[0001] This invention relates to a fabric conditioning composition suitable for conditioning
fabrics during the rinse step of a fabric laundry process.
[0002] It is known to treat fabrics with a fabric conditioning composition following a fabric
washing process which often involves the use of anionic surface active materials.
[0003] In the treatment of fabrics in the rinse cycle of a fabric laundry process it is
known in the art to add one or more conditioning agents. For instance it is known
from British Patent Specification GB-A-1 260 584 (ARMOUR) to soften fabrics in the
rinse cycle by the use of a composition containing a quaternary ammonium compound
and a tertiary amine oxide.
[0004] It is known that anionic surface active materials carried over from the wash cycle
of the fabric laundry process can have a detrimental effect on the effectiveness of
fabric conditioning compositions containing fabric softening agents which are used
in the rinse step of the fabric laundry process. This problem can be alleviated if
the fabrics are thoroughly rinsed before they are treated with a fabric conditioner,
alternatively this problem can possibly be overcome by using fabric conditioning compositions
which are not as sensitive to the presence of anionic surface active agents. Furthermore,
it is known from European patent 63 899 (UNILEVER), to overcome the problem of anionic
carry-over by the use of anionic scavengers, such as aluminium chlorohydrate.
[0005] EP-A-0,210,704 discloses a water-insoluble, water-dispersible fabric softening composition
comprising an amine, a phosphate ester and an amine oxide. The softening composition
is intended for use with detergents, to provide a softening-through-the-wash effect.
[0006] GB-A-2,160,886 discloses a solid detergent bar which is also capable of softening
fabrics during washing. The bar comprises an anionic, nonanionic, amphoteric, cationic
or zwitterionic surfactant; a builder; a long chain aliphatic amide or amine oxide;
a cellulosic derivative; a softening agent and talc, aluminium formate or calcined
sodium carbonate. The softening agent may be a quaternary ammonium salt having at
least one C
16-C
22 aliphatic radical, an imidazolinium salt, a tertiary amine or a smectic clay. The
combination of an amine and a quaternary ammonium softening agent is not, however,
specifically disclosed.
[0007] FR-A-2,593,517 describes a detergent composition which is also capable of softening
fabrics. The composition includes, inter alia, an anionic surfactant; a cationic softener,
which may be a di-lower-di-higher alkyl quaternary ammonium compound; and an ethoxylated
tertiary amine.
[0008] It is an object of the present invention to provide fabric conditioning compositions
which provide improved softening benefits to fabrics, in the absence, but also in
the presence of anionic carry-over.
[0009] It is a further object of the present invention to provide fabric conditioning compositions
which are stable, easy to prepare especially when manufacturing a product with a viscosity
above 100 mPas, and which have an attractive creamy appearance.
[0010] We have now surprisingly discovered that one or more of the above mentioned objects
can be fulfilled if in the fabric conditioning composition a cationic fabric softening
agent is combined with certain other components.
[0011] Thus, accordingly there is provided an aqueous liquid fabric conditioning composition
comprising from 1 to 60% by weight of a combination of:
(i) 20% to 90% by weight of a cationic quaternary ammonium fabric softening agent
having two C12-24 hydrocarbyl chains and a solubility in water at pH 2.5 and 20°C of less than 10g/l;
(ii) 5% to 70% by weight of an amine; and
(iii) 5% to 60% by weight of an amphoteric fabric conditioning material wherein said
amphoteric fabric conditioning material is selected from tertiary amine oxides of
the following formula:

wherein:
a) R25 and R26 are C8-24 hydrocarbyl chains, R27 is an hydrocarbylgroup containing 1-4 carbon atoms or a group -(CH2,CH2O)nH wherein n is as integer from 1 to 6;
the percentage by weight of (i), (ii) and (iii) being based on the total weight of
components (i), (ii) and (iii) in the composition.
Detailed description of the invention
[0012] Fabric conditioning compositions according to the present invention comprise at least
the following three active ingredients:
(i) a cationic tabric softening agent
(ii) an amine
(iii) an amphoteric fabric conditioning material
The cationic fabric softening agent
[0013] The cationic fabric softener material is a cationic material which is water-insoluble
in that these materials have a solubility in water at pH 2.5 and 20°C of less than
10 g/l. The materials are cationic quaternary ammonium salts having two C12-24 hydrocarbyl
chains.
[0014] Well-known species of substantially water-insoluble quaternary ammonium compounds
have the formula

wherein R
1 and R
2 represent hydrocarbyl groups trom about 12 to about 24 carbon atoms; R
3 and R
4 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.
[0015] 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 chloride and di(coconut) dimethyl ammonium methosulfate are preferred.
[0016] 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 R
3 and R
4 represent methyl, R
1 is C
13-15, R
2 is CH
2CH
2OCOR, where R is stearyl, and X is methosulphate. Materials in which R
2, R
3 and R
4 each represent methyl, R
1 is the group

where R is hardened tallow and X is methosulphate are also suitable. Ditallow dimethyl
ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut
alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate
are preferred.
[0017] Other preferred cationic compounds include those materials as disclosed in EP 239,910
(P&G).
[0018] 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.
[0019] Other preferred materials are the materials of formula

R
5 being partially hardened tallow, which is available from Stepan under the tradename
Stepantex VRH 90 and

where R
8, R
9 and R
10 are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl
group. R
6 and R
7 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.
[0020] Another class of preferred water-insoluble cationic materials are selected from the
hydrocarbylimidazolinium salts believed to have the formula:

wherein R
13 is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R
11 is a hydrocarbyl group containing from 12 to 24 carbon atoms, R
14 is an hydrocarbyl group containing from 12 to 24 carbon atoms and R
12 is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A
- is an anion, preferably a halide, methosulfate or ethosulfate.
[0021] 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.
[0022] 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).
The amines
[0023] The compositions according to the invention also contain in addition to cationic
fabric softening agents, one or more amines.
[0024] 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).
[0025] When the amine is of the formula I above, R
15 is a C
6 to C
24, hydrocarbyl group, R
16 is a C
1 to C
24 hydrocarbyl group and R
17 is a C
1 to C
10 hydrocarbyl group. Suitable amines include those materials from which the quaternary
ammonium compounds disclosed above are derived, in which R
15 is R
1, R
16 6 is R
2 and R
17 is R
3. Preferably, the amine is such that both R
15 and R
16 are C
6-C
20 alkyl with C
16-C
18 being most preferred and with R
17 as C
1-3 alkyl, or R
15 is an alkyl or alkenyl group with at least 22 carbon atoms and R
16 and R
12 are C
1-3 alkyl. preferably thee amines are protonated with hydrochloric acid, orthophosphoric
acid (OPA), C
1-5 carboxylic acids or any other similar acids, for use in the fabric conditioning compositions
of the invention.
[0026] When the amine is of formula II above, R
18 is a C
6 to C
24 hydrocarbyl group, R
19 is an alkoxylated group of formula -(CH
2CH
2O)
yH, where y is within the range from 0 to 6, R
20 is an alkoxylated group of formula -(CH
2CH
2O)
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 R
18 is a C
16 to C
22 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 R
18 is a C
16 to C
22 alkyl and that the sum total of x and y and z is within the range from 3 to 10.
[0027] Representative commercially available materials of this class include Ethomeen (ex
Armour) and Ethoduomeen (ex Armour).
[0028] Preferably the amines of type (ii) or (iii) are also protonated for use in the fabric
conditioning compositions of the invention.
[0029] When the amine is of type (iv) given above, a particularly preferred material is

where R
22 and R
23 are divalent alkenyl chains having from 1 to 3 carbons atoms, and R
24 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).
The tertiary amine oxide fabric conditioning material
[0030] The tertiary amine oxide fabric conditioning material for use in a composition according
to the invention should be a fabric substantive amphotheric material. Suitable amphoteric
materials form a particulate dispersion at a concentration of less than 1 g/l at at
least one temperature between 0 and 100°C.
[0031] It is already known, for instance from US 3,984,335 (BASF company) to use a fatty
amphoteric compound having one long hydrocarbyl chain in liquid fabric softening components.
[0032] The tertiary amine oxide compounds have two long hydrocarbyl chains, each chain having
8-24 C-atoms, preferably 10-20 C-atoms, most preferred around 16 C-atoms.
[0033] Preferably the amphoteric fabric substantive materials are water insoluble and have
a solubility in water at pH 2.5 at 20°C of less than 10 g/l. The HLB of the amphoteric
fabric substantive material is preferably less than 10.0.
[0034] Examples of amphoteric materials of the above groups and their method of preparation
are given in our co-pending European patent application EP-A-0 326 213.
[0035] Amine oxides containing two hydrocarbyl groups with at least 14 C-atoms, such as
dihardened tallow methyl amine oxide, are particularly preferred. Amine oxides have
been found to provide particularly advantageous softening effects, furthermore compositions
comprising amine oxides are generally easy to prepare, are stable and have an interesting
creamy appearance.
Optional ingredients
[0036] 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.
[0037] The composition can also contain one or more optional ingredients selected from non-aqueous
solvents such as C
1-C
4 alkanols and polyhydric alcohols, pH buffering agents such as strong or weak acids
eg. HCl, H
2SO
4, phosphoric, benzoic or citric acids (the pH of the liquid compositions ie preferably
less than 5.0), 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 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, anti-redeposition agents,
dye transfer inhibitors and ironing aids.
[0038] These optional ingredients, if added, are each present at levels up to 5% by weight
of the composition. The pH of the composition is preferably 5 or below, or adjusted
thereto.
[0039] Anti-redeposition agents particularly preferred in the compositions according to
the invention are polymers. Suitable polymers include alkyl and hydroxoyalkyl cellulose
ethers, such as methyl cellulose, and polyvinylpyrrolidone.
[0040] 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.
[0041] The compositions may also contain, in addition to the cationic fabric softening agent,
other non-cationic fabric softening agents, such as nonionic fabric softening agents.
Suitable nonionic fabric softening agents include glycerol esters, such as glycerol
monostearate, fatty alcohols, such as stearyl alcohol, alkoxylated fatty alcohols
C
9-C
24 fatty acids and lanolin and derivatives thereof. Suitable materials are disclosed
in European Patent Application 88 520 (Unilever PLC/NV case C 1325), 122 141 (Unilever
PLC/NV case C 1363) and 79 746 (Procter and Gamble). Typically such materials are
included at a level within the range of from 0.5% to 10% by weight of the composition.
Liquid compositions
[0042] The total level of the three ingredients in a liquid composition is from 1 to 60%
more preferred from 3 to 30% by weight of the composition. Based on the total weight
of the three actives, the weight of the cationic softening agent is not more than
90%, preferably between 25 and 75 %, more preferred from 40 to 60 %. especially preferred
about 50 %. The weight of the amine is not more than 70%, preferably between 10 and
60%, more preferred between 15 and 40 %, especially preferred about 25 %. The weight
of the amphoteric material is not more than 60 %. If the amphoteric material is an
amine oxide then this constitutes preferably less than 60 %, more preferred between
10 and 50 %, especially preferred between 15 and 40 %, most preferred about 25 % based
on the weight of the three actives.
[0043] The optimum weight ratio of the three active components in the fabric conditioning
composition depends on the level of anionic carried over from the wash cycle. We have
found that a weight ratio of cationic fabric softener to amine to amine oxide of about
2:1:1 provides good results under most conditions of use.
[0044] 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 cationic fabric
softening agent, amine and amphoteric material, which is then added to water with
stirring to form a dispersion and thereafter adding any optional ingredients.
[0045] 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 amine
and the amine oxide in this liquor will be between about 30 ppm and 500 ppm. The weight
ratio of the fabrics to liquor will generally be between 40:1 and 4:1.
[0046] If the compositions of the invention are added to water which contains high levels
of anionic surface active materials, a further improvement can be obtained if the
compositions contain anionic scavengers such as low molecular weight cationics. Suitable
materials include cationic compounds which have a solubility in water at pH 2.5 and
20°C of more than 5 g/l, preferably more than 10 g/l. Arquad 18 is a particularly
preferred material. (Arquad 18 is a commercially available form of hardened tallow
trimethyl ammonium chloride).
[0047] The invention will now be illustrated by the following non limiting Examples, where
Examples 1A, 1B, 2A and 2B are included for comparison purposes only. In all of the
Examples, all parts and percentages are by weight. Where commercially available materials
are referred to, the percentages quoted are those of the active ingredient therein.
Examples 1-2
[0048] Compositions were prepared according to the formulations in the following tables.
The compositions were prepared by comelting the cationic fabric softening agent, amine
and amine oxide at 80°C. (When the amine was Armeen M2HT, the ortho phosphoric acid
was added to the water prior to forming the co-melt. In contrast when ceranine HC39
was used, the acid was added after the components were dispersed). The comelt thus
formed was added to water at 80°C and then soniprobed for a few minutes to form a
disperion which was then cooled to room temperature.
[0049] The compositions were tested as follows -
40 grams of cotton terry toweling were washed for 5 minutes at 50°C with a commercially
available washing powder product, UK Persil Automatic, in a litre of Wirral water
(10°FH) in a tergotometer. 5 grams of the washing powder product was used. After separating
the wash liquor, the fabric load was rinsed twice at 25°C with Wirral water. 4ml of
a test composition was added to the second rinse. After line drying, the fabric load
was assessed for softness by a panel of experts using a paired comparison test.
| EXAMPLE NO. |
1 |
1A |
1B |
2 |
2A |
2B |
| Ingredient % |
|
|
|
|
|
|
| Arquad 2HT1 |
2.5 |
2.5 |
- |
2.5 |
2.5 |
- |
| Armeen M2HT2 |
1.25 |
- |
2.5 |
- |
- |
- |
| DHTMAO3 |
1.25 |
2.5 |
2.5 |
1.25 |
2.5 |
2.5 |
| Ceranine HC394 |
- |
- |
- |
1,25 |
- |
2.5 |
| OPA |
0.25 |
- |
0.50 |
0.25 |
- |
0.50 |
| Water |
-----balance----- |
| 1 - Dihardened tallow dimethyl ammonium chloride (ex Akzo) |
| 2 - Dihardened tallow methylamine (ex Akzo) |
| 3 - Dihardened tallow methyl amine oxide (ex (Kenobel) |
| 4 - Reaction product of two moles of hardened tallow fatty acid with one mole of N-2-hydroxyethyl
ethylene diamine (ex Sandoz). |
[0050] The results of the softness showed a preference for composition 1 over compositions
1A and 1B ie. the ternary system, containing the cationic, amine and amine oxide,
gave the best softening. The same result was obtained when compositions 2, 2A and
2B were compared.
[0051] Compositions 1 and 2 were also compared. The results showed a preference for the
product containing Ceranine HC39.
Examples 3-6
[0052] In these Examples, a comparison was made between ternary compositions in which the
amine was either protonated or unprotonated. Compositions were prepared according
to the formulations in the table by the method described above.
| Example |
3 |
4 |
5 |
6 |
| Arquad 2HT |
2.5 |
2.5 |
2.5 |
2.5 |
| Armeen M2HT |
|
|
|
|
| (i) protonated with |
1.25 |
- |
- |
- |
| OPA |
|
|
|
|
| (ii) not protonated |
- |
1.25 |
- |
- |
| DHTMAO |
1.25 |
1.25 |
1.25 |
1.25 |
| Ceranine HC39 |
|
|
|
|
| (i) protonated with |
- |
- |
1.25 |
- |
| OPA |
|
|
|
|
| (ii) not protonated |
- |
- |
- |
1.25 |
| OPA |
0.25 |
- |
0.25 |
- |
| Water |
-----balance----- |
[0053] The compositions were tested according to the method described in Examples 1 and
2.
[0054] The results show a preference for composition 3 which contained a protonated amine,
over composition 4.
[0055] When Ceranine HC39 was the amine used, Examples 5 and 6, compositions containing
the protonated and unprotonated material, gave similar results.

[0056] 5 - A dihardened tallow methyl imidazolinium salt

[0057] 7 - Hardened tallow trimethyl ammonium chloride
[0058] 8 - Dicocodimethyl ammonium chloride
[0059] 9 - Dihardened tallow imidazoline amine.
Examples 16-21
[0060] The following compositions according to the invention were prepared by the method
described above
| Example |
16 |
17 |
18 |
19 |
20 |
21 |
| Arquad 2HT |
7.5 |
6.75 |
7.50 |
8.5 |
7.5 |
5.1 |
| Ceranine HC39 |
3.75 |
3.375 |
3.75 |
- |
- |
8.5 |
| Ceranine HCA |
- |
- |
- |
4.25 |
3.75 |
- |
| DHTMAO |
3.75 |
3.375 |
3.75 |
4.25 |
3.75 |
3.4 |
| Dobanol 25-9 |
- |
- |
1.00 |
- |
- |
- |
| OPA |
0.75 |
0.22 |
0.75 |
0.85 |
0.75 |
0.70 |
| Water |
-----balance----- |