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S~JLFONATE PERFUMES
FO~
LAUNDRY AND CLEANING COMPOSITIONS
FIELD OF THE ~NVENTION
The present invention relates to laundry and cleaning products comprising
sulfonates of alcohol perfumes.
BACKGROUND OF THE INVENTION
Consumer acceptance of cleaning and laundry products is determined not
only by the perforrnance achieved with these products but the aesthetics associated
therewith. The perfume systems are therefore an important aspect of the successful
formulation of such commercial products.
What perfume system to use for a given product is a matter of carefill
consideration by skilled perfumers. While a wide array of chemicals and ingredients
are available to perfurners~ considerations such as availability, cost, and
compatibility with other components in the compositions limit the practical options.
Thus, there continues to be a need for low-cost, compatible perfurne m~tf ri~l~ useful
for cleaning and laundry compositions.
It has been discovered that sulfonates of certain perfume alcohols are
particularly well suited for laundry and cleaning compositions. In particular, it has
been discovered that sulfonates of perfume alcohols will hydrolyze to give an
alcohol perfume and the co..~;s~ollding salt. In addition, hydrolyzable sulfonates of
perf lme alcohols provide release of the perfume over a longer period of time than
by the use of the perfume itself in the laundry/cleaning compositions. Such
materi~ls therefore provide perfumers with more options for perfume ingredients
and more flexibility in forrnulation considerations. These and other advantages of
the present invention will be seen from the disclosures hereinafter.
BACKGROUND ART
Sulfonate cht~mi~ry iS described more generally in March, Advanced
Organic Chemistry, 4th Ed., pp. 352-353, 372, 404-405, 498-499 (John Wiley &
Sons,N.Y.; 1992).
Compositions of fragrance m~teti~l~ (having certain values for Odour
Intensity Index, Malodour Reduction Value and Odour Reduction Value) said to be
used as fragrance compositions in detergent compositions and fabric conditioningcompositions are described in European Patent Application Publication No.
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404,470, published December 27, 1990 by Unilever PLC. A process for scenting
fabrics washed with lipase-cont~inin~ detergents including esters of alcohol
perfumes is described in PCT application No. WO 95/04809, published February 16,1995 by Firmenich S.A
SUMMARY OF THE INVENTION
The present invention relates to laundry and cleaning compositions having a
perfume component. The perfu~ne component includes at least about 0.01% by
weight of a sulfonate of a perfume alcohol. The sulfonates of the present invention
provide a superior consumer noticeable benefit to fabrics laundered in the
compositions of the present invention.
Accordingly, a laundry and cleaning composition is provided by the present
invention. The composition comprises a perfume component having sulfonate
andlor sulfonates of perfume alcohol and/or alcohols at a level effective to provide a
perfume effect. The sulfonates have the general formulas of ~I), (II), or
combinations thereof:
(I)
R--~--O--Y
o
(II)
o
ROJ~(Z)_~_OY
wherein R and Z are independently selected from the group consi.eting of nonionic
or anionic, substituted or uns~lbstihlte~l Cl-C30 straight, branched or cyclic alkyl,
alkenyl, alkynyl, alkylaryl or aryl group; Y is a radical that, upon hydrolysis of said
sulfonate, forms an alcohol with a boiling point at 760 mrn Hg of less than about
300 ~C that is a perfilme.
The perfume component comprises from about 0.01% to about 10% by
weight of the laundry and cleaning composition.
The composition also includes ingredients useful for form~ ting laundry and
cleaning compositions. The ingredients are selected, e.g., from the group consisting
of: cationic or nonionic fabric softening agents, enzymes, enzyme stabilizers,
detersive s~ ct~nts, builders, bleaching compounds, polymeric soil release agents,
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dye transfer inhibit;ng agents, polymeric dispersing agents, suds suppressors, optical
brighteners, chelating agents, fabric softening clays, anti-static agents, and mixtures
thereof.
In accordance with another aspect of the present invention, a fabric softening
composition is provided. The fabric softening composition comprises a perfume
component at a concentration of from about 0 01% to about 10% by weight of the
fabric softening composition. In addition, the fabric softening composition includes
a fabric softening component having at least one cationic or nonionic fabric
softening agent.
The fabric softening composition can further optionally include, e.g., at least
one compound selected from the group conei~tin~ of viscosity/dispersibity
mod;fiers, pH modifiers and liquid carriers. The dispersibility modifier is selected
from the group con~icting of: single-long-chain-C10-C22 alkyl, cationic surfactant;
nonionic surfactant with at least 8 ethoxy moieties; amine oxide surfactant;
ql1~tenl~ry amrnonium salts of the ~eneral formula:
(:R2N+R3) X-
wherein the R2 group is a C10-C22 hydrocarbon group, or the corresponding ester
linkage interrupted group with a short alkylene (C I -C4~ group between the ester
linkage and the N, and having a similar hydrocarbon group, each R is a Cl-C4 alkyl
or substituted alkyl, or hydrogen; and the counterion X~ is a softener compatible
anion, and mixtures thereof.
The fabric softening component is preferably a cationic quaternary
ammonium fabric softening compound. Most preferably, it has the formula:
~(R)4-m - N- ((CH2)n - Y - R2)m ] ~
wherein: each Y is -O-(O)C-, or -C(O)-O-, m is 2 or 3; each n is independently
choserrfrom l to 4; each R is a Cl-C6 alkyl group, hydroxyalkyl group, benzyl
group, or mixtures thereof; each R2 is a Cl2-C22 hydrocarbyl or substituted
hydrocarbyl ~ub~liLuent; and X-is any softener-comp~tible anion. The 41~t~
ammonium compound can be derived from Cl2-C22 fatty acyl groups having an
Iodine Value of from greater than about S to less than about l 00, a cis/trans isomer
weight ratio of greater than about 30/70 when the Iodine Value is less than about
25, the level of unsaturation of the fatty acyl groups being less than about 65% by
weight.
In accoldallce with yet another aspect of the present invention, a method for
mtl~ring soiled fabrics is provided. The method comprises contacting a fabric
with an aqueous medium co. ~ g at least about 50 ppm of a laundry composition.
The laundry composition includes a perfume component, according to formula (I, at
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a concentration of from about 0.01% to about 10% by weight of the laundry
composition. In addition, the laundry composition used in the method inc}udes
ingredients useful for formulatin~ laundry compositions. Such ingredients include
cationic or nonionic fabric softening agents, enzymes, enzyme stabilizers, detersive
surfactants, builders, ble~ch;ng compounds, polymeric soil release agents, dye
transfer inhibiting agents, polymeric dispersing agents, suds suppressors, optical
brighteners, chelating agents, fabric softening clays, anti-static agents, and mixtures
thereof.
Accordingly, it is an object of the present invention to provide a laundry and
cleaning composition having a perfurne component including a sul~onate of a
perfume alcohol. It is another object of the present invention to provide a fabric
softening composition having a perfume component including a sulfonate of a
perfurne alcohol. It is still another object of the present invention to provide a
method for cleaning soiled fabrics by contz~çting a fabric with a laundry composition
having a perfurne component including a sulfonate of a perfurne alcohol. It is yet
another object of the present invention to provide an ester of a perfume alcoholwh~,reill the ester has at least one free carboxylate group. It is a feature of the
present invention that a sulfonate of a perfume alcohol provide a superior consumer
recognizable result to compositions in which they are included.
All pclcc~lLages~ ratios and proportions herein are on a weight basis unless
otherwise indicated. All documents cited herein are hereby incorporated by
reference.
DETAILED DESCRIPTION
The present invention relates to laundry and cle~ning compositions having a
perfume component. The composition comprises from about 0.01% to about 10% by
weight of the laundry and cleaning composition of a perfurne component comprising
sulfonate and/or s--if~-n~tçs of perfume alcohol and/or alcohols. The sulfonates have
the general forrnulas (I), (II), or combinations thereof:
(I~
C~
R--~--O--Y
CJ
~II)
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~ O
RO (Z)_ _OY
wherein R and Z are independently selected from the group consisting of nonionicor anionic, substituted or unsubstituted Cl-C30 straight, branched or cyclic alkyl,
alkenyl, alkynyl, alkylaryl or aryl group; Y is a radical that, upon hydrolysis of said
sulfonate, forms an alcohol with a boiling point at 760 n~n Hg of less than about
300 ~C that is a per~ne.
Preferably, R and Z are selected from the group consisting of substituted or
unsubstituted Cl - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl,
aryl group or ring cont~ining a herteroatom. Y is preferably a radical that uponhydrolysis of said sulfonate forms perfilme alcohol selected from the group
consisting of:
~OH
phenoxanol;
~OH
floralol;
~I ~ 'OH
~B-citronellol;
~OH
nonadyl alcohol;
o ~OH
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cyclohexyl ethanol;
0~0H
phenyl ethanol;
~OH
isoborneol;
OH
fenchol;
HO~
isocyclogeranol;
OH
(+)-linalool;
OH
dihydromyrcenol;
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\f ~OH
~3
~ 2-phenyl-1-propanol,
~ COH
2-ethylhexanol;
~=--OH
cis-3-hexenol
~'--~I"--OH
and/or 3,7-dimethyl- 1 -octanol.
The most preferred sulfonates are the p-toh~enes~ lfonates (tosylates), 4-
bromobenzenesulfonates (brosylates), and meth~n~slllfonates (mesylates) of ,B-
citronellol, phenoxanol, cis-3-hexenol, and phenyl ethanol.
Of course, one of ordinary skill in the art will recognize that other sulfonatessatisfying the general forrnula (I) or (II) can also be employed in the present
invent~n.
The perfume component of the compositions of the present invention can
include one or more additional fully, or partially, esterifie~i esters of a perfume
alcohol in conjunction with the esters of forrnula (I) described above. Suitable fully
est~rified perfurne alcohol esters which can be employed in the present invention
are disclosed in U.S. Patent Application 08/277,558 to Hartman et al. filed on July
19, 1994, U.S. Patent Application 08/499,158 to Severns et al. filed on July 7, 1995
and U.S. Patent Application 08/499,282 to Severns et al. filed on July 7, 1995, of
which the disclosures of all three are herein incol~o.~led by reference. Preferably,
the fully esterified esters of per~ume alcohols are di-esters of perfurne alcohols. Di-
esters of both allylic and non-allylic alcohols can be employed. Suitable fully
esterified esters of perfurne alcohols which can be employed in the present
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invention include digeranyl succinate, dineryl succinate, geranyl neryl succinate,
geranyl phenylacetate, neryl pheny~acetate, geranyl laurate, neryl laurate, di(b-
citronellyl) maleate, dinonadol maleate, ~~iph~noxanyl maleate, di(3,7-dimethyl-1-
octanyl) succinate, di(cyclohexylethyl) maleate, difloralyl succinate, and
di~phenylethyl) adipate and mixtures thereof.
The compositions of the present invention include liquid, granular and bar
laundry and cleaning products, which are typically used for laundering fabrics and
cleaning hard surfaces such as dishware and other surfaces in need of cleaning
and/or disinfecting. Preferred are those laundry compositions which result in
collt~tin~ the perfume component as described hereinbefore with fabric. These are
to be understood to include not only detergent compositions which provide fabriccleaning benefits but also laundry compositions such as liquid or granular rinseadded fabric softener compositions which provide softening and/or ~ntiqt~tic
benefits. ~he perfume component typically comprises from about 0.01% to about
10%, preferably from about 0.05% to about 5%, and more preferably from about
0.1 % to about 5%, by weight of the composition.
The liquid and granular fabric softener compositions ~ r~ d in the present
invention can be added directly in the rinse of a laundry process both to provide
adequate usage concentration, e.g., from about 10 to about 2,500 ppm, plt;r~lably
from about 30 to about 2000 ppm, of the biodegradable, cationic fabric softener
compound, or water can be pre-added to the particulate, solid, granular composition
to form dilute or concentrated liquid softener co,llpo~ilions that can be added to the
rinse to provide the same usage conce~ tion.
The perfume component of compositions of the present invention can also
include additional perfume ingredients in addition to the sulfonates of formula (I)
and th~ est~ iecl esters of perfume alcohols. Such additional perfume ingredients
are well-known to those of ordinary skill in the art. Typical additional pc~rulllc
colllpowlds and compositions can be found in the art including U.S. Pat. Nos.
4,145,184, Brain and Clmlmin~, issued Mar. 20, 1979; 4,209,417, Whyte, issued
June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young,
issued May 1, 1979, all of said patents being incorporated herein by reference.
In addition, the present invention includes a method for l~lln~l~rin~ soiled
fabrics. The method comprises cont~cting a fabric with an aqueous medium
co..l~;..ing at least about 50 ppm of a laundry composition co~.l~;.,i.~g a perfume
co~ ollent of formula (I) as hereinbefore described. The laundry composition is
formlll~te~l such that the aqueous medium in the laundering process has a pH of
from about 6.5 to about 12. The l~-ln~lerin~ method is conducted for a period of
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time effective to impart the desired properties to the fabric such a soil or stain
removal or fabric soi~tening.
The compositions of the present invention can also optionally include
ingredients useful for forrnulating laundrv and cleaning compositions. Such
ingredients include but are not limited to cationic or nonionic fabric softeningagents, enzymes, enzyme stabilizers, detersive surfactants, builders, ble~chin~
compounds, polymeric soil release agents, dye transfer inhibiting agents, polymeric
dispersing agents, suds suppressors, optical bri~hten~rs, chelating agents, fabric
softening clays, anti-static agents, and mixtures thereof. The compositions include
both granular and liquid laundry and cleaning compositions.
The sulforlates of the present invention hydrolyze to generate the perfume
alcohol thereby generating a pleasant odor. In this fashion, perfume alcohols can be
delivered to the fabric surface as a sulfonate and then hydrolyze to the alcohol and
release the pleasant odor.
Cationic or Nonionic Fabric Softening Agents:
The ~reftl.~d fabric softening agents to be used in the present invention
compositions are q~ ly ammonium compounds or amine precursors herein
having the formula (III) or (IV), below:
R3\ R2
+ I--(CH2)n--Q--T 1 X
Rl
(III)
or
K3\ R3
+ Nl--(CH2)n- ICH~ X ~
R3 Ql Q
Tl T2
(IV)
wherein:
each Q is -O-C(O)- or -C(O)-O- or-O-C(O)-O- or -NR4-C(o)- or -C(o)-NR4-;
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each R~ is (CH2)n-Q-T2 or T3 or R3
eachR2is(CH2)m-Q-T4 or Ts orR3;
each R3 is Cl-C4 alkyl or C l-C4 hydroxyalkyl or H;
each R4 is H or Cl-C4 aLkyl or Cl-C4 hydroxyalkyl;
Tl, T2, T3, T4, Ts are (the same or different) Cll-C22 alkyl or al~enyl;
n and m are integers from l to 4; and
X- is a softener-compatible anion, such as chloride, methyl sulfate, etc.
The alkyl, or alkenyl, chain Tl, T2, T3, T4, Ts must contain at least l l carbon~ atoms, preferably at least l 6 carbon atoms. The chain can be straight or branched.
Q, n, Tl, and T2 can be the same or different when more than one is present
in the molecule.
Tallow is a convenient and inexpensive source of long chain alkyl and
alkenyl material. The compounds wherein Tl, T2, T3, T4, T5 represents the mixture
of long chain mzlt~ri~l.e typical for tallow are particularly plef~.~d.
Specific examples of qll~t~rn~y ammonium compounds suitable for use in the
aqueous fabric softening compositions herein include:
l) N,N-di(tallowyl-oxy-ethyl)-N,N-dirnethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
3) N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl arnmonium
chloride;
S)n-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)
-N,N-dimethyl ammonium chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl arnmonium chloride;
7) N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ~mm~ nium
chloride; and
8) 1 ,2-ditallowyloxy-3-N,N,N-trimethylammonio~op~le chloride.;
and nlixLIllcs of any of the above materials.
Of these, compounds 1-7 are examples of compounds of Formula (III);
compound 8 is a conl~owld of Formula (IV).
Particularly plert;lred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl
ammoniurn chloride, where the tallow chains are at least partially unsaturated.
The level of unsaturation of the tallow chain can be measured by the Iodine
Value (I.V.) of the colrei,~onding fatty acid, which in the present case should
;fe,dbly be in the range of from S to lOO with two categories of compounds beingdistinguished, having an I.V. below or above 25.
=
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Indeed, for compounds of Formula (III) made from tallow fatty acids having
a I.V. of from 5 to 25, preferably 15 to 20, it has been found that a cis/trans isomer
weight ratio greater than about 30/70, preferably greater than about 50/50 and more
preferably greater than about 70/30 provides optimal concentrability.
For compounds of Forrnula (III~ made from tallow fatty acids having a I.V.
o~ above 25, the ratio of cis to trans isomers has been found to be less critical unless
very high concentrations are needed.
Other exarnples of suitable qll~t~ y arnmoniums of ForJnula (III) and (IV~
are obtained by, e.g.,
- replacing "tallow" in the above compounds with, for example, coco, palm,
lauryl, oleyl, ricinoleyl, stearyl, palmityl, or the like, said fatty acyl chains being
either fully ~a~ul~led, or preferably at least partly unsaturated;
- replacing "methyl" in the above compounds with ethyl, ethoxy, propyl,
propoxy, isopropyl, butyl, isobutyl or t-butyl;
- replacing "chloride" in the above compounds with bromide, methylsulfate,
formate, sulfate, nitrate, and the like.
In fact, the aniorl is merely present as a counterion of the positively charged
qu~t~ . "~y ammonium compounds. The nature of the counterion is not critical at all
to the practice of the present invention. The scope of this invention is not
considered limited to any particular anion.
By "amine precursors thereofi' is meant the secondarv or tertiary amines
corresponding to the above qll~t~rn~ry ammoniurn compounds, said amines being
sllhst~nti~lly protonated in the present compositions due to the claimed pH values.
The qll~t~rn~ly ammonium or amine precul~ol~ compounds herein are
present at levels of fiom about 1% to about 80% of compositions herein, depending
on the composition execution which can be dilute with a pr~relled level of active
from about 5% to about 15%, or conce,~ l, with a preferred level of active from
about 15% to about 50%, most preferably from about 15% to about 35%.
For the prececling fabric softening agents, the pH of the compositions herein
is an irnportant pa~dn.etcr of the present invention. Indeed, it influences the stability
of the qll~,. 11;11 y ammonium or amine ~ sOl~ compounds, especially in
prolonged storage collditions.
The pH, as defined in the present context, is measured in the neat
compositions at 20 ~C. For optimum hydrolytic stability of these compositions, the
neat pH, measured in the above-mentioned conditions, must be in the range of from
about 2.0 to about 4.5, preferably from about 2.0 to about 3.5. The pH of these
compositions herein can be regulated by the addition of a Bronsted acid.
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Examples of suitable acids include the inorganic mineral acids, carboxylic
acids, in particular the low molecular weight (C 1 -C5) carboxylic acids, and
alkylsulfonic acids. Suitable inorganic acids include HCl, HzSO4, HNO3 and
H3PO4. Suitable organic acids include forrnic, acetic, citric, methylsulfonic and
ethylsulfonic acid. Preferred acids are citric, hydrochloric, phosphoric, formic,
methylsulfonic acid, and benzoic acids.
Softening agents also useful in the compositions of the present invention are
nonionic fabric softener materials, preferably in combination with cationic softening
agents. Typically, such nonionic fabric softener materials have a HLB of from about
2 to about 9, more typically from about 3 to about 7. Such nonionic fabric softener
materials tend to be readily dispersed either by themselves, or when combined with
other materials such as single-long-chain alkyl cationic surfactant described in detail
hereinafter. Dispersibility can be improved by using more single-long-chain alkyl
cationic surfactant, mixture with other materials as set forth hereinafter, use of hotter
water, and/or more agitation. In general, the materials selected should be relatively
crystalline, higher melting, (e.g. >40 ~C) and relatively water-insoluble.
The level of optional nonionic softener in the compositions herein is
typically from about 0.1% to about 10%, preferably from about 1% to about 5%.
Preferred nonionic softeners are fatty acid partial esters of polyhydric
alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, conlaills from 2
to 18, preferably from 2 to 8, carbon atoms, and each fatty acid moiety containsfrom 12 to 30, preferably from 16 to 20, carbon atoms. Typically, such softenerscontain from one to 3, preferably 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol,
poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, t;l~llui~
pentaerythritol, sorbitol or sorbitan. Sorbitan esters and poly~,lycerol monostearate
are particularly ~lc~ll~d.
The fatty acid portion of the ester is normally derived from fatty acids having
from 12 to 30, preferably from 16 to 20, carbon atoms, typical e~amples of said fatty
acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic and behenic
acid.
Highly ~le~,.~d optional nonionic softening agents for use in the present
invention are the so~ esters, which are esterifiçd dehydration products of
sorbitol, and the glycerol esters.
Commercial sorbitan monostearate is a suitable m~ter~l Mixtures of
sorbitan stearate and sorbitan palmitate having stearate/p~lmit~te weight ratiosvarying between about 10:1 and about 1:10, and 1,5-sorbitan esters are also useful.
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13
Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol,
and polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein (e.g.
polyglycerol monostearate with a trade name of Radiasurf 7248).
Usefill glycerol and polyglycerol esters include mono-esters with stearic,
oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of
stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is
understood that the typical mono-ester contains some di- and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g., diglycerol through
octaglycerol esters. The polyglycerol polyols are formed by con~l~n~in~ glycerin or
epichlorohydrin together to link the glycerol moieties ~/ia ether linkages. The mono-
and/or diesters of the polyglycerol polyols are plcr~ d, the fatty acyl groups
typically being those described hereinbefore for the sorbitan and glycerol esters.
A.dditional fabric softening agents useful herein are described in U.S. Pat.
No. 4,661,269, issued April 28, 1987, in the names o~Toan Trinh, Errol H. Wahl,
Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat. No. 4,439,335, Burns,
issued March 27, 1984; and in U.S. Pat. Nos.: 3,861,870, Edwards and Diehl;
4,308,151, Cambre; 3,g86,075, Bt~ ~dil1o; 4,233,164, Davis; 4,401,578,
Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016, Rudkin, Clint, and Young;
and European Patent Application publication No. 472,178, by Yamarnura et al., all
of said docurnents being incorporated herein by reference.
For example, suitable fabric softener agents useful herein can comprise one,
two, or aLl three of the follow ng fabric softening agents:
(a) the reaction product of higher fatty acids with a polyamine selected from the
group con~i~ting of hydroxyalkylalkylençt1i~mines and dialkylenetri~mines and
tUl~,S thereof (preferably from about 10% to about 80%); and/or
(b) catlonic nitrogenous salts co.~l~;..i..g only one long chain acyclic aliphatic Cl5-
C22 hydrocarbon group (preferably from about 3% to about 40%); and/or
~c) cationic nitrogenous salts having two or more long chain acyclic aliphatic Clj-
C22 hydrocarbon groups or one said group and an arylalkyl group (preferably fromabout 10~/~ to about 80%),
with said (a), (b) and (c) ~>,e~,ed percentages being by weight of the fabric
softening agent component of the present invention compositions.
Following are the general descriptions of the prece-1ing (a), (b), and ~c)
- softener ingredients (including certain specific examples which illustrate, but do not
limit the present invention).
Component (a): Softening agents (actives) of the present invention can be the
reaction products of higher fatty acids with a polyamine selected from the group
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14
consisting of hydroxyalkylalkylene~ mines and dialkylenetri~min~s and mixtures
thereof. These reaction products are mixtures of several compounds in view of the
multi-functiona} structure of the polyamines.
The preferred Component (a) is a nitrogenous compound selected from the
group consisting of the reaction product mixtures or some selected components ofthe mixtures. More specifically, the preferred Component (a) is compounds selected
from the group con~i~tin~ of substituted imida_oline compounds having the formula:
~N ~
R2-NH~ Rl
wherein Rl is an acyclic aliphatic Cl5-C2l hydrocarbon group and R2 is a
divalent C~-C3 alkylene group.
Component (a) m~teri~l~ are com~nercially available as: Mazamidet~) 6, sold
by M~er Chemicals, or Ceranine@; HC, sold by Sandoz Colors & Chemicals;
stearic hydroxyethyl imidazoline sold under the trade names of ~lk~7inP(g) ST byAlkaril Chemicals, Inc., or Schercozoline~) S by Scher ChPmiç~ Inc.; N,N"-
ditallowalkoyldiethylenetri~mine, 1-tallowamidoethyl-2-tallowimi~1~7f 1ine (wherein
in the precel1in~ structure Rl is an ~liph~tic C,5-C,7 hydrocarbon group and R2 is a
divalent ethylene group~.
Certain of the Components (a) can also be first dispersed in a Bronsted acid
dispersing aid having a pKa value of not greater than about 4; provided that the pH
of the final composition is not greater than about 5. Some preferred dispersing aids
are hydrochloric acid, phosphoric acid, or methylsulfonic acid.
Both N,N"-ditallowalkoyldiethylenetriamine and 1 -tallow(amidoethyl)-2-
tallowimi~l~701ine are reaction products of tallow fatty acids and diethylenetriamine,
and are precursors ofthe c~tionic fabric softening agent methyl-l-tallowamidoethyl-
2-tallowimi-1~701iniurn methylsulfate (see "Cationic Surface Active Agents as Fabric
Softeners," R. R. Egan, Journal ofthe American Oil Chemic~l~' Society, 3anuary
1978, pages 118-121). N,N"-ditallow alkoyldiethylenetriamine and 1-
tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Chemical
Co~ ally as experim~nt~l chemicals. Methyl-l-tallowamidoethyl-2-
tallowimifl~701inium methylsulfate is sold by Witco Cht?mic~l Company under the
tr~ me Varisoft(E~) 475.
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Component (b): The prefierred Component (b) is a cationic nitrogenous salt
cont~ining one long chain acyclic aliphatic Cls-c2~ hydrocarbon group, preferably
selected from acyclic qll~t~rn~ry ammonium salts having the forrnula:
Rs -~
R4--N--R5 A-
R6
_
wherein R4 is an acyclic aliphatic Cls-c22 hydrocarbon group, Rs and R6 are
Cl-C4 saturated alkyl or hydroxy aLIcyl groups, and A- is an anion.
Examples of Component (b) are the monoalkyltrimethylammonium salts
such as monotallowtrimethylammonium chloride, mono(hydrogenated
tallow)trimethylamrnonium chloride, palmityltrimethyl amrnonium chloride and
soyatrimethylammonium chloride, sold by Witco Chemical Company under the
trade name Adogen~ 471, Adogen(~) 441, Adogen~) 444, and Adogen~) 415,
respectively. In these salts, R4 is an acyclic ~liph~tic Cl6-CI8 hydrocarbon group,
and R5 and R6 are methyl groups. Mono(hydrogenated tallow)trimethylammonium
chloride and monotallowtrimethylammonium chloride are pr~f~ d.
Other exarnples of Component (b) are behenyltrimethylammoniurn chloride
wherein R4 is a C22 hydrocarbon group and sold under the trade name E~ m~mine(~
Q2803-C by Humko Ch~mic~l Division of Witco Chemical Corporation;
soyallimethylethylarnmonium ethylsulfate wherein R4 is a Cl6-CI8 hydrocarbon
group, Rs is a methyl group, R6 is an ethyl group, and A- is an ethylsulfate anion,
sold under the trade name Jordaquat(~ 1033 by Jordan Chemical Company; and
methy~-bis~2-hydroxyethyl)-octadecylammonium chloride wherein R4 is a C,8
hydrocarbon group, Rs is a 2-hydroxyethyl group and R6 is a methyl group and
available under the trade name Ethoquad(~ 18/12 from Armak Company.
Other examples of Component (b) are 1-ethyl-1-(2-hydroxy ethyl)-2-
isoheptadecylimid~7l-1inium ethy~ fS~t~ available from Mona Tn~ ctrie~, Inc. under
the trade name Monaquat(~ ISIES; mono(tallowoyloxyethyl)
hydroxyethyldimethylammonium chloride, i.e., monoester of tallow fatty acid withdi(hydroxyethyl)dimethylammonium chloride, a by-product in the process of
m~kin~ diester of tallow fatty acid with di(hydroxyethyl)dimethylarnmoniurn
chloride, i.e., di(tallowoyloxyethyl) dimethyl~mmcniurn chloride.
Component (c): Preferred cationic nitrogenous salts having two or
more long chain acyclic aliphatic C,s-C22 hydrocarbon groups or one said group and
,
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W O 97/22682 PCT~US96/19095
16
an arylalkyl group which can be used either alone or as part of a mixture are selected
frorn the group consisting of:
(i) acyclic q~-A1ern~ry ammonium salts having the formula:
- R4 - t
R4 - I - RS A
R8
wherein R4is an acyclic aliphatic Cls-c22 hydrocarbon group, R5iS a Cl-C4
saturated alkyl or hydroxyalkyl group, R8 is selected from the group consisting of
R4 and Rs groups, and A-is an anion defined as above;
(ii) diamido quaternary ammonium salts having the formula:
O R5 0
Rl - C-N H - R2-N - R2-N H - C - Rl A-
_ R9
wherein Rl is an acyclic aliphatic Cls-C21 hydrocarbon group, each R2 is the
same or diLr~ divalent alkylene group having 1 to 3 carbon atoms, R5 and R9 are
Cl-C4 saturated alkyl or hydroxyalkyl groups, and A- is an anion;
(iii) ~liAmin~ alkoxylated qllAternA-y ammonium salts having the formula:
O R5 0
Rl--C-NH--R2-N--R2-NH--C--Rl A
(CH2CH20)nH
wherein n is equal to 1 to about 5, and Rl, R2, R5 and A- are as defined
above,
~ iv)
R'~ NH--R2--N-R--O~ R' A
wherein Rl is an acyclic Alirh~tic Cl5-C2l hydrocarbon group, R2 is the sarne ordi~erent divalent alkylene group having 1 to 3 carbon atoms, Rs are Cl-C4 saturated
,
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W O 97/22682 PCT~US96/19095
alkyl or hydroxyalkyl groups, A- is an anion and R2 is the same or different from the
other R2.
(v) mixtures thereof.
Examples of Component (c) are the well-known dialkyldi methylammonium
salts such as ditallowdimethylammonium chloride, ditallowdimethylammoniurn
methylsulfate, di(hydrogen~te~1t~llow)dimethylammonium chloride,
distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.
Di(hydrogen~te-lt~llow)di methylammonium chloride and
ditallowdimethyl~mmonium chloride are preferred. Exarnples of commercially
available dialkyldinnethyl ammonium salts usable in the present invention are
di(hydrogerl~te~lt~llow)dimethylammonium chloride (trade name Adogen~ 442),
ditallowdimethylamrnonium chloride (trade name Adogen(~ 470), distearyl
dimethylarnmonium chloride (trade name Arosurf(~ TA-100), all available from
Witco Chemic~l Company. Dibehenyldimethylammonium chloride is sold under
the trade name Kem~mine Q-2802C by Humko Chemical Division of Witco
Chemical Cu"!~"dtion.
Other examples of Component (c) are methylbis(tallowamidoethyl)(2-
hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated
tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate; these materials are
available from Witco Chemical Company under the trade names Varisoft(~) 222 and
Varisoft(E~ 110, respectively: dimethylstearylbenzyl ~mmoniwn chloride sold under
the trade names Varisoft(E~ SDC by Witco Chemical Company and Ammonyx(~) 490
by Onyx Chemical Co"~p~ly.
An even more pLcr~ d composition contains Component (a): the reaction
product of about 2 moles of hydrogen~tel1 tallow fatty acids with about 1 mole of N-
2-hydlo~y~ ylethylenerli~mine and is present at a level of from about 20% to about
70% by weight of the fabric softening co",~-nent of the present invention
compositions; Component (b): mono(hydrogenated tallow)trimethyl ammonium
chloride present at a level of from about 3% to about 30% by weight of the fabric
softening colll~onclll of the present invention compositions, Component (c):
selected from the group con~i~ting of di(hydrogen~teclt~llow)dimethylammonium
chloride, ditallowdirnethylammonium chloride, methyl-l-tallowamidoethyl-2-
tallowimitl~7olinium methy~ f~te~ diethanol ester dimethylammonium chloride,
- and mixtures thereof, wherein Component (c) is present at a level of from about
20% to about 60% by weight of the fabric softening component of the present
invention compositions; and wherein the weight ratio of said di(hydrogenated
.
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W O 97~2682 PCT~US96/19095
lg
tallow)dimethylammonium chloride to said methyl- 1 -tallowamidoethyl-2-
tallowimida~olinium methylsulfate is from about 2:1 to about 6:1.
In the cationic nitrogenous salts described hereinbefore, the anion A-
provides charge neutrality. Most often, the anion used to provide charge neutrality
in these salts is a halide, such as chloride or bromide. However, other anions can be
used, such as methylsulfate, ethyl~-llf~te, hydroxide, acetate, formate, cikate, sulfate,
carbonate, and the like. Chloride and methylsulfate are preferred herein as anion A-.
Ihe preferred fabric softening compounds of the present invention are
biodegradable quaternary ammonium compounds according to II and III as
hereinbefore described, wherein, preferably, the fatty acyl groups have an Iodine
Value (I.V.) of from greater than about 5 to less than about 100, and, also
preferably, a cis/trans isomer weight ratio of greater than about 30/70 when the I.V.
is less than about 25, the level of unsaturation preferably being less than about 65%
by weight. Preferably, the compounds with an I.V. of greater than about 10 are
capable of forming concentrated aqueous compositions with concentrations greaterthan about 13% by weight without viscosity modifiers other than normal polar
organic solvents present in the raw m~tPri~l of the compound or added eleckolyte,
and wherein any fatty acyl groups from tallow are l~refe~ably modified, especially to
reduce their odor.
When the I.V. of the fatty acyl groups is above about 20, the softener
provides excellent zmti~tzltic effect. ~nti~t~tic effects are especially in,l)ol~lt where
the fabrics are dried in a tumble dryer, and/or where synthetic materials which
generate static are used. Maximurn static control occurs with an I.V. of greater than
about 20, preferably greater than about 40. When fully saturated softener
compounds are used in the compositions, poor static control results. Also, as
tliccl]~e~l hereinafter, concelllldl~bility increases as I.V. increases. The benefits of
col,c~ 91.ility include: use of less p~c~ ing m~t~ri~l; use of less organic
solvents, especially volatile organic solvents, use of less concentration aids which
typically add nothing to ~ .f~llllance; etc.
As the I.V. is raised, there is a potential for odor problems. Surprisingly,
some highly desirable, readily available sources of fatty acids such as tallow,
possess odors that remain with the softener compounds despite the chemical and
m~-~h~nical processing steps which convert the raw tallow to fini.ched active. Such
sources must be deodorized, e.g., by absorption, ~ till~tion (inchl-lin ~7L.;~pillg
such as steam ~L,i~hlg), etc., as is well known in the art. In addition, care must be
taken to minimi7f~ contact of the reslllting fatty acyl groups to oxygen and/or
bacteria by adding antioxidants, antibacterial agents, etc. The additional expense
CA 02240816 1998-06-18
W O 97/2268~ PCT~US96/19095
19
and effort associated with the unsaturated fatty acyl groups is justified by thesuperior concentratability and/or performance. For example, diester quaternary
ammonium salt (DEQA) Cont~ining unsaturated fatty acyl groups having an I.V.
greater than about 10 can be concentrated above about 13% without the need for
additional concentration aids, especially surfactant concentration aids as discussed
hereinafter.
The above softener actives derived from highly unsaturated fatty acyl
groups, i.e., fatty acyl groups having a total unsaturation above about 65% by
weight, do not provide any additional improvement in ~nti~t~tiC effectiveness. They
may, however, be able to provide other benefits such as improved water absorbency
of the fabrics. In general, an I.V. range of from about 40 to about 65 is preferred for
concentratability, ma~cimi7~tion of fatty acyl sources, excellent softness, static
control, etc.
Highly concentrated aqueous dispersions of these softener compounds can
gel and/or thicken during low (5 ~(:~) temperature storage. Softener compounds
made from only unsaturated fatty acids minimi7Ps this problem but additionally is
more likely to cause malodor formation. Surprisingly, compositions from these
softener compounds made from fatty acids having an I.V. of from about 5 to about25, preferably from about 10 to about 25, more preferably from about 15 to about20, and a cis/trans isomer weight ratio of from greater than about 30/70, preferably
greater than about 50/50, more preferably greater than about 70/30, are storage
stable at low Lelllp~dlul~ with minim~l odor formation. These cis/trans isomer
weight ratios provide optimal concentratability at these I.V. ranges. In the I.V.
range above about 25, the ratio of cis to trans isomers is less important unless higher
concentrations are needed. The relationship between I.V. and conce~ dldbility isdescribed he.~ ~er. For any IV, the concentration that will be stable in an
aqueous cu-,l~o~ilion will depend on the criteria for stability (e.g., stable down to
about 5~C; stable down to 0~C; doesn't gel; gels but recovers on hP~ting, etc.) and
the other ingredients present, but the concentration that is stable can be raised by
adding the conc~ntr~tion aids, described hereinafter in more detail, to achieve the
desired stability.
Generally, hydrogenation of fatty acids to reduce polyunsaturation and to
lower I.V. to insure good color and improve odor and odor stability leads to a high
- degree of trans configuration in the molecule. The.~fole, diester compounds
derived from fatty acyl groups having low I.V. values can be made by mixing fully
hydrogenated fatty acid ~,vith touch hydrogenated fatty acid at a ratio which provides
an I.V. of from about S to about 25. The polylln~h~r~tion content of the touch
CA 02240816 1998-06-18
W O 97/22682 PCT~US96/19095
hardened fatty acid should be less than about 5%, preferably less than about 1%.During touch hardening the cis/trans isomer weight ratios are controlled by methods
known in the art such as by optimal mixing, using specific catalysts, providing high
H2 availability, etc. Touch hardened fatty acid with high cis/kans isomer weightratios is available commercially (i.e., Radiacid 406 from FINA~.
It has also been found that for good chemical stability of the diester
quaternary compound in molten storage, moisture level in the raw material must be
controlled and minimi7e~ preferably less than about 1% and more preferably less
than about 0.5% water. Storage temperatures should be kept as low as possible and
still ...~i..l;~i.. a fluid material, ideally in the range of from about 49~C to about
66~C. The optimum storage temperature for stability and fluidity depends on the
specific I.V. of the fatty acid used to make the softener compound and the level/type
of solvent selected. It is important to provide good molten storage stability toprovide a commercially feasible raw m~ten~l that will not degrade noticeably in the
normal transportation/storage/h~n-l~ing of the material in m~nllf~cturing operations.
It will be understood that substituents R and Rl can optionally be substituted
with various groups such as alkoxyl or hydroxyl groups. The preferred compounds
can be considered to be diester variations of ditallow dimethyl ammonium chloride
(DTDMAC), which is a widely used fabric softener. At least 80% of the softener
compound, i.e., DEQA is preferably in the diester form, and from 0% to about 20%,
preferably less than about 10%, more preferably less than about 5%, can be
monoester, i.e., DEQA monoester (e.g., co/.l;.;..i.l~ only one -Y- Rl group).
As used herein, when the diester is specified, it will include the monoester
that is nnrm~lly present in m~nllf~ctllre. For softening, under no/low d~lgent
carry-over laundry conditions the ~ cel-Lage of monoester should be as low as
possibre, preferably no more than about 2.5%. However, under high detel~ellt
carry-over conditions, some monoester is preferred. The overall ratios of diester to
monoester are from about 100:1 to about 2:1, preferably from about 50:1 to about5:1, more preferably from about 13:1 to about 8:1. Under high d~Ll~elll carry-over
conditions, the di/monoester ratio is preferably about 11:1. The level of monoester
present can be controlled in the m~nl-f~l~tllring of the softener compound.
In addition, since the foregoing compounds (diesters) are somewhat labile to
hydrolysis, they should be h~nflled rather carefully when used to form~ te the
compositions herein. For t;x~lplc, stable liquid compositions herein are form~ te~l
at a pH (neat) in the range of from about 2 to about 5, preferably from about 2 to
about 4.5, more preferably from about 2 to about 4. For best product odor stability,
when the I.V. is greater that about 25, the neat pH is from about 2.8 to about 3.5
CA 02240816 1998-06-18
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21
especially for lightly scented products. This appears to be true for all of the above
softener compounds and is especially true for the pre~erred DEQA specified herein,
i.e., having an I.V. of greater than about 20, preferably greater than about 40. The
limitation is more important as I.V. increases. The pH can be adjusted by the
addition of a Bronsted acid. pH ranges for making chemically stable softener
compositions cont~ining diester quaternary ammonium fabric softening compounds
are disclosed in U.S. Pat. No. 4,767,547, Straathof et al., issued on Aug. 30, 1988,
which is incorporated herein by reference.
Examples of suitable Bronsted acids include the inorganic mineral acids,
carboxylic acids, in particular the low molecular weight (C1-C5) carboxylic acids,
and allcylsulfonic acids. Suitable inorganic acids include HCI, H2SO~, HNO3 and
H3PO4. Suitable organic acids include formic, acetic, methylsulfonic and
ethylsulfonic acid. Prer.,ll~,d acids are hydrochloric, phosphoric, and citric acids.
Liquid compositions of this invention typically contain from about 0.5% to
about 80%, preferably from about 1% to about 35%, more preferably from about
4% to about 32%, of bio~legr~ ble diester qn~tem~ry ammonium softener active.
Concentrated compositions are disclosed in allowed U.S. Pat. Applic. Ser. No.
08/169,858, filed December 17, 1993, Swartley, et al., said application being
incorporated herein by reference.
Particulate solid, granular.compositions of this invention typically contain
from about 50% to about 95%, preferably from about 60% to about 90% of
biodegradable diester ~ t~ arnmonium softener active.
The amount of fabric softening agent (fabric softener) in liquid compositions
of this invention is typically from about 2% to about 50%, preferably from about 4%
to about 30%, by weight of the composition. The lower limits are amounts needed
to con~ribute eLr~clive fabric softening perf~)rrn~n~e when added to laundry rinse
baths in the nra~ , which is customary in home laundry practice. The higher limits
are suitable for collcent~ ed products which provide the consumer with more
economical usage due to a reduction of pa~ ging and distributing costs.
Fully forn~ tecl fabric softening compositions preferably contain, in
addition to the hereinbefore described components, one or more of the following
- ingre~lient~
Concelllldled compositions of the present invention may require organic
~ and/or inorganic co~ ;on aids to go to even higher conct;lllldlions and/or to
meet higher stability standards depending on the other ingredients. Surfactant
concentration aids are typically selected from the group con~i~ting of single long
chain alkyl cationic surf~,t~nt~; nonionic surf~ct~ntc; arnine oxides; fatty acids; or
CA 02240816 1998-06-18
W O 97/22682 PCT~US96/19095
mixtures thereo~, typically used at a level of from 0 to about 15% of the
composition.
Inorganic viscosity/dispersibility control agents which can also act like or
gm~nt the effect of the surfactant concentration aids, include water-soluble,
ionizable salts which can also optionally be incorporated into the compositions of
the present invention. A wide variety of ionizable salts can be used. Exarnples of
suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of
the Element~, e.g., calcium chloride, m~ um chloride, sodium chloride,
potassium bromide, and lithium chloride. The ionizable salts are particularly useful
during the process of mixing the ingredients to make the compositions herein, and
later to obtain the desired viscosity. The amount of ionizable salts used depends on
the amount of active ingredients used in the compositions and can be adjusted
according to the desires of the form~ tor. Typical levels of salts used to control the
composition viscosity are from about 20 to about 20,000 parts per million (ppm),preferably from about 20 to about 11,000 ppm, by weight of the composition.
Alkylene polyammoniurn salts can be incorporated into the composition to
give viscosity control in addition to or in place of the water-soluble, ionizable salts
above. In addition, these agents can act as scavengers, forming ion pairs with
anionic dchl~,cll~ carried over from the main wash, in the rinse, and on the fabrics,
and can improve softness perform~n~e These agents may stabilize the viscosity
over a broader range of tem~cldlu.~, especially at low t~lllpc~dlLll~ s, cc,nl~ucd to the
inorganic electrolytes.
Specific cx~llples of aL~ylene polyammonium salts include l-lysine
monohydrochloride and 1,5-~i~mmoniurn 2-methyl pentane dihydrochloride.
Another optional, but ~.er~ d, ingredient is a liquid carrier. The liquid
carrier employed in the instant compositions is preferably at least primarily water
due to its low cost, relative availability, safety, and environmçnt~l c~.,.p;.l;hility.
The level of water in the liquid carrier is preferably at least about 50%, most
preferably at least about 80%, by weight of the carrier. The level of liquid carrier is
greater than about 50%, preferably greater than about 65%, more preferably greater
than about 70%. Mixtures of water and low molecular weight, e.g., <about 200,
organic solvent, e.g., lower alcohols such as ethanol, propanol, is~lo~ ol or
butanol are useful as the carrier liquid. Low molecular weight alcohols include
monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric
(polyols) alcohols.
Stabilizers can be present in the compositions of the present invention. The
term "stabilizer," as used herein, includes antioxidants and reductive agents both of
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W O 97/22682 PCTrUS96/19095
23
which are well-known in the art. These agents are present at a level of from 0% to
about 2%, preferably from about 0.01% to about 0.2%, more preferably from about
0.035% to about 0.1% for antioxidants, and more preferably from about 0.01% to
about 0.2% for reductive agents. These assure good odor stability under long term
storage conditions for the compositions and compounds stored in molten form. Theuse of antioxidants and reductive agent stabilizers is especially desirable for low
scent products (low perfume).
Optionally, the compositions of the present invention can contain from 0%
to about 10%, preferably from about 0.1% to about 5%, more preferably from about0.1% to about 2%, of a soil release agent. Preferably, such a soil release agent is a
polymer. Polymeric soil release agents useful in the present invention include
copolymeric blocks of terephthS~I-S~te and polyethylene oxide or polypropylene oxide,
and the like. These agents give additional stability to the concentrated a~ueous,
liquid compositions. Therefore, their presence in such liquid compositions, even at
levels which do not provide soil release benefits, is pler~ ed.
Preferred soil release agents include a copolymer having blocks of
terephthS~ISIt~ and polyethylene oxide, crystS~ S~ble polyesters and polymers of the
generic formula:
X-(OCH2CH2)n (0-C~O)- RI-C(O)-O-R2)U-(O-C(O)- RI-C(O)-O)-(CH2CH20)n-X
in which X can be any suitable capping group, with each X being selected from the
group con~i~ting of H, and alkyl or acyl groups co..~ ;i.g from about 1 to about 4
carbon atoms, preferably methyl, n is selected for water solubility and generally is
from about 6 to about 113, preferably from about 20 to about 50, and u is critical to
formulation in a liquid composition having a relatively high ionic strength. There
should be very little mslte~sll in which u is greater than 10. Furthermore, there
should be at least 20%, preferably at least 40%, of mZlteri~l in which u ranges from
about 3 to about 5.
The Rl moieties are es~erltiSIlly 1,4-phenylene moieties. As used herein, the
term "the Rl moieties are ~s,sentiSIlly 1,4-phenylene moieties" refers to compounds
~ where the R~ moieties consist entirely of 1,4-phenylene moieties, or are partially
substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene
- moieties, or mixtures thereof. R2 can be any suitable ethylene or substituted
ethylene moieties. A more complete disclosure of these highly preferred soil
release agents is con~illcd in Eu~o~ean Patent Application 185,427, Gosselink,
CA 02240816 1998-06-18
W O 97/22682 PCTAUS96/19095
24
published June 25, 1986, the disclosure of which is incorporated herein by
reference.
Detersive Surfactant-
Detersive surfactants can be included in the compositions of the present
invention. Such compositions may comprise at least 1%, preferably from about 1%
to about 99.8%, by weight of surfactant depending upon the particular surfactants
used and the effects desired. In a highly preferred embodiment, the detersive
surfactant comprises from about 5% to about 80% by weight of the composition.
The detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or
cationic. Mixtures of these surfactants can also be used. Preferred detergent
compositions comprise anionic detersive surf~ct~ntc or mixtures of anionic
surfactants with other surfa~t~nt~, especially nonionic surfactants.
Nonlimiting examples of surf~l tAnt~ useful herein include the conventional
Cll-CI8 alkyl benzene sulfonates and primary, secondary and random alkyl sulfates,
the Cl0-Cl8 alkyl alkoxy slllf~tes, the Cl0-C~8 alkyl polyglycosides and their
co,~pollding sulfated polyglycosides, Cl2-CI8 alpha-sulfonated fatty acid esters,
Cl2-Cl8 alkyl and aLt~yl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy), Cl2-Cl8 betaines and sulfobetaines ("slllt~inPs"), Cl0-C~8 amine
oxides, and the like. Other conventional useful surfactants are listed in standard
texts.
One class of nonionic surfactant particularly useful in detergent compositions
of the present invention is con{lPn~tes of ethylene oxide with a hydrophobic moiety
to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in
the range of from S to 17, preferably from 6 to 14, more plere~ably from 7 to 12.
The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature. The
length of the polyoxyethylene group which is confl~n~e~l with any particular
hydrophobic group can be readily adjusted to yield a water-soluble compound
having the desired degree of balance between hydrophilic and hy~hobic
elements.
Especially ~ier~ d nonionic surfactants of this type are the C9-C15 primary
alcohol ethoxylates cu~ g 3-8 moles of ethylene oxide per mole of alcohol,
particularly the C14-C l5 primary alcohols cont~inin~ 6-8 moles of ethylene oxide
per mole of alcohol, the Cl2-Cls primary alcohols cont~ining 3-5 moles of ethylene
oxide per mole of alcohol, and mixtures thereof.
Another suitable class of nonionic surfactants compri.~es the polyhydroxy fatty
acid amides of the formula:
-
CA 02240816 1998-06-18
W O 97/22682 PCT~US96/19095
R2C(03n(RI)Z
wherein: Rl is H, C 1 -C8 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a
mixture thereof, preferably Cl-C4 alkyl, more preferably Cl or C2 alkyl, most
preferably Cl aLlcyl (i.e., methyl); and R2 is a C5-C32 hydrocarbyl moiety, preferably
straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl
or alkenyl, most preferably straight chain Cll-C19 alkyl or alkenyl, or mixture
thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl
chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the
case of other reducing sugars) 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 arnination reaction, more preferably Z
is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose,
lactose, galactose, rnannose, and xylose, as well as glyceraldehyde. As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn
syrup can be utilized as well as the individual sugars listed above. These corn
syrups may yield a mix of sugar components for Z. It should be understood that it is
by no means intenr~e-1 to exclude other suitable raw m~teri~l~. Z preferably will be
selected from the group consisting of -CH2-(CHOH)n-CH20H, -CH(CH2OH)-
(CHOH)n- 1 -CH2OH, -CH2-(CHOH)2(CHOR2)(CHOH)-CH2OH, where n is an
integer from 1 to 5, inclusive, and R2 is H or a cyclic mono- or poly- saccharide, and
aLkoxylated derivatives thereof. Most ~lc~ d are glycityls wherein n is 4,
particularly -CH2-(CHOH)4-CH2OH.
Builders -
De~ ;el1t builders can optionally be included in the compositions herein to
assist in controlling nnineral hardness. Inorganic as well as organic builders can be
used. Builders are typically used in fabric l~l-n-l~ring compositions to assist in the
removal of particulate soi}s.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically Comrri~ce at least about 1% builder. Liquid forrnulations typically
~ comprise from about 5% to about 50%, more typically about 5% to about 30%, by
weight, of detergent builder. Granular formulations typically comprise from about
~ 10% to about 80%, more typically from about 15% to about 50% by weight, of the
d~ g~ builder. Lower or higher levels of builder, however, are not meant to be
exçlll~le~l
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26
Inorganic or P-cont~;ning detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-
phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates
and sesquicarbonates), sulph~tec, and aluminos;licates. However, non-phosphate
builders are required in some locales. I.llpol Lal1tly, the compositions herein function
surprisingly well even in the presence of the so-called "weak" builders (as eo,llpar. d
with phosphates) such as citrate, or in the so-called "underbuilt" situation that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly thosehaving a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to
H. P. ~ieck. NaSKS-6 is the tr~<lem~rk for a crystalline layered silicate marketed by
Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na
SKS-6 silicate builder does not contain alllmimlm NaSKS-6 has the delta-Na2SiO5
morphology form of layered silicate. It can be prepared by methods such as thosedescribed in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly
preferred layered silicate for use herein, but other such layered cili~te~, such as
those having the general forrnula NaMSixO2x+1.yH20 wherein M is sodium or
hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a nurnber from O to 20,
preferably O can be used herein. Various other layered .~ilicat~s from Hoechst
include NaSKS-S, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
As noted above, the delta-Na2SiOS (NaSKS-6 form) is most ~lef~ lled for use herein.
Other silicates may also be useful such as for exarnple magnesium silicate, which
can serve as a C~iS~t;llillg agent in granular formulations, as a stabilizing agent for
oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the ~Ik~line earth and alkali metal
c~l,ol1dles as disclosed in German Patent Application No. 2,321,001 published onNovember 15, 1973.
mint cilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most ~ llly m~rk~te~l heavy duty granular
dt;te.~ell~ compositions, and can also be a significant builder ingredient in liquid
d~ ellL formulations. Alllminosilicate builders include those having the empirical
form~
Mz(zAlO2)y~ ~XH2O
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range
from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
CA 02240816 1998-06-18
VVO 97/22682 PCT~US96/19095
27
Useful aluminosilicate ion exchange materials are cornrnercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing alurninosilicate ion exchange m~teri~l~ is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange m~teri~l~ useful herein are available under the
desi~n~tions Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially
~ f~ d embodiment, the crystalline aluminosilicate ion exchange m~teri~l has the
formula:
Nal2r(AI02)~2(SiO2),2] .xH2o
wherein x is from about 20 to about 30, especially about 27. This material is known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably,
the aluminosilicate has a particle size of about 0.1-10 microns in ~ t.?r.
Organic d~ elll builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate compounds. As
used herein, "polyc~1,02~ylate" refers to compounds having a plurality of
carboxylate groups, ~l.,r~.ably at least 3 carboxylates. Polycarboxylate builder can
generally be added to the composition in acid forrn, but can also be added in the
form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium,
pU~ iu~ and lithiurn, or alkanolammonium salts are ~ierc,l~d.
Included among the polycarboxylate builders are a variety of categories of
useful m~t.?ri~l~ One illl~ol~ category of polycarboxylate builders encomp~eq
the ether polycarboxylates, including oxydisuccinale, as disclosed in Berg, U.S.Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include
cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful d~tel~ellcy builders include the ether hydroxypolycarboxylates,
copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid,the various alkali metal, ammonium and substituted ammonium salts of polyacetic
acids such as ethyl~?n~ mine tetraacetic acid and nitrilotriacetic acid, as well as
- polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble
salts thereof.
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28
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders of particular importance for heavy duty liquid
detergent for nulations due to their availability from renewable resources and their
biodegradability. Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
Also suitable in the compositions of the present invention are the 3,3-dicar-
boxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent
4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the
C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred
compound of this type is dodecenylsuccinic acid. Specific examples of succinate
builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-p~nt~(lecenylsuccinate, and the like.
Lauryls~-ccin~te~ are the ~ler...ed builders of this group, and are described inEuropean Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 137 1979 and in U.S. Patent 3,308,067, Diehl, issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., Cl2-CI8 monocarboxylic acids, can also be inco~porated into
the compositions alone, or in combination with the aforesaid builders, especially
citrate and/or the succinate builders, to provide additional builder activity. Such use
of fatty acids will generally result in a tlimimltion of sll~cin~, which should be taken
into account by the formnl~tor.
In si~ tion~ where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-l~lln(l~ring operations, the various alkali metal
phosphsltee such as the well-known sodium tripolyphosph~t~s, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as ethane-l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for
example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137
can also be used.
Blearhing Compounds -
The compositions herein may optionally contain bleachin~ agents or
ble~c~hing compositions c~ a ble~hin~ agent and one or more bleach
activators. When present, blea~hing agents will typically be at levels of from about
1% to about 30%, more typically from about 5% to about 20%, of the detergent
composition, especially for fabric l~nn~ring. If present, the amount of bleach
-
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29
activators will typically be from about 0.1% to about 60%, more typically from
about 0.5% to about 40% of the bl~rhing composition comprising the ble~hin~
agent-plus-bleach activator.
The ble~hing agents used herein can be any of the bleaching agents useful
for compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that are now known or become known. These include oxygen bleaches as
well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g.,
mono- or tetra-hydrate) can be used herein.
Another category of ble~chin~ agent that can be used without restriction
encomp~cses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include mS~f~ne~ium monoperoxyphthzlk~te
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-~-
oxoperoxybutyric acid and diperoxydoclel ~n~ioic acid. Such bl~ ing agents are
disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, Ellr~l)e~l Patent
Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent4,412,934, Chung et al, issued November 1, 1983. Highly ~"er~,.,cd ble~ in~
agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen ble~ hing agents can also be used. Suitable peroxygen ble~ in~
compowlds include sodium carbonate peroxyhydrate and equivalent "pcl~;~l,onate"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodiwm
peroxide. Persulfate bleach (e.g., OXONE, m~nllf~ctllred commercially by DuPont)can also be used.
A ~.ef~.led p~,.c~l,onate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000 micrometers,
not more than about 10% by weight of said particles being smaller than about 200micrometers and not more than about 10% by weight of said particles being largerthan about 1,250 micrometers. Optionally, the l~el~hl,ollal~ can be coated with
silicate, borate or water-soluble surf~-t~nt~ Percarbonate is available from various
c~ c.cial sources such as FMC, Solvay and Tokai Denka.
Mixtures of ble?/~ ~ling agents can also be used.
PeLO~ge11 ble~r~lin~ agents, the perborates, the p~;~bonates, etc., are
preferabLy combined with bleach activators, which lead to the in situ production in
aqueous solution (i.e., during the washing process) of the peroxy acid corresponding
to the bleach activator. Various nonlimitin~ exarnples of activators are disclosed in
U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
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4,41~2,934. The nonanoyloxybenzene sulfonate ~NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be used. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R~N(R5)C(o)R2C(o)L or RIC(O)n(Rs)R~C(O)L
wherein Rl is an alkyl group cont~ininp from about 6 to about 12 carbon atoms, R2
is an alkylene cont~inin~ from I to about 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl cont~inin~ from about 1 to about 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is displaced from the bleach
activator as a consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A ~refell~ d leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
oct~ns~rnido-caproyl)oxyben7~n~snlfonate, (6-nonanarnidocaproyl)oxybçn7tont?s~
fonate, (6-decan~mido-caproyl)oxyben7~nesl~lfonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
incorporated herein by reference. A highly l~ler~ d activator of the ben~oxazin-type is:
Il .
~N"C~
Still another class of pl~fclled bleach activators includes the acyl lactarn
activators, çspeci~lly acyl caprolactams and acyl valerolactarns of the formulae:
O O
Il C--CH2--CH2~ 0 C--CH2--CH2
CH2--CH2 'CH2--1H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining from 1 to
about 12 carbon atoms. Highly preferred lactarn activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhe~noyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, Im.1ecenoyl caprolactam, benzoyl valerolactarn,
octanoyl valerolactam, decanoyl valerolactam, lm-lecenQyl valerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
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reference, which discloses acyl caprol~ct~m.c, including benzoyl caprolactam,
adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the
art and can be utilized herein. One type of non-oxygen bleaching agent of particular
interest includes photoactivated bleaching agents such as the sulfonated zinc and/or
all-minl-m phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to
Holcombe et al. If used, detergent compositions will typically contain from about
0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
m~ng~nese compound. Such compounds are well known in the art and include, for
example, the m~ng~lt~se-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat. 5,194,416, U.S. Pat. 5,114,606; and European Pat. App. Pub.Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490Al; Preferred exarnples of
these catalysts include MnIV2(,u-0)3(1,4,7-trimethyl- 1,4,7-triazacyclo-
nonane)2(PF6)2, MnIII2(~1-O) 1 (~l-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-
(Cl04)2, MnIV4(~-0)6~ 1,4,7-triazacyclononane)4(Cl04)4, MnIIIMnIV4(~1-O) 1 (,u-
OAc)2-~ 1,4,7-trimethyl- 1,4,7-triazacyclononane)2(Cl04)3, MnIV(1,4,7-trimethyl-
1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based
bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of m~n~n~se with various complex ligands to enhance
ble~ching is also reported in the following United States Patents: 4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.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 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Enzymes -
Enzymes can be included in the compositions of the present invention for a
- variety of purposes, including removal of protein-based, carbohydrate-based, or
triglyceride-based stains from surfaces such as textiles or dishes, for the prevention
of refugee dye transfer, for example in laundering, and for fabric restoration
Suitable enzymes include proteases, arnylases, lipases, cell~ ee~, peroxi~ e~, and
mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal
and yeast origin. Preferred selections are influenced by factors such as pH-activity
-
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32
and/or stability optima, therrnostability, and stability to active detergents, builders
and the like. In this respect bacterial or fungal enzymes are preferred, such asbacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning,
stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or
personal care detergent composition. Preferred detersive enzymes are hydrolases
such as proteases, amylases and lipases. Preferred enzymes for laundry purposes
inc}ude, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly
preferred for automatic dishwashing are amylases and/or proteases, including both
current con~ elcially available types and improved types which, though more and
more bleach compatible though s~-~cPseive improvements, have a r~.n~ i"g degree
of bleach deactivation susceptibility.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount". The terrn
"cleaning effective amount" refers to any amount capable of producing a cle~ning,
stain removal, soil removal, whitening, deodorizing, or freshness improving effect
on substrates such as fabrics, dishware and the lilce. In practical terms for current
commercial ~n~cl~a,dLions, typical amounts are up to about 5 mg by weight, more
typically û.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated otherwise, the compositions herein will typically comprise from 0.001% to5%, preferably 0.01%-1% by weight of a commercial enzyme I,le~d~ion. Protease
enzymes are usually present in such commercial ~lc~ dLions at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
For certain d-cl~lgellls, such as in automatic dishwashing, it may be desirable to
il~iredse the active enzyme content of the commercial plep~aLion in order to
minim~7e the total amount of non-catalytically active materials and thereby improve
spotting/filming or other end-results. Higher active levels may also be desirable in
highly conce~ aled ~lc;l~rgel-l forrnulations.
Suitable ~mrles of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease isobtained from a strain of Bacillus, having mz1xi,.,~ . activity throughout the pH
range of 8-12, developed and sold as ESPERASE(E~ by Novo Tn~ tries A/S of
Denm~rk, hereinafter "Novo". The ~lel)aldlion of this enzyme and analogous
enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE(g) and SAVINASE~g) from Novo and MAXATASE(~) from
Tntern~tion~l Bio-Synthetics, Inc., The Netherlands; as well as Protease A as
disclosed in EP 130,756 A, Janua~y 9, 1985 and Protease B as disclosed in EP
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303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH
protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other enzymes, and a
reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred proteases include those of WO 951Q591 A to Procter & Gamble . When
desired, a protease having decreased adsorption and increased hydrolysis is available
as described in WO 9507791 to Procter & Garnble. A recombinant trypsin-like
protease for delel~enl~ suitable herein is described in WO 9425583 to Novo.
In more detail, an especially ~,~fe~led protease, referred to as "Protease D" isa carbonyl hydrolase variant having an arnino acid sequence not found in nature,which is derived from a precursor carbonyl hydrolase by substituting a differentamino acid for a plurality of amino acid residues at a position in said carbonylhydrolase equivalent to position +76, preferably also in combination with one ormore amino acid residue positions equivalent to those selected from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128,
+135, +156, +166, ~-195, +197, ~204, +206, +210, +216, +217, +218, ~222, +260,
+265, and/or +274 according to the numbering of Bacillus amyloliquefaciens
subtilisin, as described in the patent applications of A. Baeck, et al, entitled"Protease-Cont~ining Cleaning Compositions" having US Serial No. 08t322,676,
and C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes"
having US Serial No. 08/322,677, both filed October 13, 1994.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing purposes, include, for example, a-amylases described in GB 1,296,839to Novo, RAPIDASE~, Tnt~ tional Bio-Synthetics, Inc. and TERMAMYL(~),
Novo. FUNGAMYL~) from Novo is especially useful. Engineering of enzymes for
improved stability, e.g., oxidative stability, is known. See, for exarnple J. Biological
Chem.,Vol.260,No. 11,June 1985,pp6518-6521. Certainpl't;r~ dembo~1im~nt~
of the present compositions can make use of amylases having improved stability in
dt:lc~e~ such as ~u~ ic dishwashing types, especially improved oxidative
stability as measured against a reference-point of TERMAMYL(~ in commercial use
in 1993. These preferred amylases herein share the characteristic of being "stability-
enh~nced~ amylases, characterized, at a minimllm, by a measurable improvement inone or more of: oxidative stability, e.g., to hydrogen peroxide /
tetraacetylethylene~ mint? in buffered solution at pH 9-10; thermal stability, e.g., at
common wash temperatures such as about 60~C; or ~Ik~line stability, e.g., at a pH
from about 8 to about 11, measured versus the above-identified reference-point
~nylase. Stability can be measured using any of the art-disclosed technical tests.
CA 02240816 1998-06-18
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34
See, for example, references disclosed in WO 9402597. Stability-enh~nced amylases
can be obtained from Novo or from Genencor Tntern~tional. One class of highly
pl~r.~ d amylases herein have the commonality of being derived using site-directed
mutagenesis from one or more of the Baccillus amylases, especially the Bacillus a-
amylases, regardless of whether one, two or multiple amylase strains are the
immediate precursors. Oxidative stability-enh~nred amylases vs. the above-
identified reference amylase are y~ef~l~d for use, especially in bleaching, morepreferably oxygen bleaching, as distinct from chlorine ble~chin~, detergent
compositions herein. Such preferred amylases include (a) an amylase according tothe hereinbefore incorporated WO 9402597, Novo, Feb. 3, l 994, as further
illustrated by a mutant in which substitution is made, using alanine or ll~.,o~ e,
preferably threonine, of the methionine residue located in position 197 of the
B.licheniformis alpha-amylase, known as TERMAMYL~;), or the homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens,
B.subtilis, or B.stearothermophilus; (b) stability-enh~nce~l amylases as described by
Genencor Tnt~ tional in a paper entitled "Oxidatively Resi~t~nt alpha-Amylases"
p~ rl at the 207th American Chemical Society National Meeting, March 13-17
1994, by C. Mitchinson. Therein it was noted that bleaches in automatic
dishwashing detergents inactivate alpha-amylases but that improved oxidative
stability amylases have been made by Genencor from B.lichellirollllis NCIB8061.
Methionine (Met) was identified as the most likely residue to be modified. Met was
substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to
specific mutants, particularly important being M197L and M197T with the M197T
variant being the most stable expressed variant. Stability was measured in
CASCADE(E9 and SUNLIGHT(~ c) particularly ~lefe..ed amylases herein include
amylase variants having additional modification in the imme~ te parent as
described in WO 9510603 A and are available from the ~ nee, Novo, as
DURAMYL~. Other particularly ~-~ef. lled oxidative stability enh~nce(l amylase
include those described in WO 9418314 to Genencor Tnt~ tional and WO 9402597
to Novo. Any other oxidative stability-enhanced amylase can be used, for exampleas derived by site-directed mutagenesis from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other pleft;ll. d enzyme modifications
are ~ce~ihle. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH o~ between S and 9.5. U.S. 4,435,307, Barbesgoard et al, March
6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicolastrain DSM1800 or a cellulase 212-producing ~ngus belonging to the genus
CA 02240816 1998-06-18
WO 97/22682 PCT/US96/19095
Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME(~ (Novo) is
especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorg~ni~mq of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent
Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano
Ph~ reutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosurn, e.g. Chromobacter viscosum var. Iipolyticum NRRLB
3673 fi~om Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherl~n~s, and lipases ex
Pseudomonas gladioli. LIPOLASE(~ enzyme derived from Humicola lanuginosa
and commercially available from Novo, see also EP 341,947, is a preferred lipasefor use herein. Lipase and amylase variants stabilized against peroxidase enzymes
are described in WO 9414951 A to Novo. See also WO 9205249 and ~D
94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes can be used in combination with oxygen sources, e.g.,
pelca bol1ate, perborate, hydrogen peroxide, etc., for "solution ble~hin~" or
prevention of transfer of dyes or pigments rernoved from substrates during the wash
to other substrates present in the wash solution. Known peroxidases include
horseradish peroxi~i~qe, li~nin~e, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-co~ g d~h~,enl compositions are disclosed in WO
89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of t;l~yll.c materials and means for their incorporation into synthetic
de;le,~,enl compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor Tnt~ tional, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to McCarty et al. Enzymes are filrther disclosed in U.S. 4,101,457, Place et al,
- July 18, 1978, and in U.S. 4,507,219, E~ughes, March 26, 1985. Enzyme materials
useful for liquid detergent fo~ tions, and their incorporation into such
forrnulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes
for use in dc;le~ s can be stabilized by various techniques. Enzyme stabilization
techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge
et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme
CA 022408l6 l998-06-l8
~VO 97122682 PCT~US96/19095
36
stabilization systems are also described, for example, in U.S. 3,519,570. A useful
Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO
9401532 A to Novo.
~ nzyme-cont~;ninP~, including but not limited to, liquid compositions, herein
can 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 a system may be inherently
provided by other formulation actives, or be added separately, e.g., by the formulator
or by a m~nllf~turer of detergent-ready enzymes. Such stabilizing systems can, for
example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic
acids, boronic acids, and mixtures thereof, and are ~lesigned to address different
stabilizatlon problems depending on the type and physical form of the detergent
composlhon.
One stabilizing approach is the use of water-soluble sources of calcium and/or
m~nPcium ions in the finish~d compositions which provide such ions to the
enzymes. Calciurn ions are generally more effective than m~n~sium ions and are
preferred herein if only one type of cation is being used. Typical detergent
cornpositions, especially liquids, will comprise from about 1 to about 30, preferably
from about 2 to about 20, more ~l~lably from about 8 to about 12 millimoles of
calcium ion per liter of fini~hed de~ ,e.lt composition, though variation is possible
depending on factors incll-llin~ the multiplicity, type and levels of enzymes
incorporated. Preferably water-soluble calcium or m~gneeium salts are employed,
including for exarnple calcium chloride, calcium hydroxide, calcium for,nate,
calcium malate, calcium maleate, calcium hydroxide and calciurn acetate; more
generally, calcium sulfate or m~n~cium salts col,~sponding to the exemplified
calcium salts can be used. Further increased levels of Calcium and/or Magnesiurnmay of course be useful, for example for promoting the grease-cutting action of
certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S
4,537,706. Borate stabilizers, when used, can be at levels of up to 10% or more of
the composition though more typically, levels of up to about 3% by weight of boric
acid or other borate compounds such as borax or orthoborate are suitable for liquid
dt:L~lg~ use. Substituted boric acids such as phenylboronic acid, butaneboronic
acid, p-bromo~he,~lboronic acid or the like can be used in place of boric acid and
reduced levels of total boron in d~lel~ l compositions may be possible though the
use of such sl-hstitllte-l boron derivatives.
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WO 97/Z268~ PCT/US96/19095
Stabilizing systems of certain cleaning compositions, for exarnple automatic
dish washing compositions, may further comprise from 0 to about 10%, preferably
from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to
prevent chlorine bleach species present in many water supplies from ~tt~king andinactivating the enzymes, especially under alkaline conditions. While chlorine
levels in water may be small, typically in the range from about 0.5 ppm to about1.75 ppm, the available chlorine in the total volume of water that comes in contact
with the enzyme, for example during dish- or fabric-washing, can be relatively large;
accordingly, enzyme stability to chlorine in-use is sometimes problematic. Sinceperborate or percarbonate, which have the ability to react with chlorine bleach, may
present in certain of the instant compositions in amounts accounted for separately
from the stabilizing system, the use of additional stabilizers against chlorine, may,
most generally, not be çSs~?nt~ though improved results may be obtainable from
their use. Suitable chlorine scavenger anions are widely known and readily
available, and, if used, can be salts cont~;ning ammonium cations with sulfite,
bi~lllfi~e, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate,
ascorbate, etc., organic amines such as ethylen~ minetetracetic acid (EDTA) or
alkali metal salt thereof, monoethanolamine ~MEA), and mixtures thereof can
likewise be used. Likewise, special enzyme inhibition systems can be incol~oldled
such that dirr~ l enzymes have maximum compatibility. Other conventional
scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as
sodium perborate tetrahydrate, sodium perborate monohydrate and sodium
pelcalbo.lal~, as well as phosphate, con~l~n~e~l phosphate, acetate, ben70~te, citrate,
formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if
desired. In general, since the chlorine scavenger function can be ~ rolllled by
ingredlents separately listed under better recognized functions, (e.g., hydrogenperoxide sources), there is no absolute requirement to add a separate chlorine
scavenger unless a compound pclrolllling that function to the desired extent is
absent from an enzyme-co..~ g embodiment of the invention; even then, the
scavenger is added only for optimum results. Moreover, the form~ tor will exercise
a ch~ t's normal skill in avoiding the use of any enzyrne scavenger or stabilizer
- which is majorly incompatible, as formul~tell~ with other reactive ingredients, if
used. In relation to the use of ammoniurn salts, such salts can be simply ~1mixe(1
with the d~ gclll composition but are prone to adsorb water and/or liberate
ammonia during storage. Accordingly, such materials, if present, are desirably
protectedL in a particle such as that described in US 4,652,392, Baginski et al.
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W O 97/22682 PCT~US96/19095
38
Other Optional Ingredients
Other ~ref~lled optional ingredients include polymeric soil release agents,
materials effective for inhibiting the transfer of dyes from one fabric to another
during the cleaning process (i.e., dye transfer inhibiting agents), polymeric
dispersing agents, suds suppressors, optical brighteners or other brightenin~ orwhitening agents, chelating agents, fabric softening clay, anti-static agents, other
active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents
for liquid formulations, solid fillers for bar compositions" bacteriocides, colorants,
perfumes, preservatives, opacifiers, stabilizers such as guar gurn and polyethylene
glycol, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting
agents, germicides, fungicides, anti-corrosion agents, and the like.
Liquid compositions can contain water and other solvents as carriers. L4w
molecular weight primary or secondary alcohols exemplified by methanol, ethanol,propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those Cont~ining from 2 to about 6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol,
glycerine, and 1,2-propanediol) can also be used. The compositions may contain
from 5% to 90%, typically 10% to 50% of such carriers.
Process
Granular compositions can be p~ ed, for exarnple, by spray-drying (final
product density about 520 g/l) or agglomerating (final product density above about
600 g/l) the Base Granule. The l~".~ g dry ingredients can then be ~f~mixecl in
gr~mll~r or powder form with the Base Granule, for example in a rotary mixing
drum, and the liquid ingredients (e.g., nonionic surfactant and perfiune) can besprayed on.
The gr~n~ r fabric softening compositions of the present invention can be
formed by ~uing a melt, solidifying it by cooling, and then grinding and sievingto the desired size. In a three-component mixture, e.g. nonionic surfactant,
single-long-chain cationic, and DEQA, it is more pl~fe~led, when forming the
granules, to pre-mix the nonionic snrf~t~nt and the more soluble single-long-chain
alkyl cationic compound before mixing in a melt of the diester
~mmonillm çqt;on;c compound.
It is highly preferred that the primary particles of the granules have a
meter of from about 50 to about 1,000, preferably from about 50 to about 400,
more preferably from about 50 to about 200, microns. The granules can comprise
smaller and larger particles, but preferably from about 85% to about 95%, more
~ ~ = .
CA 02240816 1998-06-18
W O 97/22682 PCTAJS96/19095
preferably from about 95% to about 100%, are within the indicated ranges. Smaller
and larger particles do not provide optimum emulsions/dispersions when added to
water. Other methods of preparing the primary particles can be used including
spray cooling of the melt. The primary particles can be agglomerated to form a
dust-free, non-tacky, free-flowing powder. The agglomeration can take place in aconventional agglomeration unit (i.e., Zig-Zag Blender, Lodige) by means of a
water-soluble binder. Exarnples of water-soluble binders useful in the above
agglomeration process include glycerol, polyethylene glycols, polymers such as
PVA, polyacrylates, and natural polymers such as sugars.
The flowability of the granules can be improved by treating the surface of
the granules with flow improvers such as clay, silica or zeolite ' particles,
water-soluble inorganic salts, starch, etc.
Method of Use
In use, water can be added to the particulate, solid, granular compositions to
form dilute or concentrated liquid softener compositions for later addition to the
rinse cycle of the laundry process with a concentration of said biodegradable
cationic softening compound of from about 0.5% to about 50%, preferably from
about 1% to about 35%, more preferably from about 4% to about 32%,. The
particulate, rinse-added solid composition ~1) can also be used directly in the rinse
bath to provide adequate usage concentration (e.g., from about 10 to about 1,000ppm, preferably from about 50 to about 500 ppm, of total softener active
ingredient). The liquid compositions can be added to the rinse to provide the same
usage concc;~ d~ions.
The water t~ cldl~ for l"~p~dlion should be from about 20~C to about
90~C, preferably from about 25~C to about 80~C. Single-long-chain alkyl cationic~u,rd~ as the viscosity/dispersibility modifier at a level of from 0% to about
15%, preferably from about 3% to about 15%, more preferably from about 5% to
about 15%, by weight of the composition, are ~.~fell~d for the solid composition.
Nonionic surf~ct~nt~ at a level of from about 5% to about 20%, preferably from
about 8% to about 15%, as well as mixtures of these agents can also serve
effectively as the viscosity/dispersibility modifier.
The em~ ified/dispersed particles, formed when the said granules are added
to water to form a~ueous con~pntr~t~ typically have an average particle size of less
than about 10 microns, preferably less than about 2 microns, and more plef~ldblyfrom about 0.2 to about 2 microns, in order that effective deposition onto fabrics is
achieved. The term "average particle size," in the context of this specification,
CA 02240816 1998-06-18
W O 97/22682 PCT~US96/19095
means a number average particle size~ i.e., more than 50% of the particles have a
diarneter less than the specified size.
Particle size for the emulsified/dispersed particles is determined using, e.g.,
a Malvern particle size analyzer.
If the composition of the present invention includes a detergent or surfactant,
the compositions herein will preferably be formulated such that, during use in
aqueous cleaning operations, the wash water will have a pH of between about 6.5
and about 11, preferably between about 7.5 and 10.5. Laundry products are typically
at pH 9-11. Techniques for controlling pH at recommended usage levels include the
use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Examples
The following exarnples illustrate the sulfonates and compositions of this
invention, but are not int~n~le~l to be limiting thereof.
Exarnple 1
Phenoxanyl p-toluenesulfonate
Phenoxanol (30.00 g, 0.168 mol~ and pyridine (130 mL) are combined in a flask
fitted with a con~le~cer, int~ thermometer, mechanical stirrer and argon inlet.
The solution is cooled to -10 ~C and to it is added p-toluenesulfonyl chloride (39.28
g, 0.202 mol) in portions via Gooch tubing so as to ~ lln;ll the reaction
te~ ,cldL~ between -10-0 ~C. After 3 h, water (20 mL) is added in portions so asto keep the tt~ dlule of the reaction below 5 ~C. The reaction mixture is warmedto room Lc~ cldLul~ and then poured into a sel,~dloly fi~nnel co..l~;~,;.,g 275 mL of
ether. The layers are st;~dLt:d and the organic layer is washed with S M ~I2SO4 (75
mL), sdluldled CuS04 solution (75 mL), water (2 x 75 rnL) and s~L~dt~d NaHCO3
solution (75 mL). After drying over MgSO4, the organic layer is filtered and
concentrated to leave a light yellow liquid as phenoxanyl p-toluenesulfonate. Purity
of the product is c~etPrmintorl by thin layer chromatography and the structure
confirmed by lH and 13C NMR.
Example 2
b-Citronellyl p-toluenesul~onate
CA 02240816 1998-06-18
W O 97~2682 PCT~US96/19095
41
b-Citronellol (21.05 g, 0.128 mol) and tetrahydrofuran (140 mL) are combined in a
flask fitted with a condenser, internal thermometer, mechanical stirrer and argon
7 inlet. The solution is cooled to -78 ~C and to it is added n-butylithium ~56.3 mL,
0.141 mol, 2.5 M in hexanes) via syringe. The mixture is stirred for 60 min before a
solution of p-toluenesulfonyl chloride (39.28 g, 0.2019 mol) dissolved in 50 rnL of
tetrahydrofuran is added. After addition is complete, the mixture is stirred for 30
min at -78 ~C and then at room temperature overnight. Ether ( 100 ml) is added and
the mixture is quenched with water (100 mL). The organic layer is dried over
MgSO4, filtered and concentrated to leave a yellow-orange liquid. The oil is
purified on silica gel eluting with 20% ethyl acetate in petroleum ether to give a
light yellow liquid as b-citronellyl p-toluenesulfona~e. Purity of the product is
determined by thin layer chromatography and the structure confirme~ by lH and
13C NMR.
Exarnple 3
2-Ethylhexanyl p-tolllen~?sl-lfonate
2-Ethylhex~nol (50.51 g, 0.384 mol) and pyridine (260 mL) are combined in a flask
fitted with a condenser, intern~l thermometer, me~h~nical stirrer and argon inlet.
The solution is cooled to -5 ~C and to it is added p-tol~en~ lfonyl chloride (89.63
g, 0.416 mol) in portions via Gooch tubing so as to m~int~in the reaction
le~ cldlule -5-5 ~C. A~ter 3 h, water (40 mL) is added in portions so as to keep the
telllp~ of the reaction below 5 ~C. The reaction mixture is warmed to room
h~ c;ldL~; and then poured into a s~dldLoly funnel cont~in;ng 540 mL of ether.
The iayers are separated and the organic layer is washed with 5 M H2SO4 (2 x 140mL), saLuldted CuS04 solution (140 mL), water ~2 x 140 mL) and saturated
NaHCO3 solution (140 mL). After drying over MgSO4, the organic layer is filtered,
and concentrated to leave a light yellow liquid as 2-ethyhexanyl p~tolnen~slllfonate.
Purity of the product is detPrrnin~-cl by thin layer chromatography and the structure
confirrned by lH and 13C NMR.
Example 4
2-Ethylhexanyl 4-bromobPn7~n~sulfonate
The procedure for Exarnple 3 is repeated with the substitution of 4
bromoben7en~sll1fonyl chloride for p-toluenesulfonyl chIoride.
CA 02240816 1998-06-18
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42
Example 5
Phenoxanyl methanesulfonate
The procedure for Example 1 is repeated with the substitution of meth~n~slllfonyl
chloride for p-toluenesulfonyl chloride. T
Example 6
~ iquid fabric softener compositions according to the present invention arefonn~ t~l as follows:
A B C D E
Ingredient Wt.% Wt.% Wt.% Wt.% Wt.%
DEQA ( I ) 25.0 25.0 25.0 24.0 24.0
Ethanol 4.0 4.0 4.0 4.27 4.27
HCI 0.01 0.01 0.01 0.74 0.01
CaC12 0.46 0.46 0.46 0.75 0.46
SiliconeAntifoam (2) 0.15 0.15 0.15 0.10 0.15
Chelant (3) - - - 2.50 2.50
Soil ReleasePolymer - - - 0.50 0.50
Ammonium Chloride - - - 0.10 0.10
Preservative(4) 0-000 ~-~~~ ~-~~~ ~-~~~ ~-~~~
3 3 3 3 3
Conventionai Perfume 1.20 1.00 1.35 1.30 1.30
phenoxanyl p-toluenesulfonate 1.20
b-citronellyl p-tol~lfn~cl-lfonate 1.20
2-ethylhexanyl p-toln~nPslllfonate 1.20
2-ethylhexanyl 4- 1.20
bromobf ~ n~ lfonate
ph~n~x~nyl metl.~ lfonate 1.20
Water * * * * *
(1) Di-(soft-tallowyloxyethyl) dimethyl ammol~ium chloride
(2) DC-2310, sold by Dow-Corning
(3) Diethylenetrinitrilopentaacetic acid
(4) Kathon CG, sold by Rohm & ~Iaas
* b~l~nne
CA 02240816 1998-06-18
W O 97/22682 PCT~US96/19095
Example 7
Additional liquid fabric conditioner formulas include the following.
r F G H I J
Ingredient Wt.% Wt.% Wt.% Wt.% Wt.
%
DEQA (5) 5.40 18.16 18.16 22.7 22.7
Poly(glycerol monostearate)0.83 2.40 2.40 3.00 3.00
TallowAlcohol Ethoxylate- 250.36 1.20 1.20 1.50 1.50
HCI 0.02 0.02 0.02 0.02 0.02
CaC12 - 0.20 0.20 0.30 0.30
Silicone Anti-foam - 0.019 0.019 0.019 0.019
Soil Release Polymer 0.19 0.19 0.19 0 ~9
Pefrume 0.187 0.70 0.70 0.90 o.9o
Blue Dye 0.002 0.005 o.005 0.006 0.006
phenoxanyl p-toI~-I?neslllfonate? 0.60 1.20
2-ethylhexanyl 4- 0.60 1.20
b~omoben7l~nesI~ If onate?
phenoxanyl methanesulfonate? 1.20
Water * * * * *
(5) Di-(tallowyloxyethyl) dimethyl ammonium chloride
* balance
Example 8
A fabric con~ ion~r bar is ~l~aled having the following components
Component Wt.%
Co-Softener (6) 70.00
Neodol 45-13 (7) 13.00
Ethanol 1.00
Dye 0.01
Perfwne 0.75
phenoxanyl p-toI-I~n~slllfonate 0.60
Water *
(6) 1:2 Ratio of stearyldimethyl arnine:triple-pressed stealic acid
(7) Cl4-Cl5 linear plimary alcohol ethoxylate, sold by Shell Chemical Co.
* balance
