Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to a fabric conditioner
composition containing at least one silicon compound as
a fragrance imparting component.
It is often desired to impart to substrates, for
example fabrics such as wearing apparel and bed linen,
a fresh and pleasant smell. As the fragrance imparting
substances there are usually employed the essential oils
either individually or as blends. The fragrance imparted
by such oils is however generally of short duration.
U.S. Patent No. 3,215,719 discloses that a long
lasting fragrance may be imparted to textiles if there
are applied thereto certain silicate esters of essential
alcohols. According to the teaching of said U.S. patent
a particularly useful method of treating the textile is
to pad it through an aqueous dispersion of the silicate
ester. Such a method relies on a single relatively
heavy application of the perfume which eventually
dissipates. A more desirable arrangement would be that
which involved a more frequent application of a lower add
on of perfume, provided that such application could be
carried out during a routine operation, such as laundering,
to which the fabrics are periodically subjected. Such a
technique would enable a more frequent change of fragrance,
if desired, and would also permit renewal of the fragrance
by a sinyle household operation.
According to this invention there is provided a
fabric conditioner composition comprising a fatty alkyl
X q~
quaternary ammonium compound and as a fragrance imparting
component at least one silicon compound having in the
molecule at least one group of the general formula -OR
wherein R represents the residue remaining after removal
of the hydroxyl group from an alcohol selected from cyclic
and acyclic monoterpene alcohols, essential aryl-substituted
phenols, any other substituents attached to silicon being
selected from hydrogen atoms and organic groups free of
sulphur and phosphorous, said organic groups being joined
1~ to silicon through a silicone to carbon or silicon-oxygen-
carbon linkage.
The invention also includes a process for preparing
such a fabric conditioner composition which comprises mixing
a fatty alkyl quaternary compound and a silicon compound
as hereinabove defined.
Any silicon compound containing at least one of the
specified silicon-bonded -OR groups in the molecule may be
employed in the composition of this invention. Thus, the
silicon compound may be for example a silane, di- or poly-
silane a siloxane or asilalkylene-siloxane. Preferred
as the silicon compounds are ti) silanes represented by the
general formula
R'nSitOR)4-n
and (ii) siloxanes having at least one structural unit of
the formula
~r
8~6
~RO)bSio4 a b
any remaining units in the siloxane having the formula
R.csio4 c ~~- (II)
-2
wherein R is as defined hereinabove, R' and R" each
represent a hydrogen atom or an organic group free of
sulphur and phosphorus and attacheed to the silicon atom
through a silicon to carbon or silicon-oxygen-carbon
linkage, n is O, 1, 2 or 3, a has a value of O, 1 or 2,
b has a value of O, 1 or 2, the sum of a and b being not
greater than 3 and c has a value of O, 1, 2 or 3.
In the silicon compounds employed according to this
invention the group R represents the residue remaining
after removal of the hydroxyl group from an alcohol
selected from cyclic and acyclic monoterpene alcohols,
essential aryl-substituted aliphatic alcohols and
2Q essential aliphatic-substituted phenols. Such alcohols
are well known substances and include geraniol,
citronellol, nerol, rhodinol, menthol, isopulegol,
eugenol, vanillin, phenylethyl, alcohol, phenylpropyl,
alcohol, anisyl alcohol, and cinnamyl alcohol. If
desixed more than one type of OR group may be present in
a given molecule of the silicon compound. Depending on
the nature of fragrance desired the silicon compound may
have ~ groups derived from, for example, both geraniol
and phenylethyl alcohol or from nerol and anisyl alcohol.
8~6
The preferred alcohols are the rose alcohols and
essential aryl-substitued aliphatic alcohols.
Preferably, therefore, R represents a group selected
from -cH2cH~c(cH3)(cH2)2cH=c(cH3)~
-(CH )2CH3CH(CH2)2CH=C(CH3)2 (CH2)2C6 5, 2 3 6 5
-CH2PhOCH3 in which Ph represents phenylene, and
-CH2CH=CHC6H5.
Any substituents present in the silicon compounds
in addition to the OR groups are hydrogen atoms and/or
organic groups bonded to silicon through an SiC or SiOC
linkage. Such organic groups, including R' and R", are
preferably monovalent hydrocarbon groups, for example
alkyl, al~enyl, aryl, alkaryl or aralkyl or monovalent
groups o~osed of carbon,- hydrogen and oxygen, for
example alkoxy, alkoxyalkoxy or aryloxy. The SiC bonded
organic groups may, however, also be monovalent halo-
hydrocarbon groups such as chloroalkyl and chloroaryl.
Specific examples of the organic substituents which may
be present in addition to the OR groups are methyl,
2~ ethyl, propyl, butyl, 2,4,4-trimethylpentyl, octadecyl,
phenyl, benzyl, tolyl, methoxy, ethoxy, butoxy, methoxy-
ethoxy, phenoxy, benzyloxy, -(CH2)3~0CH2CH2)80C4Hg,
~ .
-CH2cH2cH2cH3 ~ - tCH2) 3CH2cH CH2 - (CH2) 3NH2,
2)31~ (C~2)2NH2, -CH2cH2cH(cH3)NH(cH2)2~H2 an~
(CH2)3N(CH3)2C18H37Cl. Preferably any substituents
present in addition to the OR groups are selected from
- 5 -
~'
8~6
hydrogen atoms, methyl groups and alkoxy and alkoxyalkoxy
groups having less than 5 carbon atoms.
When siloxanes are employed as the silicon compounds
according to this invention they may be homopolymers
containing only units of general formula (I) or they may
consist of such units together with one or more units
defined by general formula (II) hereinabove. Depending
on the proportions and types of units present the
siloxanes may have from less than 1.0 up to 3 total sub-
stituents per silicon atom and may vary from freely
flowing liquid to resinous solids.
Examples of the silicon compounds which can be
employed as the fragrance imparting component in the
compositions of this invention are
CH3(0CH3)2SiOR
(CH3)3
(OC2H51 3SioR
Si(OR)4
C~H5Si(OR)3
CH2~CHSi(OC2H5)(0R)2
C8H17Si(OR)3
HSi(OR)3
Cl(CH2)3 ( )3
H2N(CH232NH(CH2)3S (CH3)(0 )2
Cl(cl8H37)N(cH2)3si(OR)3
(CH3)2
X
8~6
OR OR
CH3~2Si - Si(CH3?2
r CH31 r, 3 1
(- 313 - SiO- _ - SiO - Si(CH )
_ OR _ 20 - H _ 15
C6H5 OCH3 ~6H5
CH3 - Si OSi- - OSi - CH3 and
OR CH OR
partial hydrolysates of alkoxy silanes, e.g. Si(OC2H5)4
and CH3Si(OCH3)3, wherein some or all of the alkoxy
groups have been replaced by OR groups.
The silicon compounds employed according to this
invention may be prepared by the reaction of the
appropriate alcohol e.g. geraniol or phenylethyl alcohol
with a silicon compound having silicon-bonded chlorine
atoms or hydrogen atoms. It is usually preferred
however to prepare the desired silicon compound by
reacting the essential alcohol with a silicon compound
having alkoxy or alkoxyalkoxy groups whereby some or all
of such groups are replaced by the alcohol residue.
Some reaction can take place merely by bringing the two
reactants together. It is preferred however to expedite
the reaction by the use of elevated temperatures and/or
suitable catalysts, such as potassium carbonate, sodium
hydroxide and metal organic compounds, e.g. stannous
octoate.
~ ~,
~836
As the quaternary ammonium compound lngredient of
the fabric conditioner compositions of this invention
there may be employed any such compounds which are
capable of imparting softness and/or lubricity to
textile fabrics. Examples of the types of quaternary
ammonium compounds which can be employed are the
alkyldimethyl ammonium compounds represented by the
formula
Q2N(CH3)2 ~ X
amido alkoxylated ammonium compounds represented by the
formula
(CH2CH20) nH
[Q HNCH2CH2 - N - CH2CH2NH - Q] X and
CH3
amido imidazolines represented by the formula
Q - C ~ N
CH3 - N - CH2 CH2 X
CH2 2NH& Q
in which general formulae, n is an integer, Q represents
a fatty alkyl group, and X represents for example chlorine,
bromine, iodine or the methylsulphate ICH3SO4) group, The
preferred classes of quaternary ammonium compounds are the
di(fattyalkyl) dimethyl ammonium compounds, (fattyalkyl)-
dimethylaryl ammonium compounds and the (fattyalkyl)
~attyamido imidazolinium compounds particularly those
wherein the fatty alkyl group has from 8 to 18 carbon
8~6
atoms. It is also preferred to employ the chloride,
iodide or methylsulpha~e. Specific examples of such
preferred compounds are di-tallow di-methyl ammonium
chloride, di-tallow di-methyl ammonium iodide and
2-heptadecyl-l-methyl-l-(2'-stearoylamido-ethyl)-
imidazolinium methyl sulphate.
The fabric conditioner compositions of this
invention may be prepared by mixing the silicon compound
and the quaternary ammonium compound. The proportion of
silicon compound employed is not critical and will depend,
for example, on the degree of fragrance desired and on the
particular silicon compound(s) employed. Thus, a silane
having four OR groups per molecule should be more effective
than the same weight of a high molecular weight siloxane
having four such OR groups per molecule. In general we
prefer to employ the silicon compound in a proportion of
fxom 0.01 to 20 per cent, more preferably 0.05 to 5 per
cent, by weight, based on the total weight of the
composition. More than one silicon compound may be
incorporated into the fabric conditioner composition. For
example, in order to achieve a particular fragrance
se~eral silicon compounds containing different OR groups
may be blended together. Alternatively, there may be
employed a single silicon compound wherein the OR groups
are derived from two or more different essential alcohols.
Also, if desired, the silicon compound~s) may be employed
in conjunction with one or more of the essential alcohols
per _ .
8~6
In addition to the silicon compound and
quaternary ammonium compound the compositions of this
invention may contain other ingredients which are
normally found in fabric conditioners, for example
diluents, such as isopropanol and water, and optical
brighteners.
The compositions of this invention can be employed
to treat fabrics (e.g. ~ool, cotton and synthetics~ in the
same manner as for conventional fabric conditioner.
Usually such compositions are dispersed in the wash or
rinse water to provide an add-on of about 0.01 to about
1% by weight based on the weight of the fabric. The
compositions of this invention impart softness and/or
lubricity to the treated fabric. They also impart a
fragrance which is characteristic of the alcohol(s) from
which the OR residues are derived and which is detectable
for at least several days after treatment.
The following examples in which Me represents
methyl,
X represents -OCH2CH=C(CH3)(CH2)2CH-c(cH3)2
y ~ -O(CH2)2C~3CH(c~2)2cH C(CH3)2
Z " -O(CH2)2C6H5
illustrate the invention.
Example 1.
MeSi(OMe)3 (0.1 mole; 13.6g.) was refluxed with
geraniol (0.2 mole; 30.8 g.) under a positive nitrogen
pressure for 28 hours during which time methyl alcohol
was removed by means of a Dean and 5tark apE-a~atus.
The resulting reaction mixture (Silane Al was analysed
by gas-liquid chromatography and found to have the
following composition by weight:
MeSi(:OMe)3/MeOH 2.4%
HOCH2CH=C(CH3)(CH2)2CH-C(CH3)2 14.2%
MeSi(OMe)2X 13.0~
MeSi(OMe)X2 48.6%
MeSiX3 21.9%
Using a similar procedure two more silane mixtures
Silane B and Silane C were prepared by reacting
MeSi(OMe)3 with respectively citronellol and 2-phenyl-
ethyl alcohol. The silane mixtures had the following
composition:
_ilane B
MeSi(OMe)3/MeOH 1.7%
HO(CH2)2(CH3)CH(CH2)2CH-(CH3)2 14.7%
MeSi(OMe)2Y 8.6%
MeSi(OMe)Y2 44.8~
MeSiY3 30.2%
Silane C
MeSi(OMe)3/MeOH 9.6%
HOZ 8.3%
~esi(oMe)2z 4.6%
Mesi(oMe)z2 43.6
MeZ2SiOSiZ2Me 33.9%
Silanes A, B and C were each mixed into different
samples of an 8% by weight solution of a dimethyl di(fatty-
alkyl) ammonium chloride in water the silanes being
incorporated in proportion of 0.4% by weight based on
the total weight of the composition. The compositions
were then made up into 0.6% by weight solutions in warm
(45 C) water. Pieces of Terry (cotton) cloth were
treated by rinsing in the solutions and the pieces hung
up to dry at normal atmospheric temperatures. For control
purposes cloth samples were treated with similar solutions
except that they were prepared from mixtures containing
0.2~ by weight of the essential alcohol in place of the
silane.
After l hour each of the cloth samples carried a
strong fragrance characteristic of the alcohol or
respectively the alcohol used to prepare the silane.
After 24 hours the cloths obtained using the silicon
compounds carried a much stronger fragrance than those
obtained using the alcohols. The fragrance present on
the silane-treated samples was quite strong after four
days whereas the alcohol treated cloths were indistinguish-
able in odour from an untreated cloth.
Example 2.
Geraniol (36 g.) was mixed with a poly(methyl-
hydrogen)siloxane of average composition Me3SirOSiHMe~250SiMe3
30 g.) and anhydrous potassium carbonate (0.1 g.) The
-- 12 -
mixture was heated at 80 - 95C for 16 hours during
which hydrogen was evolved. Filtration of the
reaction mixture yielded a water white viscous
polymer having the average composition
Me3Si rOSiMeH]5 1OSiMeX]200SiMe3
The siloxane was mixed with the quaternary
ammonium isopropanol solution described in Example 1
in a proportion of 0.4~ by weight. The resulting
product (0.6~) was dissolved in water (99.4%) and the
aqeous solution employed to treat Terry cloth as
described in Example 1.
After 24 hours the siloxane-treated cloths
carried a geraniol fragrance which was much stronger
than that of a control sample prepared using the
unmodified parent alcohol. This fragrance persisted
for at least four days whereas the control sample was
odourless after that time.
Example 3.
Example 2 was repeated employing cinnamic alcohol
2Q in place of the geraniol. In this case the cinnamic
odour of the siloxane-treated cloth was weaker after 24
hours than that of the control cloth. After 4 days,
however, the strength of fragrance on the siloxane-
treated cloth had increased significantly.
Example 4.
Water (2.2 g.) was added with stirring to
MeSi~OMe33 (27.2 g.). The mixture was heat~d to reflux
.~
(72C) and methanol collected by a Dean and Stark
apparatus. Geraniol (24.3 g.) was then added to the
partial hydrolysis product thus obtained and the mixture
heated for 15 hours at 90C. The methanol generated was
removed via the Dean and Stark apparatus to yield a pale
yellow, siloxane polymer having CH3,-OCH3 and X groups
bonded to the silicon atoms.
The siloxane polymer was evaluated as a fabric
conditioner ingredient by the technique described in
Example 1. After 24 hours the geraniol fragrance was
just perceptible but the strength of the odour had
increased significantly after 4 days. The control sample
prepared using the alcohol itself was odourless after
this time.
Similar results were obtained when phenyl
trimethoxysilane was reacted with geraniol and the
resulting silane mix~ure evaluated as described above.
_ 14 -
.~
