U.S. patent number 3,637,427 [Application Number 04/761,336] was granted by the patent office on 1972-01-25 for process for imparting high-elastic recovery to extensible knitted or woven fabrics and product obtained.
This patent grant is currently assigned to Nippon Rayon Kabushiki Kaisha (Nippon Rayon Co., Ltd.). Invention is credited to Kunio Amemiya, Tokuju Goto, Hiroshiro Kimura, Akio Koshimo, Hideki Matusaka, Hirohisa Nara, Motohiro Tsuruta.
United States Patent |
3,637,427 |
Tsuruta , et al. |
January 25, 1972 |
PROCESS FOR IMPARTING HIGH-ELASTIC RECOVERY TO EXTENSIBLE KNITTED
OR WOVEN FABRICS AND PRODUCT OBTAINED
Abstract
The present invention relates to a process for imparting
high-elastic recovery to extensible knitted or woven fabrics by
treating the fabric with an organic solution of low-viscosity
containing a hydroxy-terminated dimethylpolysiloxane, a
methylhydrogen polysiloxane and an organometallic catalyst.
Inventors: |
Tsuruta; Motohiro (Kyoto-shi,
JA), Kimura; Hiroshiro (Kyoto-fu, JA),
Koshimo; Akio (Kyoto-fu, JA), Nara; Hirohisa
(Kyoto-fu, JA), Goto; Tokuju (Nara-shi,
JA), Amemiya; Kunio (Kyoto-fu, JA),
Matusaka; Hideki (Kyoto-fu, JA) |
Assignee: |
Nippon Rayon Kabushiki Kaisha
(Nippon Rayon Co., Ltd.) (Kyoto-fu, JA)
|
Family
ID: |
11512439 |
Appl.
No.: |
04/761,336 |
Filed: |
September 20, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Jan 13, 1968 [JA] |
|
|
43/1829 |
Sep 20, 1967 [JA] |
|
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42/60336 |
|
Current U.S.
Class: |
442/105;
427/389.9; 427/387 |
Current CPC
Class: |
D06M
15/643 (20130101); Y10T 442/2377 (20150401) |
Current International
Class: |
D06M
15/643 (20060101); D06M 15/37 (20060101); D06m
015/66 () |
Field of
Search: |
;117/161ZA,138.8A,138.8E,138.8F,138.8N,138.8PV,139.5A ;252/8.6
;260/825 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Husack; Ralph
Claims
What is claimed is:
1. A process for imparting high-elastic recovery to extensible
bulky knitted or woven fabrics composed of textured yarns made of
synthetic fibers having an extensibility of more than 20 percent,
which comprises applying to the fabric an organic solution
containing
1. a hydroxy-terminated dimethylpolysiloxane having the general
formula:
in which n is an integer not less than 500;
2. a methylhydrogen polysiloxane having the general formula:
in which n is an integer from 15 to 50, the ratio of methylhydrogen
polysiloxane to dimethylpolysiloxane is 5 to 30 parts by weight of
methylhydrogen polysiloxane based upon 100 parts by weight of
dimethylpolysiloxane; and
3. an organic metallic catalyst, dissolved in an organic solvent
capable of dissolving said polysiloxanes and utilized in an amount
to give a solution having a viscosity of not more than 400 c.p.s.
so that 1.0 to 5.0 percent by weight of the fabric, of
polysiloxanes are deposited as solid on said fabric, and then
curing the polysiloxane treated fabric at an elevated
temperature.
2. The process of claim 1 in which said fabric is composed of
textured yarn selected from the class consisting of polyamide,
polyester, polyacrylonitrile, polyolefin, polyvinylalcohol and
mixtures thereof.
3. The process of claim 2 in which said textured yarn is
twist-set-untwist yarn, false twist yarn, stuffer box-treated yarn
or mixtures thereof.
4. The process of claim 1 in which the treating solution further
contains at least one member selected from the class consisting of
sodium alcoholate, ester silane and polyalkyl silicate.
5. The process of claim 1 in which said organometallic catalyst is
at least one member selected from the class consisting of zinc
caprylate, tin caprylate, zirconium caprylate, dibutyl tin
dicaprylate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl
tin oxide, alkyl titanate, zinc naphthenate, tin naphthenate,
zirconium naphthenate, ferric naphthenate, cobalt naphthenate, zinc
formate, zirconium formate, zinc acetate and zirconium acetate.
6. The process of claim 1 in which said organic solvent is a
hydrocarbon having carbon atoms of from one to 10.
7. The process of claim 6 in which said hydrocarbon is one member
selected from the class consisting of petroleum benzine, gasoline,
benzene, toluene, xylene, trichloroethylene, perchloroethylene and
ethyl acetate.
8. The process of claim 1 in which said fabric is cured at a
temperature of from 120.degree. to 200.degree. C.
9. The product of the process of claim 1.
Description
BACKGROUND OF THE INVENTION
Conventional processes are known for producing waterproof fabrics
by treating fabrics having relatively low extensibility with
organopolysiloxanes. For example, British Pat. No. 1,077,190
describes a process for producing waterproof fabrics by treating a
fabric with a highly viscous solution of organopolysiloxanes having
a viscosity of from 1,000 to 100,000 c.p.s. In this process,
because of the high viscosity of the solution, the interfiber voids
on the surface are filled up with the solution, which accordingly
can not penetrate sufficiently deeply into the interior of the
fabric. In addition, for the purpose of producing waterproof
fabrics, the fabric used should have a relatively low
extensibility.
SUMMARY OF THE INVENTION
It has now unexpectedly been discovered that the elastic recovery
of knitted or woven fabric having a relatively large extensibility
can be enhanced without the deminution of extensibility while the
elastic recovery of the fabric remains substantially unchanged in
both dry and wet states by treating such fabric with a low-viscous
solution of organopolysiloxanes such as hydroxy-terminated
dimethylpolysiloxane and methylhydrogen polysiloxane dissolved in a
suitable organic solvent, said solution uniformly penetrating in an
amount of from 1 to 5 percent (as solid) by weight of fabric into
the fabric.
An object of the present invention is therefore to provide a
process for imparting extensible knitted or woven fabrics with
high-elastic recovery in both dry and wet states.
Further object of the present invention is to provide such improved
fabrics .
According to the present invention, we provide a process for
imparting extensible knitted or woven fabrics with high-elastic
recovery, which comprises treating the fabric with an organic
solution having a viscosity of less than 400 c.p.s. and containing
a hydroxy-terminated dimethylpolysiloxane, methylhydrogen
polysiloxane and an organic metal catalyst so that said
hydroxy-terminated dimethylpolysiloxane and methylhydrogen
polysiloxane can be deposited in an amount of 1 to 5 percent (as
solid) by weight of fabric in said fabric, and curing the same at a
temperature of from 120.degree. to 200.degree. C.
The knitted or woven fabrics which may be used for the purpose of
the present invention have preferably an extensibility of more than
20 percent and include e.g., those composed of textured yarns made
of synthetic fibers such as fibers of polyamide, polyester,
polyacrylonitrile, polyolefin, polyvinylalcohol etc. Preferred
examples of "textured yarns" include crimped yarns such as
twist-set-untwist yarns, false twist yarn, stuffer box-treated
yarn, edge-crimped yarn, air-jetted yarn and mixtures thereof.
The term "extensibility" used in this specification denotes the
percentage of elongation of a sample piece having a width of 5 cm.
and a length of 10 cm. when burdened with a load of 1.5 kg. based
on the original length of the sample piece.
The treating solution used for the process of the present invention
may have the following composition:
1. A hydroxy-terminated dimethylpolysiloxane having the following
general formula:
in which n is an integer of not less than 500.
2. A methylhydrogen polysiloxane having the following general
formula:
in which n is an integer from 15 to 50.
3. An organometallic catalyst, for example, zinc caprylate, tin
caprylate, zirconium caprylate, dibutyl tin dilaurate, dibutyl tin
dicaprylate, dibutyl tin diacetae, dibutyl tin oxide, alkyl
titanate, zinc naphthenate, tin naphthenate, zirconium naphthenate,
ferric naphthenate, cobalt naphthenate, zinc formate, zirconium
formate, zinc acetate, zirconium acetate etc.
The foregoing components are dissolved in an organic solvent in
which the organopolysiloxanes are soluble and which does not
deteriorate the texture of the fabric and is inactive to said
substances. Preferred examples of organic solvents which may be
used for the purpose of the present invention include hydrocarbons
having carbon atoms of not more than 10 such as petroleum benzine,
gasoline, benzene, toluene, xylene, trichloroethylene,
perchloroethylene and ethylacetate.
Further, better results may be obtained by adding suitable
additives such as e.g., sodium alcoholate, ester silane, polyalkyl
silicate etc. These additives serve to improve the elastic recovery
and washability of the final products because they are capable of
cross-linking with aforesaid polysiloxanes so as to increase the
degree of the polymerization.
Sodium alcoholates are represented by the general formula: RONa, in
which R is an alkyl group having less than five carbon atoms.
Polyalkyl silicate is a polymer obtained by partially hydrolyzing
organosilicates represented by the general formula: (RO).sub.4 Si,
in which R is an alkyl group having less than five carbon atoms.
Ester silanes are represented by the general formula:
R.sub.n Si(OR').sub.4-n , in which R is an alkyl group having less
than five carbon atoms and R' is an alkyl group having less than
five carbon atoms, and n is an integer of from 1 to 3.
The treating solution of the present invention must be applied to
the fibers uniformly, and for this purpose, the
dimethylpolysiloxane of the present invention should be dissolved
in the organic solvent so as to give a low viscosity. It is
essential that the viscosity of the treating solution at 20.degree.
C. used in the present invention is less than 400 c.p.s. (as
measured by using a conventional rotary viscometer [type BL
available from Tokyo Keiki Seizo-sho. K.K., Japan]). If the
viscosity is higher than that level, the liquid is liable to remain
only the surface of the fabric, thus covering the interfiber voids
so that it hardly is possible to obtain the desired elastic
recovery. The preferred blending proportions of the components are
for example as follows:
Five to 30 (preferably 10 to 25) weight parts of methylhydrogen
polysiloxane and 0.1 to 5 weight parts of organometal catalyst per
100 weight parts of dimethyl polysiloxane. The organic solvent
should be used in sufficient amounts so that the liquid viscosity
will stay below 400 c.p.s.
There are various methods for applying the treating solution to the
fabric, but it is advantageously effected e.g., either by immersing
the fabric in the treating solution and then squeezing it, or by
coating or spraying the solution to the fabric. The amount of
deposition of the organopolysiloxanes should be 1.0 to 5.0 percent
by weight of the fabric. If such amount is less than 1.0 percent,
unsatisfactory elastic recovery may be obtained, while if it is
more than 5.0 percent, the feel of and extensibility of the fabric
may be deteriorated.
After treating the fabric, it is dried e.g., at 50.degree. to
120.degree. C. under lowest possible tension to remove the organic
solvent. The fabric is then cured e.g., at 120.degree. to
200.degree. C. under lowest possible tension thereby effecting the
cross-linkage of the organopolysiloxanes with the fibers and the
reaction between each of the organopolysiloxanes. It is desirable
to treat the fabric under minimum tension. Such low-tension
treatment will permit the extensibility prior to the treatment to
be carried over to the resultant article.
The article thus obtained has a high-elastic recovery never seen in
conventional bulky articles and its elasticity can be equal to that
of elastomer fibers. It is thus possible to obtain articles having
high-elastic recovery being equal to that of the elastomer fibers
by subjecting extensible fabric to the treatment according to the
present invention. Articles thus obtained are free from
deterioration of color fastness and washability, and can minimize
production costs.
The following nonlimitative examples illustrate the invention.
EXAMPLES
In the examples, the samples were cured by means of a conventional
short-loop baking machine (available from Hirano Kinzoku Kogyo
K.K., Japan). The extensibility and elastic recovery were
determined in the following manner:
1. Extensibility:
The extensibility was determined by using a tensile tester,
Autograph P-loo (available from Shimazu Seisakusho, K.K, Japan)
under the following conditions:
Weight of Load 1,500 g. Length of sample 10 cm. Width of sample 5
cm. Tensile speed 10 cm./min. Chart speed 20 cm./min.
2. Elastic recovery:
A similar tester and samples to those described above were used for
determining the elastic recovery. The sample was loaded with a
suitable load so as to stretch the sample to a length of 80 percent
of the elongation, which was obtained when loaded with a load of
1,500 grams. The sample was left for 1 minute. The sample was
reluxed and left for 3 minutes in reluxed state, (without tension).
The elastic recovery rate is the percentage of the recovery of the
elongation during the reluxed state and can be defined as
follows:
Elastic recovery rate = (c/b ).times.100 in which b is the length
by which the sample was stretched and c is the length by which the
sample was recovered (and a+b-c is the length of the sample after
being stretched and then retained in relaxed state for 3 minutes
without tension, where a is the length of the prestretched
sample).
3. The extensibility and elastic recovery in wet state were
determined in a similar manner to that described above after the
removal of the water content of the sample, which has been immersed
in water for 10 minutes by using a filter paper.
EXAMPLE 1
Two-stage interlock fabric (jersey) and twill-knitted fabric
knitted by using nylon bulky yarn (70 deniers/2 filaments) were
respectively immersed in a solution having the following
composition (viscosity: 40 c.p.s.) and were squeezed to give
polysiloxanes (as solid) amounting to 0.5%, 1.0%, 3.0%, 5.0%, and
7.0% by weight of the fabric respectively:
Composition of the solution: part by weight
Dimethyl polysiloxane 2.7 Methylhydrogen polysiloxane 0.3
Phenyltriethoxysilane 0.03 Dibutyl tin dilaurate 0.03
Trichloroethylene 96.94
The trichloroethylene was removed off by heating at 80.degree. C.
The fabric was then cured by using a short-loop baking machine at
155.degree. C. for 3 min. under lowest possible tension.
The jersey and twill thus obtained had the extensibility and
elastic recovery values shown in tables 1 and 2, respectively.
Key to Tables
A. Amount of polysiloxane deposited as solid (percent by weight of
the fabric)
B. Extensibility
C. Elastic recovery (in dry state)
D. Elastic recovery (in wet state)
E. Antipilling property (determined as class)
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TABLE 1 (2-stage interlock
jersey) A 0 0.5 1.0 3.0 5.0 7.0 B 61. 242.0 227.1 209.0 184.1 81.9
C 78.0 93.5 93.8 94.0 94.0 94.0 D 74.1 75.2 91.2 92.7 94.0 94.0 E 1
1 4 5 5 5
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table 2 (twill knitted
fabric) A 0 0.5 1.0 3.0 5.0 7.0 B 52.3 177.0 147.6 117.7 106.8 70.3
C 76.1 93.5 93.7 93.9 94.0 94.0 D 73.2 80.1 92.8 93.0 93.4 93.7 E 1
1 3 4 4 5
__________________________________________________________________________
it is apparent from the tables that when the deposited amount of
polysiloxanes is less than 5 percent (by weight of the fabric)
substantial increase of extensibility can be obtained. Amounts
greater than 5 percent will decrease the extensibility sharply and
the feeling of the treated fabrics will also largely deteriorate.
The elastic recovery in dried state is likely to be almost
independent on the changes of the deposited amounts of the
polysiloxanes, while the elastic recovery in wet state
significantly decreases when the deposited amount of polysiloxanes
is less than 1 percent by weight of the fabric. The antipilling
property shown in tables 1 and 2 was determined by means of the
method according to Japanese Industrial Standard (JIS) L-1076-1967,
which is similar to the so-called ICI method. The antipilling
property will be advantageous when the deposited amount of the
polysiloxanes is more than 1 percent by weight of the fabric.
From the observation described above, it appears that the
deposition of the polysiloxanes in an amount of from 1 to 5 percent
by weight of the fabric is most favorable.
EXAMPLE 2
A similar process to that described in example 1 was performed with
the exception of using the polysiloxanes in such amount that they
would be deposited in the fabric in an amount of 2 percent by
weight of the fabric (calculated as solid).
The amount of trichloroethylene was changed stepwise so as to give
the viscosities of the solution of 10, 40, 120, 250, 400, 500 and
1,000 c.p.s., respectively. The obtained results are shown in
tables 3 and 4. The results obtained are likely to be substantially
independent on the treating time.
Key to Tables
A. Viscosity of the solution (c.p.s.)
B. Extensibility (percent)
C. Elastic recovery percent (in a dry state)
D. Elastic recovery percent (in wet state)
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TABLE 3 (2-stage interlock
jersey) A 0 10 40 120 250 400 500 1,000 B 61.0 242.5 214.0 167.8
125.6 100.8 90.3 89.9 C 78.0 94.2 93.3 90.4 90.4 87.7 82.7 80.2 D
74.1 93.5 93.0 91.2 91.4 90.0 76.3 75.5
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table 4 (twill knitted
fabric) A 0 10 40 120 250 400 500 1,000 B 52.3 150.2 138.0 115.7
107.9 89.9 85.4 80.2 C 76.1 93.0 93.5 94.2 92.4 90.1 85.3 80.7 D
73.2 92.3 91.5 90.4 90.7 89.4 74.3 72.4
__________________________________________________________________________
from the tables, it is apparent that when the viscosity of the
polysiloxanes-containing solution is not more than 400 c.p.s. good
extensibility and elastic recovery rates both in dry and wet states
can be obtained; while these values are lowered by using the
polysiloxanes solution having a viscosity of more than 400
c.p.s.
EXAMPLE 3
A three-stage interlock fabric of nylon bulky yarn (70 deniers/2
filaments; jersey) was immersed in a treating solution having the
following composition, and was then dried at 80.degree. C. to
remove off the trichloroethylene.
Composition of the Solution (part by weight)
Dimethylpolysiloxane 2.8 Methylhydrogen polysiloxane 0.7 Dibutyl
tin diacetate 0.02 Trichloroethylene 96.48 Viscosity of the
solution 40 cps.
The fabric was cured at 160.degree. C. for 3 minutes under a lowest
possible tension by using the conventional short-loop baking
machine to yield a fabric having an improved extensibility, and
elastic recovery as shown in table 5.
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TABLE 5
Extensi- Elastic Condition Sample bility % Recovery %
__________________________________________________________________________
Dry Nontreated 48.2 70.2 Treated 92.6 91.2 Wet Nontreated 47.1 69.8
Treated 114.2 90.9
__________________________________________________________________________
EXAMPLE 4
A similar treatment to that described in example 3 was performed
using the nylon jersey with the exception of employing the
following treating solutions:
Composition of the solution (part by weight)
Dimethylpolysiloxane 3.0 Methylhydrogen polysiloxane 0.3 Metallic
sodium ethylate 0.02 Dibutyl tin diacetate 0.02 Trichloroethylene
96.66 Viscosity of the solution 50 cps.
__________________________________________________________________________
Organopolysiloxanes (3.5 percent calculated as solid) was thus
deposited on the fabric. The fabric was then dried at 80.degree. C.
to remove off the solvent, and was cured at 160.degree. to give a
fabric having improved extensibility and elastic recovery as shown
in table 6. The curing was performed in an analogous manner to that
described in example 3.
Key to Table
A. Extensibility before washing (percent)
B. Extensibility after washing five times (percent)
C. Elastic recovery before washing (percent)
D. Elastic recovery after washing five times (percent)
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TABLE 6
Condition Sample A B C D
__________________________________________________________________________
Dry Nontreated 48.2 50.0 70.2 68.1 Treated 130.2 128.7 94.3 95.0
Wet Nontreated 47.1 49.0 69.8 66.6 Treated 133.1 130.0 94.6 91.5
__________________________________________________________________________
The washing test was performed by using a Hitachi SC-AT Model 3
Washing Machine (commercial product available from Hitachi
Seisaku-sho K.K., Japan) and washed in a solution of 1 g./l. of
Emal (an anionic washing agent available from Kao Sekken K.K.,
Japan) at 40.degree. C. for 10 minutes. Excellent elastic recovery
in wet state, good extensibility and improved elastic recovery
after washing for 5 minutes was particularly observed.
EXAMPLE 5
A similar process to that described in example 4 was performed with
the exception that an ester silane [C.sub.6 H.sub.5 Si(OC.sub.2
H.sub.5).sub.3 ] substituted for the metallic sodium ethylate. No
washing test was made in this example. The fabric obtained also had
improved extensibility and elastic recovery as shown in table
7.
Key to Table
A. Extensibility (percent)
B. Elastic recovery (percent)
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TABLE 7
Condition Sample A B
__________________________________________________________________________
Dry Nontreated 48.2 70.2 Treated 129.3 92.3 Wet Nontreated 47.1
69.8 Treated 130.1 91.7
__________________________________________________________________________
EXAMPLE 6
A similar treatment to that described in example 4 was carried out
with the exception of substituting diethoxy pentasilane for the
metallic sodium ethylate. The properties of the fabric thus
obtained are shown in table 8. No washing test was made.
Key to Table
A. Extensibility (percent)
B. Elastic recovery (percent)
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TABLE 8
Condition Sample A B
__________________________________________________________________________
Dry Nontreated 48.2 70.2 Treated 129.3 92.3 Wet Nontreated 47.1
69.8 Treated 130.1 91.7
__________________________________________________________________________
* * * * *