 50:1, more preferably from 4:1
to 40:1, most preferably from 5:1 to 20:1.
Anionic surfactant
Essentially any anionic surfactants useful for detersive purposes are
suitable. These can include salts (including, for example, sodium,
potassium, ammonium, and substih-te-l ammonium salts such as mono-, di-
and triethano!~min~ salts) of the anionic sul~ate, sulfonate, carboxylate and
sarcosinate surfactants. Anionic sulfate surfactants are preferred.
Other anionic surf~ct~nte 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 lln.e~t~lrated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and llne~1~lrated C6-C14 diesters), N-acyl sarcosinates.
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Resin acids and hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in
or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-
C17 acyl-N-(Cl-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and
branched primary Clo-Clg alkyl sulfates, more preferably the C11-C1s
branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C1o-C1g alkyl sulfates which have been ethoxylated with
from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the
alkyl ethoxysulfate surfactant is a C11-Clg, most preferably C11-C1s alkyl
sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to
5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surf~ct~nt~ suitable for use herein include the salts of
Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-Cz
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
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glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
~ Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate sur~actants and the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herein.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CH2CH20)X CH2COO-M+ wherein ~ 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 20 % and M
is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include
those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to
Clg alkyl group, x is from 1 to 25, Rl and R2 are selected from the group
consisting o~ hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from
the group consisting of hydrogen, substihlte~l or unsubstituted hydrocarbon
having between 1 and 8 carbon atoms, and mixtures thereof.
Suita~le soap surf~ct~nts include the secondary soap surf~t~nt~ which
contain a carboxyl uI~it conn~cteA to a secondary carbon. Preferred
secondary soap sur~ct~n~ for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of 2-methyl-1-
~lnrl~c~noic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may
also be included as suds suppressors.
~ Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 linear or
branched alkyl or alkenyl group, Rl is a Cl-4 alkyl group and M is an
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alkali metal ion. Preferred examples are the myristyl and oleoyl methyl
sarcosinates in the form of their sodium salts.
Alkoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic condensates o~ alkyl phenols, nonionic ethoxylated alcohols,
nonionic ethoxylated/propo~cylated fatty alcohols, nonionic
ethoxylatelpropoxylate condensates with propylene glycol, and the nonionic
ethoxylate condensation products with propylene oxide/ethylene dt~mine
adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene oxide, particularly ethylene oxide and/or propylene oxide, are
suitable for use herein. The alkyl chain of the aliphatic alcohol can either
be straight or branched, primary or secondary, and generally contains from
~ to 22 carbon atoms. Particularly preferred are the condensation products
of alcohols having an alkyl group cont~inin~ from 8 to 20 carbon atoms
with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONRlZ wherein: R1 is H, C1-C4 hydrocarbyl, 2-
hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof,
preferable C1-C4 alkyl, more preferably Cl or C2 alkyl, most preferably
Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably
straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain Cg-
C17 alkyl or alkenyl, most preferably straight-chain Cl l-C17 alkyl or
alkenyl, or mixture thereof; and Z ;s a polyhydroxyhydrocarbyl having a
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11
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 reduc;ng sugar in a reductive
~min~tion reaction; more preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:R6CoN(R7)2 wherein R6 is an alkyl group cont~inin~ from 7 to 21,
preferably from 9 to 17 carbon atoms and each R7 is selected from the
group consisting of hydrogen, Cl-C4 allcyl, C l-C4 hydroxyalkyl, and -
(C2H40)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
con~ining from 6 to 30 carbon atoms a~d a polysaccharide, e.g., a
polyglycoside, hydrophilic group cont~inin.~ from 1.3 to 10 saccharide
units.
Preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(glYC~sYl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the allyl
groups contain from 10 to 18 carbon atoms, n is 2 or 3; t is from O to 10,
and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric surfactant
Suitable amphoteric surf~ct~nt.c for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.
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12
Suitable amine oxides include those compounds having the formula
R3(oR4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining
from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group
cont~inin~ from 2 to 3 carbon atoms, or mixtures thereof; x is from O to 5,
preferably from O to 3; and each R5 is an alkyl or hydroxyalkyl group
cont~inin~ from ~ to 3, or a polyethylene oxide group cont~inin~ from 1 to
3 ethylene oxide groups. Preferred are Clo-C1g alkyl dimethyl~min~
oxide, and C10 18 acylamido alkyl dimethyl~mint? oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions hereof. These surf~ct~nt~ can be broadly described as
derivatives of secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary ammonium,
quaternary phosphonium or tertiary sulfonium compounds. Betaine and
sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula
R(R')2N~R2COO- wherein R is a C6-C1g hydrocarbyl group, each Rl is
typically C l-C3 alkyl, and R2 is a C 1-Cs hydrocarbyl group. Preferred
betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8
acylamido~ro~alle (or ethane) ~limet~yl (or diethyl) betaines. Complex
betaine surf~t~nt~ are also suitable for use herein.
Gationic surfactants
Additional cationic surfactants can also be used in the detefgen~
compositions herein. Suitable cationic surfactants include the quaternary
ammonium surf~ct~nt~ selected from mono C6-C16, preferably C6-Clo N-
,
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13
alkyl or alkenyl ammonium surfactants wherein the rem~ining N positions
are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
I:)etergent compositions
Detergent compositions may be form~ te-l cont~ining the cationic esters of
the present invention, and the above me~tioned cationic ester cont~inin~
surfactant systems, in combination with additional detergent components.
Perfume-cont~inin~ d~tel~,ellL compositions are particularly favoured.
Preferably, the level of incorporation of the surfactant system is from 1%
to 95 %, more preferably from 3 % to 60 %, most preferably from 5 % to
40% by weight of the deLel~el,L composi~ion. The level of incorporation of
the cationic ester surfactant is preferably from 0.1% to 50%, more
preferably from 0.5% to 30%, most preferably from 1.0% to 10% by
weight of the detel~;ellL composition.
Detergent compositions cont~ining one or more additional deterg,ellt
components selected from the group consisting of an ~lk~linity system,
bleaches, builders, organic polymeric co;mpounds, enzymes, suds
suppressors, lime soap dispersants, soil suspension and anti-redeposition
agents and corrosion inhibitors are thus envisaged. The precise nature of
these additional components, and levels of incorporation thereof will
depend on the physical form of the composition, and the precise nature of
the w~hin~ operation for which it is to be used.
Alk~linity system
Detergent compositions herein may contain from 1.5% to 95%, preferably
from 5% to 605~, most preferably from 10% to 40% by weight of the
composition of an ~lk~linity system comprising components capable of
providing ~lk~linity species in solution. By ~lk~lini~y species it is meant
herein: carbonate, bicarbonate, hydroxide and the various silicate anions.
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14
Such ~lk~linity species can be formed for example, when ~lk~line salts
selected from aLkali metal or ~lk~line earth carbonate, bicarbonate,
hydroxide or silicate, including crystalline layered silicate, salts and any
mixtures thereof are dissolved in water. Alkali metal percarbonate and
persilicate salts are also suitable sources of ~lk~linity species.
Examples of carbonates are the ~lk~line earth and alkali metal carbonates,
including sodium carbonate and sesqui-carbonate and any mixtures thereof
with ultra-fine calcium carbonate such as are disclosed in German Patent
Application No. 2,321,001 published on November 15, 1973. Alkali metal
percarbonate salts are also suitable sources of carbonate species and are
described in more detail in the section ~inorganic perhydrate salts' herein.
Suitable silicates include the water soluble sodium silicates with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being
preferred, and 2.0 ratio being most preferred. The silicates may be in the
form of either the anhydrous salt or a hydrated salt. Sodium silicate with
an SiO2: Na20 ratio of 2.0 is the most preferred silicate. Alkali metal
persilicates are also suitable sources of silicate herein.
Preferred cryst~llin~ layered silicates for use herein have the generalformula
NaMSix02x + 1 ~YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a
number from 0 to 20. Crystalline layered sodium silicates of this type are
disclosed in EP-A-0164514 and methods for their preparation are disclosed
in DE-A-3417649 and DE-A-3742043. Herein, x in ~e general formula
above preferably has a value of 2, 3 or 4 and is pre~erably 2. The most
preferred material is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.
The crystalline layered silicate material is preferably present in granular
detergent compositions as a particulate in intim~te admixture with a solid,
water-soluble ionisable material. The solid, water-soluble ionisable
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material is selected from organic acids, organic and inorganic acid salts and
~ mixtures thereof.
A preferred detergent composition herein comprises
(a) from 1 % to 90 % by weight of the composition of a surfactant
system comprising an anionic surfactant and a cationic ester
surfactant in accord with the present invention at a weight ratio of
anionic to cationic ester surfactant of from 3:1 to 15:1; and
(b) from 1.5 % to 95 ~ by weight of the composition of an ~lk~l~nity
system comprising ~lk~line salts selected from the group consisting
of alkali metal or ~lk~line earth carbonate, bicarbonate, hydroxide or
silicate, including crystalline layered silicate, salts and any mixtures
thereof.
Water-soluble builder compound
The detergent compositions herein preferably contain a water-soluble
builder compound, typically present at a level of from 1 % to 80~ by
weight, preferably from 10% to 70% by weight, most preferably from 20%
to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble
monomeric polycarboxylates, or their acid forms, homo or copolymeric
polycarboxylic acids or their salts in which the polycarboxylic acid
comprises at least two carboxylic radicals se~al~ted from each other by not
more that two carbon atoms, borates, phosphates, and mixtures of any of
the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and perform~nre.
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16
Suitable carboxylates cont~ining one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~inin~ two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well
as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates
cont~inin~ three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate derivatives such as
the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates cont~inin~ four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
l,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates cont~ininp: sulfo substituents include the sulfosuccinate
derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in
U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described
in British Patent No. 1,439,000. Preferred polycarboxylates are
hydroxycarboxylates cont~inin~ up to three carboxy groups per molecule,
more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric
acid rnixtures are also co~ nl~lated as useful builder components.
Borate builders, as well as builders cont~ininp: borate-forming materials that
can produce borate under detergent storage or wash conditions are useful
water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
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17
potassium orthophosphate, sodium polymeta/phosphate in which the degree
of polymerization ranges from about 6 to 21, and salts of phytic acid.
~ Partially soluble or insoluble builder compound
The detergent compositions herein may contain a partially soluble or
insoluble builder compound, typically present at a level of from 1% to 80
by weight, preferably from 10% to 70% by weight, most preferably from
20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates .
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(AlO2)z(SiO2)y]. xH2O 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, cont~ining from 10% to 28%,
more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic crystalline aluminosilicate ion
exchange materials are available under the designations Zeolite A, Zeolite
B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the
formula
Na 12 [Al~2) 12 (sio2)l2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite ~ has the formula Na86
[(Alo2)86(sio2)lo6~. 276 H2O.
Organic peroxyacid bleaching system
A preferred feature of deteLgent compositions herein is an organic
peroxyacid bleaching system. In one preferred execution the bleaching
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18
system contains a hydrogen peroxide source and an organic peroxyacid
bleach precursor compound. The production of the organic peroxyacid
occurs by an in situ reaction of the precursor with a source of hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate bleaches. In an alternative preferred execution a preformed
organic peroxyacid is incorporated directly into the composition.
Compositions cont~inin~ mixtures of a hydrogen peroxide source and
organic peroxyacid precursor in combination with a preformed organic
peroxyacid are also envisaged.
Inorganic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal,
preferably sodium salt at a level of from 1% to 40% by weight, more
preferably from 2 % to 30% by weight and most preferably from 5% to
25 ~ by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate
salts are normally the alkali metal salts. The inorganic perhydrate salt may
be included as the crystalline solid without additional protection. For
certain perhydrate salts however, the preferred executions of such granular
compositions utilize a coated form of the material which provides better
stora~e stability for the perhydrate salt in the granular product. Suitable
coatings comprise inorganic salts such as alkali metal silicate, carbonate or
borate salts or mixtures thereof, or organic materials such as waxes, oils,
or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in ~e form of
the monohydrate of nominal formula NaB02H202 or the tetrahydrate
NaB02H202 3H20- .
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates herein. Sodium percarbonate is an addition compound having a
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19
form~lla corresponding to 2Na2~O3.3H202, and is available commercially
as a crystalline solid.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use
in the detergent compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen
peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally
peroxyacid bleach precursors may be represented as
o
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on perhydroloysis the structure of the peroxyacid produced is
o
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a
level of from 0.5% to 20% by weight, more preferably from 1 % to 15%
by weight, most preferably from 1.5% to 10~ by weight of the detergent
compositions.
Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide
range of classes. Suitable classes include anhydrides, esters, imides,
lactams and acylated derivatives of imidazoles and oximes. Examples of
useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231
and EP-A-0170386.
Leaving ~roups
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The leaving group, hereinafter L group, must be sufficiently reactive for
the perhydrolysis reaction to occur within the optimum time frame (e.g., a
wash cycle). However, if L is too reactive, this activator will be dif~lcult to
stabilize for use in a bleaching composition.
Pre~erred L groups are selected from the group consisting of:
_0~ o~Y and --~~
~ --N N --N--C--CH--R4
1 3 L~ R3 Y
y
IR3 r
--O--C H=C--C H=C H2 --O--C H=C--C H=C H2
Il Y ~
-~11--R1 ~CH2-C\ --N C/
O O
F~3 0 Y
--~C--CHR4 , and I S--CH--R4
R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
cont~ininp; from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining from
1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
Any of Rl, R3 and R4 may be substituted by essentially any functional
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21
group including, for example alkyl, hydroxy, alkoxy, halogen, amine,
~ nitrosyl, amide and ammonium or alkyl ~mmmonium groups
~ The preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+,
-N + (R3)~X- and O < --N(R3)3 and most preferably -SO3-M + and
-C~2 M wherein R is an alkyl chain cont~inin~ from 1 to 4 carbon
atoms, M is a cation which provides solubility to the bleach activator and X
is an anion which provides solubility to the bleach activator. Preferably, M
is an alkali metal, ammonium or substituted ammonium cation, with sodium
and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate or acetate anion.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
perhydrolysis.
Preferred alkyl percall,oxylic precursor compounds of the imide type
include the N-,N,NlNl tetra acetylated alkylene fli~mines wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the allylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ mine (TAED) is particularly pl~felled.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-
tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium
nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate
(ABS) and pent~cetyl glucose.
Amide substituted alkyl peroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable
herein, including those of the following general formulae:
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22
R1----C----N----R2---C--L R1 --N -C ~ 2~C L
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an
alkylene group Cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an
alkyl group cont~ining 1 to 10 carbon atoms and L can be essentially any
leaving group. Amide substituted bleach activator compounds of this type
are described in EP-A-0170386.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on
perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds
include the substih-te~l and unsubstituted benzoyl oxybenzene sulfonates,
and the benzoylation products of sorbitol, glucose, and all saccharides with
benzoylating agents, and those of the imide type including N-benzoyl
succinimide, tetrabenzoyl ethylene ~ mine and the N-benzoyl substituted
ureas. Suitable imidazole type perbenzoic acid precursors include N-
benzoyl imi~1~7O1e and N-benzoyl benzimidazole. Other useful N-acyl
group-cont~ining perbenzoic acid precursors include N-benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.
Typically, cationic peroxyacid precursors are formed by substitlltin~ the
peroxyacid part of a suitable peroxyacid precursor compound with a
positively charged functional group, such as an ammonium or alkyl
~mmmonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the solid detergent
compositions as a salt with a suitable anion, such as a halide ion.
,
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23
The peroxyacid precursor compound to be so cationically substihlte~ maybe a perbenzoic acid, or substituted derivative thereof, precursor compound
as described hereinbefore. Alternatively, the peroxyacid precursor
compound may be an alkyl percarboxylic acid precursor compound or an
amide subst;tuted alkyl peroxyacid precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP
87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/298650, 08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substitl-teA alkyl or benzoyl oxybenzene sulfonates, N-
acylated caprolactams, and monobenw,yltetraacetyl glucose benzoyl
peroxides. Preferred cationic peroxyacid precursors of the N-acylated
caprol~ct~m class include the trialkyl ammonium methylene benzoyl
caprol~st~m~ and the trialkyl ammonium methylene alkyl caprol~çt~m~.
Benzoxazin organic peroxyacid precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed
for example in EP-A-332,294 and EP-A-482,807, particularly those having
the formula:
~ NoC R1
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
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Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, a
preformed organic peroxyacid, typically at a level of from 1% to 15% by
weight, more preferably from 1 % to 10 5~ by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide
substituted compounds of the following general formulae:
R1 C N ~ pC2--C OOH R1 N C R2 C--OOH
O R5 0 or R5 0 0
wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1
to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl group
cont~inin~ 1 to 10 carbon atoms. Amide substituted orgar~ic peroxyacid
compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydorlec~n~-lioc acid, diperoxytetr~lec~nedioc acid and
diperoxyhe~ lec~n~-lioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic acid and N-phthaloyl~minoperoxicaproic acid are also
suitable herein.
Bleach catalyst
The detergent compositions optionally contain a transition metal cont~inin~;
bleach catalyst. One suitable type of bleach catalyst is a catalyst system
comprising a heavy metal cation of defined bleach catalytic activity, such
as copper, iron or m~n~nese cations, an auxiliary metal cation having little
or no bleach catalytic activity, such as zinc or all~mim-m cations, and a
sequestrant having defined stability con~t~nt~ for the catalytic and auxiliary
metal cations, particularly ethylene~i~minetetraacetic acid,
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ethylene~ minetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the m~n~nese-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred
examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)2, MnIV4(u-C))6(1,4,7-triazacyclononane)4-
(ClO4)2, MnIIIMnIV4(u-o)l(u-oAc)2-(l ,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)3, and mixtures thereof. Others are described
in European patent application publication no. 549,272. Other ligands
suitable for use herein include l,5,9-trimethyl-1,5,9-triazacyclodorlec~n~,
2-methyl- 1,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane,
1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S.
Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear
manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-
triazacyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as
disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~np;~nese
(III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy
compound having at least three consecutive C-OH groups. Other examples
include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate
n~ls, including N4MnIII(u-O)2MnIVN4) +and [Bipy2MnII~(u-
0)2MnIVbipy23 -(C104)3.
Further suitable bleach catalysts are described, for example, in European
patent application No. 408,131 (cobalt complex catalysts), European patent
applications, publication nos. 384,503, and 306,089 (metallo-porphyrin
catalysts), U.S. 4,728,455 (m~ng~n~se/multidentate ligand catalyst), U.S.
4,711,748 and European patent application, publication no. 224,952,
(absorbed m~n~nese on aluminosilicate ratalyst)~ U.S. 4,601,845
(aluminosilicate support with m~n~nese and zinc or m~gnesium salt), U.S.
4,626,373 (m~nf~nese/ligand catalyst), U.S. 4,119,557 (ferric complex
catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)
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26
~n~ n 866,191 (transition metal-cont~inin~ salts), U.S. 4,430,243
(chelants with m~n~nese cations and non-catalytic metal cations), and U.S.
4,728,455 (m~n~nese gluconate catalysts).
Heavy metal ion sequestrant
The detergent compositions herein preferably contain as an optional
component a heavy metal ion sequestrant. By heavy metal ion sequestrant it
is meant herein components which act to sequester (chelate) heavy metal
ions. These components may also have calcium and magnesium chelation
capacity, but preferentially they show selectivity to binding heavy metal
ions such as iron, m~n~nese and copper.
Heavy metal ion sequestrants are generally present at a level of from
0.005% to 20%, preferably from 0.1% to ~0%, more preferably from
0.25 % to 7.5 % and most preferably from 0.5 ~ to 5 ~ by weight of the
compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane l-hydroxy disphosphonates and nitrilo trimethylene
phosphonates.
Preferred among ~e above species are diethylene tri~mine penta
(methylene phosphonate), ethylene tli~min~ tri (methylene phosphonate)
hexamethylene ~ mine 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
ethylene~ minotetracetic acid, ethylenetri~mine pentacetic acid,
ethyle~ mine disuccinic acid, ethylen~ mine diglutaric acid, 2-
hydroxypropylen~ mine disuccinic acid or any salts thereof. Especially
preferred is ethylene~ min~-N,N'-disuccinic acid (EDDS) or the alkali
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27
metal, ~lk~line earth metal, ammonium, or substinlted ammonium salts
thereof, or mixtures thereof.
~ Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid derivatives such as 2-hydroxyethyl ~ cetic 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 ,B-~l~nine-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.
~P-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable sequestrants derived from collagen, keratin or casein.
EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.
Dipicolinic acid and 2-phosphonobutane 1,2,4-tricarboxylic acid are alos
suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylen~ mine-N-
N'-diglutaric acid (EDDG) and 2-hydroxypropylene~ min~-N-N'-
disuccinic acid (E~PDDS) are also suitable.
Enzyme
Another preferred ingredient useful in the de~e~,en~ compositions is one or
more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases, cll~in~e~ amylases, neutral and ~lk~line proteases, esterases,
cellulases, pectinases, lactases and peroxidases conventionally incorporated
into deter~,enl compositions. Suitable enzymes are discussed in US Patents
3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold
under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase
by Novo Industries A/S (Denmark), those sold under ~e tradename
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28
~x~t~e, Maxacal and Maxapem by Gist-Brocades, those sold by
Genencor International, and those sold under the tradename Opticlean and
Optimase by Solvay Enzymes. Protease enzyme may be incorporated into
the compositions in accordance with the invention at a level of from
0.0001 ~ to 4 % active enzyme by weight of the composition.
Preferred amylases include, for example, oc-amylases obtained from a
special strain of B licheniformis, described in more detail in GB-1,269,839
(Novo). Preferred commercially available amylases include ~or example,
those sold under the tradename Rapidase by Gist-Brocades, and those sold
under the tradename Termamyl and BAN by Novo Tn~ stries A/S.
Amylase enzyme may be incorporated into the composition in accordance
with the invention at a level of from 0.0001% to 2% active enzyme by
weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 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 obt~in~l, for
example, from a lipase producing strain of Humicola sp., Thermomyces
sp. or Pseudomonas sp. including Pseudomonas pseudoalcali~enes or
Pseudomas fluorescens. Lipase from chemically or genetically modified
mllt~nt~ of these strains are also useful herein. A preferred lipase is derived
~rom Pseudomonas pseudoalcaligenes, which is described in Granted
European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by clonin~ the gene from
Humicola l~ml~inosa and expressing the gene in Asper~illus orvza, as host,
as described in European Patent Application, EP-A-0258 068, which is
commercially available from Novo Industri A/S, Bagsvaerd, Denmark,
under the trade name Lipolase. This lipase is also described in U.S. Patent
4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic polymeric compound
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29
Organic polymeric compounds are preferred additional components of the
detergent compositions herein, and are preferably present as components of
~ any particulate components where they may act such as to bind the
particulate component together. By orga~ic polymeric compound it is
meant herein essentially any polymeric organic compound commonly used
as dispersants, and anti-redeposition and soil suspension agents in detergent
compositions, including any of the high nnolecular weight organic
polymeric compounds described as clay flocc~ t;ng agents herein.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level o~ from 0.1 % to 30 ~, preferably
from 0.5 % to lS %, most preferably from 1 % to 10~ by weight of the
compositions.
Examples of organic polymeric compoun~s include the water soluble
organic homo- or co-polymeric polycarboxylic acids or their salts in which
the polycarboxylic acid comprises at least two carboxyl radicals separated
from each other by not more than two carbon atoms. Polymers of the latter
type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of MWt 2000-5000 and their copolymers with maleic
anhydride, such copolymers having a molecular weight of from 20,000 to
100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-351629.
Terpolymers cont~ining monomer units selected from maleic acid, acrylic
acid, polyaspartic acid and vinyl alcohol, particularly those having an
average molecular weight of from S,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the
detelgellL compositions herein include cellulose derivatives such as
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methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose
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 400~).
Suds suppressing system
The detergent compositions herein, when forrnulated ~or use in machine
washing compositions, preferably comprise a suds suppressing system
present at a level of from 0.0~ % to 15%, preferably from 0.05% to 105~,
most preferably from 0. ~ % to 5 % by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of
compounds which act such as to depress the fo~min~ or sudsing produced
by a solution of a detergent composition, particularly in the presence of
agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone
antifoarn 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 ~e industry, encompasses a variety of relatively high
molecular weight polymers cont~inin~ 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
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31
2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids, and salts thereof, for use as suds suppressor
typically have hydrocarbyl chains of 10 to 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), i~atty acid esters of
monovalent alcohols, aliphatic C~g-C40 ketones (e.g. stearone) N-alkylated
amino triazines such as tri- to hexa-alkylmel~mines or di- to tetra
alkyl~ mine chlortriazines formed as products of cyanuric chloride with
two or three moles of a primary or secondary amine cont~inin~ 1 to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate
esters.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most
preferably a silicone antifoarn compound comprising in
combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75 % to 95 % by weight of the silicone antifoam
compound; and
(ii) 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
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32
ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a
level of from 0.55~ to 10%, preferably 1 % to 10% by weight; a
particularly preferred silicone glycol rake copolymer of this type is
DCO544, commercially available from DOW Corning under the
tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C16-
C1g ethoxylated alcohol with a degree of ethoxylation of from 5 to
50, preferably 8 to 15, at a level of from 5~ to 80%, preferably
10 % to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-
A-0210731 and comprises a silicone antifoam compound and an organic
carrier material having a melting point in the range 50~C to 85~C, wherein
the organic carrier material comprises a monoester of glycerol and a fatty
acîd having a carbon chain cont~inin~ 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 cont~ining from 12 to 20 carbon atoms, or a mixture thereof,
with a melting point of from 45~C to 80~C.
Clay softenin~ system
The detergent compositions may contain a clay softening system comprising
a clay mineral compound and optionally a clay flocc~ ting agent.
The clay mineral compound is preferably a smectite clay compound.
Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790,
3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-
A-313,146 in the name of the Procter and Gamble Company describe
suitable organic polymeric clay flocc~ ting agents.
Polymeric dye transfer inhibitin~ a~ents
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33
The detergent compositions herein may also comprise from 0.01% to 10
~, preferably from O.OS ~ 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, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:
p
(I) Ax
R
wherein P is a polymerisable unit, and
00 0
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 where~o the nitrogen of the N-O group
can be attached or wherein the nitrogen of the N-O group is part of these
groups.
The N-O group can be represented by the following general
structures:
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34
R1) X-N-(R2)Y
(R3)zor N-(R1 ~x
wherein Rl, R2, and ~3 are al;phatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and
wherein the nitrogen of the N-O group can be attached or wherein the
nitrogen of the N-O group forms part of these groups. The N-O group can
be part of the polymerisable unit (P) or can be attached to the polymeric
backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected
from aliphatic, aromatic, alicyclic or heterocyclic groups. Qne 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.
Other suitable polyamine N-oxides are the polyamine oxides whereto the
N-O group is ~ hed to the polymerisable unit. A preferred class of these
polyamine N-oxides comprises the polyamine N-oxides having the general
formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups
wherein the nitrogen of the N-O functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to
1000,000.
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b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having an average molecular weight range of from 5,000 to 50,000. The
preferred copolymers have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP"~ having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinylpyrrolidones are commercially vailable from ISP
Corporation, New York, NY and Montreal, ~'~n~ under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30
(average molecular weight of 40,000), PVP K-60 (average molecular
weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
PVP K-15 is also available from ISP CoIporation. Other suitable
polyvinylpyrrolidones which are commercially available from BASF
~ Cooperation include Sokalan HP 165 andl Sokalan HP 12.
d) Polyvinyloxazolidone
The delelgellt compositions herein may also utilize polyvinyloxazolidones
as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones
have an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimi(1~7.ole
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric dye transfer inhibiting agent. Said polyvinylimidazoles
preferably have an average molecular weight of from 2,500 to 400,000.
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36
Optical brightener
The detergent compositions herein also optionally contain from about
0.005 ~ to 5 % by weight of certain types of hydrophilic optical
brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formuIa:
R~ R2
N~O~ I ~C=C~ N
R2 So3M SO3M Rl
wherein Rl is selected from ~nilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methyl~min~, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
~ When in the above formula, Rl is ~nilin~, R2 is N-2-bis-hydroxyethyl and
M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-
bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and
disodium salt. This particular brightener species is commercially marketed
under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corpora~ion.
Tinopal-UNPA-GX is the preferred hydrophilic optical briglltellef useful in
the delelgellt compositions herein.
When in the above formula, Rl is ~nilino, R2 is N-2-hydroxyethyl-N-2-
methyl~mino and M is a cation such as sodium, the brightener is 4,4'-
bis[(4-anilino-6-(N-2-hydroxyethyl-N-methyl~min~ )-s-triazine-2-
yl)aminol2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the tradename Tinopal
5BM-GX by Ciba-Geigy Corporation.
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37
When in the above formula, Rl is anilino, R2 is morphilino and M is a
- cation such as sodium, the brightener is 4,4'-bisr(4-anilino-6-morphilino-s-
triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This
particular brightener species is commercially marketed under the tradename
Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening a~ents
Cationic fabric softening agents can also be incorporated into the detergent
compositions herein. Suitable cationic fabric softening agents include the
water insoluble tertiary amines or dilong chain amide materials as disclosed
in GB-A-l 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5 % to 15 ~ by weight, normally from l ~o to 5 % by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the detergell~
compositions herein include perfumes, colours and filler salts, with sodium
sulfate being a preferred filler salt.
pH of the compositions
The present deter~ellt compositions preferably have a pH measured as a
1% solution in distilled water of at least 10.0, ~leferably from 10.0 to
12.5, most preferably from 10.5 to 12Ø
Form of the compositions
The deteLgellL compositions herein can take a variety of physical forms
including granular, tablet, bar and liquid forms. The compositions are
particularly the so-called concentrated granular detergent compositions
adapted to be added to a w~hin~ machine by means of a dispensing device
placed in the machine drum with the soiled fabric load.
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The mean particle size of the components of granular compositions in
accordance with the invention should preferably be such that no more that
5% of particles are greater than 1.7mm in diameter and not more than 5%
of particles are less than 0. lSmm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the composition into a number of fractions (typically 5 fractions)
on a series of Tyler sieves. The weight fractions thereby obtained are
plotted against the aperture size of the sieves. The mean particle size is
taken to be the aperture size through which 50~ by weight of the sample
would pass.
The bulk density of granular detergent compositions herein typically have a
bulk density of at least 600 g/litre, more preferably from 650 g/litre to
1200 g/litre.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 e~ elllily to allow the contents of the
funnel to be emptied into an axially aligned cylindrical cup disposed below
the funnel. The funnel is 130 mm high and has internal diameters of 130
mm and 40 mm at its respective upper and lower extremities. It is
mounted so that the lower e~l~elllily is 140 mm above the upper surface of
the base. The cup has an overall height of 90 mm, an internal height of 87
mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed from
the cup by passing a straight edged implement eg; a knife, across its upper
edge. The filled cup is then weighed and the value obtained for ~e weight
of powder doubled to provide a bulk density in g/litre. Replicate
measurements are made as required.
Surfactant agglomerate particles
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. 39
The surfactant system herein is preferably present in granular compositions
in the form of surfactant agglomerate particles, which may take the form of
flakes, prills, marumes, noodles, ri~bons, but preferably take the form of
granules. The most preferred way to process the particles is by
agglomerating powders (e.g. aluminosilicate, carbonate) with high active
surfactant pastes and to control the particle size of the resultant
agglomerates within specified limits. Such a process involves mixing an
effective amount of powder with a high active surfactant paste in one or
more agglomerators such as a pan agglomerator, a Z-blade mixer or more
preferably an in-line mixer such as those manufactured by Schugi (Holland)
BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder
Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9,
Postfach 2050, Germany. Most preferably a high shear mixer is used, such
as a Lodige CB (Trade Name).
A high active surfactant paste comprising from 50% by weight to 95 ~ by
weight, preferably 70% by weight to 85 % by weight of surfactant is
typically used. The paste may be pumped into the agglomerator at a
temperature high enough to m~int~in a pumpable viscosity, but low enough
to avoid degradation of the anionic surfactants used. An operating
temperature of the paste of 50~C to 80~C is typical.
n~lry washing method
Machine laundry methods herein typically comprise treating soiled laundry
with an a~ueous wash solution in a washing machine having dissolved or
dispensed therein an effective amount of a machine laundry detergent
composition in accord with the invention. By an effective amount of the
de~ genl composition it is meant from 40g to 300g of product dissolved or
dispersed in a wash solution of volume from S to 65 litres, as are typical
product dosages and wash solution volumes commonly employed in
conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method. The dispensing device is charged with the deter~,el~ product, and
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is used to introduce the product directly into the d~m of the washing
machine before the commencement of the wash cycle. Its volume capacity
should be such as to be able to contain sufflcient detergent product as
would normally be used in the w~hing method.
Once the washing machine has been loaded w;th laundry the dispensing
device cont~in~ 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 cont~inment 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 contact with the wash water.
To allow for release of the detelgenl 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 permea~e to
liquid but impermeable to the solid product, which will allow release ~ r
dissolved product. Preferably, the detergent product will be rapidly
released at the start of the wash cycle thereby providing transient localised
high concentrations o~ product in the drum of the w~hin~ machine at this
stage of the wash cycle.
Preferred dispensing devices are reusable and are designed ;n such a way
that container integrity is m~int~inlo-l in both the dry state and during the
wash cycle. Especially preferred dispensing devices for use with the
composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and
EP-A-0288346. An article by J.Bland published in Manufacturing
Chemist, November 1989, pages 41-46 also describes especially preferred
dispensing devices for use with granular laundry products which are of a
type commonly know as the "granulette". Another preferred dispensing
device for use with the detergent compositions herein is disclosed in PCT
Patent Application No. WO94/11562.
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Especially preferred dispensing devices are disclosed in European Patent
- Application Publication Nos. 0343069 & 0343070. The latter Application
discloses a device comprising a flexible sheath in the form of a bag
extending from a support ring defining an orifice, the orifice being adapted
to admit to the bag sufficient product for one washing cycle in a washing
process. A portion of the washing nnedium flows through the orifice into
~he bag, dissolves the product, and the solution then passes outwardly
through the ori~lce into the washing medium. The support ring is provided
with a m~kin~ arrangemnt to prevent egress of wetted, undissolved,
product, this arrangement typically comprising radially extending walls
extending from a central boss in a spoked wheel configuration, or a similar
structure in which the walls have a helical ~orm.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a water
impermeable protective material so as to retain the colltellls" such as is
disclosed in European published Patent ~pplication No. 0018678.
Alternatively it may be forrned of a water-insoluble synthetic polymeric
material provided with an edge seal or closure designed to rupture in
aqueous media as disclosed in European published Patent Application Nos.
0011500, 0011501, 0011502, and 00119~8. A convenient form of water
frangible closure comprises a water soluble adhesive disposed along and
sealing one edge of a pouch formed of a water impermeable polymeric film
such as polyethylene or polypropylene.
Pack~ for the coml)osilions
Commercially marketed executions of the bleaching compositions can be
packaged in any suitable container includling those constructed from paper,
cardboard, plastic materials and any suitable l~min~tes. A preferred
pack~in~ execution is described in European Application No.
94921505.7.
Abbreviations used in Examples
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. 42
In the detergent compositions, the abbreviated component identifications
have the following me~nin~:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C 15 linear alkyl sulfate
CxyEzS : Sodium C lx~C ly branched alkyl sulfate
condensed with z moles of ethylene oxide
C45E7 : A C14 15 predomin~ntly linear primary alcohol
condensed with an average of 7 moles of ethylene
oxide
C25E3 : A C12 15 branched primary alcohol condensed
with an average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol condensed
with an average of 5 moles of ethylene oxide
CEQ : RlcoocH2cH2.N~(cH2cH3oH)(c~3)2 with
R1 = C1 1- C 13
QAS : R2 ~ N + (cH3~2(c2H4oH) with R2 = C 12 - C 14
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and coconut oils.
TFAA : C16-C1g alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate offormula
Na12(A1~2Si~2)12. 27H20 having a primary
particle size in the range from 0.1 to 10
micrometers
NaSKS-6 : Cryst~llin~ layered si~icate of formula
~ -Na2Si20s
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate wi~ a particle size
between 200,um and 900~Lm
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
distribution between 400,um and 1200,um
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43
Silicate : Amorphous Sodium Silicate (SiO2:Na20; 2.0
ratio)
Sodium sulfate: Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size dListribution between 425,um and
850 ,um
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename
Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO Tn-lll.ctries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Tn-lllstries A/S under the tradename
Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Tn~ stries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20-H202
PBl : Anhydrous sodium perborate monohydrate bleach
of nominal formula NaBo2.H2o2
Percarbonate : Sodium Percarbonate of nominal formula
- 2Na2C03-3H202
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
TAED : Tetraacetylethylen~ min~
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44
DTPMP : Diethylene tri~mine penta (methylene
phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in
bleach dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-~nilin~-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene
oxy and terephtaloyl backbone
SRP 2 : Die~oxylated poly (1, 2 propylene terepht~l~te)
short block polymer
Silicone antifoam: Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1.
~lk~linity : % weight equivalent of NaOH, as obtained using
the ~lk~linity release test method described herein.
In the following Fx~mrles all levels are quoted as % by weight of the
composition:
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l~xample 1
Into a 500 ml round-bottom flask fitted with a short Vigreux column
attached to a condenser fitted with a measuring cylinder was added methyl
dodecanoate (36.0g, 0.168 mol), N-methyldiethanolamine (120.0g, 1.00
mol) and sodium methoxide (O.Sg, 0.015 mol). The reaction was heated to
reflux for 2.5 days, collecting the methanol in the measuring cylinder.
The reaction mixture was dissolved in chloroform (350 ml), washed with
saturated sodium chloride solution ~2xlO0 ml), and dried over magnesium
sulfate. The chloroform was removed by rotary evaporation to give the
ester amine as a brown liquid. dissolved in acetone (300 ml).
Into a 500 ml round-bottomed flask fitted with dry-ice condenser / drying
tube and magnetic stirrer and cooled with a dry-ice acetone bath was added
the acetone solution of the ester amine obtained as above. The reaction
mixture was cooled to -10 ~C and methylbromide (30 ml, 99g, 1.04 mol)
was added via gr~ te~l cylinder to the reaction. The reaction was kept
between -10 ~C and 0 ~C ~or 4 hours and then allowed to warm to room
temperature. After st~n~lin~ overnight, a quantity of solid product formed.
The product was collected by filtration, washed with acetone, placed in an
evaporating dish and dried overnight in a vacuum dessicator over
phosphorus pentoxide to give the desired cationic ester (16g, 24% yield
based on methyl do~ec~noate).
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46
E~ample 2
The following laundry detergent compositions A to F were prepared in
accord with the invention:
A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 5.4 3.4 2.4 3.4
CEQ 2.0 0.8 1.0 1.5 0.8 0.8
QAS - - 0. 8 - - 0.4
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
- Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
D ET P M P 0.25 0.25 0.25 0.25 0.25 0.25
H E D P 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.26 0.26 0.26 0.26 0.26 0.26
Amylase 0.1 0.1 0.1 0.1 0.1 0.1
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47
MA/AA 0.3 0 3 0.3 0 3 0 3 0 3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15bleach (ppm) ppm ppm ppm ppm ppm ppm
Brightener 1 0.09 0.09 0.09 0.09 0.09 0 09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to
100%
Density in g/litre 630 670 670 500 670 670
~lk~linity 6.8 6.8 6.8 18.5 18.5 18.5
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48
Example 3
The following granular laundry detergent compositions G to I of bulk
density 750 g/litre were prepared in accord with the invention:
G H
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5
CEQ 0.8 2.0 2.0
STPP 10.7
Zeolite A - 19.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate 16.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8
Sodium sulfate 39.8 - 14.3
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49
PB4 5.0 12.7
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0 04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
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Example 4
The following detergent formu}ations, in accord with the present invention
were prepared, where J is a phosphorus-cont~inin~ detergent composition,
K is a zeolite-cont~inin~ detergent composition and L is a compact
detergent composition:
J K L
Blown Powder
STPP 14.0 - 14.0
Zeolite A - 20.0
C45AS 9.0 6.0 8.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 9.0
TAS 2.0
CEQ 1.5 3.0 3.5
Silicate 7.0 8.0 8.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 26.0 23.0 25.0
PB4 18.0 18.0 10
PB1 4.0 4 0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
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51
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
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52
Example 5
The following nil bleach-cont~inin~ detergent formulations of particular use
in the washing of colored clothing, in accord with the present invention
were prepared:
M N O
Blown Powder
Zeolite A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
CEQ 2.0 1.5 1.3
DTPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfilme 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVIIPVNO 0.5 0.5 0.5
Alcalase 0.5 0.3 0.9
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Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density ~g/litre) 700 700 700
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~xample 6
The following detergent formulations, in accord with the present invention
were prepared:
P Q R S
LAS 12.0 12.0 12.0 10.0
Q~S 0.7 1.0 - 0.7
TFAA - 1.0
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
CEQ 2.0 1.5 1.0 1.0
STPP 30.0 18.0 15.0
Silicate 9.0 7.0 10.0
Carbonate 15.0 10.5 15.0 25.0
Bicarbonate - 10.5
DTPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0. 8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05
Photoactivated 70ppm 45ppm - 10ppm
bleach (ppm)
Bri~,htellel 1 0.2 0.2 0.08 0.2
PBl 6.0 ~.0 - -
NOBS 2.0 1.0
R~l~nce 100 100 100 100
(Moisture and
Miscellaneous)
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Example 7
The following detergent formulations, in accord with the present invention
were prepared:
T U V
Blown Powder
Zeolite A 10.0 15.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 10.0 8.0 10.0
C45AS 4.0 5.0 7.0
CEQ 2.0 2.0 2.Q
Silicate - 1.0 7.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 28.0 26.0 20.0
DTPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfate - 6.0
Balance (Moisture 100 100 100
and Miscellaneous)
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:l~xample 8
The following high density and bleach-cont~inin~ detergent formulations, in
accord with the present invention were prepared:
W X Y
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodim sulfate 0.0 5.0 0.0
LAS 3.0 2.0 3.0
QAS - 1.5 1.5
CEQ 2.0 1.5 2.0
DTPMP 0.4 0.4 0.4
C M C 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 4.0 4.0 4.0
T AS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
- Carbonate 8.0 8.0 6.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
CarboIlate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PBl 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
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Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
B~l~n~e (Moisture and 100.0 100.0 100.0
Miscellaneous~
Density (g/litre) 850 850 850
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Example 9
The following high density detergent formulations, in accord with the
present invention were prepared:
Z AA
Agglomerate
C45AS 11.0 14.0
CEQ 3.0 3.5
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Arnylase 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
