Note: Descriptions are shown in the official language in which they were submitted.
2~ 87~9
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FABRIC SOFTENING COMPOSITION
The present invention relates to fabric softening
compositions suitable for softening fabrics in the rinse
step of a fabric laundry process.
It has been proposed in DE 33 12 328 (BENCKISER) to
prepare fabric softening compositions comprising a
combination of fabric softening materials and organic
acids, in specific polycarboxylic acids. The compositions
as disclosed in this document, however, are of low active
levels of up to about 10% by weight. These compositions
of low active level are of lamellar structure, wherein the
molecules of the fabric softening material form an
onion-like configuration comprising concentric flayers of
softening material, between which is trapped an aqueous
phase containing the dissolved acid ingredient. By
increasing the active level of these formulations, an
onset of instability and/or gel formation is observed when
the active level exceeds a certain critical level of about
13% by weight of the composition. Therefore up till now
it was believed to be impossible to formulate stable
fabric softening compositions containing high levels of
fabric softening materials in combination with organic
- 2 - C7185
acids.
Surprisingly, it has now been found that by further
increasing the active level of these compositions, a
second class of stable liquid fabric softening
compositions can be made. These compositions,
unexpectedly are isotropic, they do not comprise a
structure of active ingredients. These isotropic
compositions are preferred over lamellar compositions in
that they are more resistant to temperature fluctuations,
and they allow a more flexible use of ingredients.
Accordingly, the present invention relates to
isotropic liquid fabric softening compositions comprising
(i) at least 20% by weight of a fabric softening
material î and
it at least 5% by weight of an organic acid.
Preferably the isotropic compositions of the present
invention are clear or translucent. Softening
compositions which are clear are sometimes particularly
appreciated by the consumex, because of their fresh and
natural appearance. Clear compositions can be made by
ensuring that all ingredients of the composition are
completely dissolved in the liquid phase.
The fabric softening material
Compositions according to the invention contain at
least 20% by weight of a fabric softening mat rial. This
material may be selected from cationic, nonionic and
amphoteric softening materials, and mixtures thereof.
2~7~91
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Suitable cationic fabric softener materials include
water-insoluble cationic materials having a solubility in
water at pi 2.5 and 20C of less than lOg/l. Highly
preferred materials are cationic quaternary ammonium salts
having two C12_14 hydrocarbyl chains.
Well-known species of substantially water-insoluble
quaternary ammonium compounds have the formula
N \ l X
l R R4 J
wherein Rl and R2 represent hydrocarbyl groups 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.
epresentative examples ox these quaternary softeners
include ditallow dimethyl ammonium chloride; ditallow
dimethyl ammonium methyl sulfate; dihexadecyl dimethyl
ammonium chloride; di(hydrogenated tallow) dimethyl
ammonium methyl sulfate; dihexadecyl diethyl ammonium
chloride; di(coconut) dimethyl ammonium chloride.
Ditallow dimethyl ammonium chloride, di~hydrogenated
tallow) dimethyl ammonium chloride, di(coconut~ dimethyl
ammonium methosulfate are preferred.
Suitable materials also include dialkyl ethoxyl
methyl ~mmonium methosulphate based on soft fatty acid,
7 g`$
- 4 - C7185
dialkyl ~thoxyl methyl ammonium methosulphate based on
hard fatty acid, and a material in which R3 and R4
represent methyl, Rl is C13 15' R2 is CH~CH20COR, where R
is stearyl, and X is methosulphate. Materials in which
R2, R3 and R4 each represent methyl, R1 is the group
O O
I
CH2 CH CH2
I
O C R
where R is hardened tallow and X is methosulphate or R2 is
methyl,
R3 and R4 each represent -CH2-O-C-R, where R is hardened
tallow, R1 is CH2CH2OH and X is methosulphate are also
suitable.
Preferably cationic softeners are used which have an
active melting point (transition from Lb to L state of
less than 25C, more preferred less than 20C. Examples
of these materials are di-unhardened-tallow dimethyl
ammonium chloride end di coconut dimethyl ammonium
chloride.
Other preferred cationic compounds include those
materials as disclosed in EP 239,gl0 (P&G), which is
included herein by reference. / ,-~
7 9
I- 5 - C7185
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.
Other preferred materials are the materials of
formula
R5 C - O - CH2-CH2 N+ CH2-CH2-OH
/ \ CH3SO4
R5 C - O - CH2-CH2 c~3
R5 being talow, which is available from Stepan under the
tradename Stepantex VR~ 9O
and
R6COOCH2
/ CH--S~H2N R8RgRloX
/
R7COO
where R~, R9 and R1o are each alkyl or hydroxyalkyl groups
containing from 1 to 4 carbon atoms, or a benzyl group.
i~6 and R7 are Mach an alkyl or alkenyl chain containing
from 11 to 23 carbon atoms, and X is a water soluble
anion, substantially free of the corresponding monoester.
2 7 8
- 6 - C7185
Another class of preferred water-insoluble cationic
materials are the hydrocarbylimidazolinium salts believed
to have the formula:
CH CH2
O
+ 11
N C \ R12 A-
R13
R14
wherein R13 is a hydrocarbyl group containing from 1 to 4,
preferably 1 or 2 carbon atoms, R11 is a hydrocarbyl group
containing from 8 to 25 carton atoms, R14 is an
hydrocarbyl q~oup 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.
Preferred imida~olinium salts include l-methyl-~-
(tallowylamido-) ethyl -2-tallowyl-4,5-dihydro
imidazolinium methosulfate and 1-methyl-1-
(palmitoylamido) ethyl -2-octadecyl-4,5-dihydro-
imidazolinium chloride. Other useful imidazolinium
materials are 2-heptadecyl-1-methyl-1- (2-stearylamido)-
ethyl-imidazolinium chloride and 2-lauryl-1-
hydroxyethyl-1-oleyl-imidazolinium chloride Also
suitable herein are the imidazolinium fabric softening
components of US patent No 4 127 489, incorporated by
reference.
2~ ~7~
- 7 - C7185
Representative commercially available materials of
the above classes are the quaternary ammonium compounds
Arquad 2HT (ex AKZO); Noramium M2SH (ex CEKA); Aliquat-
2HT (Trade Mark of General Mills Inc), Stepantex Q185 (ex
Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex
Stepan); Synprolam FS (ex ICI) and the imidazolinium
compounds Varisoft 475 trade Mark of Sherex Company,
Columbus Ohio) and Rewo~uat W7500 (Trade Mark of REWO).
The fabric softening materials may also comprise
instead of or in addition to cationic fabric softening
agents, one or more amines.
The term "amine" as used herein can refer to
(i) amines of formula
~15
I
R16 N (I)
I
R17
wherein R15 Rl~ and ~17 are defined as below;
(ii) amines of formula
,
118 120
R19 N _ (CH2)n - ON - - R
. (II) m
7g`9
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wherein R18l Rlg, R20 and R~l, m and n are defined as
below.
(iii)imidazolines of formula
CH2 -- CH2
1 1
N N - 2 4 1 - - C _ _ R
C R12
I
14 III
Rll, R12 and R14 are defined as above.
(iv) condensation products formed from the reaction of
fatty acids with a polya~ine 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), incorporated herein by
reference.
When the amine is of the formula I above, R15 is a C6
to C24, hydrocarbyl group, R16 is a Cl to C24 hydrocarbyl
group and R17 is a C1 to C10 hydrocarbyl group. Suitable
amines include those materials from which the quaternary
ammonium compounds disclosed above are derived, in which
R1s is R1~ R16 iS R2 and R17 is R3. Preferably, the amine
is such that both R15 and R16 are C6-C~ alkyl with
C16-C18 being most preferred and with R17 as C1 3 alkyl,
or R15 is an alkyl or alkenyl group with at least 22
carbon atoms and R16 and R12 are Cl 3 alkyl. Preferably
:L 8 & 9
- g - C7185
these amines are protonated with hydrochloric acid,
orthophosphoric acid (OPA), C1 5 carboxylic acids or any
other similar acids, for use in the fabric conditioning
compositions of the invention.
When the amine is of formula II above, R18 is a C6 to
C24 hydrocarbyl group, R19 is an alkoxylated group of
formula ~tCH2CH20)yH, where y is within the range from 0
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
13. 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 a y
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.
Preferably the amines of type (ii) or lit are also
protonated for use in the fabric conditioning compositions
of the invention.
When the amine is of type (iv) given above, a
particularly preferred material is
2~7~
I- 10 - ~7185
/ R22H
23 N
O / \ O
11/ \11
24 C--R
where R22 and R23 are divalent alkenyl chains having from
1 to 3 carbons atoms, and R24 is an acyclic aliphatic
hydrocarbon chain having from 15 to 21 carbon atoms. A
commercially available material of this class is Ceranine
HC39 (ex Sandoz).
Alkoxylated fatty amides or amines may also be used
as fabric softening materials in compositions of the
invention. Suitable materials are for instance disclosed
in EP 159 921 (Unilever) and EP 159 919 (Unilever). The
fabric softening material may also comprise instead of or
in addition to the above mentioned softening materials one
or more fabric substantive amphoteric fabric softening
materials. Suitable amphoteric materials form a
particulate dispersion at a concentration of less than
lg/l at least one temperature between 0 and 100C. For
the purpose of this invention a fabric substantive
amphoteric material is preferably an amphoteric or
zwitterionic tertiary or quaternary ammonium compound
having either one single very long hydrocarbyl side chain
or two long hydrocarbyl chains. From these compounds the
use of amphoteric or zwitterionics ammonium compounds
having two long hydrocarbyl chains is particularly
preferred for many reasons including costs, ease of
processing and better stability and performance.
2~ 78;~
C7185
Amphoteric or zwitterionic ammonium compounds
preferably have two long hydrocarbyl chains, each chain
having ~-24 C-akoms, preferably 10-20 C-atoms, most
preferred around 16 C-atoms.
Suitable amphoteric fabric substantive materials for
use in a fabric treatment composition according to the
invention are for instance: ampholytes, hydrocarbyl
betaines, hydrocarbylamide betaines, glycinates,
propionates and tertiary amine oxides. These materials
are described in our co-pending patent application
EP 89200545.5.
Particularly preferred amphoteric softening materials
are tertiary amine oxides of the following formula
131
~27 ---(CH2)q N t R26
O O Ir
wherein:
a) R25 and R26 are C8 25 hydrocarbyl chains, R27 is an
hydrocarbyl group containing 1-4 carbon atoms or a
g P (CH2~C~2)nH~ R28~ R29, R30 are -(CH2)-, which
can be interrupted with -O-, -CONH-, -COO- etc, R31
is R27, r is 0 or 1, n is an integer from 1-6, X, Y
are SO3, SO or COO ;
or
b) R25 is a C16~50 hydrocarbyl chain, R26, R~7 are
hydrocarbyl groups containing 1-4 carbon atoms or a
2~87~
- 12 - C7185
g P ( H2CH2)nH R28~ R29, R30 are -(CH2)n- which
can be interrupted by -O-, -COHN-, -COO-, etc, R31 is
R27, r is Q or 1, n is an integer from 1-6, X, Y are
SO3, So2 or COO-.
Preferably the amphoteric fabric substantive
materials are water soluble and have a solubility in water
at pH 2.5 at 20~C of less than 10g/1.
The HLB of the amphoteric fabric substantive material
is preferably less than 10Ø
xamples ox amphoteric materials of the above groups
and their method of preparation are given in our
co-pending European patent application 89200113.2.
The compositions may also contain, instead of or in
addition to the above mentioned fabric softening agents,
non-cationic fabric softening agents, such as nonionic
fabric softening agents. Suitable nonionic fabric
softening agents, include glycerol estersl such as
glycerol mono stearate, fatty alcohols, such as stearyl
alcohol, alkoxylated fatty alcohols Cg-C24 fatty acids
such as Dobanol 91-6 (SHELL) and lanolin and derivatives
thereof. Suitable materials are disclosed in European
Patent Application 88 520 (Unilever PLCfNV case C1325),
122 141 (Unilever PLC/NV case C1363) and 79 746 (Procter
and Gamble, the disclosure of which are incorporated
herein by reference.
Preferably compositions of the invention contain at
least Rome cationic fabric softPning materials.
Preferably at least 50% of the fabric softening material
is a cationic fabric softener material.
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Thy total level of softening material is more than
20% by weight, more preferred more than 30% by weight,
most preferred more than 35% by weight of the composition.
Generally the total level of softening materials in the
composition will be less than 70~ by weight, more
preferred less than 60% by weight, typically between ~0
and 50% by weight.
Preferably, the compositions of the present invention
contain substantially no anionic material, in particular
no anionic surface active material. If such materials are
present, the weight ratio of the cationic fabric softening
agent to the anionic material should preferably be more
than 5.1.
The organic acid material
The organic acid material for use in compositions of
the present invention may be selected from the group of
mono-, di-, tri- or polycarboxylic acids preferably having
a total number of carbon atoms of 8 or less, preferably 4
or less.
- Examples of suitable organic acid materials are
succinic acid, malic acid, tartaric acid, citric acid,
glutaric acid, acetic acid, propionic acid, and lactic
acid or mixtures thereof. For obtaining stable products
within a wide range of concentrations, the use of lactic
acid and acetic acid is preferred. For obtaining products
with a particularly interesting appearance and good colour
stability it is preferred to use citric acid.
The level of acid material in the composition
calculated on an anhydrous basis) of the acid material,
is at least 5% by weight of the composition more preferred
7~
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more than 10~. Generally the level of acid material will
be less than 50%, more preferred less than 40%, typically
between 15% and 35% by weight of the composition.
Qptional inqredients
The composition can also contain one or more optional
ingredients selected from non-aqueous solvents such as
Cl-C4 alkanols and polyhydric alcohols, pH suffering
agents, rewetting agents, viscosity modifiers such as
electrolytes, for example calcium chloride, antigelling
agents, perfumes, perfume caxriers, ~luorescers,
colourants, hydrotropes, antifoaming agents, hydrocarbons,
antiredeposition agents, enzymes, optical brightening
agents, opacifiers, stabilisers such as guar gum and
polyethylene glycol, emulsifiers, anti-shrinking agents,
lanolin or lanolin like materials, 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 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, are each
present at levels up to 5~ by weight of the composition,
except for the hydrocarbons and the non-a~ueous solvents
which may be included at levels of up to 30%. The pH of
the composition is preferably below the pK of the organic
acid, more preferred at least one unit below the pK,
typically between 2.0 and 5Ø
Soil-release agents particularly preferred in the
compositions according to the invention are polymers.
- 15 - C7185
Suitable polymers include alkyl and hydroxyalkyl cellulose
ethers, such as methyl cellulose, and
polyvinylpyrrolidone.
Silicones can be included in the compositions as the
ironing aid, rewetting agent or the antifoaming agent.
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.
Fatty acid materials or other nonionic extenders can
also be included in compositions of the present invention.
Suitable materials and their amounts are for instance
disclosed in EP 13780 (P&G~ and DE 29 43 606 (Unilever).
The balance of the composition is preferably water.
Although water-free systems are also within the ambit of
the invention, preferably the amount oP water in the
composition is more than 20~ by weight, more preferred
more thall 25% by weight. Generally the water level will
be less than 70~, more preferred less than 60%, most
preferred less than 55%, typically between 55% and 25%.
The viscosity of the product is preferably less than
250 mPas at 106 5-1.
In use compositions of the present invention may be
prediluted or dosed in concentrated form into the rinse-
cycle of a fabric washing process. Prefsrably the
material is used at a concentration of between 0.01 and
2g/ll especially betweerl 0.1 and lg/l.
;7~
. - 16 - C7185
The invention will be further illustrated by means of
the following examples:
Example I
Fabric softening compositions containing water,
tartaric acid (on a dry basis) and a cationic fabric
softening material Prapagen 3445 ~70% di-unhardened tallow
di-methyl ammonium chloride 20% isopropylalcohol, 10%
water) were prepared by mixing under light agitation,
For each composition the structure and appearance
were assessed, the results are given in table 1, and
graphically expressed in figure 1.
2~8~89
- 17 - C7185
WATER/
PRAPAGEN/
COMPOSITION TARTARIC (%) RESULT
_______ _____. _________________ _______________________
1. 80/10/10 lamellar/milky
2. 70/10/20 lamellar/milky
3^ 60/10/30 lamellar/milky
4. 50/10/40 lamellar/milky
5. 40/10/50 gel
6. 70/20/10 gel
7. 60/20/20 gel
8. 50/20/30 gel
9. ~0/20/40 gel
10. 60/30/10 gel
11. 50/30/20 gel
12. 40/30/30 isotropic/clear
13. 30/30/40 phase separation
14. 50/40/10 gel
15. 40/40/20 isotropic/clear
16. 30/40/30 phase separation
17. 20/40/40 phase separation
18. 40/50/10 isotropic/clear
19. 30/50/20 isotropic/clear
(some phase separation)
Those examples clearly show that lamellar/milky
products are formed at low active concentrations; by
increasing the active level, unacceptable gelled products
are obtained, but surprisingly by further increasing the
active levels isotropic/clear compositions can be obtained
(compoisitions 12 t 15, 18 and 19 according to the present
invention).
go
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Example II
Example 1 was repeated while tartaric acid was
replaced my citric acid. The results are expressed in
table 1 and figure 2.
WATER/
PRAPAGEN/
COMPOSITION CITRIC (%) RESULT
_______________________________~___________________ ____
20. 80/10/10 lamellar/milky
21. 70/10/20 lamellar/milky
22. 60/10/30 lamellar/milky
23. 50/10/40 gel
24. 70/20/10 gel
25. 60/20/20 gel
26. 50/20/30 gel
27. 40/20/40 gel
28. 60/30/10 gel
29. 50/30/20 gel
30, 40/30/30 isotropic/clear
31. 30/30/40 phase separation
32. 50/~0/10 isotropic/clear
33. 40/40/20 isotropic/clear
34. 30/40/30 isotropic/clear
35. 40/50/10 phase separation
3~. 30/50/20 phase separation
Again, surprisingly isotropic liquids according to
the invention (Compositions 30, 32, 33, 34) can be
formulated by increasing the lavel of fabric softening
materials. Especially interesting was the clear natural
yellow appearance of the product, no decolouration was
observed during storage.
~878~
- 19 - C7185
EXAMPLE III
Example I was repeated while replacing tartaric acid
by acetic acid ox by lactic acid.
By using acetic acid isotropic/clear compositions
could be formulated even at levels of PRAPAGEN of 50% or
more. At lower concentrations a similar behaviour as
observed for tartaric acid was observed: lamellar systems
at low concentrations, and gelled systems at intermediate
concentrations of softening material.
By using lactic acid, similar results as with acetic
acid are observed. This indicates that for stability
reasons, especially at high levels of softening materials
the use of acetic acid and lactic acid is preferred.
EXAMPLE IV
By replacing tartaric acid by propionic acid
isotropic/clear compositions can be formulated even at
levels of acid as low as 5%. Typical formulations are:
Formulation % by weight
A B C D
Arquad 2T 40 40 40 40
Isopropylalcohol 0 5 11 0
Propylene glycol 10 10 10 0
Propionic acid10 10 5 30
Water - balance - -
