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Description  |
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This invention relates to cationic surfactant compositions and to processes
for preparing them.
Certain quaternary ammonium salts containing at least one long-chain
aliphatic hydrocarbon group in the molecule are cationic surfactants which
can be used as fabric softeners in the rinse following a washing process.
The only ones of commercial importance as fabric softeners up to the
present have two long-chain aliphatic hydrocarbon groups, for example di
(hardened tallow) dimethylammonium chloride and
2-heptadecyl-1-methyl-stearoylamidoethyl imidazoline methosulphate.
Cationic surfactants containing only one long-chain aliphatic hydrocarbon
group are also fabric softeners, but problems arise in formulating them
into stable liquid dispersions.
Cationic surfactants with valuable fabric-softening properties that contain
only one long-chain aliphatic hydrocarbon group in the molecule are more
water-soluble than those of corresponding structure with two such groups,
and this gives rise to problems in formulating them as aqueous
concentrates. Aqueous concentrates of such quaternary ammonium salts,
containing for instance 6% by weight, are readily obtained by dispersing
them in hot water and cooling. However, many such quaternary ammonium
salts, for instance 3-acyloxy-2-hydroxy-propyl trimethylammonium
chlorides, thus provide concentrates that initially have a sufficiently
low viscosity for easy pouring, but tend to form gels on storage at
ambient temperatures and often become difficult, if not impossible, to
pour. Others, for instance cetylpyridinium bromide, provide concentrates
that tend to separate into two layers as the salt begins to crystallise
out, so that the concentrate becomes inhomogeneous on standing.
It has been found that the tendency to form gels or become inhomogeneous
can be avoided by formulating the quaternary ammonium salt as a partial
complex with an anionic surfactant, but that both the ratio of quaternary
ammonium salt to the anionic surfactant and the method of forming the
complex are critical for providing a stable concentrated liquid dispersion
in which quaternary ammonium cationic is present in particles having a net
positive charge so that these are substantive to fabric and confer
softening properties.
Aqueous liquid compositions containing complexes derived from quaternary
ammonium salt softeners and anionic surfactants have already been
disclosed in the patent literature. Such literature disclosures are in
principle concerned with the formulation of quaternary softeners with two
long-chain aliphatic hydrocarbon groups and although mention is made of
the more soluble compounds with only one such group, the special problems
they present have never been recognised. Usually no specific directions
are given for their formulation and they are treated as wholly analogous
to the more insoluble softeners. Thus British Pat. No. 1,453,093 discloses
fabric softening compositions containing a cationic softener and soap with
a weight ratio of from 1:1 to 1:2 of cationic softener to soap and refers
to homogeneous liquids containing them. Mention is made of a wide range of
cationic softeners including quaternary ammonium salts with one or two
long-chain aliphatic hydrocarbon groups. The only instructions given for
formulation of liquid compositions are in connection with a softener with
two long-chain aliphatic hydrocarbon groups and attempts to formulate
corresponding compositions with softeners having only one such group have
resulted in inhomogeneous compositions.
Where specific instructions are given in this literature for formulating
liquid compositions with softeners having only one long-chain group
reliance is placed on methods applied for compositions with softeners
having two long-chain groups. Thus U.S. Pat. No. 3,920,565 concerns
aqueous liquid compositions containing fabric softener and soap in
properties corresponding to a range of from 0.5:1 to 30:1 by weight, and
instructions are given for formulating softeners with single long-chain
groups in manner analogous to that given for ditallow-dimethylammonium
chloride. It has been found that when typical softeners with one
long-chain group are used to prepare aqueous dispersions following this
disclosure inhomogeneous products are obtained.
Other patents which disclose liquid compositions containing softener are,
with the respective anionic surfactants concerned, British Pat. No.
1,434,831 (higher aliphatic or ethoxylated higher aliphatic alcohol
sulphates), and British Pat. No. 1,408,525 and U.S. Pat. No. 3,997,453
(aromatic and other sulphonates). These likewise contain disclosures which
do not recognise the special problems inherent in the formulation of
single long-chain softeners.
It has now been discovered that stable liquid dispersions containing
positively charged particles of quaternary ammonium salt softeners with
single long-chain groups can be prepared if ratios of quaternary salt to
anionic surfactant within critical ranges are employed and the quaternary
salt and anionic surfactant are brought together in such a way that a
homogeneous liquid phase is formed before the complex-containing softener
particles are generated.
The critical range of ratios of single long-chain quaternary ammonium salt
to anionic surfactant has been found to be within from 1.1:1 to 5:1,
expressed as the ratio of normalities of these substances, where normality
is the molar concentration divided by the number of effective cationic or
anionic charges present in the quaternary ammonium salt and anionic
surfactant respectively. Within these limits of normality ratios the
operative limits have been found to be specific to the particular
quaternary ammonium salts and anionic surfactants employed, and can be
determined by a process of simple testing. The effective ratio ranges
found for a series of quaternary ammonium salts and anionic surfactants is
given in the following table. The prior art disclosures of relative
proportions of quaternary ammonium salts and anionic surfactants are
without relation to the capacity of a quaternary ammonium salt to form a
complex with an anionic surfactant by the combination of one cation with
one anion to form an insoluble salt that is reflected in the normality
ratios referred to above, which do not take account of the molecular
weights of the anions and cations, but the corresponding normality ratios
can be calculated from the weight ratio ranges using the molecular weights
of the compounds of lowest and highest molecular weight disclosed, the
quaternary ammonium salts being those having one long-chain aliphatic
hydrocarbon group, and these calculated normality ratio ranges are given
in the table for comparison.
The ranges of figures in the table are the ranges of normality ratios
expressed as quaternary ammonium salt to 1 of anionic surfactant.
______________________________________
Quaternary ammonium salts
Stearyltrimethylammonium chloride
A
Tallow fatty acid acylcholine chloride
B
3-Behenoyloxy-2-hydroxypropyltrimethyl-
ammonium chloride C
______________________________________
Anionic surfactants
A B C
______________________________________
Sodium stearate 1.2-3.0
Sodium soap of tallow
fatty acids 1.1-1.6 1.8-2.6
Sodium random
secondary C.sub.13 -C.sub.17
alkane sulphonate
1.3-2.0 1.5-3.5
Sodium C.sub.15 -C.sub.18
olefin sulphonate
1.4-1.8
Sodium linear C.sub.10 -C.sub.15
alkylbenzene
sulphonate 1.5-3.0 2.0-3.5
______________________________________
Minimum Maximum
ratios ratios
______________________________________
Fatty acid soaps
British Patent
1,453,093 0.13-0.66 0.25-1.33
U.S. Pat. No. 3,920,565
0.28-0.68 16.7-41.1
Alcohol sulphates
British Patent
1,434,831 0.98-2.91 4.9-14.6
Sulphonates
British Patent
1,408,525 0.66-1.20 33-60
U.S. Pat. No. 3,997,453
2.0-3.6 53-96
______________________________________
There is no specific disclosure of the preparation of aqueous liquid
concentrates in these prior publications of stable dispersions containing
positively charged particles of quaternary ammonium softeners with single
long-chain groups, and to prepare these it is necessary both to select a
normality ratio within the operative range for the particular quaternary
ammonium salt and anionic surfactant concerned and to employ a method of
formulation which gives a homogeneous liquid phase before generating the
complex-containing softener particles. It has been found that compositions
of the invention cannot be obtained using the methods of formulation
disclosed in British Pat. Nos. 1,434,831 and 1,453,093 and U.S. Pat. No.
3,920,565 even using normality ratios within the range 1.1:1 to 5:1: the
selection of normality ratio within this range is essential using the
anionic surfactants of British Pat. No. 1,408,525 and U.S. Pat. No.
3,997,453, whereas all the normality ratios of specific compositions they
describe lie between 10:1 and 20:1: the employment of such high ratios
results in solubilisation by the excess quaternary ammonium salt so that
the compositions do not have a clear point above 95.degree. C. and a
stable dispersion of positively charged particles of softening agent is
not obtained.
The present invention provides a pourable liquid fabric softening
composition of uniform turbidity comprising a dispersion in an isotropic
aqueous medium of positively charged particles of softening agent with a
melting point of below 95.degree. C., which particles comprise a
quaternary ammonium salt fabric softener having one straight-chain
aliphatic hydrocarbon radical with from 12 to 24 carbon atoms, the
chloride salt of whose cation A has a Krafft point in water of less than
95.degree. C., complexed with the anion B of an anionic surfactant salt
having one straight-chain aliphatic hydrocarbon group with from 12 to 24
carbon atoms, the normality ratio of A to B being in the range from 1.1:1
to 5:1, the total weight of A and B present being from 2 to 15% by weight
of the composition, and the composition having a clear point of above
95.degree. C.
A composition of uniform turbidity can be recognised simply by visual
observation of a sample which has been placed in a test tube and allowed
to stand for 24 hours at ambient temperature. The isotropy of the aqueous
medium can be recognised by placing a sample of the composition on a
slide, covering the slide with a glass slip and observing the sample under
a microscope between crossed polarisers using bright field illumination at
magnification .times.100: a uniformly dark appearance of the continuous
phase indicates that the liquid medium of the sample is isotropic. The
presence of positively charged particles of softening agent in the
composition can be recognised by dispersing it in demineralised water to
give a 0.01% concentration based on the total weight of quaternary
ammonium salt and anionic surfactant present, subjecting a sample of the
diluted composition to a potential difference and observing under a
microscope the direction of motion of the softener particles present:
movement towards the negative pole indicates that the particles are
positively charged. The melting point of particles of softening agent can
be determined by placing in a hot stage microscope a sample of composition
on a glass slide covered by a glass cover slip and observing the
temperature at which melting of the particle occurs as a change in shape
of the particles indicating deformation of liquid droplets when the cover
slip is moved over the slide. The Krafft point (Kp) of the quaternary
ammonium chloride can be determined by heating an aqueous dispersion
containing 2% by weight of it to a temperature at which a transparent
solution is obtained, cooling it, and observing the temperature at which
it becomes cloudy. The clear point of the composition can be determined by
heating a sample to 95.degree. C.: lack of optical clarity at this
temperature is taken as showing that the clear point is above 95.degree.
C.
Quaternary ammonium salt fabric softeners, the chloride salt of whose
cation A has a Krafft point in water of less than 95.degree. C., that are
suitable for use in the compositions of the invention are to be found
within the class of compounds having the structure R'--AR.sub.3 N.sup.+
X.sup.-, where R' is a straight-chain aliphatic hydrocarbon radical having
from 12 to 24 carbon atoms, A represents a single bond or a group
--COOR"--, --OOCR"--, --CONHR"--, --NHCOR"--, --SO.sub.2 NMR"--, or
--Y.sub.m (OCH.sub.2 CH.sub.2).sub.n -- where R" is an alkylene or
hydroxyalkylene group having from 1 to 3 carbon atoms, and Y is a
phenylene group, m is 0 or 1 and n is 1 to 3, and (a) each group R is an
alkyl or hydroxyalkyl group having from 1 to 6 carbon atoms or a benzyl
group, or (b) 2 or 3 of the groups R taken together with the nitrogen atom
represent a heterocyclic radical and any remaining group R is an alkyl or
hydroxyalkyl group having from 1 to 6 carbon atoms or a benzyl group, and
X.sup.- is an anion. Preferably the quaternary ammonium salt has one of
the structures R.sup.1 R.sub.3 N.sup.+ X.sup.-, R.sup.1 OOCCH.sub.2
R.sub.3 N.sup.+ X.sup.-, R.sup.1 COOCH.sub.2 CH.sub.2 R.sub.3 N.sup.+
X.sup.-, R.sup.1 CONHCH.sub.2 CH.sub.2 R.sub.3 X.sup.+ X.sup.- and R.sup.1
COOCH.sub.2 CHOHCH.sub.2 R.sub.3 X.sup.+ X.sup.-, where R.sup.1 is a
straight-chain aliphatic hydrocarbon group having from 12 to 24 carbon
atoms, and either (a) each group R is an alkyl or hydroxyalkyl group
having from 1 to 6 carbon atoms or a benzyl group, or (b) 2 or 3 of the
groups R taken together with the nitrogen atom represent a heterocylic
radical, and any remaining group R is an alkyl or hydroxyalkyl group
having from 1 to 6 carbon atoms or a benzyl group, and X.sup.- is an
anion. The aliphatic hydrocarbon groups R and R.sup.1 can be alkyl or
alkenyl groups.
Thus is such compounds where appropriate R' and R.sup.1 can be a cetyl,
n-heptadecyl, stearyl, oleyl, n-eicosyl or n-tetracosyl group; R can be a
methyl, ethyl, propyl, hydroxyethyl, hydroxypropyl or benzyl groups, 2
groups R taken together with the nitrogen atom can represent a
morpholinium, piperidinium or pyrollidinium group, and 3 groups R taken
together with the nitrogen atom can represent a pyridinium group; and
R.sup.1 CO can be a palmitoyl, stearoyl, arachidoyl, erucoyl, behenoyl or
lignoceroyl group. The anion X.sup.- is preferably the anion of a strong
acid, and can for example be a halide or methosulphate. An anion can carry
a double charge, as with sulphate, and in such an instance X.sup.-
represents half a unit group. Particularly valuable are compositions in
which the quaternary ammonium salt is a C.sub.14 to C.sub.20 alkyl
trialkylammonium salt, especially where the latter alkyl groups are each
methyl. Mixtures of quaternary ammonium salts can be used, for example a
salt in which one or more of the radicals R' or R.sup.1 is derived from an
intermediate containing mixed radicals. Thus a group R', R.sup.1 or
R.sup.1 CO can be a mixture of long-chain aliphatic hydrocarbon or acyl
radicals corresponding to hydrogenated tallow fatty acid, or technical
behenic acid containing minor proportions of acids other than behenic
acid.
Specific examples of suitable quaternary ammonium salts are
celtyltrimethylammonium bromide
stearyltrimethylammonium chloride (Kp 11.degree. C.)
cetylbenzyldimethylammonium chloride (Kp 16.degree. C.)
myristoyloxyethyl trimethylammonium iodide
stearoyloxyethyl trimethylammonium chloride
tallow fatty acylcholine chloride (Kp 40.degree. C.)
eicosyloxycarbonylmethyl trimethylammonium chloride
stearoylaminoethyl triethylammonium chloride
behenoylaminopropyl trimethylammonium chloride (Kp 60.degree. C.)
cetylsulphonylaminoethyl trimethylammonium methosulphate
stearyloxyethyleneoxyethyl tripropylammonium chloride
cetylpyridinium chloride (Kp 15.degree.-17.degree. C.)
3-cetyloxy-2-hydroxypropyl trimethylammonium chloride
3-behenoyloxy-2-hydroxypropyl trimethylammonium chloride (Kp 54.degree.
C.).
The preparation of such compounds is already described in the cationic
surfactant literature, for instance that of acyloxyhydroxypropyl
trialkylammonium salts is described in British Pat. No. 980,003.
The anion B of an anionic surfactant salt can be provided by a
water-soluble or water-dispersible alkali metal salt of an organic acid
having one straight-chain aliphatic hydrocarbon radical with from 12 to 24
carbon atoms, especially a sodium or potassium salt, or a corresponding
ammonium or substituted ammonium salt. Alternatively the anion B can be
provided by the corresponding free organic acid. The organic polar group
of the salt or acid can be carboxylate, sulphate or sulphonate, and the
anion-providing compound can have more than one such polar group. Examples
of suitable organic acids providing the anion are natural and synthetic
aliphatic carboxylic acids having from 12 to 24 carbon atoms, for instance
myristic, palmitic, stearic, oleic and behenic acids, especially those of
the soaps obtained by splitting triglyceride oils, for instance tallow
fatty acid, which is a mixture of fatty acids consisting mainly of
palmitic, stearic and oleic acids; alkylsulphuric acids having from 12 to
24 carbon atoms, for instance lauryl, cetyl, and palmityl hydrogen
sulphates; alkane and olefin sulphonic acids having from 12 to 24 carbon
atoms, for instance lauryl, myristyl, cetyl and stearyl sulphonic acids,
and especially olefin sulphonates derived by reaction of sulphur trioxide
with linear .alpha.-olefins, or by reaction of alkanes with sulphur
dioxide and chloride and subsequent hydrolysis, or by reaction of olefins
with bisulphites; alkylether sulphuric acids obtained by reaction of molar
quantities of alcohols having from 12 to 24 carbon atoms with 1 to 15 mols
of ethylene oxide and subsequent reaction of the condensation products
with sulphur trioxide; alkylbenzene sulphonic acids whose alkyl groups
contain from 12 to 24 carbon atoms, for instance dodecylbenzene sulphonic
acid; alkyl sulphosuccinates whose alkyl groups have from 12 to 24 carbon
atoms, derived by reacting maleic acid esters with bisulphites;
acyloxysulphonic acids, for instance acyloxyethyl and
3-acyloxy-2-hydroxypropyl sulphonic acids, whose acyl groups have from 13
to 25 carbon atoms, for example lauroyloxyethyl and stearoylhydroxypropyl
sulphonic acids; and .alpha.-carboxyalkyl sulphonic acids whose
carboxyalkyl groups have from 13 to 25 carbon atoms, for instance
sulphonated lauric and palmitic acids. Preferably the anion is one in
which there is present an alkyl or alkenyl group having from 16 to 24
carbon atoms.
It has been found that when certain combinations of specific quaternary
ammonium salts and alkyl sulphates are employed the complexes produced are
highly crystalline, possibly because of lack of water in the complex, so
that particles of them settle out rapidly from the dispersion obtained,
which is not therefore of uniform turbidity. Such particles have a melting
point above 95.degree. C. and do not provide compositions of the
invention. It is therefore necessary to choose the specific quaternary
ammonium salt and alkyl sulphate combination so that this is avoided, as
illustrated in Example 18 below.
The ratio of the normalities of the cation A and anion B in the
compositions of the invention is from 1.1:1 to 5:1. Normality is the molar
concentration divided by the number of effective cationic or anionic
charges present in a molecule of quaternary ammonium salt or
anion-providing compound respectively. The relative molar proportions are
thus adjusted according to the numbers of cationic and anionic groups in
those parts of the molecules providing ions carrying a large non-polar
group. Hence one molar proportion of an anion-providing compound with one
anionic group, for instance a fatty acid soap, is present with from 1.1 to
5 molar proportions of a quaternary ammonium salt having one cationic
group, and one molar proportion of an anion-providing compound with two
anionic groups, for instance a fatty acid sulphonate, is present with from
2.2 to 10 molar proprotions of a quaternary ammonium salt having one
cationic group.
The concentration of the quaternary ammonium salt is preferably from 4 to
12% by weight of the composition. The compositions can contain minor
amounts, for instance from 1 to 20%, of a hydrophilic organic solvent, for
example isopropyl alcohol or hexylene glycol (2-methylpentane-2,4-diol).
Nonionic surfactants, for instance condensates of linear and
branched-chain aliphatic alcohols or carboxylic acids having from 8 to 22
carbon atoms with from 6 to 30 mols of ethylene oxide per mol of alcohol
or acid, can be included in the compositions in minor amounts. The
compositions can also contain perfume and colourants. The electrolyte
content of the compositions should be low enough to avoid flocculation.
The pH of the compositions will generally be between 2.5 and 9.
The concentration of water in a composition is from 98 to 85% by weight of
the total of A,B and water present, and taking into account the presence
of other minor ingredients is generally from 60 to 95% by weight of the
total composition.
The viscosity of the composition depends on the size and numbers of the
dispersed particles present, at least 75% of the particles generally being
of diameter less than 10 microns. The viscosity can be chosen according to
the prevailing user habit: for instance it can be within the ranges of
from 15 to 80 cP or of from 100 to 150 cP.
A process for preparing a composition of the invention is one in which a
homogeneous liquid mixture of the quaternary ammonium salt and
anion-providing compound (prepared by heating to a suitable elevated
temperature, in a solvent if desired) is mixed with water and subjected to
shear at an elevated temperature until a dispersion is formed. In
conducting the process the quaternary ammonium salt and anion-providing
compound in the liquid phase can be mixed with water at a suitable
elevated temperature, any colourant and ingredients other than perfume
added, and the mixture subjected to shear to form an emulsion which is
then cooled with stirring to form the aqueous dispersion, and any perfume
required is then dispersed in the composition. Preferably the temperature
at which the dispersion is formed is in the range of from 45.degree. to
85.degree. C.; the precise temperature is adjusted to the particular
ingredients used by simple testing to give the viscosity desired. The
quaternary ammonium salt as manufactured may be available as a paste in
admixture with an organic solvent, for instance acyloxyhydroxypropyl
trimethylammonium chlorides are generally available mixed with a minor
amount of isopropyl alcohol or hexylene glycol containing some water.
The compositions of the invention are used as fabric softeners by addition
to the rinse cycle in the normal way, and in amounts equivalent to those
normally applicable to the quaternary ammonium salts. The invention
includes a process for the softening of fabrics in which a composition of
the invention is dispersed in water and fabric is contacted with the
resulting dispersion, preferably containing from 0.002 to 0.035% of the
quaternary ammonium salt.
The invention is illustrated by the following Examples in which amounts are
by weight and temperatures are in .degree.C., and the methods given above
were used to determine the composition characteristics.
Preparation I of quaternary ammonium salt
Technical behenic acid (5.6 parts, containing 63.7% behenic acid, 0.9%
palmitic acid, 22.3% stearic acid, 12.4% arachidic acid and 0.7%
lignoceric acid) was mixed with isopropyl alcohol (4.2 parts) and the
mixture heated until a clear solution was obtained: a solution of
glycidyltrimethylammonium chloride (2.8 parts) in demineralised water (1.4
parts) was added and the charge heated with stirring under reflux for 21/2
hours, giving 14 parts of a product containing
3-behenoyloxy-2-hydroxypropyl trimethylammonium chloride (59.6%, MW 475.7,
Kp 58.degree. ), isopropyl alcohol (29%) and water (9%), with by-products
and unreacted starting material (2.4%).
Preparation II of quaternary ammonium salt
The product of Preparation I (1 part) was heated to a temperature at which
it became clear, and mixed with diethyl ether (10 parts), which
precipitated crystals of the quaternary salt. These crystals were removed
by filtration, washed with acetone and dried under reduced pressure.
EXAMPLES 1 AND 2
A mixture of cetyltrimethylammonium bromide (9 parts MW 364), a commercial
sodium linear C.sub.10 -C.sub.15 alkyl benzene sulphonate (containing
91.8% of sulphonate, MW 358, 4.6% sodium sulphate, 0.4% sodium chloride
and 1.9% water, 6.34 parts), isopropyl alcohol (8 parts) and water (4
parts) was heated to and maintained at 70.degree. until it was wholly
liquid. Sufficient demineralised water at 70.degree. to bring the weight
of the composition to 200 parts was added and the mixture stirred for 2
minutes and allowed to cool to ambient temperature.
A second composition was prepared in the same way, but with 4.75 parts of
the anionic surfactant.
______________________________________
Example
Composition % 1 2
______________________________________
Quaternary ammonium salt
4.5 4.5
Anionic surfactant (active)
2.91 2.18
Cation 3.51 3.51
Anion 2.72 2.04
Total cation and anion
6.23 5.55
Normality ratio, cation/anion
1.5 2.0
Mp of softening agent particles
<30.degree.
<30.degree.
______________________________________
EXAMPLES 3 TO 8
A mixture of stearyltrimethylammonium chloride (15.18 parts, containing 49%
of the quaternary salt, Kp 11.degree., MW 345.8, dissolved in aqueous
isopropyl alcohol), a commercial sodium soap of tallow fatty acid (4.61
parts, containing 99% of anionic surfactant, MW 299), isopropyl alcohol (5
parts) and water (5 parts) was heated to and maintained at 70.degree.
until it was wholly liquid. Sufficient demineralised water at 70.degree.
to bring the weight of the composition to 200 parts was added and the
mixture stirred for 1 minute and allowed to cool to ambient temperature.
Further compositions were similarly prepared using the same quaternary
ammonium salt in various proportions with the following anionic
surfactants.
______________________________________
Example
4 A commercial random secondary C.sub.13 -C.sub.17 alkane
sulphonate detergent containing 73.3% of the
active surfactant, MW 318, with 1,2% sodium
sulphate and 24.7% water.
5 A commercial C.sub.15 -C.sub.18 olefin sulphonate detergent
containing 92.7% sodium olefin sulphonate
(MW 329), 1.5% sodium sulphate, 1.8% sodium
chloride and 2.6% water.
6 the alkyl benzene sulphonate detergent of
Examples 1 and 2.
7 A mixture of a commercial sodium soap of
coconut fatty acid containing 89.3% of the
soap, MW 229, with the remainder salt and
water, and the sodium soap of tallow fatty
acid of Example 3, the two soaps being present
in molecular equivalent amounts of anionic
surfactant (average MW 264).
8 A mixture of the tallow soap of Example 3
and the random secondary alkane sulphonate
of Example 4 in molecular equivalent amounts
of anionic surfactant.
______________________________________
The contents of the resulting compositions and their normality ratios and
softening agent particle melting points were as follows:
__________________________________________________________________________
Example No.
Composition % 3 4 5 6 7 8
__________________________________________________________________________
Quaternary ammonium salt
3.72 3.90
3.85
4.34 3.90
3.67
Anionic surfactant
(active) 2.28 2.18
2.23
1.75 2.11
2.32
Cation 3.34 3.50
3.46
3.90 3.50
3.30
Anion 2.10 2.02
2.07
1.64 1.93
2.15
Total cation and anion
5.44 5.52
5.53
5.54 5.43
5.45
Normality ratio, cation/
anion 1.4 1.65
1.65
2.55 1.4 1.4
Mp of particles
50.degree.
<40.degree.
60.degree.
35- 40.degree.
<40.degree.
40.degree.
__________________________________________________________________________
EXAMPLE 9
A mixture of stearyltrimethylammonium chloride (142.8 parts, containing 51%
of the quaternary salt, Kp 11.degree., MW 345.8, dissolved in 75% aqueous
isopropyl alcohol), a commercial sodium soap of tallow fatty acid (25.4
parts, containing 93% of anionic surfactant, MW 299 with the remainder
salt and water), a commercial oleic acid (23.6 parts), and water (10
parts) was heated to and maintained at 70.degree. until it was wholly
liquid. This mixture was added during 1 minute to demineralised water
(1792 parts) at 70.degree. with stirring, the dispersion cooled to
40.degree. and perfume (6 parts) added; after further stirring the
composition was cooled to ambient temperature for storage. The composition
had the following content and normality ratio, with softening agent
particles melting at below 95.degree..
______________________________________
Composition %
______________________________________
Quaternary ammonium salt 3.64
Anionic surfactant and oleic acid
2.36
Cation 3.27
Anion 2.28
Total cation and anion 5.55
Normality ratio, cation/anion
1.3
______________________________________
The viscosity of the composition measured with a Haake Rotovisko Concentric
Cylinder viscometer at a shear rate of 110 sec.sup.-1 was 20 cP.
EXAMPLES 10 TO 13
Compositions were prepared employing as quaternary ammonium salt tallow
fatty acyl choline chloride, that is, the ester derived from choline and
tallow fatty acid, containing 95.7% of active cationic surfactant and
having MW 398.5 and Kp 40.degree..
A mixture of this tallow acyl choline ester (9.23 parts) and the tallow
soap of Example 3 (2.77 parts), isopropyl alcohol (8 parts) and water (4
parts) was heated to and maintained at 70.degree. until it was wholly
liquid; demineralised water was added to bring the composition to 200
parts and the mixture was stirred for 1 minute and allowed to cool to
ambient temperature.
Further compositions were similarly prepared using as anionic surfactant
various proportions of the alkane sulphonate of Example 4, the olefin
sulphonate of Example 5 and the alkyl benzene sulphonate of Example 6,
giving compositions respectively of Examples 11, 12 and 13.
The contents of the composition and their normality ratios and softening
agent particle melting points were as follows.
______________________________________
Example No.
Composition % 10 11 12 13
______________________________________
Quaternary ammonium salt
4.42 4.05 3.96 4.78
Anionic surfactant (active)
1.37 2.00 2.04 1.23
Cation 4.16 3.82 3.73 4.50
Anion 1.26 1.86 1.90 1.15
Total cation and anion
5.42 5.68 5.63 5.65
Normality ratio, cation/anion
2.4 1.6 1.6 3.5
Mp of particles 50.degree.
<95.degree.
<95.degree.
40.degree.
______________________________________
EXAMPLES 14 TO 16
Compositions were prepared using as quaternary ammonium salt the
3-behenoyloxy-2-hydroxypropyltrimethylammonium chloride containing 93.2%
of active surfactant described above in Preparation II, and as anionic
surfactant, sodium stearate, MW 306.
The quaternary ammonium salt (9.66 parts) and sodium stearate (4.63 parts),
isopropyl alcohol (10 parts) and water (5 parts) were mixed and heated to
and maintained at 80.degree. until the mixture was wholly liquid.
Sufficient demineralised water at 80.degree. to bring the weight of the
composition to 200 parts was added, the mixture stirred for 2 minutes and
allowed to cool to ambient temperature. Further compositions were prepared
using reduced amounts of the stearate.
The contents, normality ratios and softening agent particle melting points
of the compositions were as follows.
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Example No.
Composition % 14 15 16
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Quaternary ammonium salt
4.5 4.5 4.5
Anionic surfactant (active)
2.32 1.93 1.45
Cation 4.28 4.28 4.28
Anion 2.16 1.78 1.34
Total cation and anion
6.44 6.06 6.62
Normality ratio, cation/anion
1.25 1.5 2.0
Mp of particles 60.degree.
60.degree.
60.degree.
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EXAMPLE 17
A composition was prepared using as quaternary ammonium salt the
behenoyl-hydroxypropyltrimethylammonium chloride of Preparation I above,
containing 59.6% of active surfactant, 30% isopropyl alcohol and 10.4%
water, and the quaternary salt having MW 475.7 and Kp 58.degree..
To this product (40 parts) was added tallow fatty acid (MW 277, 8 parts)
and colourant (0.03 parts), and the mixture heated to 60.degree. with
stirring: demineralised water (352 parts) at 60.degree. was added and the
cloudy mixture stirred vigorously for 30 minutes at 60.degree., the
resulting emulsion cooled to ambient temperature, and perfume (0.6 parts)
finally incorporated with stirring.
The resulting composition contained 5.96% of quaternary ammonium salt, 2.0%
of active anionic surfactant, 5.67% of the cation and 2.0% of the anion,
the total of cation and anion being 7.67%, the normality ratio of cation
to anion being 1.75:1, and the softening agent particle mp was 50.degree..
EXAMPLES 18 AND 19
To the quaternary ammonium salt preparation of Example 17 (14.69 parts) was
added a commercial C.sub.16 -C.sub.18 primary alkyl sulphate detergent
(containing 95.6% of active anionic surfactant, MW 353, Kp 35.degree.,
3.40 parts), isopropyl alcohol (5 parts) and water (4 parts) and the
mixture heated to and maintained at 70.degree. until completely clear:
demineralised water (150 parts) at 70.degree. was added with stirring for
1 minute, and the composition finally made up to 200 parts by addition of
further water. A further composition was prepared in the same way from
16.1 parts of the quaternary ammonium salt, 2.57 parts of a commercial
linear C.sub.10 -C.sub.15 alkyl benzene sulphonate detergent containing
93.7% anionic surfactant (MW 358, Kp 6.degree.) and 3.5% sodium sulphate,
3 parts of isopropyl alcohol and 4 parts of water.
The softening agent particle melting points of the compositions were below
95.degree.. The contents of the resulting compositions and their normality
ratios were as follows.
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Example No.
Composition % 18 19
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Quaternary ammonium salt
4.38 4.80
Anionic surfactant (active)
1.63 1.21
Cation 4.17 4.57
Anion 1.48 1.13
Total cation and anion
5.65 6.70
Normality ratio, cation/anion
2.0 3.0
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EXAMPLES 20 AND 21
To the quaternary ammonium salt of Example 17 (Preparation I, 40 parts) was
added oleic acid (8 parts) and the mixture was heated to 80.degree. with
stirring: demineralised water (352 parts) at 80.degree. was added and the
mixture stirred for 30 minutes at this temperature and then cooled to
ambient temperature. A similar composition was prepared with half the
amount of oleic acid replaced by water.
The contents of the compositions and their normality ratios and softening
agent particle melting points were as follows.
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Example No.
Composition % 20 21
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Quaternary ammonium salt
5.96 5.96
Anionic surfactant (active)
2.00 1.00
Cation 5.67 5.67
Anion 2.00 1.00
Total cation and anion
7.67 6.67
Normality ratio, cation/anion
1.75 3.55
Mp of particles 30.degree.
30-40.degree.
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EXAMPLE 22
A composition was prepared as in Example 21, but using the sodium tallow
fatty acid soap of Example 3 (4 parts) instead of oleic acid, and with a
mixing temperature of 70.degree.; the composition contained 5.96% of
quaternary ammonium salt, 1.0% of active anionic surfactant, 5.67% of the
cation, 0.92% of the anion, the total of cation and anion being 6.59% and
the normality ratio of cation to anion being 3.75:1. The softening agent
particles had mp 60.degree..
EXAMPLES 23 TO 27
To the quaternary ammonium salt product of Preparation I above (40 parts)
was added anionic surfactant (8 parts) and the mixture heated with
stirring to 80.degree.. Demineralised water (352 parts) at 80.degree. was
added and the cloudy mixture stirred at 600 rpm at 80.degree. for 15 min.,
and cooled to ambient temperature. Compositions were prepared in this way
using the following anionic surfactants.
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Example
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23 A commercial 3-acyloxy-2-hydroxypropyl sulphate
detergent containing 82% sodium salt (MW 382),
in which the acyl groups were derived from
coconut oil fatty acid.
24 An alkane sulphonate detergent containing 80%
sodium stearyl sulphonate (MW 356) and 16%
sodium sulphate.
25 A commercial C.sub.15 -C.sub.18 olefin sulphonate detergent
containing 94% sodium olefin sulphonate (MW
329), and 2.3% sodium sulphate.
26 A commercial linear C.sub.10 -C.sub.15 alkyl benzene
sulphonate detergent containing 80% anionic
surfactant (MW 356) and 16% sodium sulphate.
27 A sulphonated fatty acid sodium salt prepared
from a mixture of 2% myristic, 49% palmitic,
46% stearic and 3% other saturated and un-
saturated long-chain fatty acids, and contain-
ing 34% sodium fatty acid sulphonate (MW 400),
4.5% sodium soap (MW 298), 2% sodium sulphate
and 57% water.
______________________________________
The contents, normality ratios and softening agent particle mp of the
compositions were as follows.
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Example No.
Composition % 23 24 25 26 27
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Quaternary ammonium salt
5.96 5.96 5.96 5.69 5.96
Anionic surfactant (active)
1.64 1.6 1.88 1.6 0.77
Cation 5.67 5.67 5.67 5.67 5.67
Anion 1.54 1.45 1.75 1.45 0.72
Total cation and anion
6.21 7.12 7.42 7.12 6.39
Normality ratio, cation/anion
2.9 2.8 2.2 2.8 3.1
Mp of particles <95.degree.
<95.degree.
60.degree.
50.degree.
<95.degree.
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All the compositions of Examples 1 to 27 were of uniform turbidity with a
clear point of above 95.degree. and were dispersions in an isotropic
aqueous medium of positively charged p | | |
