Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
9A
C 7146 (R~
FABRIC-'rR~A'rM~NT ('MPQSITION
The present invention relates to a fa~ric-treatment
composition, which i8 especially suitable for use in the
rinse cycle of a fabric-washing proce6s. In particular,
the present invention relates to a ~abric-treatment
5 composition comprising a water-ln~olllhl ~ cationic
fabric-conditioning material and a hydrocarbon material.
It has been suggested in GB 2,007,734 to combine a
water-insoluble cationic conditioning material and a
10 material having oily/fatty properties ln a fabric-
treatment concentrate. These concentrates, however, are
disadvantageous in that they can often not easily be
diluted to form well dispersed liquid fabric-treatment
compositions, especially of high active level, without
15 the addition of substantial amounts of 601vents to aid
dispersion .
It has also been suggested in GB 1, 601, 360 to
incorporate a water-insoluble cationic material and a
20 hydrocarbon material into a fabric-treatment
composition, the weight ratio of water-insoluble
cationic material to hydrocarbon material being between
5:1 and 1:3, for enhanced ease of ironing, anti-
wrinkling and reduced material costs. The preferred
25 hydrocarbon materials for use in these compositions are
liquid at ambient temperature.
It may be desirable to form fabric-treatment
compositions comprising suostantial amounts o~ materials
30 which are less costly than conventional cationic fabric-
treatment materials.
It may also be desirable to develop fabric-treatment
compositions ~hich provide additional anti-wrinkling
35 benefits, while maintaining an acceptable level of
softening performance. It is often also desirable to
_ _ _ _ _ .. . _ .. . . _ _
2 2~03494 C 7146 (R)
formulate fabrLc-treatment compositions of relatively
high active level, for reducing packaging costs.
Surpri~ingly, it has been found that fabric-treatment
compositions fulfilling one or more of the above-defined
objectives can be formulated by using a combination of a
water-insoluble cationic fabric-conditioning Dlaterial
and a specific mixture of hydrocarbons. In particular,
it has been found that a mixture of hydrocarbons which
has a thermal phase transition temperature (TPTT), as
measured by the Perkin & Elmer thermal analysis system,
of between 27- and 38-C is specifically advantageous.
The Perkin & Elmer thermal analysis system measures the
heat flow into a material to be heated as a function of
the temperature of the material. By investigating a
material at various temperatures, a temperature profile
is obtained. Such a temperature profile usually has one
or more peaks, each peak corresF~nrl;n~ to a maximum for
the heat flow into the material at a specific
temperature. The temperature corr~cpc~ in~ to the major
peak in the temperature profile is referred to as the
ther~nal phase transition temperature. Generally a high
TPTT corresponds to a high softening temperature of the
material.
Therefore, the present invention relates to an aqueous
lic~uid fabric-treatment composition comprising
i) a water-insoluble cationic fabric-conditioning
3 0 material, and
ii) a hydrocarbon compositiOn having a thermal phase
transition ~ lul~ associated with softening of the composition,
which lies between 27C and 3~C. The hydrocarbon composition is a
mixture of a liquid hycllu~llbul~ material and a semi-solid or solid
hydrocarbon material, the material being in a weight ratio which lies
in the range from 3:1 to 1:3, the ratio of water in soluble cationic
material to hydrocarbon mixture being about 10:1 to 110.
B -
~ 2003494
-2a -
The water-insoluble cationic fabric softener can be any
fabric-substantive cationic ~ that has a
solubility in water at pH 2 . 5 and 20 C of less than 10
g/l. Highly preferred materials are quaternary allunonium
3 2003494 C 7146 (R)
optionally substituted or interrupted by functional
groups such as -OH, -o-, -CONH, -COO-, etc.
Well-known species of substantially water-insoluble
5 quaternary ammonium c c have the formula:
Rl /R3
N X~
R2 R~
-- --
wherein Rl and R2 represent hydrocarbyl groups of 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
15 halide, methyl sulphate and ethyl sulphate radicals.
Representative examples of these quaternary softeners
include ditallow dimethyl ammonium chloride, ditallow
dimethyl ammonium methyl sulphate, ~i;hPYA-leCyl dimethyl
l;tlm chloride, di(hydrogenated tallow alkyl)
20 dimethyl ammonium chloride, dioctadecyl dimethyl
~ n;llm chloride, dieicosyl dimethyl ammonium chloride,
didocosyl dimethyl i ~n;llm chloride, di(hydrogenated
tallow) dimethyl ~n;l~m methyl sulphate, ~l;h~YA~ryl
diethyl ammonium chloride and di(coconut alkyl) dimethyl
25 ammonium chloride. DitalloW dimethyl ammonium chloride,
di (hydrogenated tallow alkyl) dimethyl ammonium
chloride, di (coconut alkyl) dimethyl ammonium chloride
and di(coconut alkyl) dimethyl ammonium methosulphate
are preferred. other preferred quaternary ammonium
corn~ounds are disclosed in EP 239 910 rl~hl iChP,l October 7,
1987 .
Another class of preferred water-insoluble cationic
materials are the alkyl imidazolinium salts believed to
have the formula:
4 2~03~94 C 7146 (R)
l H2 ICH2 O
N~C~N~C2H~--N--C--R~ A-
I R6 Rs
R~
wherein R6 ls an alkyl or hydroxyalkyl group containing
from 1 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 Rg is hydrogen or an alkyl group
containing from 1 to 4 carbon atoms and A- is an anion,
preferably a halide, meth~sUlrhAte or ethosulphate.
Preferred imidazolinium salts include l-methyl-l-
(tallowylamido) ethyl-2-tallowyl-4, 5-dihydro-
imidazolinium methosulphate and l-methyl-l-
(palmitoylamido) ethyl-2-octadecyl-4, 5-dihydro-
imidazolinium chloride. Other useful imidazolinium
materials are 2-heptadecyl-1-methyl-1-(2-stearylamido)
ethyl-imidazol inium chloride and 2-lauryl-1-
hydroxyethyl-l-oleyl-imidazolinium chloride. Also
suitable herein are the iTni~lA7~11 in~um fabric-softening
components of U. S . Patent N- 4 ,127, 489 .
Other suitable cationic softener materials for use in
compositions of the present invention are amines which
are used at relatively low pH values to effect at least
the partial protonation thereof. Suitable water-amine
~abric Gofteners have, in protonated form, a solubility
in water at pH 2 . 5 and 20-C of less than 10 g/l .
Preferably the relatively in-soluble amine materials are
selected from the following groups:
X
C 7146 tR)
~ 5 2~03494
(i) amines of formula
Rls
R16--N (I)
R17
wherein R15, R16 and R17 are defined as below;
(ii) imidazolines of formula
CH.- CH2 O
N~C~N C2H~ ---C---R7
R9
Rs
III
wherein R7, R8 and R9 are def ined as above .
(iii) cr~n~l~ncation products formed from the reaction
of fatty acids with a polyamine selected from the group
25 consisting of hydroxy alkylalkylPne~ m;nPc and
dialkylenetriamines and mixtures thereof. Suitable
materials are disclosed in European Patent Application
199 382 (Pro~ter and GalrLole).
30 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 Cl to C10 hydrocarbyl group.
Suitable amines include those materials from which the
guaternary - -nil~m compounds disclosed above are
35 derived, in which R15 is Rl, R16 is R2 and R17 i5 R3-
Preferably, the amine is such that both R15 and R16 are
C6-C20 alkyl with C16-C18 being most preferred and with
~ 2003494
C 7146 (R)
R17 as Cl_3 alkyl, or R15 is an alkyl or alkenyl group
with at least 22 carbon atoms and R16 and R12 are C1_3
alkyl .
5 Preferably these amines are protonated with
hydrochloric acid, orthophosphoric acid (OPA), Cl_5
carboxylic acids or any other similar acids suitable for
use in the fabric conditioning compositions of the
invention .
lo
The hydrocarbon composition can be composed of various
fabric-substantive hydrocarbon materials, each being
suitable for inclusion in fabric-treatment compositions,
provided that the total hydrocarbon composition has a
15 TPTT of between 27 and 38OC.
Suitable hydrocarbon materials for use ln the
hydrocarbon composition include hydrocarbon materials
comprising a linear or branched alkyl chain and
20 preferably comprising an average of from 12 to 50 carbon
atoms per molecule, preferably ~rom 12 to 30 carbon
atoms. Preferably, the hydrocarbon materials are either
alkanes or alkenes. Relatively small amounts of non-
alkyl substituent groups may be present, provided the
25 hydrocarbon nature of the product is not substantially
af f ected .
Examples of suitable hydrocarbon materials for use in
the hydrocarbon composition are the liquid hydrocarbon
30 materials o~ natural source. Other liguid hydrocarbon
materials including the liquid fractions derived from
crude oil, 6uch as mineral oil or liquid paraffins and
bracked hydrocarbons.
35 Examples of solid or semi-solid hydrocarbon materials
are the paraffinic materials of longer chain length, and
~IydLvy~{~lted versions of some of the liquid materials
mentioned above.
_ _ _ . .... _ . _ . . _ . _
7 2 ~ 0 3 4 9 ~ c 7146 (R)
A particularly useful c~ ' n~t;on of hydrocarbon materials
is a mixture of mineral oil (~M85 ex Daltons Company) and
petroleum jelly (~Silkolene 910 ex Daltons), wherein the
5 weight ratio of mineral oil to petroleum j elly is chosen
such that the TPTT of the mixture is more than 27C and
less than 3 8C . In our experiments this result was obtained
by using a ratio of mineral oil to petroleum jelly of less
than 3:1, preferably from 2:1 to 1:3. Mineral oil is a
10 liguid mixture of linear and branched hydrocarbons having
an average number of carbon atoms per molecule of 26.
Petroleum jelly is a semi-solid mixture of linear and
branched h~!dLu~dLb~lls hdving an average nurnber of carbon
atoms per molecule of 26, and having a softening
15 temperature of about 50C.
Fabric-treatment compositions according to the present =-
invention will preferably have a total level of water-
soluble cationic material and hydrocarbons composition of
20 from 2 to 70% by weight of the composition, the ~ ;n~l~r
of the composition being pr~,~ ;ni~ntly water optionally
plus minor ingredients. Preferably, the total amount of
water-insoluble cationic material and hydrocarbon
composition is more than 3% by weight, more preferably
25 between 4 and 50% by weight, most preferably between 8 and
35% by weight, the amount especially preferred being
between 15 and 2596 by weight.
A preferred fabric-treatment composition according to the
3 0invention comprises:
i) 55 . 5 - 92% water
ii) 1. 5 - 5 5% water-insoluble cationic mdterial
iii) 6 - 2996 hydrocarbon composition
iv) 0.5 - 1096 water-soluble cationic mdterial.
~ denotes trade mdrk
-7a- 20034~4
The weight ratio of water-insoluble cationic material to
hydrocarbon composition can be varied in a broad range,
but is preferably between 10:1 and 1:10, more preferably
between 5:1 and 1:7, the range from 2:1 to 1:5 being
especially preferred.
The pH of the fabric-treatment composition is preferably
between 2 and 7, more preferably from 3 and 6,
perii~71y preferred from 3 to 4.5. The viscosity of the
fmbrio-tremt~er,t composition i- pre~ o
/
/
B
C 7146 (R)
cPs at 110 5-l (Haake viscometer) . 2 Q O ~ 4 ~ 4
In addition to the water-insoluble cationic material and
the hydrocarbon composition, the fabric-treatment
5 composition may comprise one or more ingredients which
are suitable for incorporation in fabric-
treatment compositions. Examples of these optional
ingredients are nonionic, amphoteric or zwitterionic
fabric-treatment materials. ~p~c~11y preferred is the
10 use of glycerol monostearate.
The compositions may also contain, in addition to the
cationic fabric softening agent, other non-cationic
fabric softening agents, such as nonionic fabric
15 softening agents. Suitable ~nni~n;c fabric softening
agents include glycerol esters, such as glycerol mono-
stearate, fatty alcohols, such as stearyl alcohol,
alkoxylated fatty alcohols Cg-C24 fatty acids and
lanolin and derivatives thereof. Suitable materials are
20 disclosed in European Patent Application 88 520
(Unilever PLC/NV case C 1325), 122 141 (Unilever PLC/~V
case C 13631 and 79 746 (Procter and Gamble)
~pically such materials are included at a level within
tbe range of from 0.5g to 1096 by weight Or the
25 composition.
The compositions may also contain one or more
ingredients selected from non-aqueous solvents such as
Cl-C4 alkanols and polyhydric alcohols, pH-buffering
30 agents such as weak acids, e.g. phosphoric, benzoic or
citric acid (the pH of the compositions being preferably
less than 6.0~, rewetting agents, viscosity modifiers,
silicones, anti-gelling agents, perfumes, perfume
carrierS, fluorescers, colourants, l1YdLUI Lu~,es, anti-
35 foaming agents, anti-redeposition agents, enzymes,
optical brightening agents, opacifiers, stabilizers such
as guar gum and polyethylene glycol, anti-shrinking
9 2003~9~ C 7146 (R)
agents, anti-wrinkle agents, fabric-crisping agents,
spotting agents, soil-release agents, g~
fungicides, antioxidants, anti-corrosion agents,
preservatives, dyes, bleaches and bleach precursors,
5 drape-imparting agents an* antistatic agents.
Preferably the level of solvent materials as referred to
above is less than the level of cationic fabric softener
materials in the composition. l~ore preferably the level
10 of solvents is less tham 75 ~, more preferred less than
50 % based on the weight of the catlonic fabric softener
material. Typically compositions of the invention are
substantially free from solvents.
15 Advantageously, the fabric-treatment composition
according to the invention also comprises a small amount
of water-soluble cationic material. Examples of suitable
materials of thls nature are given in GB 1,601,360.
other suitable water-soluble cationic materials include
20 polyamine materials, preferably di2mine materials,
wherein each nitrogen atom is connected to three other
atoms. A preferred diamine water-soluble catlonic
material of this nature is ~Eth ~ T13 ~ex AXZ0
Chemie) which is an N,N' ,N'-tris (2-hydroxyethyl) N-
25 tallow 1,3-diaminopropane. The amount of water-soluble
cationic material is preferably less than the amount of
water-insoluble cationic material. Preferably the amount
of water-soluble cationic material will be from 0 . 5 to
10% by weight of the composition.
CompositionS according to the invention can be prepared
by any method suitable for preparing dispersed,
emulsified systems. A preferred method involves the
forming of a molten premixture of the active materials
35 in water at an elevated temperature, adding additional
water to obtain the desired active ~ v..cel.~r~.tion, and
then cooling to ambient temperature. When desired, some
minor ingredients such as electrolytes, colouring
denotes trade mark
2003~94 C 7146 (R)
agents, etc. may be post-dosed. A second preferred
method involves the forming of the product by phase
inversion of a water in hydrocarbon: 1 ~i nn~ wherein
the xationic material is either part of the hydrocarbin
5 phase or added as a separate predispersion. This method
is especially advantageous, because this provides very
finely divided hydrocarbon particles in the fLnal
product .
lO In use, the fabric-treatment compositions according to
the invention are preferably used in the final rinse of
the washing cycle of an ordinary washing machine. The
amount of fabric-treatment composition to be added is
mainly flerPnfl~nt on the active concentration of the
15 composition and the volume of the water used in the
rinsing cycle. Preferably, the dose is chosen such that
the concentration of active material (softener plus
hydrocarbon material) in the rinse water i8 from o. 05 to
3 . o g/l, preferably from 0 . 5 to 2 . 0 g/l .
The invention will be further illu6trated by means of
the following examples.
In the acc -nylng drawings, F1gs l ~nd 2 are graphs
illu~trating the result8 of testg performed on compos1tions
~repAred ~c~ordln~ t--th~ ~l~pl~.
C 7146 (R)
11
~Amele I 2~3~94
Fabric-treatment compositions A-F were prepared as
follows. The cationic materials and the hydrocarbon
5 materials were mixed, melted and heated to a temperature
of 70'C, The molten actives were added to water of 70-C
while mixing at high speed with a Silverson mixer. After
being mixed for 10 minutes, the compositions were
cooled to roo~ temperature by rapid chilling in an ice
10 bath while being stirred gently.
The following composltions were obtained. All amounts
are in welght percentages, related to the total
composition .
Ç ~ _ E
Arquad 2HT 5 5 5 5 5 5
M85 15 11.3 10 7.5 3.7
Petroleum jelly - 3.7 5 7.5 11.3 15
2 0 Ethoduo~een 2 2 2 2 2 2
water balance
TPTT
hydrocarbon <<20-C 25-C 28 C 32-C 37-C 39.5-C
composition
The TPTT of the hydrocarbon material was measured by
using the Perkins & Elmer thermal analysis system. The
temperature profiles of the hydrocarbon compositions as
used in the compositions B-F are shown in Figure l For
30 the mineral oil no temperature profile is given, as the
TPTT value for this material would be far less than
20-C.
Compositions A-F were tested as follows:
Softn~cs assaCc~ nt
4 pieces of harshened terry towel and 8 pieces of
unharshened terry towel, the 12 pieces weighing in total
^ denotes trade mark
X
12 20~3~9~ C 7146 (R)
150 g, were rinsed at room temperature for 5 minutes in
1 litre of demin-water with 1 g of fabric-conditioning
composition. The pieces of towel were sa,ueezed to re~ove
excess water, spin-dried for 30 seconds and line dried.
5 The pieces of towel were ~:sessPd by a trained panel of
4 persons by the Round Robin method. The softening score
was expressed in arbitrary units, a higher softening
score indicating a better softening.
10 Cr~A~;na ass~
Two pieces of 9 x 9 inches of 50/50 polyester/cotton,
two pieces of 9 x 9 inches of 67/33 polyester/cotton and
two pieces of g x 9 inches of cotton/poplin were rinsed
15 at room temperature for 5 minutes in 1 litre of demin-
water with 1 g of fabric-conditioning composition. The
fabrics were sa~ueezed to remove excess water, spun for
10 seconds, further squeezed in a clenched fist for 10
seconds and subse~uently line dried. The pieces were
20 ~ç:s~s~-d by a trained panel of 4 persons by the Round
Robin method. The creasing score was expressed in
arbitrary units, a higher creasing score indicating less
creasing .
25 The results of the tests are represented in Pigure 2.
Thi~ figure clearly shows that hydrocarbon co~positions
C-E having a TPTT of between 27- and 38-C ~how a
perfect balance of a good creasing score and adea,uate
softening performance.
Composition A, outside the invention and not shown in
Figure 2, shows a softening which is slightly better
than composition B, but has a significantly lower
creasing score than compositions C-E.
3s
Composition B, outside the invention, is unsatisfactory
in that a low creasing score is found.
13 2ao3~94 7146 (R)
Composition F, outside the invention, is unsatisfactory
in that the softening score i6 unacceptably low.
Exam~le II
The following composition was prepared:
N85 12 . 3
Petroleum jelly 6;1
Adogen 442 4 . 6
Ethoduomeen 1. 5
Calcium chloride 0. 01
minor amounts of colouring agents, perfumes
15 This composition showed a satisfactory balance of anti-
wrinkling and softening.
S~eçificatiQrl of materi~l ~
Arquad 2}~T di-hardened tallow-dimethyl
ammonium chloride (ex Atlas)
^Adogen 442 di-hardened tallow-dimethyl
ammonium chloride
~I85 (ex Daltons) mineral oil, average C number
of 24
Petroleum jelly Silkolene 910 ex Daltons
Company, average C nulDber of 26
Ethoduomeen T13 tAK~0) N,N' ,N' -tris (2-hydroxyethyl)
N-tallow 1, 3-diaminopropane.
^ denotes trade mark
14 2003494 c 7146 (R)
EXAMI'L~ III
A B
(as 1~ ai)
V" A~EN 442 SHE~EX 3.3 3~3
dln~thyl am~nium
c~oride
Hi~ral oil Sirius 85 DQltc~s Co 10.8 10.8
Pet Jelly Sil1colene 910 Dalt~ns Co 5.4 5.4
I~oco di~thyl A~lo~n 462 Sherc~c 2.2 2.2
am~niu~ c~dorioa
Glycerol.~ Unich~na 1.65 1.65
C~ Cls alc~hol 3 Dobanol 25-3 Shell TK ~. 1.1 1.1
etl~yl~te
~,N,N-tris-(2 Et~ 113 Aleo 1.24 1.24
Ey~y(ethyl) -N-
tall~- 1, 3-di~no
P~
n~_~v.~ , Proxel I~L2 ICI 0.02 0.02
Perfin)a Ko~la 188 IE~ 0.60 0.60
l~ye DAs AE Cassell~ 0 004 0,0~4
A~e fi~al TP 226 Union Carbid~ 1.5 1.5
~t~r to bal~e
The above compositions were made by preheating the Sirius 85, the
Silkolene 920, the Adogen 462, the GMS and the Dobanol 25-3 to 60
C and adding water to this premix under stirring. This provides a
water in oil type emulsion, which upon further addition of water
is phase reversed to a oil in water type ~ on ~ wherein the
oil phase is very f inely dispersed. To this oil in water phase is
added a predispersion of the Adogen 442 and the Etod~ T13,
which had been prepared by heating the two materials to 60 C
followed by the addition to water under stirring. The final
product is obtained by adding the re~-in1nq lngredients to the
mixture of the two ~ p~rF:ione:.
