U.S. patent number 3,619,281 [Application Number 04/797,682] was granted by the patent office on 1971-11-09 for process for the improvement of textiles by the use of silicones and hardening accelerators.
This patent grant is currently assigned to Institut fur Silikon-und Fluorkarbon-Chemie. Invention is credited to Christian Dathe, Horst Kroning, Richard Muller.
United States Patent |
3,619,281 |
Kroning , et al. |
November 9, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR THE IMPROVEMENT OF TEXTILES BY THE USE OF SILICONES AND
HARDENING ACCELERATORS
Abstract
Process for the improvement of fibrous materials, particularly
in the finishing of textiles, by the use of silicones and hardening
accelerators, which comprises treating the materials with aqueous
emulsions of silicones and using as hardening accelerators an
addition compound of aminoalkyltrifluorosilane and hydrofluoric
acid. The fibrous materials thus treated exhibit an excellent and
lasting water repellence and a high resistance to rubbing off of
colors.
Inventors: |
Kroning; Horst (Dresden,
DT), Dathe; Christian (Radebeul, DT),
Muller; Richard (Radebeul, DT) |
Assignee: |
Institut fur Silikon-und
Fluorkarbon-Chemie (Radebeul, DT)
|
Family
ID: |
25171524 |
Appl.
No.: |
04/797,682 |
Filed: |
February 7, 1969 |
Current U.S.
Class: |
427/381; 524/837;
524/838; 525/478; 528/12; 528/31; 442/102; 428/447; 525/474;
525/509; 528/21 |
Current CPC
Class: |
D06M
15/643 (20130101); Y10T 442/2352 (20150401); Y10T
428/31663 (20150401) |
Current International
Class: |
D06M
15/643 (20060101); D06M 15/37 (20060101); D06m
015/66 () |
Field of
Search: |
;117/161,140,139.4,139.5
;260/29.2,29.4,46.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Perrone, Jr.; Mathew R. P.
Claims
what we claim is:
1. In a process for improving fibrous materials, particularly for
finishing textiles, wherein an emulsion of a finishing agent is
applied to the textile substrate, the thus treated textile is then
dried and finally cured to obtain the finished article, the
improvement comprising impregnating said fibrous materials with a
liquor containing aqueous emulsions of alkylhydrogenpolysiloxanes
or a mixture thereof with dialkylpolysiloxanes, in combination with
a hardening catalyst consisting of an addition compound of an
aminoalkylfluorosilane and hydrofluoric acid.
2. The process as defined in claim 1, wherein the ratio of silicone
content in the emulsion and the hardening catalyst is 100 parts by
weight of silicone: 0.1 to 50 parts of catalyst.
3. The process as defined in claim 2, wherein said ratio is 100
parts by weight of silicone: 1 to 30 parts of catalyst.
4. The process as defined in claim 1, wherein the silicone compound
in the emulsion is lower alkylhydrogenpolysiloxane and the addition
product in the impregnating liquor is
gamma-aminopropyltrifluorosilane-hydrogenfluoride of the formula
NH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SiF.sub.3.sup.. HF.
5. The process as defined in claim 1, wherein the silicone compound
in the emulsion is methylhydrogenpolysiloxane and the addition
product in the impregnating liquor is
gamma-aminopropyltrifluorosilane-hydrogenfluoride of the formula
NH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SiF.sub.3.sup.. HF.
6. The process as defined in claim 1, wherein the silicone compound
in the emulsion is lower alkylhydrogenpolysiloxane in mixture with
lower dialkylpolysiloxane, the impregnating liquor also containing
a urea-formaldehyde precondensate as crease-proofing agent, and the
addition product consists of
gamma-diaminoethylene-propyltrifluorosilane-bis-hydrogenfluoride of
the formula NH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 CH.sub.2
SiF.sub.3.sup.. 2HF.
7. The process as defined in claim 1, wherein the silicone compound
in the emulsion is methylhydrogenpolysiloxane in mixture with
dimethylpolysiloxane, the impregnating liquor also containing an
urea-formaldehyde precondensate as crease-proofing agent, and the
addition product consists of
gamma-diaminoethylene-propyltrifluorosilane-bis-hydrogenfluoride of
the formula NH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 Ch.sub.2
SiF.sub.3.sup.. 2HF.
Description
The present invention relates to a process for the improvement of
fibrous materials, for instance, for finishing textiles by means of
silicones.
It is known that for finishing textiles, solutions or aqueous
emulsions of dialkylpyolysiloxanes and/or of
alkylhydrogenpolysiloxanes can be used, both called "silicones"
hereinafter. In order to make the silicones adhere to the materials
to be finished, at reduced hardening temperatures, it is necessary
to use simultaneously some condensation accelerators or catalysts.
It has already been suggested to use as catalysts organometallic
compounds, e.g. tin, zinc or lead salts of carboxylic acids, and
also inorganic compounds such as zirconyl oxide-chloride and lead
nitrate together with the above-named silicones; one of the
purposes of the finishing treatment is, for instance, hydrophobing
or rendering water repellent.
It is moreover known to use as hardening agents water-soluble
aminoalkylsilanes, e.g. gamma-aminopropyltriethoxysilane.
The above-mentioned products have however a number of shortcomings
which decrease the possibility of their use. Thus the metal salts
of long-chain carboxylic acids active as hardening agents are water
insoluble, and it is therefore necessary to convert them into
stable dispersions miscible with water before they can be used in
the finishing operations. However, it is difficult to be sure that
these dispersions will be truly stable and it is not impossible
that instable impregnating liquors will thus result.
It is a further disadvantage that the use of metal salts as
catalysts incurs a considerable decrease in resistance of the
colors against rubbing off. Therefore catalysts containing the
above-described metal salts cannot be used when the fibrous
materials are supposed to have a high resistance to such rubbing
off of colors.
As to aminoalkylsilanes, these have a slightly alkaline reaction in
water; when using alkyl- or arylhydrogenpolysiloxanes as
hydrophobing agents, hydrogen splitting will soon occur with
decomposition of the alkyl(aryl)hydrogenpolysiloxane, and that
renders impregnating liquors useless after a short time.
Furthermore, aminoalkylsilanes are easily subject to gelling. Up to
the present, there are no agents known to counteract the
gelling.
It is the object of the present invention to provide a process
which will permit to avoid the shortcomings of the methods hitherto
known in the improvement, particularly the hydrophobing treatment,
of fibrous materials with the use of silicones.
It is a further object to provide a process for providing on
textiles a permanent hydrophobing finish.
It is yet another object to provide a finishing process for fibrous
materials in cases in which high resistance to rubbing off of
colors is required.
Other objects and many of the attendant advantages will be readily
appreciated as the same becomes better understood by reference to
the following detailed description.
It has now been found that in the process of improving the
properties of fibrous materials, more particularly the finishing of
textiles, the shortcomings caused by the presence of
aminoalkylsilanes can be eliminated by using aminoalkylsilanes
which have been treated with hydrofluoric acid. In the
last-mentioned treatment, very stable addition products of
aminoalkyltrifluorosilanes with hydrofluoric acid are obtained
which proved to be very effective when added to known emulsions of
silicones as hardening catalysts. Even gelled aminoalkylsilanes and
distillation residues of aminoalkylsilanes can be used, which are
otherwise not suitable for the preparation of such addition
products.
The preparation of the addition products is not the subject matter
of the present invention; they may be made in accordance with U.S.
Pat. application Ser. No. 572,890 filed Aug. 17, 1966 by Christian
Dathe, one of the coinventors of this application, and others, and
entitled "Production of Amino-Organofluorosilicates," issued as
U.S. Pat. No. 3,458,555 of July 29, 1969. The addition products are
obtained as crystalline, water-soluble products of the general
formula NR.sub.2 (CH.sub.2).sub.n SiF.sub.3.sup.. mHF, in which R
stands for hydrogen, an organic group or an organic amino group,
e.g. -C.sub.2 H.sub.2 NH.sub.2 or -CH.sub.2 CH.sub.2 NHCH.sub.2
CH.sub.2 NH.sub.2, n= 1 to 8, preferably 3 and 4, and m .ltoreq.
the number of N atoms in the molecule, but at least 1. The
compounds have considerable stability to water and they are used in
combination with aqueous silicone emulsions for making fibrous
materials, such as textiles, water repellent.
As already mentioned, the impregnating liquor prepared with
silicone emulsions and the addition products have extraordinary
stability and lead to a hydrophobing finish which is laundry-proof
and resistant to chemical cleaning, while allowing the materials to
maintain their complete resistance to rubbing off of colors.
The quantity of the addition product to be used as hardening
accelerator or catalyst, calculated on the silicone content of the
emulsion, is not critical. In general, 0.1 to 50 parts by weight,
preferably 1 to 30 parts, of the addition product are used per 100
parts by weight of silicone. The quantity is partly dependent on
the type of fabric, its material, its weave, and the desired
finishing effect. It is advantageous to make a preliminary test to
determine the desirable amount of the addition product in each
individual case.
The process according to the invention is especially suitable when
the silicone component consists of lower
alkylhydrogenpolysiloxanes, e.g. methylhydrogenpolysiloxanes or
mixtures of the same with lower dialkylpolysiloxanes, e.g.
dimethylpolysiloxanes.
The catalyst according to the invention also favorably affects the
stability of the impregnating liquor in the presence of products
for rendering the materials crease-proof, for instance in the
presence of urea-formaldehyde precondensates.
The invention will now be more fully explained in a number of
examples, but it should be understood that these are given by way
of illustration and not of limitation and that many changes in the
details can be made without departing from the spirit of the
invention.
In the following all parts are given by weight, unless stated
otherwise.
EXAMPLE 1
a. Preparation of the Silicone Emulsion
To 50 parts of a solution consisting of 60 percent of a
methylhydrogenpolysiloxane having a viscosity of 16 cst.
(20.degree. C.) and 40 percent of test benzine, we add
successively, while stirring, 1.5 parts of a nonylphenoxypolyglycol
ether and 48.5 parts of water; the so obtained preliminary emulsion
is homogenized in a homogenizer which permits adjustment to 150
atm. superpressure.
b. Effecting the Impregnation
A mixed fabric consisting of 67 parts of polyester fiber and 35
parts of cotton is treated with an aqueous impregnating liquor of
the following composition: 30 g./l. of the silicone emulsion as
described in a. and 2.5 g./l. of
gamma-aminopropyltriflourosilane-hydrogenflouride, NH.sub.2
CH.sub.2 CH.sub.2 CH.sub.2 SiF.sub.3.sup.. HF, made according to
the above-mentioned U.S. Pat. No. 3,458,555.
The impregnating liquor does not exhibit any splitting off of
hydrogen upon use of polyhydrogensiloxanes and remains stable for a
period of at least 24 hours. It imparts to the fabric the following
properties:
treated not treated
__________________________________________________________________________
Spraying test according to "Spezitex-Hydrophob" 1 5
Crease-restoring angle .alpha.60 according to TGL 0-53 830
131.degree. 105.degree. Resistance to rubbing according to TGL 0-54
021 5 5
__________________________________________________________________________
it should be added at this point, by way of explanation, that
"Spezitex" is a collective trademark registered in the German
Democratic Republic, the use of which is limited by a strict
adherence to a number of tests set down in a circular dated June
1964.
Briefly stated, hydrophobing tests are carried out on a 20
cm..sup.2 flat piece of textile specimen inclined at 45.degree. to
the horizontal plane, which is sprayed with water from a height of
15 cm. The hydrophobing effect is indicated by the degree of
adherence of the drops to the surface of the textile, and is graded
as follows:
1. Drops of water running off completely;
2. Slight adherence of drops on the sprayed surface;
3. Slight wetting of the sprayed surface;
4. Noticeable wetting of larger areas;
5. Complete soaking of the sprayed specimen.
"TGL" stands for "Technische Guete und Lieferbedingungen," an
official/German-language/designation for accepted specifications of
the German Democratic Republic, comparable to ASTM in U.S.A.
EXAMPLE 2
a. Preparation of the Silicone Emulsion
In a high-speed stirrer Type "Ultra-Thurrax," made by the film
Janke & Kunkel, Staufen, German Federal Republic:
17 parts dimethylpolysiloxane having a viscosity of 1000 cst.
(20.degree. C.),
13 parts methylhydrogenpolysiloxane having a viscosity of 50 cst.
(20.degree. C.),
20 parts test benzine,
3 parts of a polyoxyethylene-sorbitane ester of a fatty acid,
and
47 parts water.
b. Effecting the Impregnation
A cotton fabric is finished by treating it with an impregnating
liquor of the following composition:
250 g./l. of an approx. 50 percent urea-formaldehyde precondensate,
4 g./l. ammonium chloride,
2 g./l. glacial acetic acid,
50 g./l. the silicone emulsion prepared under a/ and
10 g./l.
gamma-diaminoethylenepropyltrifluorosilane-hydrogenfluoride,
NH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 CH.sub.2
SiF.sub.3.sup.. 2HF, made according to the U.S. Pat. No.
3,458,555.
The impregnating liquor, which remains effective for at least 8
hours, imparts to the cotton fabric the following high-quality
properties:
Spraying test according to "Spezitex-Hydrophob" 1 to 2 Spraying
test after three washings in soap and soda 2 to3 Crease-restoring
angle .alpha.60 according t o TGL 0-53 830 12 6.degree. Resistance
to rubbing according to TGL 0-54 021 5
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