Note: Descriptions are shown in the official language in which they were submitted.
~2'~ 3
62301-1272
BACKGROUND OF THE INVENTION
The present invention relates to fabric softener
compositions adapted for the use in the rinse cycle of a
laundering process and in particular to concentrated aqueous
fabric softener compositions which are stable at both low and
hlgh ambient temperatures, i.e. such compositions do not form
a gel, and which are easily dispersed in water when used.
Compositions containing quaternary ammonium salts
having at least one long chain hydrocarbyl group are commonly
used to provide a fabric softening benefits when employed in a
laundry rinse operation; for example, see U.S. Patents
3,349,033; 3,644,203; 3,946,115; 3,997,453; 4,073,735 and
4,119,545.
For most aqueous softener compositions containing
cationic quaternary ammonium compounds as active ingredients,
the concentration of such cationics has r in general, been
limited to the range of about 3 to 6~ by weight (see U.S.
Patent 3,904,533 and U.S. Patent 3,920,565). Such a low
concentration is generally necessitated by the fact that
cationics form ~els in water systems at concentrations at above
about 8%,and whilethe useof electrolytes to lowertheViscosity f
such compositions is known (see in particular U.S. Patent
4,199,545), such electrolytes are far from satisfactory. From
a functional point of view, the electrolytes often do not
perform as required particularly at concentrations of the
cationics in the neighborhood of about 12-15%. Further, while
the performance of the electrolytes may mitigate some of the
gelling problem, their use is far from satisfactory in
,~ ~
~L2~61~3
62301-1272
providing a highly concentrated a~ueous system of cationics
which does not gel or severely change in viscosity within the
usual range of temperatures encountered in the handling thereof,
for example 0F (about -18C) up to about 140~F (about 60C). In
U.S. Patent 3,681,241 a concentrated fabric softening emulsion
is described which consists essentially of 3.5 ot 6.5 parts by
weight of a compound represented, for example, by distearyl
dimethyl a~nonium chloride, from 3.5 to 6.5 parts by weight of an
alkyl amido imidazoliunium alkylsulfate, and from 0 to 3 parts by
weight of a different but similar fatty amido imidazolinium
alkylsulfate, the latter allegedly providing low temperature
stability for the composition. The total actives contemplated
range from abou-t 8 to 13%.
In British application 2053249A published February 4,
1981, there are disclosed cationic fabric softening composicions
containing 15 to 60% by weight of cationic softener, 25 to 75
by weight of an aqueous medium, and 0.5 to 40% by weight of a
specified watersoluble polymer.
In U.S. Patent 3,97~,076 there are disclosed ~uaternary
ammonium-containing softening composition of conventional
cationic concentrations,i.e. about 3% to about 6~. Thesecompositions
are characterized by the very small particle size of the
substantially water-insoluble quaternary ammonium softening
compound, i.e. 90% by weight of the quaternary ammonium compounds
exists asparticles which will pass through a 1~2 micron filter.
The compositions are described as a combination of the cationic
softener, a C8 to C20 alkyl alcohol with from about 0,1% to
61
about 2.0% of a non-ionic surfactant having a HLB of from about
8 to about 15, and preferably from about 10 to about14. The
~i
~ 6~3 62301-1272
preferred non-ionics have a lipophilic hydrocarbyl moiety
equivalent of 9 to 15 carbon atoms with 7 to 13 ethylene oxide
hydrophilic moieties. This patent does not relate to the problem
of stability of concentrated aqueous cationic softening
compositions but rather to improving the level and unifoxmity
of softening using conventional concentrations.
Each of U.S. Patents 4,076,63~; 4,157,307 and 4,233,164
disclose~ quaternary ammonium softening containing inter ~ia,
"protonated" ethoxylated amine, but none of these disclose salts
of the amine, let alone with high molecular weight organic acids
(i.e. higher fatty acids e.g. C12 to C30; alkyl aryl sulfonic
acids e.g. C12 to C18 alkyl benzene sulfonic acids; C12 to C30
paraffin (alkyl) sulfonic acids; C12 to C30 olefin sulfonic
acids; the mono- ~ di-phosphoric acid esters of C8 to C30
alcohols including the ethoxylates of such alcohols with from one
to 100 moles of ethylene oxide). U.S. Patent 4,118,327 describes
conventional cationic concentration (0.1 to 10% preferably 1 to
8% by weight) with phosphate organoesters as anti-static agents.
SU~ARY OF THE INVENTION
The present invention provides low and high temperature
stable, concentrated, aqueous softener compositions based upon
quaternary ammonium softening compounds and a minor amount of an
amine salt of an ethoxylated long chain amine with a long chain
organic acid and electrolyte. Water-soluble polymers such as
polyethyleneglycol (e.g. M.W. 400) are a preferred optional
ingredient.
33
DETAILED DESCRIPTION OF THE INVENTION
The compositions of the present invention are stable
aqueous compositions which contain a high concentration of the
cationic fabric softener which is a water dispersible quaternary
ammonium compounds as hereinafter described, and an amine salt,
also as hereinafter described.
Thus, according to the present invention, there is
provided a stable, aqueous, concentrated fabric softening composition
comprising about (A) 12 to 20% by weight of a cationic softener
of the formula:
1 / 3 1 ~ X
L R2 \ R
wherein Rl, R2, R3 and R4 are aliphatic radicals of Cl to C30
with at least two being alkyl of C14 ~o C30; (B) 1 to 5% ~y weight
of an amine salt and ~C) 0.5 to about 5% by weight of an electrolyte.
In another aspect the present invention provides a
method for preparing a composition as defined above which comprises
first preparing an aqueous solution of the amine in warm water
at a temperature up to about 80C and thereafter (a) adding cationic
softener in melted form to form a gel, cooling said gel to below
40C, and then adding electrolyte to break the gel, or ~b) adjusting
the pH with alkaline material to above about 10, adding the cationic
softener in melted form, readjusting the pH to below 7, cooling
to about room temperature and then adding electrolyte to adjust
the viscosity, or (c) adding electrolyte to the cooled aqueous
solution followed by the cationic softener in melted form and
cooling to room temperature.
The aqueous compositions of this invention contain
-- 5 --
~'~4L~6(~3
at least about 12% cationic so-ftener up to about 20% thereof,
said cationic softener having the general formula I
_
R - - - N ~ R Y
R
wherein the R groups are selected from Cl to C30 aliphatic, prefer-
ably alkyl or alkenyl, aryl (e.g. phenyl, tolyl, cumyl, etc.);
aralkyl (e.g. benzyl, phenethyl, etc.); and the halo, amide,
hydroxyl, and carboxy substituents thereof; with the proviso
that at leas-t one R is C14 to C30 and preferably C14 to C18,
and the others are lower alkyl, and more preferably at least
two R's are C14 to C18 and the others are lower alkyl of Cl to
C4 (and most preferably methyl or ethyl), and Y is a water-
solubilizing anion such as chloride, bromide, iodide, fluoride,
sulfate, methosulfate, nitrite, nitrate, phosphate and carboxylate
(i.e. acetate, adipate, propionate, phthalate, benzoate, oleate,
etc.). Typical cationics of formula I include the following:
distearyl dimethyl ammonium chloride
ditallow dimethy] ammonium chloride
dihexadecyl dimekhyl ammonium chloride
distearyl dimethyl ammonium bromide
di~hydrogenated tallow) dimethyl ammonium bromide
distearyl, di~isopropyl) ammonium chloride
distearyl dimethyl ammonium methosulfate
The amine salts contemplated herein are based upon
ethoxylated long chain amines and long-chain organic acids.
The amines are typically C12 to C30 aliphatic amines~ and pre-
ferably C12 to C20 amines and admixtures thereof reacted witll
from one to about 100 moles of ethylene oxide. Tlle amines may
46~3
also be reacted with propylene or butylene oxide and then with
ethylene oxide. The final oxyalkylated amine should be a water-
soluble product. Of particular value are the amines derived
from natural fatty acids such as the Armeens and Ethomeens and
these generally comprise a mixed alkyl ranging from C10 to C18,
12 16' C12 to C15, or C16 to C18 and the like. Preferred
ethoxylated amines are those containing from about 5 to about
50 moles of condensed ethylene oxides and more preferred are
ethoxylated amines with about 10 to about 35 moles condensed
ethylene oxide. Most preferred contain 12 to 20 moles of ethy-
lene oxide.
The third ingredient is an electrolyte ~ionic) material
preferably in an amount of from about 0.1 to about 1.5% by weight.
The use of an electrolyte acts not only to control viscosity
but also consists in stabilizing the system against gelling
phase inversion at high temperatures~ e.g. above about ~0C.
- 6a -
6~3
62301-1272
Particularly suitable electrolytes include sodium chloride
and calcuim chloride. Other useful electrolytes include sodium
formate, sodium nitrite, sodium nitrate, sodium acetate among
others as well as water-soluble salts of other cations such as
potassium, lithium, magnesium, ammonium and the like.
Minor amounts of lower alkanols may be used
particularly where it is desired to further modify the viscosity.
In general, alcohols tend to lower the viscosity at ambient
temperatures, although moderate amounts may effect a lowering of
the phase inversion temperature. The preferred compositions of
this invention exhibit phase inversion temperatures above about
80C and preferably above about 90C with amounts of alcohol in
the range of about 1 to about 10% by weight. Particularly
suitable alcohols are ethyl and isopropyl alcohol.
In addition to the foregoing components of the
softening compositions of this invention, there may also be
included numerous conventional, supplemental~ and optional
ingredients which do not adversely affect the stability and/or
functional characteristics of the instant compositions. Thus,
for example, there may be present the ubi~uitous perfumes,
dyes, pigments, opacifiers, germicides, optical brighteners,
anti-corrosion agents (e.g. sodium silicate) water-soluble
polymers, anti-static agents and the like. Where used, each
may comprise from 0.01% to about 5~ by weight of the composition.
It is, of course, recognized and understood that
most available chemical materials and particularly those
containing an hydrocarbyl moiety are generally mixtures of
closely related moieties. Thus, the long chain alkyl
substituents (R) in the cationics used in this invention may
--7--
~Z~t~6~3 62301-1272
not only be a single carbon length chain but more probably a
mixture. In this regard a particularly useful quaternary set
wherein the alkyl groups are derived from tallow may contain
about 35% C16 and 60% C18 and minor amounts of C14 and even
others. Similarly, the aliphate.
The fabric softening compositions of this invention
must have in addition to viscosity and phase stability, the
requisite viscosity (i.e. for pourability) and water-dispers-
ibility in the rinse cycle (or any other form of dilution prior
to use) which the consumers have come to accept and demand
from their use of the less concentrated products. Thus the
products contemplated herein may have viscosities ranging from
about 30 cps to about 250 cps and preferably from about 40 cps
to about 120 cps.
In addition to affording excellent dispersibility
characteristics in water, the amine salts used therein
contributes softening as well so that, for example, a
concentrate of 12% quaternary compound and 2% amine salt is not
merely equivalent to 2X a conventional 6% cationic composition
but is almost 2-5 times as effective.
The general procedures for preparing the composition
herein are several in number, the final product varying somewhat
in stability. The selected procedure depend in the components
used and differ in the order of material addition and the
processing conditions.
A typically preferred procedure (A) involves adding
the non-ionic material and coloring, if any, to the formula
weight of water which is about 70C. To this solution there is
,~ .
6~)3
62301-1272
slowly added the cationic softener in "melted" form (50-60C)
to which the amine salt has already been added. Usually a gel
will form. The mixture is cooled to about 40C. and then the
electrolyte is added to break the gel~ The composition is then
cooled to room temperature with stirring. A modification of
procedure (A) involves adjusting the pH to about 12 before
adding the melted cationic. In this case no gel forms. After
cooling to about 40C, the pH is readjusted to 5 to 6, cooled
with stirring to room temperature and then electrolyte is used
to adjust the viscosity (Procedure B)~ Still another
procedure (C) involves adding the non-ionic and electrolyte to
at least 80% of warm water (about 40C), and then the cationic
softener and amine salt as in procedure (A). Generally, no
gel will form. The rest, if any, of the water is then added,
and the composition is then cooled with agitation to room
temperature.
The following examples will serve to illustrate the
present invention without being deemed limitative thereof. Parts
are by weight unless otherwise indicated.
Example 1
Following Procedure (A) described above, l part of
polyethylene glycol (M~.400) & 1.2 parts of 0.2~ color solution
are dissolved in about 70 parts of water at a temperature of
about 70C. To this solution are slowly added 17.6 parts of
distearyl dimethyl ammonium chloride (75% active and containing
about 10% isopropanol and the balance water)is inmelted formto
which has been previously added 3.7 parts Ethomeen T25* and
~Z~6~3 62301-1272
1.3 parts of dodecyl benzene sulfonic acid (Temperature = 55C)
with stirring. A gel is formed. The gel is cooled down to
about 40C and then 0.5 parts of calcium chloride dihydrate
are added. The mixture is cooled to room temperature (about
20C) with stirring. A stable product results with a
viscosity of about 100 cps. *Tallow amine (40% C16; 60% C18)
condensed with 15 moles of ethylene oxide. Ethomeen is a
Trade Mark.
Example 2
The procedure of Example 1 is repeated utilizing the
following parts of (A) cationic (active), (B) amine, (C)
sulfonic acid and (D) electrolyte.
(a) A = 12; B = 1.0; C = 0.32; D = 0.5
(b) A = 14; B = 1.5; C = 0.52; D = 0.5
(c) A = 16; B = 1.8; C = 0.63; D = 0.7
(d) A = 18; B = 2.5; C = 0.88; D = 1.0
Example 3
Example 1 and 2 are repeated utilizing in place of
distearyl dimethyl ammonium chloride the following:
(a) ditallow dimethyl ammonium chloride
(b) distearyl dimethyl ammonium methosulfate
(c) di(hydrogenate tallow) dimethyl ammonium bromide
(d) di-hexadecyl dimethyl ammonium chloride
(e) distearyl diethyl ammonium chloride
Example 4
Examples 1, 2 and 3 are repeated adding in all
instances 1 part of polyethylene glycol (MW400) with the amine
salt in the
--10--
~Z~6(~3
first step of the process of the preparation.
Polyethylene glycol (MW400) is illustrative of low mole-
cular weight, water-soluble polymers which may be used if desired in
the softening compositions of this invention. Among other useful
polymers reference is made to British published application 2053249A
described above. The compositions of this invention may include any
and all of such polymers and other water-soluble polymers as well.
In the compositions of this invention one may use from 0.1% to 20%
by weight of the total composition of these materials.
Example 5
Each of the foregoing examples 1 to 4 is repeated using as
the electrolyte the following:
(a) sodium chloride
(b) sodium nitrate
(c) sodium formate
(d) ammonium bromide
(e) potassium chloride
(f) calcium nitrate
(g) lithium acetate
(h) magnesium chloride
Example 6
Each of Examples 1 to 5 is repeated, composition-wise, but
following the Procedure (B) for making the compositions. In this
procedure the change in the processing described in Example 1 in-
volves adjusting the p}l to 12 with sodium hydroxide after dissolution
of the amine salt (and polyethylene glycol where used), and re-
adjusting the pH to 5 - 6 with hydrochloric acid after the
~ ~ ~ . . ~ ~ ~ 4 6 ~ 3
;~ '
'`:
ad~ition of the cationic. At this point no gel forms as in
Procedure (~). Tl-c lectrolyte ls added a~ter the misture llns
been cooled to room temperature.
; Example 7
Each of Examples 1 to 5 is repeated again, compositions-
wise but following Procedure (C) to prepare the compositions.
In this procedure the amine salt (and the water soluble
polyethylene glycol where used) is dissolved in 80% of the
formula weight of water at a temperaeure of 35-40C. The
electrolyte is then added, followed by the melted cationic. The
remaining formula weight of water is then added and thereafter
the mixture is cooled to room temperature with stlrring.
Example 8
Following procedure (A) described above, 1 part of poly~
!lethylene glycol (M.W. 400) and 1.2 parts of 0.2~ color solution
are dissolved in about 70 parts of water at a temperature of
about 70C.
To this solution are s,lowly added 17.6 parts of ditallow
dimethyl ammonium chloride (75% active and containing about 10%
isopropanol and the balance water) in melted form to which has
previously added 2 parts Ethomeen T 25 (tal~ow am~ne-40% C16,
l~ 60% C18) condensed with 15 moles of ethylene oxide~ and o.62 of
i stearic acid (temperature=55 C) with stirring. A stable pro-
duct results with a vlscosity of about 100 cps.
Example 9
Example 8 is repeated ueilizing the parts of cationic~
amine and the electrolytes of Example 2 and at the same time
varyin~ the stearic acid so that it is stoichlometric to the
amount of amine.
124~603
Example 10
Example 9 is repeated by replacing stearic acid with
stoichiometric amount of following acids: laurlcl cis-9 dodecenioc ,
myristic, cis-9 tetradecenoic, pentadecanio, cis-9 pentadecenioc,
palmitic, cis-9 hexadecenioc, heptadecanoic, cis-9 heptadecenoic,
oleic, linoleic, linolenic, - eleostearic, 4 oxo cis-9 trans 11,
trans 13 octadecatrienoic, ricinoleic, dihydroxystearic, non-
adecanoic, eicosanoic, cis-ll eicosenoic, cis-9 eicosenoic, .
eicosadienoic, eicosatrienoic, arachidonic, eicosapentaenoic,
docosanoic, cis-13 docosenoic, docosadienoic, docosatetraenoic,
4.8.12.15.19 docosapentaenoic, docosahexanoic, tetracosanoic,
tetracosenoic, 4.8.12.15.18.21 tetracosahexaenoic and mixtures
there of.
Example 11
Example 9 and 10 are each repeated replacing on one
hand the quat with those of Example 3 and additionally repeating
all of these examples utilizing in the composition 1 part of
polyethylene glycol (MW 400).
The aqueous softening cdmpositions of this invention ar~
generally applicable zs other such compositions, particularly
useful in the rinse cycle of an automatic laundry machine. In
such operations as well as in any other desired method of ~reating
clothes, the compositions are usually employed to pro~ide generall
an active concentratlon of from about 0.005X to 0.3% based on the
weight of clothes tr~ated p~eferably 0.007~ to about 0.2Z an~
most preEer-bl~ fr ~m a~o~C 0.012 to abo~t 0.15Z.
,~
.~ 1 13
