Note: Descriptions are shown in the official language in which they were submitted.
%~9 t~
FABRIC SOFTENING COMPOSITION
The presant in~ention relates to a ~abric softening
composition, in particular a fabric softening composition
containing a water-insoluble cationic fabric softening
agent, a fatty acid and other nonionic surfactants.
One of the problems associated with fabric softening
compositions is the physical instability of such
~; compo~itions when stored. This problem is accentuated if
storage occurs at various cycling temperatures inluding
those below the freezing point, since irreversible gels
can be formed.
It has been proposed (European published patent
application No 21476 published January 7, 1981) to add
a protonated di-polyethoxy monoalkyl amine, a lower
alcohol and, optionally, a nonionic fabric conditioning
agent to control the physical stability of a
.
composition containing a quaternary ammonium abric
~ ~ 25 softener, the alcohol being additional to that present
; - in the softener;raw material. The disadvantage with the
~ compositions clisclosed is that the physical stability is
~' :
:
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-- 2 --
only achieved if both the amine and alcohol are added to the
compositi.on.
We have now found that the addition of a nonionic
surfactant to a composition containing a cationic fabric
softening agent and a fatty acid gives a co~position which is
stable after one and multiple freeze thaw cycles without the
necessity of adding additional alcohol.
Thus, according to the invention there is provided a
liquid fabric softening composition comprising
(i) an aqueous base;
(ii) from 1% to 6% by weight of a water-insoluble
cationic fabric softening agent;
(iii) at least 0.2~ by weight of a C8 C24 alkyl or
alkenyl monocarboxylic acid; and
(iv) a nonionic surfactant,
wherein the mole ratio of the cationic fabric softening
agent to the nonionic surfactant is within the range from
40:1 to 3:1 and wherein the mole ratio of the cationic
fabric softening agent to the said monocarboxylic acid
is at least 1:1.
The water-insoluble cationic fabric softening agent can
be any fabric-substantive cationic compound which has a
solubility in water at pH 2.5 and 20C of less than 10 g/1.
Highly preferred materials are quaternary ammonium salts
having two C12-C2b alkyl or alkenyl chains, optionally
substituted or interrupted by functional groups such as -OH,
-O-, -CONH-, -COO-, etc.
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Well known species of substantially water-in oluble
quaternary ammonium compounds have the formula
~ R1 R3 1 +
2 ~4
_ ~
wherein R1 and R2 represent hydrocarbyl groups having from
about 12 to about 24 carbon atoms; R3 and R4 represent
hydrocarbyl groups containing from 1 to about 4 carbon
atoms; and X is an anion, preferably selected from
halide, methyl sulfate and ethyl sulfate radicals.
RepresPntative examples of these quaternary
softeners include ditallow dimethyl ammonium chloride;
ditallow dimethyl ammonium methyl sulfate; dihexadecyl
dimethyl ammonium chloride; di(hydrogenated tallow alkyl)
dimethyl ammonium chloride; dioctadecyl dimethyl ammonium
: chloride; dieicosyl dimethyl ammonium chloride; didocosyl
: dimethyl ammonium chloride; di(hydrogenated tallow)
dimethyl ammonium.methyl sulfate; dihexadecyl diethyl
ammonium ohloride; di~coconut alkyl) dimethyl ammonium
chloride. Also suitablé are dialkyl ethoxyl methyl
ammonium sulphates based on soft or hard fatty acids.
Ditallow dimethyl ammonium chloride, di(hydrogenated
tallow alkyl~:dimethyl ammonium chloride, di(coconut
alkyl3 dimethyl ammonium chloride and di(coconut alkyl)
dimethyl ammonium methosuIfate are preferred.
.
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Ano~her class of preferred wate.r-insoluble cationic
materials are the alkylimidazolinium salts believed to
have the formula:
S CH~- - CH2
+ ll
~ N - C2H4 - I - C R7
C R~
R6
R8
wherein R6 is an alkyl or hydroxyalkyl group containing
from l to 4, preferably 1 or 2 carbon atoms, R7 is an
alkyl or alkenyl group containing from 8 to 25 carbon
atoms, R8 is an alkyl or alkenyl group containing from 8
to 25 carbon atoms, and R9 is hydxogen or an alkyl
containing from 1 to 4 carbon atoms and A is an anion,
preferably a halide, methosulfate or ethosulfate.
Preferred imidazolinium salts include l-methyl-1-
(tallowylamido-) ethyl -2-tallowyl- 4,5-dihydro imidazo-
linium methosulfate and l-methyl-l- (palmitoylamido)
: ethyl -2~octadecyl-4,5- dihydro- imidazolinium chloride.
Other useful imidazolinium materials are 2-heptadecyl-1-
methyl l-(2-stearylamido)- ethyl imidazolinium chloride
. - , . . .
and 2-lauryl-1-hydroxyethyl- oleyl-imidazolinium
chloride. Also suitable herein are the imidazolinium
fabric softening components disclosed in US patent
No 4 127 489 issued November 28, 1978. Mixtures of
various cationic fabric softening agents can also be
used.
The level of the cationic fabric softening agent in
the composition is preferably more than 1% by weight,
most preferably from 3% to 6~ by weight.
~91~0;~
--5--
Suitable fatty acids which can be used in the
present invention are Ca-C2,, alkyl or alkenyl linear or
branched chain monocarboxylic acids or polymers thereof.
Preferably saturated fatty acids are used, in particular,
hardened tallow C16-C18 fatty acids. Mi~tures of various
fatty acids can also be used.
The level of the fatty acid in the composition is
preferably less than 8% by weight, most preferably from
0.2% to 2.5% by weight.
The mole ratio of the cationic fabric softening
agent to the fatty acid is at least 1:1, and preferably
is within the range 4:1 to 9:1.
Suitable nonionic surfactants which can be used
include in particular the reaction products of compounds
havin~ a hydrophobic group and a reactive hydrogen atom,
for example aliphatic alcohols, acids, or alkyl phenols
with alkylene oxides, expecially ethylene oxide either
alone or with propylene oxide. Specific nonionic
surfactants are alkyl (C6-C22) phenols-ethylene oxide
condensates, generally up to 25 EO, i.e. up to 25 units
of ethylene oxide p0r molecule, the condensation products
o~ aliphatic (C8-C22) primary or secondary linear or
branched alcohols with ethylene oxide, generally up to 40
EO, and products made by condensation of ethylene oxide
with the reaction products of propylene oxide and
ethylenediamine. Other so-called nonionic surfactants
include amine oxides, alkyl polyglycosides, ethoxylated
castor oils, and sorbitan esters.
Preferably, ~he level of the nonionic surfactant is
within the range from 0.1 to 4.5% by weight, most
preferably from 0.15% to 3% by weiyht. The mole ratio of
the cationic fabric softening agent to the nonionic
surfactant is within the range from 40:1 to about 3:1.
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The composition can also contain one or more
optional ingredients selected from non-aqueous solvents
such as C1-C4 alkanols and polyhydric alcohols (although
the bene~its of this invention can be obtained without
the addition of these materials), pH buffering agents,
such as weak acids e.g. phosphoric, benzoic or citric
acids (the pH of the compositions are preferabl~ lesq
than ~.0), rewetting agents, viscosity modifiers, such as
electrolytes and C9-C24 fatty acids included at levels
from about 20 to 6000 ppm, antigelling agents, perumes,
perume carriers, fluorescers, colourants, hydrotropes,
antifoaming agents, antiredeposition agents, enzymes,
optical brightening agents, pacifiers, stabilisers such
as guar gum and polyethylene glycol, anti-shrinking
agents, anti-wrinkle agents, fabric crisping agents,
anti-spotting agents, soil-release agents, germicides,
fungicides, anti-oxidants, anti-corrosion agents,
preservatives such as Bronopol (Trade Mark), a
commercially available form of 2-bromo-2-nitropropane-
1,3 diol, dyes, bleaches and bleach precursors, drape
imparting agents, antistatic agents and ironing aids,
such as silicones.
These optional ingredients, if added, are each
present at levelQ up to 5~ by weight of the composition.
Suitable silicones for use in the compositions
according to the invention include predominantly linear
polydialkyl or alkylaryl siloxanes in which the alkyl
groups contain one to five carbon atoms. The siloxanes
can be amido or amino substituted. When the siloxane is
amine substituted the amine group may be quaternised.
The composition may also contain, in addition to the
cationic fabric softening agent, other non-cationic
fabric softening agents, such an nonionic fabric
0Z
--7--
softening agents. Suitable nonionic fabric softening
agents include lanolin and derivatives thereof. Suitable
materials are disclosed in European published patent
application No 88 520 (Unilever published September 14,
1983). Typically such materials are included at a level
within the range of from 0.5% to 10% by weight of the
composition.
In use, the fabric conditioning composition of the
invention may be added to a large volume of water to form
a liquor with which the fabrics to be treated are
contacted. Generally, the total concentration of the
cationic fabric softening agent, the fatty acid and the
nonionic surfactant in this liquor will be between about
30 ppm and 500 ppm. The weight ratio of the fabrics to
liquor will preferably be less than about 25:1, mo~t
preferably between about 10:1 and about 4:1.
The compositions of the in~ention may be prepared by
a variety of methods. One suitable method is to form a
molten mixture of the cationic fabric softening agent and
the fatty acid, add this molten mixture to ~ater with
stirring to form a dispersion and thereafter add the
nonionic surfactant and any optional ingredients.
Another suitable method is to add the nonionic surfactant
to the molten mixture before the dispersion is formed.
The invention will now be illustrated by the
following non-limitin~ examples. In the examples all
wei~hts are expressed as weight % of the active material.
~,
129B~L30~2
EXAMPLE_l
A liquid fabric softening composition was made as
follows.
The cationic fabric soften:Lng agent and the fatty
acid were premixed and heated together until clear (60-
75C). The molten mixture thus formed was added over a
period of at least one minute, via a dip pipe, to water
at 45-60C, with constant stirring to form a dispexsion.
Other minor ingredients including perfume were added with
constant stirring whilst the temperature of the
dispersion was greater than 35C. The nonionic surfactant
was most preferably added after the mixture had cooled to
35C or below.
In this Example, the amounts of component materials
used were such that the final product had the following
composition expressed as weight %.
*Arquad 2HT 3.6%
*Pristerene 4916 0.6%
*Nonidet LE 6T 0.25~
Perfume 0.13%
Approx. mole ratio of
cationic:nonionic 11.1
For compàrison purposes Example 1 was repeated
except that the Nonidet Le 6T was excluded from the
composition (Example lA).
Both products were assessed visually after recovery
from 1, 3 and 6 freeze thaw cycles.
A freeze thaw cycle in this context involves storing
100g of product in a screw-capped polyethylene bottle for
*denotes trade mark
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16 hours at a temperature of 12C or less. Such low
temperatures are eq~ential to ensure that the products
are completely fro~en. The product is then allowed to
thaw at ambient temperatures for 8 hours.
After 1 freeze thaw cycle Example 1 gave a
composition which was slightly thicker than normal.
After 3 and 6 freeze thaw cycles Example 1 gave a
composition which had normal rinse conditioner rheology
i.e. was mobile and could be poured in a continuous
stream. Example lA after 1, 3 and 6 freeze thaw cycles
gave a composition which was just mobile but which did
not pour in a continuous stream.
The re~ults show that the addition of a small amount
of a nonionic surfactant to a composition containing a
cationic fabric softening agent and a fatty acid gives a
product with improved appearance and flow characteristics
which are maintained even after 6 freeze thaw cycles.
EXANPLE 2
This Example demonstrates the effect of
replacing Nonidet LE 6T by other nonionic surfactants.
Compositions with the followi~g formulations expressed as
weight % were prepared by the method previously
described.
Arquad 2HT 3. 6 %
Pristerene 4916 0.6~
Nonionic 0.4%
Perfume 0.13~
For comparison purposes a composition containing no
nonionic (Example 2L) was prepared and tested. In
Example 2A a level of AP& 300 of 0.2% rather that 0.4%
was used. Each composition was subjected to the
following cap dispenser test after 1 and 3 freeze thaw
cycles.
o~
--10--
Products were allowed to recover fxom freezing and a
known amount (usually 20 grams) was weighed into an
internally screw threaded cap with a total capacity of
approximately 25 cm3 and of known weight. Th~ cap was
then inverted over a waste container for 10 seconds and
re-weighed. The results obtained are expressed as a
percentage of the amount of product weighed into the cap.
Prior ~o freezing, the samples were found to leave up to
approximately 10~ residue in the cap.
The results were as follows:
15Ex No Nonionic Cap Dispenser Approx Mole
Surfactant Test l% residue) ratio of
No. of freeze/thaw Cationic to
cycles Nonionic
1 3
2A APG 300 69 31 13:1
B DMC AO 27 16 4:1
C *Dobanol 91-6 3429 7:1
D *Dobanol 45-18 8545 16:1
E *Etocas 35 80 45 39:1
F *Genapol 0-050 8336 8:1
G *Genapol 0-200 5953 18:1
H Nonidet LE 6T 3636 7:1
I Nonyl Phenol 20EO 24 46 17:1
J *~ergitol 15-S-7 49 38 8:1
K *Tween 20/*Span 20
(50:50) 46 42 10:1
L None 73 68
*denotes trade mark
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The results obtained show that the beneficial effect
of adding a small amount of nonionic surfactant to a
composition containing a cationic fabric softening agent
and a fatty acid is retained if the Nonidet LE 6T is
replaced by one of a variety of other nonionic
surfactants. For some nonionic surfactants the optimum
effect i8 achieved after several freeze thaw cycles.
Similar beneficial results can also be obtained if
the Nonidet LE6T is replaced by *Tween 20, *Alfol 1214-
7, *Alfol 1214-11, *Alfol 1214-13, *~ri; 30, *Brij 35,
*Lutensol A07, *Lutensol AO8, and Synperonic All.
EXAMPLE 3
Thi~ example demonstrates the effect of increasing
levels of nonionic surfactant on the freeze-thaw
stability of a 4.2~ active with a ratio of Arquad
2HT:Pristerene 4916 of 6:1 by weight and a perfume level
of 0.13%. The compositions were prepared by the method
previously described. The levels of nonionic are
expressed in terms of wt% of the final formulation. The
products were assessed after one freeze thaw cycle via a
cap dispenser test described above.
*denotes trade mark
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- 12 - C.3163
LevelApprox.
Ex NoNonionic ~ wt % ResidueMole Ratio
_
Cationic:
Nonionic
3AEtocas 35 0.4 80 39:1
~" 1.0 47 16:1
C" 2.0 62 8:1
D" 4.0 16 4:1
10 ~ " 6.0 13 3:1
F" 8.0 11 2:1
GAPG 300 0.2 69 ~ 13:1
H" 0~5 57 5:1
I" 1.0 40 3:1
15 J " 2.0 22 1:1
K" 3.0 17 1:1
L" 4.0 Sep 1:1
MDobanol 45-18 0.4 85 16:1
N" " 1.0 31 7:1
20 0 " " 2.0 15 3:1
P" " 4.0 13 2:1
Q" " 6.0 Sep 1:1
RGenapol 0-200 0.4 59 18:1
S" " 1.0 21 7:1
25 T " " 2.0 12 4:1
: U " " 4.0 9 2:1
V" " 8.0 Sep 1:1
WNonidet LE 6T 0.1 100 27:1
X 0.25 53 11.1
Y " " 0.4 36 7:1
Z " " 0.6 33 5 1
AA " " 0.8 19 3:1
BB " " 1.0 Sep 3:1
where Sep - Phase Separation
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13 - C.3163
The results show that high levels of r~onionic
surfactant, (low mole ratios of cationic to nonionic)
promote instability to freeze thaw cycling.
EXAMPLE 4
This example demonstrates the effect of low levels of
Nonidet LE 6T on formulations other than those containing
4.2~ active and a 6:1 weight ratio of cationic fabric
softening agent to fatty acid. The compositions were
prepared as descr.ibed above and the percentage ingredient
refers to their weight ~ in the final product.
EX No A B C D
-- ------__________________
ingredient
DMDHTAC 3.2 3.2 4.8 4.8
20 HTFA 0.3 0.3 1.2 1.2
Perfume 0.12 0.12 0.33 0.33
~onidet LE 6T 0.2 - 0. 4
Approx. Mole ratio
Cationic to Nonionic 12:1 9:1
The compositions were evaluated according to the cap
dispe~ser test as described above.
Ex No % Residues
4A 38
B gel
C 25
D 80
~L~9:~L30Z
- 1~ - C.3163
In both cases the addition of the nonionic surfactant
was found to improve the appearance and flow
characteristics of the product.
EXAMPLE 5
Compositions with the following formulations were
prepared as described above. Once again the amount of
each ingredient refers to weight ~ in the final product
composition.
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- 16 - C.3163
The compositions were assessed visually after
recovery from 1 freeze thaw cycle. In each case the
addition of a nonionic surfactant improved the appearance
and flow characteristics of the composition. This
S Example ~emonstrates that the beneficial effect of ad~ing
nonionic surfactant is not restricted to compositions
containing Arquad 2HT and Pristerene 4916.
EXAMPLE 6
In this example the softening performance of the
following compositions were examined.
Example No.
15 Ingredient % 6A 6B*
Arquad 2HT 3.6 3.6
Pristerene 4916 0.6 0.6
Dobanol 14-18 0.21
20 Perfume 0.13 0.13
mole ratio of
Arquad 2HT:Dobanol 14-18 30.1
* comparative example
The softening performance was assessed after one
freeze/thaw cycle by subjective evaluation by a panel of
expert graders.
The compositions were dispersed in tap water to give
dilute aqueous dispersions containing 0.01~ of active
insredients. Four pieces of cotton towelling (50 grams)
were rinsed in a tergotometer with one litre of the
aqueous dispersion at ambient temperature for 5 ~inutes.
''1~
1;~9~;~0~
17 - C.3163
! The fabrics were then spun-dry and line dried over
night. The compositions were found to give a similar
softening benefit. However, after one freeze/thaw cycle
the composition containing no nonionic surfactant (Example
6B) was just mobile but did not pour in a continous stream
whereas the composition according to the invention was
slightly thicker than normal rinse conditioner rheoloqy
but could still be poured in a continuous stream.
- 18 - C.3163
NOTES
Alfol 1214-7: C12-C1~ straight chain alcohol (with an
even number of carbon atoms), ethoxylated
with an average of 7 ethylene o~ide groups
per molecule.
Alfol 1214-11: As Alfol 1214-7, but with an average
of 11 ethylene oxide groups per molecule.
Alfol 1214-13: As Alfol 1214-7, hut with an average of 13
ethylene oxide groups per molecule.
APG 300: Alkyl Polyglycoside based on a Cg-C
alcohol and having an average of 1.6
glycosidic rings per mole of alcohol
(supplied as a 51~ active solution).
Ar~uad 2HT: Commercially available form of dlhardened
tallow dimethyl ammonium chloride
~DMDHTAC)(supplied as a 75~ active
paste).
BriJ 30: C12-C14 straight chain alcohol (with an
even number of carbon atoms and ~f natural
origin) ethoxylated with an average of 4
ethylene oxide groups per molecule.
Brij 35: As Brij 30, but with an average of 23
ethylene oxide groups per molecule.
DMC AO: Dimethyl coco amine oxide supplied as 30
solution.
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- 19 - C.3163
Dobanol 91-6: C9-Cll branched chain primary alcohol,
ethoxylated with an average of 6
ethylene oxide groups per molecule.
Dobanol 45-18: C14-C15 branched chain alcohol,
ethoxylated with an average of 18 ethylene
oxide groups per molecule.
Etocas 35: Castor oil ethoxylated with an average of
35 ethylene oxide groups per molecule.
Genapol 0~050: Oleyl alcohol ethoxylated with an average
of 50 ethylene oxide groups per molecule.
Genapol 0-200: Oleyl alcohol ethoxylated with an average
of 200 ethylene oxide groups per
molecule.
Lutensol OA7: C13-C15 branched chain alcohol ethoxylated
with an average of 7 ethylene oxide groups
per molecule.
Lutensol oA8: As Lutensol OA7, but with an average of 8
ethylene oxide groups per molecule.
Nonidet LE 6T: Similar material to Dobanol 91-6 except
that it is topped to remove volatile
materlals .
0 Nonyl phenol 20EO: Nonylphenol ethoxylated with 20
ethylene oxide groups per molcule.
Pristerene 4916: Commercially available form of hardened
tallow fatty acid (HTFA).
Sp~n 20: Sorbi.an monolaurate.
L3C~
- 20 - C.3163
*Stepantex Ql85: A dialkylethoxymethyl ammonium
methosulphate based on soft fatty
acid.
~tepantex VP85: A dialkylethoxymethyl ammonium
methosulphate based on hard fatty
acid.
Synperonic All: C13-C15 branched chain alcohol
ethoxylated with an average of 11
ethylene oxide groups per molecule.
Tergitol 15-S-7: C1l-C15 secondary alcohol ethoxylated
with an average of 7 ethylene oxide
groups per molecule.
Tween 20: Polyoxyethylene sorbitan monolaurate
containing 20 ethylene oxide groups per
molecule.
Tween 20/Span 20: A S0/50 weight % mixture.
(50:50)
Varisoft 222: Diamidoquaternary based on soft tallow.
.
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;~ *denotes trade mark
~ '
