Note: Descriptions are shown in the official language in which they were submitted.
~o~~~~~
- 1 - C7193
FABRIC SOFTENING
The present invention relates to a fabric softening
composition, in particular to an aqueous based fabric
softening composition containing one or more amines as
active materials.
It is known to treat fabrics, particularly after
washing, with fabric softening agents in order to improve
the feel of the fabrics and, in the case of clothes, to
improve comfort in wear. Traditionally, fabric softening
agents are applied from an aqueous liquor which is made up
by adding a relatively small volume of a fabric softening
composition to a large volume of water, for example during
the rinse cycle in an automatic washing machine. The
fabric softening composition is usually an aqueous liquid
product containing ~. cationic fabric softening agent, most
typically a quaternary ammonium salt such as ditallow
dimethyl ammonium chloride.
For a number of reasons it would be preferred if
alternative softeners to the quaternary ammonium salts
could be used in aqueous liquid products for example to
~n~~.~28
- 2 - C7193
replace or partially replace the quaternary ammonium salts
with softeners which are most environmentally friendly or
less costly, easier to handle or less prone to causing
skin reaction. However this replacement or partial
replacement with alternative softeners should maintain or
substantially maintain the softening performance of the
product.
Amine fabric softening agents provide a potential
solution to these problems however, one of the problems of
amine containing fabric softener compositions for use in
the rinse is that they often do not soften as well as
compositions comprising quaternary ammonium softener
materials.
EP 0 043 622A (Procter and Gamble) discloses certain
concentrated fabric softening compositions comprising
water-insoluble imidazoline salts and a viscosity control
system.
EP 0 194 127 (Procter and Gamble) discloses a certain
fabric softening composition comprising a tertiary amine
softener and a soil release polymer for application to
fabrics in a tumble dryer.
GB 2 192 909 (Colgate-Palmolive) discloses certain
detergent compositions for fabric washing which can
comprise amine complexes to soften during the wash.
It is an object of the present invention to formulate
fabric softening compositions comprising one or more
amines as the active materials. It is a further object of
the present invention to provide fabric softening
compositions which are environmentally acceptable.
It has now been found that the softening performance
of amine containing fabric softener compositions can
2!721 12$
- 3 - C7193
significantly be improved by incorporation of fatty acid
materials in the composition. Furthermore compositions of
the invention have the advantage that they can easily be
prepared and that they are of acceptable stability and
viscosity.
Accordingly the present invention relates to a fabric
conditioning composition comprising an amine softener
material, a non-saponified fatty acid material and a buffer acid, the
pH of the composition being less than 6.5.
The term "amine" as used herein can refer to any
amine material which can be used for the softening of
fabrics, for example one or more amines of the following
formula can be used:
(i) amines of formula
I 15
R16 N (I)
R17
wherein R15, R16 and R17 are defined as below;
(ii) amines of formula
R1$ R20
R19 N (CH2)n N R21
(II) m
i$
2~ ~ ~ 128
- 4 - C7193
wherein R18, R19, R20 an3 R21, m and n are defined as
below.
(iii) imidazolines of formula
CH2 CH2
O
N N C2H4--N--C--R11
C R12
R14 III
wherein R11, R12 and R14 are defined as below.
(iv) condensation products formed from the reaction of
fatty acids with a polyamine selected from the group
consisting of hydroxy alkylalkylenediamines and
dialkylenetriamines and mixtures thereof. Suitable
materials are disclosed in European Patent Application
199 382 (Procter and Gamble).
When the amine is of the formula I above, R15 is a C6
to C24, hydrocarbyl group, R16 is a C1 to C24 hydrocarbyl
group and R1~ is a C1 to C10 hydrocarbyl group. Suitable
amines include those materials wherein both R15 and R16
are C6-C20 alkyl with C16-C18 being most preferred and
with R1~ as C1-3 alkyl, or R15 is an alkyl or alkenyl
group with at least 22 carbon atoms and R16 and R12 are
C1-3 alkyl.
When the amine is of formula II above, R18 is a C6 to
C24 hydrocarbyl group, R19 is an alkoxylated group of
formula -(CH2CH20)yH, where y is within the range from 0
'~~ 1 12~
- 5 - C7193
to 6, R20 is an alkoxylated group of formula -(CH2CH20)zH
where z is within the range from 0 to 6 and m is an
integer within the range from 0 to 6, and is preferably 3.
When m is,0, it is preferred that R18 is a C16 to C22
alkyl and that the sum total of z and y is within the
range from 1 to 6, more preferably 1 to 3. When m is 1,
it is preferred that R18 is a C16 to C22 alkyl and that
the sum total of x and y and z is within the range from 3
to 10.
Representative commercially available materials of
this class include *Ethomeen (ex Armour) and *Ethoduomeen
(ex Armour).
When the amine is of formula (III), R11 is a
hydrocarbyl group containing from 8 to 25 carbon atoms,
R14 is an hydrocarbyl group containing from 8 to 25 carbon
atoms and R12 is hydrogen or an hydrocarbyl containing
from 1 to 4 carbon atoms and A is an anion, preferably a
halide, methosulfate or ethosulfate.
It is highly preferred that the amines of the types
(i), (ii) or (iii) are protonated for use in the fabric
conditioning compositions of the invention. Preferably
acids with a buffer action are used to effect protonation
and diminish the unwanted effects of anionic actives
carried over from the main wash. Suitable buffer acids
for use in the invention are citric acid, phosphoric acid,
hydrochloric acid, sulphuric acid and benzoic acid.
Preferred buffer acids are citric and phosphoric acids.
The amine and buffer acid may be used in a molar ratio of
from 5:1 to 1:10 amine to buffer acid but preferably the
buffer acid is used in molar excess to the amine so that
molar ratios of from 1:1 to 1:10 are preferred.
*denotes trade mark
11 12~
- 6 - C7193
Preferred amine materials are materials of formula
(i), which comprise two long alkyl groups and one short
alkyl group. Especially preferred is the use of
dihardened tallow methyl amine, as marketed under the
trade mark ARMEEN M2HT (Atlas).
In this specification the expression hydrocarbyl
group refers to alkyl or alkenyl groups optionally
substituted or interrupted by functional groups such as
-OH, -O-, -CONH, -COO-, etc.
The level of amine softener materials is preferably
more than 1% by weight of the composition, more preferred
more than 2%, most preferred more than 3%. Preferably the
level of amine softener materials will not exceed 70% by
weight of the composition, more preferred the level is
less than 30%, especially preferred are compositions
comprising from 3 to 20% by weight of amine softener
materials.
The fatty acid material or salt thereof, can be any
mono-, di- or tri-carboxylic acid comprising an alkyl or
alkenyl chain having from 8 to 28 carbon atoms or salts
thereof. Preferred fatty acid materials or their salts
may be represented by the formula:
R1COOR2
wherein R1 is a straight or branched alkyl or alkenyl
chain having from 8 to 2E carbon atoms, and wherein R2 is
hydrogen or a cation. Preferred cations are alkali metal
ions or alkali earth metal ions, more preferred sodium,
potassium or calcium.
~~~~~28
- C7193
Preferred is the use of a non saponified fatty acid
material. Especially preferred is the use of free fatty
acids having a chain length of from 12 to 18, such as
oleic acid, lauric acid, tallow fatty acid etc.
Preferably the level of fatty acid material is more
than 0.1% by weight of the composition, more preferred
more than 0.2%, especially preferred are systems
comprising more than 0.5% of fatty acid material. The
level of fatty acid material will usually not exceed 50%
by weight of the composition, more preferred the level of
fatty acid material is less than 30%, typically from 0.5
to 10% by weight of the composition.
The weight ratio of amine softening material to fatty
acid material is preferably from 10:1 to 1:10, more
preferred from 9:1 to 1:1, most preferred from 7:1 to 3:1.
Surprisingly it has been found that compositions
according to the invention can be further improved by
incorporating therein a nonionic material of specific HLB
value. Preferred nonionic materials for use in
compositions of the invention have an HLB value in the
range from 7.0 to 21.0, more preferred from 9.0 to 19.0,
especially preferred from 10.0 to 18Ø It is believed
that the nonionic materials may contribute in two ways to
a quality improvement of the compositions of the
invention: firstly the softening per~eoraaance may be
enhanced and secondly the viscosity of the product is
decreased.
It has also been found that nonionic materials of
relative low HLB are especially useful for use in
compositions of low active level, while compositions of
high active level preferably comprise nonionic materials
of relative high HLB. Preferably compositions, wherein
2!~2~.~.28
- 8 - C7193
the total level of amine and fatty acid material is from 5
to 10% by weight of the composition comprise a nonionic
material having an HLB of between 9.0 and 13.0;
compositions wherein the active level is from 10-15% by
weight of the composition, preferably comprise a nonionic
material of HLB between 11.5 and 16.5. An active level of
15-20% by weight corresponds to a preferred HLB value of
from 14.0-19.0; compositions of active level between 20
and 25% preferably comprise a nonionic material of HLB of
between 16.5 and 21Ø Preferred nonionic materials are
alkoxylated fatty alcohols, preferably containing a fatty
alcohol having from 8-28 carbon atoms, said alcohol being
ethoxylated with from 2-50, preferably from 4-40
ethoxy-groups.
Preferably the level of nonionic material is more
than 0.1% by weight of the composition, more preferred
more than 0.2%, especially preferred are systems
comprising more than 0.5% of nonionic material. The level
of nonionic material will usually not exceed 50% by weight
of the composition, more preferred the level of nonionic
material is less than 30%, typically from 0.5 to 10% by
weight of the composition.
Surprisingly it has been found that a further
improvement in the softening performance can be obtained
by incorporating a fatty acid ester material of a short
chain polyol into the fabric conditioning composition of
the invention. The ester materials for incorporation into
a product of the present invention is preferably a mono-
di- or triester of a C1-5 polyol with a fatty acid
material. Preferably the polyol is ethylene glycol,
glycerol or propylene glycol. Preferred fatty acid
materials comprise an alkyl or alkenyl chain of from 8 to
28 carbon atoms, preferably from 12 to 20 carbon atoms.
- 9 - C7193
Especially suitable are fatty acid materials selected from
lauric acid, tallow fatty acid, hardened tallow fatty
acid, coconut fatty acid, stearic acid or mixtures
thereof .
Particularly preferred are the di-esters of fatty
acid materials and polyols. Especially the di-fatty acid
of ethylene glycol. Specifically preferred is the use of
ethylene glycol distearate.
Preferably the level of fatty ester materials is more
than 0.1% by weight of the composition, more preferred
more than 0.5%. Preferably the level of fatty ester
material does not exceed the 30%, more preferably the
level is less than 20%, most preferred between 0.7 and
10%.
Compositions of the present invention may comprise in
addition to the above mentioned amine, fatty acid and
optional materials one or more other softener materials
selected from cationic, amphoteric and nonionic softening
materials. Suitable materials are for example described
in EP 239 910 (P&G), US 3 915 865 (STEPAN) and
US 4 137 180 (Lever Brothers). Preferably the weight
ratio of these additional softening materials to the total
of the two above mentioned essential softening materials
is less than 3:1, more preferred less than 1:1, especially
preferred less than 0.5:1.
Compositions of the present invention may take a
variety of forms such as liquids, pastes and gels.
Preferably compositions of the present invention are
liquids, comprising an aqueous phase. Preferably the
water level in such aqueous liquids is from 97 to 20% by
weight of the composition, more preferred from 95 to 70%.
2!~~1 129
- 10 - C7193
The composition can also contain one or more optional
ingredients selected from non-aqueous solvents such as
C1-C4 alkanols and polyhydric alcohols, rewetting agents,
viscosity modifiers such as electrolytes, for example
calcium chloride, antigelling agents, perfumes, perfume
carriers, fluorescers, colourants, hydrotropes,
antifoaming agents, antiredeposition agents, enzymes,
optical brightening agents, opacifiers, stabilisers such
as guar gum and polyethylene glycol, emulsifiers,
anti-shrinking agents, anti-wrinkle agents, fabric
crisping agents, anti-spotting agents, soil-release
agents, germicides, linear or branched silicones,
fungicides, anti-oxidants, anti-corrosion agents,
preservatives such as *Proxel, ascoric acid, 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.
These optional ingredients, if added, preferably are
present at levels up to 5% by weight of the composition.
The liquid compositions according to the inventions
may be prepared by a variety of methods. One suitable
method is to form a molten mixture of the amine materials
and the fatty acid materials eventually in combination
with other softening materials, and adding this premix to
water under stirring to form a dispersion and thereafter
adding any optional ingredients.
Compositions of the present invention preferably have
a pH of less than 7.0, more preferred less than 5.0,
especially preferred are compositions which have a pH of
between 2.0 and 4.0, especially from 3.0 to 4Ø
*denotes trade mark
~U~~~?~
- 11 - C7193
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
amine compound and the fatty acid ester compound in this
liquor will be between about 30ppm and 1000ppm. The
weight ratio of the fabrics to liquor will generally be
between 1:1 to 1:10.
Surprisingly it has also been found that a decrease
in the pH in the rinse liquor provides a further increase
in softening performance of compositions of the invention.
The pH of a rinse liquor comprising the amine and fatty
acid materials in a total concentration of from 30 to
1000ppm (preferably around 200ppm) is preferably less than
6.5, more preferred less than 6Ø This low pH is
preferably effected by acidifying ingredients such as
phosphoric or citric acid which are already present in the
fabric softener; if necessary, however, separate
ingredients may be added to the rinse water for lowering
the pH.
The invention will be further illustrated by means of
the following examples.
The following compositions were made by pre-heating a
mixture of amine, fatty acid and nonionic and dispersing
the mixture in water. In all the examples the amine
materials were protonated with an equimolar amount of
citric acid. The compositions were tested by adding 2g of
the compositions to 1 litre of water (11 FH) and rinsing
therein 3 pieces of terry towelling (total weight 48g) for
5 minutes at 100 rpm. The pieces of cloth were line dried
~~ ~ 112
- 12 - C7193
and assessed for softness by a trained panel of 8 persons.
A higher score indicates a better softening.
INGREDIENT ($wt) ~ $ S
Armeen M2HT 6.4 6.0 7.5
Fatty acid 1) 1.1 1.5 --
nonionic 2) 1.1 1.5 --
softening score 0.25 0.48 -0.36
1) Hardened tallow fatty acid
2) coconut alcohol ethoxylated with 5E0 groups (HLB 10)
These results clearly show an increase in performance
for softening compositions which comprise amines in
combination with fatty acid materials.
$XAMPLE 2
Composition D was prepared as in example 1 and
compared to a commercially available rinse conditioner
containing a conventional dihardened tallow dimethyl
ammonium chloride softener material. A 2.5kg load of
terry towelling was washed at 60°C in an AEG *Lavamat570
with water of 26 FH in the presence of 100g *Persil
Automatic (UK). To the last rinse cycle of the washing
process an amount of softener material was added
corresponding to the indicated levels of active material.
The cloths were line dried and assessed for softness by a
trained panel of 8 persons; a higher softness indicates a
better softening.
*denotes trade mark
Gtr
~ ~ ~ 1 12'. $
- 13 - C7193
INGREDIENT (%wtZ Q
Armeen M2HT 6.0
fatty acid 1) 1.5 --
nonionic 2) 1.5 --
*DTDMAC --
4.5
grins active 3) 4 7 10 4 7 10
softening score 2.7 5.1 5.2 4.0 4.8 5.3
1j Hardened tallow fatty acid
2) coconut alcohol ethoxylated with 5E0 groups (HLB 10)
3) for composition D the total amount of amine plus fatty
acid per rinse, for compositions E the total amount of
DTDMAC per rinse.
This example shows that, surprisingly amine
containing softening compositions can be formulated which
are almost as effective as commercial available softener
materials comprising environmentally less preferred
quaternary ammonium materials.
EXAMPLE 3
Compositions F and G were prepared as in example 1,
and compared to a commercially available softener material
on the basis of dihardened tallow dimethyl ammonium
chloride. A 2.5kg load of desized terry towelling cloths
was washed at 60°C in a Siemens washing machine with water
of 26 FH in the presence of 100g of Persil Automatic (UK).
100g of the compositions F-H was added to the last rinse
cycle, the cloths were line dried and assessed for
softness by a trained panel of 8 members, a higher
softening score indicates a better softening.
*ditallowdimethylammonium chloride
X
202128
- 14 - C7193
INGREDI ENT ~( $wt ) E
Armeen M2HT 6.0 5.2 --
fatty acid 1) 1.5 1.3 --
nonionic 2j 1.5 1.3 --
EGDS 3j -- 1.0 --
citric acid 4) i.o 1.0 --
DTDMAC -- -- 4.5
softening score 0.01 0.65 -0.87
1) Hardened tallow fatty acid
2) coconut alcohol ethoxylated with 5E0 groups (HLB 10)
3) ethylene glycol distearate
4) amount of citric acid on top of the citric acid used
for protonating the amine.
These results clearly illustrate that the addition of
a polyol ester further increases the softening performance
of compositions of the invention.
The following compositions were prepared as in
example 1 and tested as in example 3.
~Q~~~~~
- 15 - C7193
s~ $
Armeen M2HT 6.0 6.0 6.0
Fatty acid 1) 1.5 1.5 1.5
nonionic 2) 1.5 1.5 1.5
citric acid 4) 3.0 4.25 8.0
pH (in rinse) 6.5 5.9 4.9
softening score -0.38 0.12 0.33
1) Hardened tallow fatty acid
2) coconut alcohol ethoxylated with 5E0 groups (HLB 10)
4) amount of citric acid on-top of the citric acid used
for protonating the amine.
This example illustrates that by lowering the pH in
the rinse water, a better softening can be obtained.
The following compositions were prepared as in
example 1. The viscosity of the products was measured at
110 s-1.
221128
- 16 - C7193
TNGREDTENT l$~~)
Armeen M2HT 12.0 12.0 13.0 13.0
fatty acid 3) 3.0 3.0 2.0 2.0
nonionic 1 1) 3.0 -- 2.0 -
nonionic 2 2) -- 3.0 -- 2.0
CaCl2 0.01 0.01 0.01 0.01
viscosity MPa.s 40 275 25 275
1) coconut alcohol ethoxylated with 20E0 groups (HLB 16)
2) coconut alcohol ethoxylated with 5E0 grops (HLB 10)
3) hardened tallow fatty acid
These results illustrate that for obtaining products
of low viscosity, preferably at high active levels a
highly ethoxylated nonionic of relative high HLB is used.
