U.S. patent number 3,876,459 [Application Number 05/374,848] was granted by the patent office on 1975-04-08 for treatment of fibres.
This patent grant is currently assigned to Dow Corning Limited. Invention is credited to Peter Martin Burrill.
United States Patent |
3,876,459 |
Burrill |
April 8, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Treatment of fibres
Abstract
Wool is rendered resistant to shrinkage on washing by treatment
with from 0.1 to 10% by weight of a composition obtained by mixing
(A) a polydiorganosiloxane having terminal silicon-bonded hydroxyl
radicals and (B) an organosilane RSiR'.sub.n X.sub.3-n, in which R
is a monovalent radical containing at least two amine groups, R' is
alkyl or aryl, X is alkoxy and n is 0 or 1, and/or a partial
hydrolysate and condensate of the silane. The applied composition
is thereafter cured.
Inventors: |
Burrill; Peter Martin
(Glamorgan, WA) |
Assignee: |
Dow Corning Limited (London,
EN)
|
Family
ID: |
23478443 |
Appl.
No.: |
05/374,848 |
Filed: |
June 29, 1973 |
Current U.S.
Class: |
427/387; 428/375;
8/127.6; 428/447 |
Current CPC
Class: |
D06M
15/643 (20130101); D06M 15/6436 (20130101); Y10T
428/31663 (20150401); Y10T 428/2933 (20150115) |
Current International
Class: |
D06M
15/37 (20060101); D06M 15/643 (20060101); C08h
019/04 () |
Field of
Search: |
;8/127.6,128A ;117/141
;260/46.5E |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
594,901 |
|
Nov 1947 |
|
GB |
|
746,307 |
|
Mar 1956 |
|
GB |
|
Primary Examiner: Schulz; William E.
Attorney, Agent or Firm: Fleming, Jr.; Robert F.
Claims
1. A process for the treatment of keratinous fibres which comprises
applying thereto from 0.1 to 10% by weight, based on the weight of
the fibres, of a composition comprising the product obtained by
mixing (A) a polydiorganosiloxane having terminal silicon-bonded
hydroxyl radicals and a molecular weight of at least 750, at least
50 percent of the organic substituents present in the
polydiorganosiloxane being methyl radicals, any other radicals
being monovalent hydrocarbon radicals having from 2 to 30 carbon
atoms, (B) up to 50 parts by weight per 100 parts (A) of an
organosilicon compound selected from the group consisting of
organosilanes of the general formula RSiR'.sub.n X.sub.3.sub.-n
wherein R represents a monovalent radical of less than 21 carbon
atoms composed of carbon, hydrogen, nitrogen and, optionally,
oxygen, which radical contains at least two amine groups and is
attached to silicon through a silicon to carbon linkage, R'
represents a radical having less than 19 carbon atoms selected from
the group consisting of alkyl radicals and aryl radicals, each X
represents an alkoxy radical having from 1 to 14 inclusive carbon
atoms and n is 0 or 1, and partial hydrolysate and condensate
products of said organosilanes, and (C) in amount from that
sufficient to significantly reduce the time and temperature
required to cure the composition to 20 parts based on the weight of
(A) and (B) of an organosilicon compound selected from the group
consisting of (i) silanes of the general formula R".sub.m
SiZ.sub.4.sub.-m wherein R" represents a substituent selected from
the group consisting of hydrogen atoms, monovalent hydrocarbon
radicals having from 1 to 18 carbon atoms and monovalent
halogenated hydrocarbon radicals having from 1 to 18 carbon atoms,
Z represents a radical selected from the group consisting of alkoxy
radicals and alkoxyalkoxy radicals having from 1 to 4 inclusive
carbon atoms and m is 0 or 1, and (ii) partial hydrolysates and
condensates of
2. A process as claimed in claim 1 wherein (C) is employed in a
proportion of from 1 to 20 percent by weight based on the total
weight of (A) and
3. A process as claimed in claim 1 wherein (B) is an organosilane
having the general formula RSiX.sub.3 in which R is selected from
the group consisting of --(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2
NH.sub.2 and --CH.sub.2 CHCH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2
NH.sub.2 radicals and each X is selected from the group consisting
of methoxy and ethoxy
4. A process as claimed in claim 3 wherein the composition is
applied to
5. A composition comprising the product obtained by mixing (A) a
polydiorganosiloxane having terminal silicon-bonded hydroxyl
radicals and a molecular weight of at least 750, at least 50
percent of the organic substituents in the polydiorganosiloxane
being methyl radicals, any other substituents being monovalent
hydrocarbon radicals having from 2 to 30 carbon atoms, (B) an
organosilicon compound selected from the group consisting of
organosilanes of the general formula RSiR'.sub.n X.sub.3.sub.-n
wherein R represents a monovalent radical composed of carbon,
hydrogen, nitrogen and, optionally, oxygen, which radical contains
at least two amine groups and is attached to silicon through a
silicon to carbon linkage, R represents a radical having less than
19 carbon atoms selected from the group consisting of alkyl
radicals and aryl radicals, each X represents an alkoxy radical
having from 1 to 14 inclusive carbon atoms and n is 0 or 1, and
partial hydrolysate and condensate products of said organosilanes,
and (C) an organosilicon compound selected from the group
consisting of (i) silanes of the general formula R".sub.m SiZ.sub.
4.sub.-m wherein R" represents a substituent selected from the
group consisting of hydrogen atoms, monovalent hydrocarbon radicals
having from 1 to 18 carbon atoms and monovalent halogenated
hydrocarbon radicals having from 1 to 18 carbon atoms, Z represents
a radical selected from the group consisting of alkoxy radicals and
alkoxyalkoxy radicals having from 1 to 4 inclusive carbon atoms and
m is 0 or 1, and (ii) partial hydrolysates and condensates of (i)
wherein component (B) is employed in a proportion of from 0.5 to 15
percent by weight based on the weight of (A) and component (C) is
employed in a proportion of from 1 to 20 percent by
6. A composition as claimed in claim 5 which also comprises an
organic solvent.
Description
This invention relates to a process for the treatment of keratinous
fibres.
It has been proposed to reduce the shrinkage of wool on washing by
treatment with various organosilicon compounds. For example in U.K.
Pat. Nos. 594,901, 613,267 and 629,329 it is proposed to reduce the
normal tendency of wool to shrink by treating the wool with certain
alkyl or aryl silanes. In U.K. Pat. No. 746,307 there is disclosed
a process for preventing the shrinkage of wool by treating the wool
with a composition consisting of a diorganopolysiloxane, in which
the organic substituents are alkyl, phenyl or alkenyl, and a
siloxane containing silicon-bonded hydrogen atoms.
While the known processes have conferred a degree of shrink
resistance on woollen fabrics this effect has not been durable to
laundering. There has consequently been a need for a shrink
resistant treatment having improved durability to washing and which
imparts to the fibres a durable soft handle.
We have now discovered that the above recited advantages of
durability of handle and shrink resistance may be realised by
treatment of keratinous fibres with certain siloxane
compositions.
According to this invention there is provided a process for the
treatment of keratinous fibres which comprises applying thereto
from 0.1 to 10% by weight, based on the weight of the fibres, of a
composition comprising the product obtained by mixing (A) a
polydiorganosiloxane having terminal silicon-bonded hydroxyl
radicals and a molecular weight of at least 750, at least 50
percent of the organic substituents in the polydiorganosiloxane
being methyl radicals, any other substituents being monovalent
hydrocarbon radicals having from 2 to 30 carbon atoms and (B) an
organosilane of the general formula RSiR'.sub.n X.sub.3.sub.-n
wherein R represents a monovalent radical composed of carbon,
hydrogen, nitrogen and, optionally, oxygen, which radical contains
at least two amine groups and is attached to silicon through a
silicon to carbon linkage, R' represents an alkyl radical or an
aryl radical, each X represents an alkoxy radical having from 1 to
14 inclusive carbon atoms and n is 0 or 1, and/or a partial
hydrolysate and condensate of said organosilane, and thereafter
curing the applied composition.
The invention also includes keratinous fibres whenever treated by
the said process.
The polydiorganosiloxanes (A) are linear or substantially linear
siloxane polymers having terminal silicon-bonded hydroxyl radicals.
Such polydiorganosiloxanes have about two, that is from about 1.9
to 2, organic radicals per silicon atom and methods for their
preparation are well known in the art. The polydiorganosiloxanes
should have an average molecular weight of at least 750 and
preferably from 20,000 to 90,000.
At least 50 percent of the silicon-bonded organic substituents in
the polydiorganosiloxane are methyl, any other substituents being
monovalent hydrocarbon radicals having from 2 to 30 carbon atoms,
for example alkyl and cycloalkyl radicals, e.g. ethyl, propyl,
butyl, n-octyl, tetradecyl, octadecyl and cyclohexyl, alkenyl
radicals e.g. vinyl and allyl and aryl, aralkyl and alkaryl
radicals e.g. phenyl, tolyl and benzyl. A small proportion of
hydroxyl radicals may be attached to non-terminal silicon atoms in
the polydiorganosiloxane. However, such non-terminal hydroxyl
radicals should preferably not exceed about 5% of the total
substituents in the polydiorganosiloxane. The preferred
polydiorganosiloxanes are the polydimethylsiloxanes i.e. those
represented by the formula ##SPC1##
in which a is an integer preferably having a value such that the
polydiorganosiloxane has a viscosity of from 100 to 50,000 cS at
25.degree.C.
Component (B) of the compositions employed in the process of this
invention is an organosilane of the general formula RSiR'.sub.n
X.sub.3.sub.-n wherein R, R', X and n are as defined hereinabove or
may be a partial hydrolysate and condensate of said organosilane.
Such organosilanes are known substances and they may be prepared as
described, for example, in U.K. Pat. Nos. 858,445 and 1,017,257. In
the general formula of the organosilanes the radical R is composed
of carbon, hydrogen, nitrogen and, optionally, oxygen and contains
at least two amine (which term includes imine) groups. It is
attached to silicon through a silicon to carbon linkage, there
being preferably a bridge of at least 3 carbon atoms separating the
silicon atom and the nearest nitrogen atom or atoms. Preferably
also, R contains less than about 21 carbon atoms and any oxygen is
present in carbonyl and/or ether groups. Examples of the operative
R substituents are --(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2,
--(CH.sub.2).sub.4 NHCH.sub.2 CH.sub.2 NHCH.sub.3,
--CH.sub.2.CH.CH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2,
--(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2
NH.sub.2, ##SPC2##
and (CH.sub.2).sub.3 NH(CH.sub.2).sub.2 NHCH.sub.2 CH.sub.2
COOCH.sub.3. Each of the X substituents may be an alkoxy radical
having from 1 to 14 carbon atoms, preferably from 1 to 4 carbon
atoms. Examples of X radicals are methoxy, iso-propoxy, hexoxy and
decyloxy. When present R' may be any alkyl or aryl radical,
preferably having less than 19 carbon atoms, e.g. methyl, ethyl,
propyl, octyl or phenyl. Preferred as component (B) are the
organosilanes having the general formula RSiX.sub.3 wherein R
represents the --(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 or
the --CH.sub.2 CHCH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2
radicals and each X represents the methoxy or ethoxy radicals.
In the practice of this invention the product obtained by mixing
components (A) and (B) is applied to keratinous fibres. When
components (A) and (B) are mixed together at normal or elevated
temperatures they react, at least partially. The product applied to
the fibres will therefore usually comprise, at least in part, a
reaction product of (A) and (B) rather than a simple mixture of
these two. The composition may be applied to the keratinous fibres
using any suitable application technique, for example by padding or
spraying. Most conveniently the composition is applied in the form
of a dispersion or solution in a liquid carrier. Preferably the
compositions are applied as a solution in an organic solvent.
Solvents which may be employed include the hydrocarbons and
chlorinated hydrocarbons, for example toluene, xylene, white spirit
and perchloroethylene. A particularly convenient method of treating
the fibres is by application from an organic solvent solution
employing a conventional dry-cleaning machine. When application
from an aqueous medium is desired it is preferred to employ as
component (B) organosilanes in which X contains 3 or more carbon
atoms and to partially react (B) with (A), or with both (A) and
(C), prior to emulsification.
The relative proportions of (A) and (B) employed in the preparation
of the mixture may vary between fairly wide limits. Preferably from
0.5 to 15 parts by weight of the silane (B) are employed per 100
parts by weight of (A), but proportions of (B) in excess of 15
parts, for example up to 50 parts or more are operative.
Following application of the composition the treated fibres are
dried and the deposited composition cured. Drying and curing may be
carried out by merely exposing the treated fibres to normal
atmospheric temperatures (about 20.degree.C) for periods of from
several hours to several days. If desired, however, this step may
be expedited by the use of elevated temperatures, e.g. from
60.degree. - 140.degree.C. Curing is believed to be initiated by
traces of water. Under normal conditions the moisture present in
the atmosphere and/or in the applied composition is sufficient for
this purpose. If necessary, however, the water content of the
curing environment may be supplemented.
According to a further aspect of this invention we have found that
the time and/or temperature required for cure of the applied
composition may be significantly reduced if there is incorporated
in the applied composition certain silanes or partial hydrolysates
thereof. In a preferred method of carrying out this invention
therefore the composition applied to the fibres has incorporated
therein a third component (C) which is (i) a silane of the formula
R".sub.m SiZ.sub.4.sub.-m, where R" is a hydrogen atom or a
monovalent hydrocarbon radical or monovalent halogenated
hydrocarbon radical, Z is an alkoxy or alkoxy alkoxy radical having
from 1 - 4 inclusive carbon atoms and m is 0 or 1 and/or (ii) a
partial hydrolysate and condensate of the said silane. Compositions
comprising (A), (B) and (C) are novel and are included within the
scope of this invention.
In the general formula of the silane (i) R" may be hydrogen atom or
a monovalent hydrocarbon radical or halogenated hydrocarbon
radical, for example alkyl, e.g. methyl, ethyl, propyl, butyl,
hexyl, decyl, octadecyl, alkenyl e.g. vinyl or allyl, aryl, aralkyl
or alkaryl e.g. phenyl, tolyl or benzyl, halogenoalkyl e.g.
chloromethyl, bromoethyl or 3,3,3-trifluoropropyl and halogenoaryl
e.g. chlorophenyl. The radical Z may be for example methoxy,
ethoxy, propoxy or methoxyethoxy. Preferably Z is methoxy or ethoxy
and R", when present, is methyl. Examples of the silanes (i) and
their partial hydrolysis and condensation products (ii) are
methyltrimethoxysilane, ethyltrimethoxysilane,
n-propyltriethoxysilane, phenyltriethoxysilane, tetraethyl
orthosilicate, n-butyl orthosilicate, ethyl polysilicate and
siloxanes containing both silicon-bonded methyl radicals and
methoxy radicals.
Component (C) is best incorporated into the composition by mixing
with components (A) and (B) prior to dispersion or solution. The
proportion of (C) employed is not narrowly critical. Preferably it
is present in a proportion of from 1 to 20 percent by weight based
on the total weight of (A) and (B).
Use of component (C) expedites curing of the applied composition
and enables a more consistent improvement in shrink resistance to
be obtained. The extent of the advantage obtained will vary
somewhat depending on the nature of (C). As an indication, however,
the presence of methyltrimethoxysilane in the composition enables
significant shrink resistant properties to be obtained after
several minutes cure at about 70.degree.C or by exposure to normal
atmospheric temperatures for a period of from 4 to 24 hours.
The time and/or temperature required for curing the applied
composition may also be reduced by incorporating in the composition
a siloxane condensation catalyst. Such catalysts may be employed in
place of or in addition to the silane component (C). Substances
which function as siloxane condensation catalysts are well known in
the art. Particularly suitable catalysts for use in the process of
the present invention are the metal organic compounds, for example,
the titanium alkoxides and chelates e.g. tetrabutyl titanate,
tetra-isopropyl titanate and di-isopropoxytitanium
di(ethylactoacetate), and metal carboxylates e.g. stannous octoate,
dibutyltin dilaurate, dibutyltin diacetate and lead octoate. The
catalysts are employed in conventional catalytic proportions,
normally from 0.1 to 5% by weight based on the combined weights of
(A) and (B).
The use of siloxane condensation catalysts as described hereinabove
can, however, significantly reduce the useful (bath) life of the
compositions. In general therefore, the use of the siloxane
condensation catalyst is less preferred than the incorporation of
the silane (C) as a means of expediting curing.
The process of this invention finds application in the treatment of
keratinous fibres to endow such fibres with a resistance to
shrinkage on washing and also with a durable soft handle. The
fibres may be treated in any form, any example of yarns, knitted or
woven fabrics or made up garments. They may be present as the sole
fibres or as blends with other types of fibre. Where improved
handle of the treated fibres is the primary consideration, this may
be achieved by depositing on the fabric as little as 0.1% of its
weight of the composition. When a significant level of shrink
resistance is required a somewhat higher level of application of
the composition, e.g. from about 0.5 to 10%, preferably from 1 to
5%, is more appropriate. The weight of composition applied to the
fibres, as referred to herein, means the weight of active
ingredients namely (A) and (B), or (A), (B) and (C), deposited on
the fibres.
If desired the treated fibres may be endowed with a firmer handle
by including in the applied composition a resinous organosiloxane
polymer, for example a resinous copolymer of (CH.sub.3).sub.3
SiO.sub.0.5 and SiO.sub.2 groups.
The following examples, in which the parts are expressed by weight,
illustrate the invention. The partial condensate of CH.sub.3
Si(OCH.sub.3).sub.3 employed in certain of the examples was
prepared by refluxing the silane with aqueous sodium hydroxide
solution (0.25% by weight NaOH) for 3 hours. The partial condensate
was then recovered after neutralisation and removal of
volatiles.
Example 1
A composition was prepared by mixing Polydimethylsiloxane having
terminal .tbd.SiOH groups and M.Wt. = 45,000 (3000cS at
25.degree.C) 90 parts (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.3
NHCH.sub.2 CH.sub.2 NH.sub.2 5 parts CH.sub.3 Si(OCH.sub.3).sub.3 5
parts
Three parts by weight of the composition were then dissolved in 97
parts by weight of toluene. This solution was used to treat 3
samples of 1:1 cover factor, knitted 2'28s botany wool fabric by
padding at 100% mangle expression. After treatment the samples were
allowed to air dry at 22.degree.C for 1 hour and then placed in an
air circulating oven at 120.degree.C for 5 minutes.
A square of 20 cm. side was marked out on each of the treated
samples employing a template and the samples were then washed in
1.25% by weight phosphate buffer solution (pH7) containing 1
g./litre of sodium dioctyl sulphosucciante. The temperature of the
wash water was 40.degree.C and washing was carried out in a
domestic automatic washing machine.
After 5 minutes the wash was interrupted and the dimensions of the
marked square measured with the fabric in the wet state. The wash
was then continued for 6 hours after which time the marked square
was measured again.
The area felting shrinkage of the samples was then calculated
according to the formula
% Area felting shrinkage (FS) = % width shrinkage (WS) .times. %
length shrinkage (LS)
WS .times. LS/100
The width shrinkage and length shrinkage were determined according
to the formula
Width or length shrinkage = dimension after 5 minutes - dimension
after 6 hours.
The average value of percentage area felting shrinkage for the 3
samples was 0.2%. The value obtained with control samples of
untreated wool was 72%.
Example 2
The procedure of Example 1 was repeated except that the fabric
samples were of chlorinated wool and washing of the samples was
carried out in an International Cubex Machine according to the
method of International Wool Secretariat Specification W.S.S. 128,
Test Method No. 185 (Superwash specification).
In this case the value of area felting shrinkage obtained was
3.3%.
Example 3
Four compositions, designated A to D, were prepared by mixing:
Polydimethylsiloxane as employed in Example 1. x parts X.sub.3
Si(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 y parts Partial
condensate of CH.sub.3 Si(OCH.sub.3).sub.3 z parts
The values X.sub.3, x, y and z in the composition were as
follows:
X.sub.3 x y z ______________________________________ A (OC.sub.2
H.sub.5).sub.3 86.2 12 1.8 B (On--C.sub.4 H.sub.9).sub.3 83.3 15
1.7 C (On--C.sub.6 H.sub.13).sub.3 82.5 16 1.5 D
(OCH.sub.3)(On--C.sub.8 H.sub.17).sub.2 82.5 16 1.5
______________________________________
Three parts of each of the compositions was then dissolved in 97
parts of perchloroethylene and the compositions employed to treat
samples of knitted botany wool fabric (2'28s, 1:1 cover factor) by
padding at 100% mangle expression. After treatment the samples were
allowed to dry and cure at 25.degree.C for 24 hours.
On completion of the 24 hour curing period the shrinkresist
properties of the wool samples following washing were measured
according to the procedure employed in Example 2. In each case the
area felting shrinkage was less than 10%.
Example 4
The procedure of Example 1 was repeated except that the methyl
trimethoxysilane component was omitted from the composition and the
aminosilane was employed at a level of 10 parts per 90 parts of
polydimethylsiloxane. Cure of the applied composition in this case
was brought about by exposing the treated fabric to a temperature
of about 25.degree.C for 4 days.
The area felting shrinkage for the treated fabrics was measured
according to the procedure of Example 2 and a value of 14%
obtained.
Example 5
A composition was prepared by mixing:
Polydimethylsiloxane having terminal .tbd.SiOH 88.2 parts groups
and M.Wt. = 60,000 (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.3 NHCH.sub.2
CH.sub.2 NH.sub.2 10 parts Partial condensate of CH.sub.3
Si(OCH.sub.3) 1.8 parts
Three parts of the composition were dissolved in perchloroethylene
(97 parts) and the solution applied to samples of knitted botany
wool (2'28s, 1:1 cover factor) by padding at 100% mangle
expression. The samples were then exposed to the air at 25.degree.C
for 24 hours and the area felting shrinkage measured after washing
according to Example 2. A value of 5% was obtained.
Example 6
Three compositions were prepared according to the following
formulation
Polydimethylsiloxane of Example 1 88.2 parts (CH.sub.3 O).sub.3
Si(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 10 parts Silicate
1.8 parts
In each of the three compositions the silicate component was
respectively ethyl polysilicate, tetraethyl orthosilicate, and
tetra(n-propyl) orthosilicate.
Three solutions were prepared by dissolving three parts of each of
the compositions in perchloroethylene (97 parts) and the
compositions then applied to knitted botany wool (2'28s, 1:1 cover
factor) by padding at 100% mangle expression. After being allowed
to air dry for 24 hours at 22.degree.C the area felting shrinkage
of the samples after washing was measured according to the
procedure of Example 2. In each case the area felting shrinkage was
less than 10%.
Example 7
The procedure of Example 1 was repeated except that the composition
was prepared by mixing,
Polydimethylsiloxane as Example 1 95 parts (CH.sub.3 O).sub.2
CH.sub.3 Si(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 5
parts
The washing period was 3 hours, and curing was carried out for 30
minutes at 120.degree.C. The area felting shrinkage of the treated
samples after washing was 1%.
Example 8
Compositions were prepared by mixing,
The compositions were applied to samples of botany wool by padding
from 3% solutions in perchloroethylene. The samples were then dried
by exposure to the ambient atmosphere (21.degree.C) for 4 hours.
Measurement of the area felting shrinkage according to the
procedure of Example 2 gave a value of 3.6% for the composition
containing silane (a), 1.3% for (b) and 14.1% for (c).
* * * * *