[0001] The present invention relates to fabric softening compositions suitable for softening
fabrics in the rinse step of a fabric laundry process.
[0002] 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 bilayers 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 acids.
[0003] 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.
[0004] Accordingly, the present invention relates to isotropic liquid fabric softening compositions
comprising
(i) at least 20% by weight of a fabric softening material; and
(ii) at least 5% by weight of an organic acid.
[0005] Preferably the isotropic compositions of the present invention are clear or translucent.
Softening compositions which are clear are sometimes particularly appreciated by the
consumer, 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
[0006] Compositions according to the invention contain at least 20% by weight of a fabric
softening material. This material may be selected from cationic, nonionic and amphoteric
softening materials, and mixtures thereof.
[0007] Suitable cationic fabric softener materials include water-insoluble cationic materials
having a solubility in water at pH 2.5 and 20°C of less than 10g/l. Highly preferred
materials are cationic quaternary ammonium salts having two C₁₂₋₁₄ hydrocarbyl chains.
[0008] Well-known species of substantially water-insoluble quaternary ammonium compounds
have the formula

wherein R₁ 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.
[0009] Representative examples of 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.
[0010] Suitable materials also include dialkyl ethoxyl methyl ammonium methosulphate based
on soft fatty acid, dialkyl ethoxyl methyl ammonium methosulphate based on hard fatty
acid, and a material in which R₃ and R₄ represent methyl, R₁ is C₁₃₋₁₅, R₂ is CH₂CH₂OCOR,
where R is stearyl, and X is methosulphate. Materials in which R₂, R₃ and R₄ each
represent methyl, R₁ is the group

where R is hardened tallow and X is methosulphate or R₂ is methyl,
R₃ and R₄ each represent
-CH₂-

-C-R, where R is hardened tallow, R₁ is CH₂CH₂OH and X is methosulphate are also suitable.
[0011] Preferably cationic softeners are used which have an active melting point (transition
from Lb to L state) of less than 25°C, more preferred less than 20°C. Examples of
these materials are di-unhardened-tallow dimethyl ammonium chloride and di coconut
dimethyl ammonium chloride.
[0012] Other preferred cationic compounds include those materials as disclosed in EP 239,910
(P&G), which is included herein by reference.
[0013] 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.
[0014] Other preferred materials are the materials of formula

R₅ being talow, which is available from Stepan under the tradename Stepantex VRH
90
and

where R₈, R₉ and R₁₀ are each alkyl or hydroxyalkyl groups containing from 1 to 4
carbon atoms, or a benzyl group. R₆ and R₇ are each 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.
[0015] Another class of preferred water-insoluble cationic materials are the hydrocarbylimidazolinium
salts believed to have the formula:

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 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.
[0016] Preferred imidazolinium salts include 1-methyl-1-(tallowylamido-) ethyl -2-tallowyl-4,5-dihydro
imidazolinium methosulfate and 1-methyl-1-(palmitoylamido) ethyl -2-octadecyl-4,5-dihydroimidazolinium
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.
[0017] 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 Rewoquat W7500 (Trade
Mark of REWO).
[0018] The fabric softening materials may also comprise instead of or in addition to cationic
fabric softening agents, one or more amines.
[0019] The term "amine" as used herein can refer to
(i) amines of formula

wherein R₁₅ R₁₆ and R₁₇ are defined as below;
(ii) amines of formula

wherein R₁₈, R₁₉, R₂₀ and R₂₁, m and n are defined as below.
(iii)imidazolines of formula

wherein R₁₁, R₁₂ and R₁₄ are defined as above.
(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), incorporated herein by reference.
[0020] 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 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 R₁₅ is R₁, R₁₆ is R₂ and R₁₇ is R₃. Preferably, the amine
is such that both R₁₅ and R₁₆ are C₆-C₂₀ 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 C₁₋₃ alkyl. Preferably 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.
[0021] When the amine is of formula II above, R₁₈ is a C₆ to C₂₄ hydrocarbyl group, R₁₉
is an alkoxylated group of formula -(CH₂CH₂O)
yH, where y is within the range from 0 to 6, R₂₀ is an a group of formula -(CH₂CH₂O)
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 alkyl and that the sum
total of x and y and z is within the range from 3 to 10.
[0022] Representative commercially available materials of this class include Ethomeen (ex
Armour) and Ethoduomeen (ex Armour).
[0023] Preferably the amines of type (ii) or (iii) are also protonated for use in the fabric
conditioning compositions of the invention.
[0024] When the amine is of type (iv) given above, a particularly preferred material is

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).
[0025] 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 1g/l at least
one temperature between 0 and 100°C. 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.
[0026] Amphoteric or zwitterionic ammonium compounds preferably have two long hydrocarbyl
chains, each chain having 8-24C-atoms, preferably 10-20C-atoms, most preferred around
16C-atoms.
[0027] 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.
[0028] Particularly preferred amphoteric softening materials are tertiary amine oxides of
the following formula

wherein:
a) R₂₅ and R₂₆ are C₈₋₂₅ hydrocarbyl chains, R₂₇ is an hydrocarbyl group containing
1-4 carbon atoms or a group -(CH₂,CH₂O)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, SO²- or COO⁻;
or
b) R₂₅ is a C₁₆₋₅₀ hydrocarbyl chain, R₂₆, R₂₇ are hydrocarbyl groups containing 1-4
carbon atoms or a group -(CH₂CH₂O)nH-, R₂₈, R₂₉, R₃₀ are -(CH₂)n- which can be interrupted by -O-, -COHN-, -COO-, etc, R₃₁ is R₂₇, r is 0 or 1, n
is an integer from 1-6, X, Y are SO₃, SO²⁻ or COO-.
[0029] 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/l.
[0030] The HLB of the amphoteric fabric substantive material is preferably less than 10.0.
[0031] Examples of amphoteric materials of the above groups and their method of preparation
are given in our co-pending European patent application 89200113.2.
[0032] 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 esters,
such as glycerol mono-stearate, fatty alcohols, such as stearyl alcohol, alkoxylated
fatty alcohols C₉-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
PLC/NV case C1325), 122 141 (Unilever PLC/NV case C1363) and 79 746 (Procter and Gamble),
the disclosure of which are incorporated herein by reference.
[0033] Preferably compositions of the invention contain at least some cationic fabric softening
materials. Preferably at least 50% of the fabric softening material is a cationic
fabric softener material.
[0034] The 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 40 and 50%
by weight.
[0035] 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
[0036] 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.
[0037] 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.
[0038] 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 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.
Optional ingredients
[0039] The composition can also contain one or more optional ingredients selected from non-aqueous
solvents such as C₁-C₄ alkanols and polyhydric alcohols, pH buffering agents, rewetting
agents, viscosity modifiers such as electrolytes, for example calcium chloride, antigelling
agents, perfumes, perfume carriers, fluorescers, 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.
[0040] 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-aqueous 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 5.0.
[0041] Soil-release agents particularly preferred in the compositions according to the invention
are polymers. Suitable polymers include alkyl and hydroxyalkyl cellulose ethers, such
as methyl cellulose, and polyvinylpyrrolidone.
[0042] 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.
[0043] 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).
[0044] The balance of the composition is preferably water. Although water-free systems are
also within the ambit of the invention, preferably the amount of water in the composition
is more than 20% by weight, more preferred more than 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%.
[0045] The viscosity of the product is preferably less than 250 mPas at 106 s-1.
[0046] In use compositions of the present invention may be prediluted or dosed in concentrated
form into the rinse-cycle of a fabric washing process. Preferably the material is
used at a concentration of between 0.01 and 2g/l, especially between 0.1 and 1g/l.
[0047] The invention will be further illustrated by means of the following examples:
Example I
[0048] 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.
[0049] For each composition the structure and appearance were assessed, the results are
given in table 1, and graphically expressed in figure 1.
COMPOSITION |
WATER/PRAPAGEN/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. |
40/20/40 |
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) |
[0050] These 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, 15, 18 and 19 according to the present invention).
Example II
[0051] Example 1 was repeated while tartaric acid was replaced by citric acid. The results
are expressed in table 1 and figure 2.
COMPOSITION |
WATER/PRAPAGEN/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. |
50/40/10 |
isotropic/clear |
33. |
40/40/20 |
isotropic/clear |
34. |
30/40/30 |
isotropic/clear |
35. |
40/50/10 |
phase separation |
36. |
30/50/20 |
phase separation |
[0052] Again, surprisingly isotropic liquids according to the invention (Compositions 30,
32, 33, 34) can be formulated by increasing the level of fabric softening materials.
Especially interesting was the clear natural yellow appearance of the product, no
decolouration was observed during storage.
EXAMPLE III
[0053] Example I was repeated while replacing tartaric acid by acetic acid or by lactic
acid.
[0054] 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.
[0055] 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
[0056] 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 acid |
10 |
10 |
5 |
30 |
Water |
balance |