CONDITIONNEUR DE TISSUS DURANT LE CYCLE DE LAVAGE OU DE RINCAGE

WASH CYCLE OR RINSE CYCLE FABRIC CONDITIONING COMPOSITIONS

Abrégé anglais

IR 4718/4737
WASH CYCLE OR RINSE CYCLE FABRIC CONDITIONING COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
Fabric conditioning aqueous liquid emulsions are provided
which impart softness and antistatic properties to laundered
fabrics as a wash-cycle additive for through-the-wash use or
alternatively as a rinse cycle additive. The dispersed phase of
the liquid emulsions comprise complexes of specified tertiary
amines and multi-functional carboxylic acids in combination with
unreacted amine and a minor amount of one or more specified alkyl
cellulose ethers to enhance high temperature emulsion stability.

Revendications

WHAT IS CLAIMED IS:
1. A wash cycle or rinse cycle-additive aqueous liquid emulsion for
providing softness and anti-static properties to fabrics treated
therewith in a laundry bath without adversely affecting fabric
cleaning comprising
(A) from about 1 to 30%, by weight of a particulate fabric
conditioning composition having a median particle diameter
greater than about 10 microns comprising:
(a) a fabric conditioning amount of a multi-functional
carboxylic acid complex of a tertiary amine formed from
the reaction of (i) a tertiary amine having the general
formula
<IMG>
wherein R1 is methyl or ethyl, and R2 and R3 are each
independently an aliphatic group having from 12 to 22
carbon atoms, and (ii) a multi-functional carboxylic acid
selected from the group consisting of citric acid, and di
and tri carboxylic acids having from 21 to 54 carbon
atoms;
(b) unreacted tertiary amine having the general formula
defined above, said unreacted amine being present in an
amount of at least 0.2 times the stoichiometric amount of
tertiary amine required to form the multi-functional
carboxylic acid complex of (a); and
(c) an emulsion stabilizing amount of an alkyl cellulose
ether selected from the group consisting of
methylcellulose, hydroxypropylmethyl cellulose and
derivatives of hydroxyethyl cellulose wherein the
terminal hydrogen of the hydroxyether group is replaced
by an alkyl chain having from 10 to 24 carbon atoms, and
mixtures thereof, said alkyl cellulose ether having a
26

molecular weight of at least 25,000 the dispersed phase
of the liquid emulsion being essentially comprised of
said particles of fabric conditioning composition;
(B) from about 0.1 to 10%, by weight of one or more emulsifying
agent 8; and
(C) the balance water.
2. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the tertiary amine is methyl distearyl amine.
3. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the tertiary amine is methyl di(hydrogenated tallow
amine.
4. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein R2 and R3 are each an alkyl group.
5. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the multifunctional carboxylic acid is citric acid.
6. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein said unreacted amine is present in an amount of from
about 0.3 to 6 times the stoichiometric amount of tertiary amine
reacted to form said complex.
7. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the fabric conditioning composition is present in an
amount of from about 5 to about 20%, by weight.
8. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein further contain a compound for providing anti-static
properties additional to that provided by said fabric conditioning
composition.
9. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the alkyl cellulose ether is present in an amount
from about 0.5% to 1%, by weight.
10. A wash cycle or rinse cycle-additive liquid emulsion according to
claim 1 wherein the viscosity of the aqueous liquid emulsion is
substantially unaffected by the presence of the alkyl cellulose
ether.
27

62301-1775
11. A process for imparting softness and anti-static properties to
fabrics comprising the step of contacting the fabrics in a laundry
wash or rinse liquor with an effective amount of a particulate
fabric conditioning composition having a median particle diameter
greater than about 10 microns comprising:
(a) a fabric conditioning amount of a multi-functional carboxybic
acid complex of a tertiary amine formed from the reaction of (i)
a tertiary amine having the general formula:
<IMG>
wherein R1 is methyl or ethyl, and R2 and R3 are each
independently an aliphatic group having from 12 to 22 carbon
atoms, and (ii) a multi-functional carboxylic acid selected from
the group consisting of citric acid, and di and tricarboxylic
acids having 21 to 54 carbon atoms;
(b) unreacted tertiary amine having the general formula defined
above, said unreacted amine being present in an amount of at
least 0.2 times the stoichiometric amount of tertiary amine
required to form the multi-functional carboxylic acid complex of
(a); and
(c) an emulsion stabilising amount of an alkyl cellulose ether
selected from the group consisting of methylcellulose,
hydroxypropylmethyl cellulose and derivatives of hydroxyethyl
group is replaced by an alkyl chain having from 10 to 24 carbon
atoms, and mixtures thereof, said alkyl cellulose ether having a
molecular weight of at least 25,000.
-28-

12. A process in accordance with claim 11 wherein the multifunctional
carboxylic acid is citric acid.
13. A process in accordance with claim 11 wherein the tertiary amine is
methyl di (hydrogenated tallow) amine.
14. A process in accordance with claim 11 wherein the reacted amine is
present in an amount of from about 0.3 to 6 times the said
stoichiometric amount.
15. A process for preparing a stable wash cycle or rinse cycle-additive
aqueous liquid emulsion according to Claim 1 comprising the steps
of:
(a) providing an aqueous liquid containing a mixture of (i) a fabric
conditioning amount of the multi-functional carboxylic acid
complex of a tertiary amine as defined in Claim 1; (ii)
unreacted tertiary amine as defined in Claim 1; and (iii) an
alkyl cellulose ether as defined in Claim 1;
(b) heating the aqueous liquid prior to or subsequent to step (a) to
a temperature sufficient to at least melt the mixture of
carboxylic acid complex and reacted tertiary amine;
(c) introducing into said aqueous liquid a first portion of an
emulsifying agent, said first portion being an amount selected
to form upon mixing with said aqueous liquid emulisified
particles containing components (i), (ii), and (iii) and having
a median particle diameter greater than about 10 microns;
(d) mixing the aqueous liquid with the first portion of emulsifying
agent to form an emulsion containing the aforesaid emulsified
particles as the dispersed phase;
(e) cooling the resulting emulsion to a temperature sufficiently
below the melting point of the particles formed in step (d) to
at least partially solidify said particles; and
(f) introducing into the emulsion following step (e) a second
portion of one or more emulsifying agents to adjust the HLB
29

value of the emulsion to that required for high-temperature
phase stability.
16. A process in accordance with Claim 15 wherein in step (a) the
mixture of carboxylic acid complex and unreacted amine is introduced
into the aqueous liquid at a temperature below its melting point and
wherein subsequent to step (a) said aqueous liquid is heated to a
temperature sufficiently above the melting point of the mixture.
17. A process in accordance with Claim 15 wherein the tertiary amine in
said fabric conditioning composition is methyl di(hydrogenated)
tallow amine.
18. A process in accordance with Claim 15 wherein the multifunctional
carboxylic acid in said fabric conditioning composition is citric
acid.
19. A process in accordance with Claim 15 wherein the amount of
unreacted tertiary amine in the aqueous liquid is from about 0.3 to
3 times the stoichiomtric amount of amine reacted to form the
carboxylic acid complex.
20. A process in accordance with Claim 15 wherein the amount of
unreacted tertiary amine in the liquid is from about 5 to 30%, by
weight, of said liquid.
21. A process in accordance with Claim 15 further including the step of
introducing a viscosity modifier and optionally other adjuvants into
said aqueous liquid.
22. A process in accordance with Claim 15 wherein in step (d) the
emulisified particles of of fabric conditioning composition have a
median diameter of from about 25 to 50 microns.

Description

2068949
8ACKGROUND OF l`HE INVENTION
Thls invention relates to novel aqueous liquid emul~ions
u~eful a~ throuqh-the-wa~h or rin~e cyele-additive fabric
eondit~oning composit$on~ and their method of manufaeture, ~uch
fabrLc conditlonin~ eompo~itions providing softening and
antistatic bonefits to laundered fabric8 without adversely
affecting cleaning
A large number of compositions have been dl~clo~ed whieh
~mpart softening and antiatatlc proportLes to laundered fabrica
G norally, theJe contain catLonic eompounds, e~peeLally q~aternary
moonLum ~alt~ Suoh eompo-itlons are wldoly m-rk-tod for hom4
u-- ln th- fosm of mul~lon- whleh mu~t b- ~dd-d to th- w--hlng
m ehlne durlnq th- rln-- cyelo If th~ Qmuls10n- ar- add-d durlng
th- wash cyele, th- catlonle f~brle condltlon-rJ m y lnt-raet wlth
nlonlc surfactantJ pseJ~nt Ln th wa~hlng eo~po-ltlon 80 a~ to
r-nder a portion of ~-eh of sueh eatlonLe eompound and anlonle
urfaetant unavallable for eLther c~--n~ng or fabrle eondLtLonlng
Another m--n~ of provldlng f brle eondLtloning whleh h--
~ttalnod oe- eomm relal sueea~ to add th- eondltlonlng ag-nt
whlle th- eloth0~ ar- b-lng machlne drled
Whll- fabrie eondltlonlng durlng eithor th- rln~- and/or
drylng cyele- can b- effeetlv-, both method~ of condit~oning are
more ineonvenient than a through-the-wa~h msthod where the
eond~t~onlng agent iJ added with the dotergRnt compo~it$on at tho
LnLtiation of the wa~h cyele
Compositions are known whleh can be added to a wa~h$ng
machine at the start of the wa~h cyele and effectlvely provLde
. . . ... . . . .

2~68949
fabrics with a deterqency treatment during the wash cycle and a
fabric conditioning treatment during either the rinsing operation
or subsequently when the fabrics are heated in a machine dryer.
Composit~ons of this type are known in the art as through-the-wash
fabric conditioners. An important advantage of such compositions
is that they obviate the need for adding a separate fabric
cond$tloning product in the rinse cycle or in a machLne dryer.
~hrough-the-wash type conditioning agents are well known in
the art. European Patent Application No. 0,123,400, published
Octob0r 31, 1984 discloses fabric condLtloning agent~ comprising
salts of specified tert$ary amines and carboxylic acids wh$ch are
utilized in the form of nodules which pass virtually unchanged
through the wash and rin~e and condition the fabr$c when heated in
a dryer. The nodule~ are meant to be added to the laundry wash
llquor at the beglnning of the wash cycle along with a
conv ntlonal d-tergent. ~uropean Patent Publlcatlon No. 0,133,804
publlshed March 6, 1985 d$scloses detergent comporlt$ons
contalning clay fabrLc soften-rs and part$cle- of a complex of a
long chain amine and a fatty acid. U.S. Patant No. 4,514,444 to
Ives di w loses a fabric cleaning/condit~on$ng composition
compris$ng carboxylic acld salts of a tertiary amine in
comb$nat$on with polyethylene glycol. U.S. Patent No. 4,375,416
to Cr$sp et al. d{sclosos a t-xt~le ~oftenLng deterg-nt
compoaitlon comprirlng a sp cifled class of tertLary am$neJ with a
m ctlte-type clay in a detergent compo~itlon ~uch that ~oftening
b-nef$ta are prov$ded wlthout impalring cleaning performance.
Other recent prior art relating to the field of the invention
$nclude~ U.S. Patent No. 4,237,155 to Kardouche whlch di~closen a
dryer-added fabric condit$on$ng agent comprised of a carboxylic
acid salt of a tert$ary amine. ~ritish Patent 1,514,276 discloses
the u~e of tertiary amine composit$ons as wash-cycle fabric

2~68949
softeners
u.s. Patent 4,808,086 to Evans et al di~clo~e~ dryer-added
fabric conditioning article~ comprised of a fabric softening agent
and a soil relea~e agent which may be certain defined
hydroxyethers of cellulose. The soil release agent may be present
in amounts up to 70~, by weight, of the compo~ition and preferably
from about 25 to 50~.
European Patent Application 331,237 nam$ng 8utterworth et al
a~ inventors dlscloses fabric cond$tioning compo~itlons containing
a polymeric thlckener for fabric ~oftening compositlon~. The
polymeric thickenern are hydrophobically modlfled cellulose
ether~, and the preferred ~oftening material~ are quaternary
ammonium compounds. Insofar as conventional quat rinse-cycle
40ftening compositions have very low viscositles in the absence of
lS thlckenQrs ~i.e. generally about 30-40 cps.), the Butterworth et
al European patent ~oeks to provide a thlckened quat softening
composltlon. R forrlng to ~able 4 o~ th- ~utterworth et al
European Patent, for exumple, the unthlck-ned control 1~ ~hown to
have a vlscoslty of 5 whlch upon addltlon of a deslqnated
hydroxyethyl cellulo~e at weight percent~ of 0.13 and 0.15~,
re~pect~vely, L~ shown to be raised to 7B and 101, a vLscosity
lncrea~e of one order of magnitude. ~he carboxyllc acid-amine
complexe~ of the preaent $nvention, on the other hand, are
r-latlvely thlck compositlona at u~eful concentratlon of 5 to 10~,
by welght, ha~lng vl~cosltle~ of about 500 cps. at room
t~mpeLaturo. ~ nce, th- comblnatlon of carboxyllc acld-amine
complexes a~ heroin described with a thickener of any type i~
unnece~ary and unde~irable. By way of comparison, the addition
of an alkyl cellulose either to a fabric conditioning compoeition
ln accordance with the invention provide~ esnentially no increase
in vi~co~ity to the resultant composit10n, and, in ~ome inatances,
even cau~es the viscosity to be lowered.

20689~9
Complexes of specified tertiary amine3 and carboxylic acids
have been previously disclosed a~ through-the-wa~h fabric
conditioners in u.s. Patent No. 4,828,722 to Steltenkamp. In U.S~
Patent 4,869,836 to Harmalker there is described the combination
of unreacted tertiary amine with a complex of reacted tertiary
amine and multi-functional carboxylic acid. The resultinq fabric
conditioners are used advantageously in the form of aqueou~ liquid
emulaions. Whlle thece emuleions are generally effective for
fabr~c conditioning, they nevertheleee are often de~tabili~ed or
suffer poor performance when ~ubjected to extreme condition~, f3uch
ac elevated temperature~, i.e. above ll0~. Concequently, there
remainQ a need for providing an effective fabric-conditioning
llquid emulsion capable of beinq ueed ae either a wach-cycle or
rlnae-cycle additive, and which ia highly etable at elevated
t-mperature~.
S~M~AR~ OP T~ lNVENSlON
Th- pre~ent lnventlon provldee a warh cycle or rln~e cycle-
addLtlve aqueou~ llquid emul~lon for provldlng ~oftneas and antl-
ctatlc propertie~
to fabrics treated therewith in a laundry bath without advereely
afect1ng fabric cleaning comprieing
(A) from about l to 30~, by we~ght of a particulate fabr~c
condltlonlng compoaltlon havlng a medlan partlcle
dlame1:er greater than about l0 microne comprlelng:
~a) a fabrlc condltlonlng amount of a multl-functional
carboxylic acid complex of a tertiary amine formed
from the reaction of ti) a tertiary amine having
the general formula:
Rl2
R, N R,
wherein R, ic methyl or ethyl, and R~ and R3 are
each independently an aliphatic group having from
.. ... . .. . ... . . .

2068949
wherein R, ia methyl or ethyl, and R2 and ~3 are
each independently an aliphatic group having from
12 to 22 carbon atoms, and (ii) a multi-~unctional
carboxylic acid selected from the group consisting
of citric acid, and di and tricarboxylic acids
having from 21 to 54 carbon atom~;
(b) unreacted tertiary amine having the general
formula defined above, said unreacted amine being
pre~ent in an amount of at lenst 0 2 times the
~toichLometric amount of tertiary amlne reguired
to form the multl-functional carboxylic acid
complex of (a~; and
(e) an emulsion stabilizing amount of an alkyl
c-llulose ether s-lected from the group con~isting
of m-thylcellulo~Q, hydroxypropylm-thyl cellulo~e
nd d-rlvatlv-~ of hydroxy-thyl c-llulo-e wh-rein
th t-rmlnal hydrog n of th hydroxy-th-r group i~
r placed by an al~yl ch-ln having from 10 to 24
carbon atom~, and mixture~ thereof, sald alkyl
c-llulor- ether having a molecular weight of at
l-a-t 25,000, th- d$~perned pha~e of th- llguid
emulslon b-lnq e~--ntlally comprls-d of ald
~rtlcle- of fabrlc condltlonlng compo~ltlon
(~) fso~ about 0 1 to 10~, by welght of on- or more
2S emul-lfy~ng ag-nt~J and
(C) the balance water
The most effect~ve fabric condit~oning compositlons of the
invention contain an amount of unreacted tertlary amine varying
from about 0 3 to 6 times the stoichiometric amount of reacted
amine in the complex, preferably from about 0 6 to 6 t~es the
said stolchiometric amount Where, for example, the multi-

2~68~
~unctional carboxylic acid selected to form the complex i5 citric
acid, the stoichiometric amount of reacted amine in the complex is
3 mole~ of amine per mole of citric acid
The term ~complex a~ used throughout the specification and
claim~ refera to the reaction product of the above dencribed
tertiary amine and carboxylic acid, and characterize~ such
reaction product in terms of the pr$mary conctituent thereof which
Ln a complex rather than a salt of the acid and amine The basi~
of ~uch characterl~ation is explained hereinafter in the
npecification Although the appl$cant doen not wi~h to be limited
by any theory regardlng the nature of such reaction product, it i8
believed to be an equil$brium mixture compriued of the acid-amine
complex (about 80~, by we$qht) and the ac$d-amine nalt (about 20e,
by weight) Accord$ngly, aJ uned herein, the term ~complex~
Lncludea both the acLd-amine complex formsd by the react$on of the
t-rt$ary am$ne and carboxyllc acld a~ w-ll aa th- relatlvely minor
umount of salt in equLllbrlum th-rewith
In accordance with a preferred n~hod$ment of th- invention,
the aqueouu liguid emulaion containa ad~ùvantc ~uch as perfumsc,
colorantu, brlghtenera, foam ~tablllzera and the like and,
optionally further include~ an ant$~tatic compo~Ltion dlctinct
from the dofined fabrlc condltioning compocition to enhance the
anti-ntat$c propertiea of the l$quid emulnlon A prefQrred
addLtLonal anti-utatLc co~poaitLon for th$n purpose ia tallow
n-odecanamLd-
ln accordance with the proceus a~pect of the invention,
uoftnene and anti-~tatic propertiea are imparted to fabric~ by
contacting ~uch fabrica in a laundry bath or rin~e liquor with an
aqueous liquid emul~ion containing an effecti~e amount of a
particulate fabric conditioning compo~ition having a medlan
particle diameter greater than about 10 micron~, which fabric

2~68~49
conditioning compo~ition comprises
a) a fabric conditioning amount of a multi-functional
carboxylic acid complex of a tertiary amine formed
from the reaction of (i) a tertiary amine having
the general formula
R2
R~ N - - R~
wh-rein R~ is methyl or ethyl, and R2 and R~ are
e-ch lndependently an aliphatic group having from
12 to 22 carbon atoms, and ~iL) a multi-functional
carboxylic acid selectQd from the group consisting
of citric acid, and di and tricarboxylic acids
h-~ing from 21 to 54 carbon atomo;
(b~ unreacted tertlary amine hav~ng the general
formula defLned abo~e, sald unreacted amine being
pr --nt ln an amount of at leaJt O 2 tLme- th-
tolchlometrlc amount of tertl y amlne r-gulred
to form the multl-functlonal carboxylic acld
complex of (a~t and
(c) an emul~lon stabLlizing amount of an alkyl
ccllulose ether selected from the group consisting
of m thylc-llulo~e, hydroxypropylm-thyl collulos-
2S nd derivative- of hydroxyethyl celluloae wh-reLn
th- t-rm~nal hydrogen of tho hydroxyether group iJ
r-placed by an alkyl chain having from 10 to 24
c rbon atomo, and mixture~ thereof, said alkyl
c-llulose ether hav$ng a molecular weight of at
least 25,000
Although the applicants do not wish to be bound by any theory
of operation, it is believed that the alkyl cellulose ether
incorporated into the liquid emulsion of the in~ention forms at
. . . .. . .

20689~9
least a partial coating upon the particles of fabric conditioning
composition which are formed upon emulsification Thit3 coating
appears to substantially prevent particle break-down over a wide
range of temperatures as well a~ the undesired subsequent
coalescence of smaller partlcles of acid-amine complex into larger
aggregate particles, a problem characterietic of liquid emul~ions
known in the art containing particulate complexes of carboxylic
acld and amine wh$ch are typically susceptible to high temperature
breakdown and concomitant product separat$on It has further been
dlscovorE!d that for partlculate compoEtitionE~ having a median
part$cle diameter above about lO microne, and more preferably at
med$an particle sizeEt from about 25 to SO microne, the fabric
cond$t$oning, physical stab$11ty and flow character$st~cs of the
ro2tult$ng llquid emulEllon are at an opt$mum ~ccordingly, for the
lS fabrlc cond$tionlng composLtions of the invent$on the des$red
r-nget of part~cle Etize i~ able to bo malnta$nctd ov-r a broad ranqe
o~ t mperaturs extendlng from amblont to above th- m-lt$ng po$nt
of th- carboxyl~c acid - amlne compltax, typ$cally about lloqF.
DrT~ 3æ 2E~CRIPTTQN or TH~ TNVENTION
The fabric cond$t$on$ng composLtlont3 of the $nventlon are
co~prisetd of three es-Gtnt$al componontEt The flrst and Etecond
contponents are, re~poct$vetly, a compllax of tortlary am$no wlth a
~ultl-functional carboxyllc acld a- here$n defined and unreacted
t-rt$ary amlne The suitable tertlary antine~ are repreEtentsd by
th- g-neral formula
R2
t
R~- N - R~
wherein R~ is methyl or ethyl, and R2 and Rl are each Lndcpendently
an aliphatic group hav$nq from 12 to 22 carbon atome Fxamples of
35preferred amine~ include methyl dLstearyl amine, ethyl dit3tearyl

amine, methyl di(hydrogenated tallow) amine, ethyl di(hydrogenated
tallow) amine, methyl diolelylamine, methyl dicoconut amine,
methyl dilaurylamine, and methyl dipalm oil amine
The multi-functional carboxylic acid utilized in the pre~ent
invention is selected from among citric acid and di and tri
carboxylic acids having 21 to 54 carbon atoms Moet preferred for
u~e herein is citrLc acid Among the other preferred acids are a
dlcarboxylLc ac$d having 21 carbon atome e g 5 (or 6)-carboxy-4
hexyl-2-cyclohexene-1-octanoic acid (aold commercially under the
tradename WQstvaco Diacid 1550 by Westvaco Corporat~on) dimerized
oleic acld (sold commercially under the tradenamQ Dlmer Acid by
Emery IndustrieA); and a C~ trlmer of oleic acid
Th- amlne-multlfunctional carboxylic acld complexe~ of the
lnventlon are gen-rally prepared by fonming a mlxture of amine and
multLcarboxyllc acld, pr-ferably in a lar ratLo of amLne to
carboxyllc acld above that requlr-d for th- otolchlometrlc
r--ctlon co a~ to provLdo th- denlred amount of unr-acted amLne in
th- reactlon product, and heat~nq such mLxture to a tQmp-rature
~ufflcient to form a melt
Por the example of a tertlary amln- havlng a m-ltlng point
b-low that of the carboxyllc acld, proparntion ie convenlently
effectod by f~rst h-atlng the amln- to it~ m ltlng polnt
~g-nerally about 35 to 4Sq:) and th-n addlng th-roto th-
multlcarboxyllc acld, auch a~ for example cltrlc acid, in the form
2S ot a olld ~h- r-~ultLng mLxture i~ then heated to a tempQrature
below th- m-ltlng poLnt of the carboxyllc acld, but ~ufflcient to
form a molten m$xture In th- care of c~tric acld, heatlng the
r-actant to a temperature of about 115C for about fl~e to ten
minute~ will form a molten mixture ha~ing a meltlnq point (about
50C) intermediate of the citric acid and the amine The molten
mlxture comprisec the reaction product of amine-multicarboxylic

" ~689 ~9
acid complex in equilibrium with a minor amount of amine-
carboxylic acid salt
In an alternate embodiment, the amine and carboxylic acid are
reacted in a stoichiometric ratio to form the complex followed by
the addition of unreacted tertiary amine to the resulting reaction
product Th~ embodLment is particularly advantageous where it is
de~lred to employ an unreacted amine in the fabric condition
eompo~ltion whieh ls dlfferent rom the reaeted amine ~his may
b- des~rable in some iDstanees for purpones of economy
The determination of the nature of the reaction product can
b- Lllustrated in ter~D of the reaetion between methyl
dl~hydrogenated tallow) amine and dimerized oleie aeid which were
mlxed and heated followlng the general proeedure de~eribed above
xeept th-t in thls in-tanee the amlne having a melting point
bOVQ th- earboxylle aeld 1- added in aolld form to dlm0rized
olele aeld whleh ~ llquld at amblent temperature Th- r-~ultlng
r-aetlon produet wa- ld-ntlfled a~ a w -k hydrogen bonded eomplex
(80 wt ~) ln eqyllibrlum wLth the eorre~pondlng salt (20 wt ~l
~dentifleation was ba~ed on meaeurements involving melting points
and speetro~eopie teehnlque~ Th eomplex m-lted at 28 to 31C
whlch iJ lntermedlate between the melting point of the amine (34
to 38~C) and the earboxylle aeld ~4 to 5C) Thl~ Lndleate- the
formation of a eomplox rath-r than an amlne salt, th- latter belng
eharaet-rlzod by a ~harp m-ltlng polnt hlgher than the
eorr-~pondinq ~mln-
Th- Infra red speetrum of the eomplex shows the presenee of
two moderate earbonyl bands at wavelengths of 1709 cm~ and 1550 em
~ The 935 em~ wavelength indlcative of H-bonding of the
particular free carboxyllc aeid i8 ab~ent, indieating the presence
of a eomplex rather than salt formation By means of ESCA
(Election Spectroscopy for Chemical Analysis) mea~urements, it was
... . . . . . .

2068~9
determined that the reaction product ~as about 20~ am~ne ~alt and
80~ of the amine-carboxylic acid complex The chemical shift of
the ionic nitrogen of the salt was different than that of the
neutral nitrogen of the complex The relative amounts of these
two nitrogen signals provide the basis for determining the
relative amount of amine nalt versus amine complex
An alky cellulose ether is the thlrd eosential component of
th- partlculate fabric cond$tLoning compo~itLon Sultable alkyl
c-llulose ethers are ~elected from among methylcellulose and
hydroxypropylmethyl cellulose, sold under the trademark "Methocel"
by Dow Chemical Company; hydroxypropylcellulose, ~old under the
trademark "~luceln by Hercules Chemical Company; and derivatives
of hydroxyethyl cellulose ~ B C) where~n the torminal hydrogen of
the hydroxy2ther group is r-placed by an alkyl chaln having from
10 to 24 carbon atome, such HEC d-rlvatlve~ b-ing ~old und~r the
tr-demark "Natrosol Plus" by H~rcule~ Ch mLcal Comp-ny, and are
xtenslvely described in U S Patont 4,228,27~ le-usd Octobsr 14,
1980 The amount of alkyl c-llulos- ether present Ln the
particulate fabric condltioning composltlon i8 generally from
about 0 1 to 5~, by weight, of the aqueouJ liquid emulsLon, and
prefer~bly, from about 0 1 to 1~, by ~ ight, and most preferably
from about 0 1 to 0 5~ in order to provlde the rsquLsLto high
t-Dp~rature stab~llty to th- partlcl-s of fabric condltloning
compo~it~on It 1~ b~lleved that the alkyl c~llulose ethsr must
b- of sufficlent vi~co~ity Ln th- emulsLon to doposit on the
urface of the emulsion partlcles and form an elastic film or
coatLng thereon Hence, the molecular weight of the cellulose
ether required for this stablllzing purpose i3 at lea~t 25,000 and
preferably at least 30,000
The aqueous liquid emulslon of tho invention may be
advantageously added to the laundry bath or to the rinse liquor
.. . .. . . . . . .

20689~9
independent of any laundry detergent compo~ition or may
conveniently be added to the ~aundry bath during the wa~h cycle in
conjunction with a liquid or granular detergent compo~ition
The method of preparation of the aqueouc emul~ion i~
predicated upon forming an emul~ion or ~u~pen~ion which i~ ~ta~le
over a practical range of temperatures, and particularly at high
temperature, namely, it doe~ not undergo phase separation at
t-mporatures up to about 120F, and, Ln addition, th- particle~ of
fabrlc conditioning composition wh$ch comprise the dispersed phace
of the emulaion must be of the requi~ite ~ize to deposit on washed
fabrics during the wa-h cycle It has been di~covered that when
present in an emul~ion at part$cle size~ having a median diameter
above about 10 microns, preferably from about 25 to 100 microns,
and most preferably from about 25 to 50 ~icrons, the composit$on
of th- lnventlon i~ capable of prov$d~ng ef~ectlve softening and
antl-~tat propertle~ to wa~hed fabrlcs wh-rea~ at partlcle- slze~
b-low ~uch value fabrlc cond$tlonlng i~ often adver~-ly affected
Although the appllcant doe- not wi~h to be bound by any theory, it
lz bel~eved that part$cle s$zee of above about 10 microns are
r-quired in order to effect deposit$on of sa~d partlcle~ on
fabr$cs in the wa~h water, such partlcle size limitntlon not being
cr$tical for rln~e cycle softening
So ln~ure hlgh temp rature ~tabil~ty and the avoidancu o~
phase -paratlon, tho ~L8 ~hydrophllic-l$pophllic balance) value
o~ th- emul~lon 1- preforably r-gulated to within a predetermined
range required for stabil$ty by the add$t$on of ~uitable
emulsifying agents The requ$red range of HLB 1~ read$1y
determined by trial and error for each partlcular combinat$on of
tertiary amine and carboxylic acid utilized in the composition of
the invention For the particular in tance where citric ac$d and
methyl di(hydrogenated tallow) methyl amine are uaed to form the
., . ,. ~ .. . . .. .. . . .. . .. .. . .... . .. . .

2068349
fabric conditioning composition, the HL~ of the emulsion muqt be
from about ll s to 12 5 to achieve the deeired high temperature
stability
The liquid emulsion compositions preferably contain from
about 5 to about 30~, and most preferably from about 7 to about
20~ of the fabric condltioning composition of the invention, based
on the total welght of the emuls$on compo~itlon At nuch
concentratlons, an effective amount of fabrlc cond$tioning
compositlon i8 provided to the waflh fabr$c when dispensing an
amount of the liquid emuls$on to the waf~h or rinse cycle of an
automatic washlng machlne comparable to the amounts added by users
of commercial liquid fabric conditioners
Nonion$c ~urfactants are among the preferred emulsifying
agent~ for preparlng an ess~ul~$on $n accordance with th- invention
ha~lng th- de-lr-d ~tablllty, vl-cofs$ty and partlcle sLze of
S-brlc condlt$oning cosapos$t$on $n the dL-persed phafse ~aong the
u-eful ~aulalfylng agenta ar N odol 25-3 ~-n ethoxylated alcohol
old by Shell Chsmical Cosapany caaprL0$ng a fatty alcohol
averaging about 12 to lS carbon atomf~ with about 3 mole~ of
ethylene oxida p-r mole of alcohol); N odol 25-12; and Neodol 45-
13 N-odol 25-3 and 45-13 are partlcularly preferred for thl~
purpofss .
~h- pr-par~tlon oS th- emulfllon in convenlently effected $n
thr~e stag-~s ~n th- flr~t fstag- th- fabr$c cond$tlon$ng
cosapo~ltlon, preferably at a t-mperature above itsl melt$ng point,
lc added to an aqueou~ liquid, preferably water, along with a
f$rf~t portlon of an emulsify$ng agent, such first portlon being an
amount selected to form upon mlxing with the fabric conditionLng
composit$on particles of emulsified fabric condit$oning
composition having a medlan diameter above about 10 microns The
order of addition of the fabric conditioning composition and the
14
.. . . .... . . ~ . . . . . . .

20689~9
fir~t portion of emulsifying agent i8 not critical It i9
preferred that the aqueous Liquid be preheated to a temperature
corre~ponding to at lea~t the melting point of the fabric
conditioning composition if the latter i8 introduced a~ a liquid
This is to insure that the emulsified particle~ formed in the
first stage are in liquid form In an alternate embodiment, the
fabric conditLoning composition is introduced into the aqueous
llguid a~ a solid, following which tbe liquid is heated to a
tomperature sufflciently above the melting point of the
conditioning composition such that upon mixing the conditioning
compo~itlon with the first portion of emul3ifying agent, there is
provided an emulsion containing as the dispersed phase liquid
particles of fabric condltion$ng composition having the desired
partlcle size
In th- -cond ~tag- th- r-~ultlnq ~mul~lon i~ coolod to a
t~Dp ratur- sufficlently b-low the m-lting point of th- fabric
conditloning composltlon 80 a~ to at lea-t partlally solidlfy the
mulslf~ed particle~ and form a su~pen~lon of solid particles in
the aqueou~ liquid
Tn the thlrd stage, a second portlon of one or more
emuls~fylng agents is added ~o the emul~lon or ~u~pension formed
in th- ocond stage 80 a~ to ad~uat the HLB value to that r-quired
for hlgh t mp ratur- ~tablllty Shl- K~B value can be
convenlently d~terminod by a ~lmple trial and error technique A~
d-flned h-roln, the characterization of ~hlgh temperature
~tability~ for a liquid emulsion in accordance with the invention
rofers to its being able to be maintained at 120~ for at least 24
hours w$thout the occurrence of phase ~eparat$on After the
formation of the emulsion in the third stage, electrolytes ~uch a~
calc$um chloride dihydrate, or sodium chloride may be added as
viscosity modif$ers, if needed, a~ well ag defoaming material~ to
.. . . . . . . ..

206~9~9
enhance proper mixing of the components by inhibiting phase
separation resulting from foam agitation Other optional
component~ include colorant~ and perfume which are advantageouqly
added ~equentially under agitation
S The emulgified particle~ in the dispersed phase of the
emul~ion are not all of uniform ~ize and comprise a broad
dlstribution of particle sizes, but it is required that the median
dlameter of such partlcles be above 10 microns A preferred
particle size i~ that having a mean dLameter of from about 25 to
50 microns ~asurement of the emulslfied partlcles is most
conveniently carried out at the end of the third ~tage when the
flDal emulsion is formed rather than at the end of the first stage
where the relatl~ely strong assoc~ation of the emulslf~ed
p-rtlcles may make the partlcle ~lze m-asurement ~omewhat les~
accurat-
Tho aforemontloned thr-e-stage method of preparatlon i~
predlcated upon utlllzlng a fabrlc condltlonlng compo~ltlon ha~lng
a m-ltlng polnt above amblent temperaturQ such that ln th- flrst
tage o f preparatlon only a llmlted amount of emul~lfying agent i~
added to prov~de the desLred size of emulslfled partlcles as a
dl~persed liquid phase Thereafter upon cooling, the di~per~ed
partLcle~ ~olldlfy, allowlng addlt~onal amounts of emul~lfylng
gont to b- add-d to th- emulalon wlthout causing any dlmLnutLon
ln partlcle slz- Thu-, th- HLB of the emulslon can be
lndopendently ad~u~ted to the de~LrQd range wlthout affecting the
~lze of the particles ln the dlspersed pha~e

2068949
EXAMPLE 1
A liquid emulqion in accordance with the invention was prepared as
follow~
To 0. 3 grams of Methocel A4C~, a methylcelluloae marketed by
Dow Chemical Company, there was added 5 grams of deionized water
at 70C and mixed to form a paste This pa~te was added to 79 46
grams of water at 25C and thoroughly mixed to obtain a uniform
dlspersLon, whlch was then heated to 43C
AmLne citrate complex was prepared by adding 0 65 gram~ of
anhydrous citric acLd to 9 35 grams of melted methyl
di(hydrogenated tallow) amine (sold commercially as Armeen M2HT by
Akzo Chemicals Incorporated) corresponding to a molar ratio of
tertlary amine to citr$c acid of 5 2 to 1 and the mixture heated
tlll all the citric acid is melted and dLssol~ed in the amine
~approx$mate temperatur-sll5C~ Th- solutlon was th~n cooled to
room t mperatur- wh-re lt sol~d~fled
Th- am~ne cltr-to compl-x plu- the unreacted amln- wa~
th-reafter m-lt-d by h-atlng to about 7orC and added to the
m thylcellulose dispersion described above at 43C under gentle
agltation to form a smooth, whlte emul~lon havinq a cream-llke
consi~tency Thls emulslon was cooled to approximately 40 C and
0 2 grams of Neodol 45-13 ~a tradenam- for a Shell Chemlcal
Company d-tergent whlch 1~ a condensatlon product of a mixture of
f~tty alcohols a~-raglng about 14 to 15 carbon atoms wlth about 13
moles of ethylen- ox~d- p-r mole of alcohol) dissolved in G 8
grams water wa~ added to it while mixing The emulsion was
gradually cooled to 25C to let the particle~ solidify
The particle ~ize of the di~persed phase as determined by a
HIAC/ROKO Particle Size Analyzer ~Model PA 720) marketed by
Pacific Scientific Company was about 35 microns mean diameter
Such Analyzer u~es establiahed light blocking principleq for

2~68949
mea~uring the particle size mean diameter whereby the mea~ured
particles interrupt a continuous light beam when pa~sing through a
~ensing zone which, in turn, cause~ a reduction in the amount of
light reaching a photo detector. Thig technique is particularly
advantageous for mea~uring particle sizes larger than the normal
range of particles conventionally mcasured by light scattering
techniques.
To thi~ solution there was added, while mixing, 0.6 gram~ of
N-odol 45-13 dissolved in 2.4 grams water followed by 0.35 gram~
of Neodol 25-3. ~he HLB of the emulsion following the addition of
the~e emulsifying agents was about 12.
A commercial defoaming material (0.02 grams) was then added
to the re~ult$ng emuls~on followed by the addit~on of ad~uvants
~uch a~ perfume (0.5 gram~) dye (.015 grams) and preservative (0.1
gram of Uc~rc$de marketed by Unlon Carblde Corporat~on), all whLle
mlxlng. A mlnor a~ount of ~ con- (0.2S gr~m~ of Dow Corning
193) w-J th-n addsd to modlfy th- vl~co~lty.
~h re~ulting emul~lon wa~ h~ghly utable over a temperature
range from amblent to at lea~t llOqr, and, $n particular, did not
man$fest any partlcle break down and pha~e ~eparation when aged at
hlgh temperature, namely a mln$mum of 24 hours at a te~perature of
110~ or above.

2~689~9
EXAMPLE 2
A liquid emulsion of the invention was prepared utilizing as
the alkyl cellulose ether a derivatfve of hydroxyethyl cellulo~e
(HEC) in which the hydroxyl hydrogen of the ethyl hydroxyl group
on the 5th carbon of the ring ia replaced by a fatty alkyl chain
having from 10 to 24 carbon atoms Such HEC derivative polymers
are ~old under the trademark "Natrosol Plus" by Hercules Chemical
Company
An amine-citrate complex wa~ prepared by adding 0 654gms of
anhydrous cltric acid cry~tal~ to 9 34gms of molten methyl-di
~hydrogenated tallow) tertiary amine (sold commercially as Armeen
M2HT by Akzo Chemicals, Inc ~ and the mixture wan maintained at a
temperature of about 115C unt~l the citr~c acld complexed with
the amine The resulting binary mixture with exce~s-free amine
wa- cooled to room temperature under ambient condltlon- to obtain
a whlte ~olld cake
D-lonlz-d wat-r ~89 ~3gm~) w-~ h-ated to about 48 C uaing a
b nch top hot plate Amlne-citrate complex (9 994gms) prepared
according to the aforementioned procedure was melted in a
mLcrowave oven and added slowly to the above hot water under
gentle agitation u~ing a paddle mixer ~he mLxlng wa~ continued
for about 10-15 mlnuter and the re-ulting milky emul~on wa-
cooled to 40 C and malntalned at thl~ t~mperature
~o thl~ amine-citrate emul~lon th-re wa- then slowly added
0 06 gra~- of th- above d-~crLbed HEC derlvative polymer whlle
malntaining gentle agltation The emulsion wa0 mixed for an
addltional 10 minute~ and then allowed to cool to ambient
temperature (approximately 25C) To the above cooled emulsion
0 2 gram~ of liquld Neodol 25-13 (marketed by Shell Chemical
company) wa0 added followed by the addition of color and perfume
to complete the prototype preparation The above method of
.. ..

2~689~9
preparation resulted in a smooth and milky emulsion having cream
like con~istency.
The particle size of the emulsion waQ meaQured u~ing OlympuQ
8M-2 microscope and the average particle size was found to be in
the range of 15-25 microns. The emulgion did not separate or
manife~t any particle disintegration when heated to a temperature
of about 110~. This was confirmed by a hot-stage video-
microscopy. The emulsion wa~ stable over a range of temperature
from ambient to llO~. The emul~ion was also stable under heat-
cool t110~ to ambient~ cycling conditions.
.. . . . . .

2~68949
EXAMPLE 3
To demonstrate the improved stability of a fabric
conditioning liquid emulsion in accordance with the invention, a
compari~on wa~ made with the emul~ion described in U S Patent No
4,869,836 to Harmalker, in Example 5, the disclo~ure of which i8
incorpor~ted herein by reference ~he fabr$c condltioning
composlt~on~ de~cribed in the Harmalker patent are ~imilar to that
d-~cribed hereln except for the absence of an alkyl cellulo~e
ether .
The particle ~ize of an emulsion prepared a~ ~et forth in
Example 1 abo~e was mea~ured at room temperature with the
HIAC~ROKO partlcle size analyzer $he partlcle ~ize wa~ about 35
micron~ mean dlameter No change in particle size was noted after
about 24 hours A ~econd aample of the same emulsion wa~
malntaln~d at a temperature of about 1107 for 24 hourc and lt~
partlcle ~izo th-n mea~ured Th- r--ultlng particle ~Lze wa~
unchanged, about 35 mlcron~ mean dlnmeter
8y way of compari~on, a llquld emuls$on was prepared in
accordance with ~xample 5 of U S 4,869,836 and it~ mea~ured
partlcle ~ize at room tomparature wa- about 35 microns m-an
dLameter No change in partlcle sizo wa~ noted after about 24
hours A -cond ~ample o f thLs ~ame emul~lon wa~ malntalned at a
t-mp-rature of about llOqF for 24 hour~ and the re~ultlng m-a~ured
partlcle ~ize wac balow 10 mlcron~ m-an dlameter, indLcating
lnctabLl~ty of the emul~lon at ele~ated tsmperatures

20689~g
EXAMPLE 4
A commercial granular detergent compo~ition designated herein
as Control ~" wa~ used in thi~ example and had the following
composition
Control A
ComDonent We$aht Percent
Linear alkylbenzene ~ulfonate 4
Sodium fatty alcohol sulfate 9
Sodium ethoxy alcohol sulfate 3
Polyethoxylated alcohol 0 7
Pentasodium tripolyphosphate 31
Sod~um pyrophosphate 7
Sodlum carbonate 9
Sodlum ~ulfate 16
Sodlum sillcate 5
MolsturQ and ad~uvant~ Balance
Tho followLng waohlng procedure wa~ uo-d to evaluate the
efflcacy of a composition in accordance with the invention (the
compooition ofExample 1) and a comparatLve compo~ition as
d-scrlbad in the aforemontLoned U S Patent 4,869,836, Example 5
thereof Each of tho aforementioned llquid composltlono ~n an
amount of 90 gramo wa- addod along wlth 86 qrams of Control A to a
U S top-loadlnq wa-hlng machine A 6 1/2 lb ballaot wa-h load
comprl~ed of cotton and synthetic f~brics was wa~hed with 64
lltors of water at 90P using a fourteen minute wash cycle with
rlnse and spin operations followed by drying for one hour in an
electric dryer The waohing and dry~ng ~tep~ were then repeated
and following the second drying operation the fabrics were
evaluated for their anti-static properties by visual inspection
The terry towel~ in each wash load were then equilibrated to 40%
22

~068949
humidity overnight and the following day were evaluated for
softness by a six member panel. The resultg of the static and
softness evaluation for each of the te~ted compositions i9
described in Table 1.
s

2~6~9~
ESAMPLE 5
~he phy~iral characteri~tic~ of the liquid emul~ion of the
inve~tion described in Example 1 wa~ compared with a liquid
emulsion not in accordance with the invention containing a
S cellulo~e ether derivative such a~ de~cribed in U S 4,808,086 to
Evan~ et al
A composition "D" wa~ prepared following the exact procedure
of Example 1 except that in place of the Methocel A4CR of Example
1 present at 0 3~ there waa ~ub~tituted Methocel A15LV, a methyl
cellulo~e ~old by Dow Chemical, whlch io dloclo~ed in U S
4,808,086 at Table 1, Column 9 a~ a ~oil releaae agent The
weight present of thL~ methyl celluloae in the compo~ition wae
10%, a concentratlon ~ubstantially below the most preferred weight
range of 25-S0~ of the fabric condltloning compooitlone
r-commended by the Evan~ et al patent at col 1, line 54
Sh- reoult~nq compooition ~D~ wao a non-flowable, non-
pourable thlck paote
A ~econd compo~ltlon ~E~ was prepared following the exact
procedure of Example 1 except that in place of Methocel A4C~ at
0 3~, there wa~ 3ubstltuted Polymer JR-125 whlch i8 deccribed in
U S 4,808,086 at column 2, llne 61 ao a ~oll relea~e agent Thls
polymer wa~ u~ed ln tho compoeltlon at a welght percent of 10~,
b-low the moot pr-ferred welght range of 25-50~ recommended for
lto u~e by the Evano et al patent
Th- re-ult~ng composltlon ~E~ wa~ a non-flowable, non-
pourable thlck paote
8y way of comparieon, the liquid emulsion of Example 1 wa~
readily pourable having a vi~co~ity of about 600 centipoi~e at
room temperature
24

2068949
TAPLE 1
PERFORMANCE OF FAERIC CONDITIONING COMPOSITIONS OF THE INVENTION
Formulation Softness (a) Static (b)
Control A -- Very heavy
Control A + comparative compoaition +3 Light to none
Of U S Patent 4,869,836
Control A + compo~ition of invention +4 None
(E:xample 1 )
conditions wash cycle, 90~ for 14 minute~; base compon$tion 84g of Control A
. . . _ . _
(a) Softne~s difference in softness measured is ba~ed on a scale of 1 (very harsh)
to 10 (very soft) relative to Control A a~ evaluated by a aix-mQ~ber panel
A differ-nce of one u~it or greater i~ con~idered slgnificant Control A
provided a noftne~s of from 3 to 4 when evaluated, on an absolute ba~is, on a ~cale
of 1 to 10
~b) Th- antl-~tatic propertle- w-r- characterized visually
.. . . .