U.S. patent number 3,852,402 [Application Number 05/304,576] was granted by the patent office on 1974-12-03 for process for the preparation of polyvinyl alcohol fibers.
Invention is credited to Toshio Kimura, Susumu Kousaka, Shoichi Tanaka.
United States Patent |
3,852,402 |
Tanaka , et al. |
December 3, 1974 |
PROCESS FOR THE PREPARATION OF POLYVINYL ALCOHOL FIBERS
Abstract
Process for the preparation of polyvinyl alcohol fibers
comprising: I. spinning an aqueous polyvinyl alcohol spinning
solution containing boric acid or a borate salt thereof; Ii.
coagulating the spun polyvinyl alcohol solution in an aqueous
solution containing sodium or potassium hydroxide and sodium
sulfate to obtain fibers; Iii. roller drawing said fibers; Iv.
neutralizing said fibers V. wet-heat drawing said fibers; Vi.
rinsing said fibers with water to adjust the amount of residual
boric acid or borate salt to 0.2 to 0.9% by weight of polyvinyl
alcohol; Vii. dehydrating and drying said fibers; and Viii.
dry-heat drawing said fibers to a total drawing ratio of at least
1,300 percent.
Inventors: |
Tanaka; Shoichi
(Kurashiki-City, JA), Kousaka; Susumu
(Kurashiki-City, JA), Kimura; Toshio (Nara-City,
JA) |
Family
ID: |
27460403 |
Appl.
No.: |
05/304,576 |
Filed: |
November 7, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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90816 |
Nov 18, 1970 |
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Foreign Application Priority Data
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Nov 25, 1969 [JA] |
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44-94790 |
Apr 30, 1970 [JA] |
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45-37354 |
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Current U.S.
Class: |
264/185;
264/210.2; 264/210.6; 264/210.7 |
Current CPC
Class: |
D01F
1/10 (20130101); D01F 6/14 (20130101) |
Current International
Class: |
D01F
6/02 (20060101); D01F 6/14 (20060101); D01f
007/00 () |
Field of
Search: |
;264/185,21F
;260/29.6BM,91.3VA |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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34-2061 |
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Apr 1959 |
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JA |
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37-5822 |
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Jun 1962 |
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JA |
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37-14422 |
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Jul 1962 |
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JA |
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166,444 |
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Dec 1964 |
|
SU |
|
Primary Examiner: Woo; Jay H.
Attorney, Agent or Firm: Kaufman & Kramer
Parent Case Text
This application is a continuation-in-part of co-pending
application Ser. No. 90,816 filed Nov. 18, 1970 and now abandoned.
Claims
What is claimed is:
1. Process for the preparation of polyvinyl alcohol fibers
comprising:
i. spinning an aqueous polyvinyl alcohol solution comprising 10 to
30 percent by weight of a polyvinyl alcohol having a degree of
polymerization ranging from 1,200 to 3,500 and 1 to 5 percent boric
acid or a substantially water soluble borate salt thereof based on
the weight of polyvinyl alcohol;
ii. coagulating the spun polyvinyl alcohol solution in an aqueous
solution containing 10 to 100 gms/liter sodium or potassium
hydroxide and 100 to 330 gms/liter sodium sulfate to obtain
fibers;
iii. roller drawing said fibers;
iv. neutralizing alkali adhered to said fibers with acid;
v. wet-heat drawing said fibers;
vi. rinsing said fibers with water to adjust the amount of residual
boric acid or borate salt to 0.2 to 0.9 percent by weight of
polyvinyl alcohol;
vii. dehydrating and drying said fibers; and
viii. dry-heat drawing said fibers to a total drawing ratio of at
least 1,300 percent, thereby obtaining polyvinyl alcohol fibers
exhibiting the following high temperature properties:
Yarn tenacity at 120.degree. c. -- at least 7.5 gms/denier
Yarn initial modulus at 120.degree. C. -- at least 100
gms/denier
Yarn creep at 135.degree. C. -- less than 2 percent.
2. Process as defined in claim 1 wherein the fibers are rinsed with
water to adjust the amount of residual boric acid or borate salt to
0.2 to 0.7 percent by weight of polyvinyl alcohol.
3. Process as defined in claim 1 wherein the spinning solution is
maintained at a pH of from 3 to 5.
4. Process as defined in claim 3 wherein the pH of the spinning
solution is adjusted by addition thereto of an inorganic acid,
organic acid or mixture of an organic acid and a salt of an organic
acid.
5. Process as defined in claim 1 wherein the fibers are dry-heat
drawn to a total drawing ratio of from 1,300-1,800 percent.
Description
The present invention relates to a process for the preparation of
polyvinyl alcohol fibers which exhibit excellent properties at high
temperature such as yarn tenacity, yarn initial modulus and yarn
creep.
Generally, polyvinyl alcohol (PVA) fibers surpass other synthetic
fibers in breaking strength and initial modulus, and have recently
found wide use in many fields, for instance, fiber reinforced
plastics (FRP). It is a well-known fact that PVA fibers which are
drawn to the drawable limit and minimized in heat-shrinkage exhibit
outstanding breaking strength and initial modulus. However, PVA
fibers, like many other synthetic fibers, undergo a deterioration
in properties at high temperature in proportion to the rise in the
temperature.
The primary object of the present invention is to obviate the above
deficiencies in synthetic fibers by providing a process for
preparing PVA fibers having excellent properties at high
temperature. More particularly, the synthetic fibers produced in
accordance with the present invention are superior to conventional
PVA fibers with respect to yarn tenacity, yarn initial modulus and
yarn creep. Radial-ply tires which utilize the PVA fibers produced
by the present invention in the cord of the breaker give excellent
results in the plunger test, high speed test, cornering power test,
tread wear-resistance test and durability test.
The PVA synthetic fibers produced by the present invention exhibit
high crystallinity and molecular orientation, and are characterized
by the high temperature properties indicated below and by the
amount of boric acid (H.sub.3 BO.sub.3) or a borate salt thereof
contained therein, the properties at high temperature being as
follows:
yarn tenacity at 120.degree.C at least 7.5 g/d yarn initial modulus
at 120.degree.C. at least 100 g/d yarn creep at 135.degree.C. less
than 2% boric acid or borate 0.2 to 0.9% by weight salt content of
PVA
Generally speaking, the extensibility of synthetic fibers increases
in proportion to the rise in temperature, and the strength and yarn
initial modulus decrease. It can be easily speculated that this
phenomenon occurs because movement is initiated in the molecular
chain of the fiber in regions of low molecular orientation upon
heating the fiber. This movement is soon transmitted to regions of
the fiber where molecular orientation is intense. It is therefore
important in the improvement of the properties at high temperature
of a synthetic fiber to suppress the movement of molecular chains
as much as possible. This can be achieved either by (1)
intensifying the orientation of the molecular chains to such an
extent as to prevent them from moving, or (2) adding to the polymer
a material which hinders the movement of molecular chains. These
two remedies, however, when separately employed are not capable of
achieving the objects of the present invention, i.e., property
improvement at high temperature such as improvement in yarn
tenacity, yarn initial modulus may be expected in a method wherein
a conventional PVA fiber is subjected to post-treatment with boric
acid; however, the same process will also result in a remarkable
decrease in yarn tenacity.
It has been found in accordance with the present invention that the
essential factor which fulfills the primary object of the present
invention is a fibrous structure wherein the orientation of the
molecular chains is quite intense as a whole but which contains a
substance to prohibit the movement of the molecular chains where
the molecular orientation is relatively loose. That is, a portion
or all of the boric acid or borate salt thereof contained in the
fiber may combine with the PVA in relatively loose orientation, to
prohibit the movement of the molecular chains caused by heating.
When the amount of boric acid or borate salt does not measure up to
0.2 percent by weight of PVA, it is insufficient to restrain the
chain movement. When the boric acid or borate salt content exceeds
0.9 percent, it will prevent the molecular chains from being highly
oriented, thereby causing reduction of the yarn strength.
The PVA fibers of the present invention can be produced by a
process comprising: preparing an aqueous solution of PVA which
contains boric acid or borate salt thereof (the spinning solution);
spinning in a coagulating bath comprising a major amount of water,
sodium hydroxide or potassium hydroxide and sodium sulfate, said
materials being present in the coagulating bath in a predetermined
amount; drawing the resulting fibers between rollers; neutralizing
any alkali adhered to the fibers with acid; wet-heat drawing of the
fibers; water-rinsing to adjust the amount of boric acid remaining
in the fiber to be within a predetermined range; dehydrating and
drying; and, dry-heat drawing.
The concentration of the coagulating bath, which has heretofore
been used in the conventional wet spinning method to produce PVA
fibers containing no boric acid or borate, is almost saturated with
sodium sulfate, when sodium sulfate is used as the dehydrating salt
in the bath. This is done because the fibers will stick to one
another due to insufficient coagulation, when the concentration of
the dehydrating salt in said bath is lower than 100 g/l.
Accordingly, the coagulating bath used in the present invention is
further combined with sodium hydroxide or potassium hydroxide in a
predetermined amount, thereby facilitating the spinning of spinning
solutions containing boric acid or borate. The properties of the
PVA fiber thus produced depend very little on the temperature. It
is often observed that when the content of sodium sulfate is high
in the coagulating bath, the drawability of the product tends to
decrease. The PVA synthetic fibers produced in accordance with the
present invention exhibit superior drawability and less temperature
dependency as compared with conventional PVA fibers which contain
no boric acid.
In accordance with the present invention, it has been found that
the aqueous spinning solution of PVA containing boric acid or a
borate salt thereof can be coagulated to produce PVA synthetic
fibers having yarn tenacity, yarn initial modulus and yarn creep
which hardly depend on the temperature. The method of the present
invention comprises spinning an aqueous solution of PVA containing
boric acid or a borate salt thereof into a coagulating bath being
kept strongly alkaline by the addition of 10 to 100 g/l sodium
hydroxide or potassium hydroxide and 100 to 330 g/l sodium sulfate,
which is then subjected to subsequent treatments such as roller
drawing, alkali neutralization, water-rushing to adjust the residue
of boric acid in the fiber to a range of 0.2 to 0.9 percent by
weight of PVA, dehydration and drying, and dry-heat drawing.
It is preferable to add boric acid or a borate salt thereof to the
spinning solution in an amount ranging between 1 and 5 percent by
weight of PVA.
Boric acid or any water soluble borate salt thereof can be employed
in accordance with the present invention. Any borate salt which is
substantially soluble in the aqueous spinning solution can be
suitably employed, as for example, the alkali metal borates such as
sodium borate, potassium borate and the like. The solution is
maintained weakly acidic, specifically between pH 3 and pH 5. The
pH of the solution can be regulated, if necessary, by addition of
an acid thereto. Acids which can be added to the solution can be,
for example, an inorganic acid such as sulfuric acid, nitric acid
and hydrochloric acid; an organic acid such as acetic acid,
tartaric acid, etc.; or a combination of an organic acid and a salt
of an organic acid, e.g. citric acid and sodium citrate, acetic
acid and sodium acetate, tartaric acid and potassium tartrate,
tartaric acid and sodium citrate, etc.
When the spinning solution has a pH lower than 3, the rate of
coagulation in the coagulating bath will be slower, and corrosion
of the apparatus occurs due to the high acidity. On the other hand,
when the pH is higher than 5, the solution becomes unstable causing
an increase in viscosity thereby greatly damaging the spinning
conditions.
The concentration of PVA in the spinning solution preferably ranges
between 10 and 30 percent by weight; the average degree of
polymerization of the PVA ranges from 1,200 to 3,500 and preferably
ranges from 1,500 to 3,000. The spinning solution is spun into a
strongly alkaline coagulating bath containing mainly water and
sodium hydroxide or potassium hydroxide in a range of 10 to 100 g/l
and sodium sulfate in a range of 100 to 330 g/l. Sodium hydroxide
or potassium hydroxide concentrations of less than 10 g/l result in
unfavorable effects such as reduction in the coagulating rate and
reduction of drawability at the time of spinning. It is considered
undesirable to exceed a sodium hydroxide or potassium hydroxide
concentration of 100 g/l because gelling action due to alkali
becomes so active, as to decrease the spinnability of the spinning
solution causing such properties as the yarn tenacity, yarn initial
modulus and yarn creep to be inferior. When the concentration of
sodium sulfate is less than 100 g/l, gelling action due to alkali
overpowers the dehydration and coagulating action of the sodium
sulfate. This causes swelling of the fiber at the time of
coagulation, which adversely affects the quality of the product. On
the other hand, concentrations of sodium sulfate exceeding 330 g/l
cause deformation in the fiber's cross section to substantially an
elliptical cross section since dehydration and coagulating action
overpowers other actions. The deformed section of the fiber is a
cause of reduction in drawability.
In the present invention, the PVA fiber thus spun is subjected to
subsequent conventional treatments such as roller drawing,
neutralization of alkali by the use of acid, wet-heat drawing, and
is then water-rinsed to adjust the amount of boric acid remaining
in the fiber to be in a range of 0.2 to 0.9 percent by weight of
PVA. The residue of boric acid after water-rinsing should be more
than 0.2 percent by weight of PVA because swelling of the fiber at
the time of rinsing may occur when it is less than said amount. The
swelling of the fiber will cause a slack in the fiber, which can
then be caught in the rollers resulting in an unstable operation,
thereby decreasing such properties as the yarn tenacity, yarn
initial modulus and yarn creep.
These drawbacks are not observed in the present invention because
the residue of boric acid present in the fiber may either react
with PVA to effect formation of inter-or intra-molecular
cross-linkings, hang on the PVA chains, or remain unreacted. This
is one of the characteristic features of the present invention.
When the amount of said boric acid exceeds 0.9 percent by weight,
the drawability of the fiber will decrease resulting in a decrease
in the absolute values of the yarn tenacity and yarn initial
modulus.
Thus, by selecting the optimum conditions for coagulation, the
process can be stabilized for production of fibers having high
drawability. Moreover, by so determining the conditions for
water-rinsing as to maintain the residue of boric acid in a range
of 0.2 to 0.9 weight percent and preferably in a range of 0.2 to
0.7 weight percent, products having properties hardly dependent on
temperature are obtained without reducing the dry-heat
drawability.
In the present invention, it is necessary to conduct the dry-heat
drawing of the PVA fiber subsequent to water-rinsing, dehydration
and drying, in order to achieve a total drawing ratio of more than
1,300 percent. If the total drawing ratio is less than 1,300
percent, it is difficult to obtain PVA fiber exhibiting the
above-mentioned properties. According to this invention, the PVA
fiber can be drawn to a total drawing ratio of 1,800 percent.
The properties of PVA fiber thus obtained are: yarn tenacity at
120.degree. C. of at least 7.5 gms/denier (g/d); yarn initial
modulus at 120.degree. C. of at least 100 g/d; and yarn creep at
135.degree. C. of less than 2 percent (elongation rate under the
load of 1 g/d for 60 minutes). The fibers contain 0.2 to 0.9
percent of boric acid or a borate salt and preferably contain 0.2
to 0.7 percent of boric acid or a borate salt. The fibers of the
present invention are superior to conventional PVA fibers
containing no boric acid or borate with respect to high temperature
properties.
The measurement of boric acid remaining in the synthetic fiber can
be conducted in accordance with the following method:
A fiber weighing in terms of PVA approximately 2g is placed in a
crucible, to which is added 0.1 mole/1 aqueous sodium hydroxide
solution to cover the fiber. After placing the crucible in a dryer
at 105.degree. C. for one night, it is baked in an electric furnace
at 400.degree. C. to 500.degree. C. for 60 minutes. The fiber in
the crucible is then placed in a beaker, to which is added
ion-exchanging water and maintained as it is for 60 minutes. A few
drops of phenolphthalein indicator are added to the beaker.
Whereupon, 0.1 mole/1 hydrochloric acid is added until the color
turns from red to yellow. After boiling for 30 to 60 minutes, it is
cooled and neutralized to pH 7 by sodium hydroxide or hydrochloric
acid addition as may be required. Mannite is added to the beaker
and the solution is again neutralized to pH 7 by titrating with 0.1
mole/1 sodium hydroxide. The volume (cc) being titrated is
measured. The amount of boric acid remaining in the fiber is
calculated by the following equation wherein W(g) is the weight of
PVA in the test product measured in accordance with the method
given above, and f and v(cc) are the strength and the titrated
volume, respectively, of the 0.1 mole aqueous solution of sodium
hydroxide:
0.62 .times. f .times. v/W
The dry break strength or tenacity is determined according to JISL
1070. Thus the sample of the fiber is twisted 8 times per 10 cm,
dried at 105.degree.C, for 3 hours and then immediately tested for
break strength with a sample having a length of 20 cm, at a drawing
speed 10 cm/min., using a constant speed elongating tensile
strength tester which has polyurethane film at the jaw face of the
fastener.
The initial modulus can be obtained from the stress-strain curve
given by the determination of the above dry break strength, in
reference to JISL 1073. For the determination at room temperature,
it is carried out in a room kept at 20.degree.C, while for the
determination at high temperatures, the upper and lower fastener of
the tester is in an atmosphere of an electric oven kept at
120.degree.C and the test performed until breaking of the sample
occurs.
The following examples further define, describe and compare the
polyvinyl alcohol fibers of the present invention and their methods
of preparation. Parts and percentages are by weight unless
otherwise indicated.
EXAMPLE 1
10kg of an aqueous spinning solution containing 1.7kg of PVA with a
degree of polymerization of 1,750 and degree of saponification of
99.5 mole percent, and 34g of boric acid and a sufficient amount of
nitric acid to adjust the pH to 4.3 is prepared. The spinning
solution is passed through spinning nozzles comprising 600 spinning
holes, 0.08mm in diameter into a coagulating bath containing 30g/l
of sodium hydroxide and 230g/l of sodium sulfate. The fiber thus
spun is then taken out of the bath at a rate of 10m/min., and then
subjected to subsequent treatments such as; roller drawing of 100
percent, neutralization in a bath comprising 70g/l of sulfuric acid
and 300g/l of sodium sulfate; wet-heat drawing of 150 percent;
water-rinsing to adjust the amount of boric acid to be 0.45
percent; dehydration and drying; and dry-heat drawing of 220
percent. The final product obtained is drawn to a total drawing
ratio of 1,500 percent.
The product thus obtained exhibits a yarn tenacity of 9.3g/d at
120.degree. C., yarn initial modulus of 135g/d at 120.degree. C.
and yarn creep of 1.4 percent at 135.degree. C.
In Table 1 below, comparative examples are provided which
illustrate the effects on yarn properties of variations in process
conditions and boric acid concentration. The conditions employed in
Example 1 and the resulting yarn properties obtained are also set
forth to assist in the comparison.
TABLE 1
__________________________________________________________________________
Example Compari- Compari- Compari- Compari- Compari- Compari-
Compari- 1 son 1 son 2 son 3 son 4 son 5 son 6 son
__________________________________________________________________________
7 Manufacturing Conditions Material: Polymerization degree of PVA
1,750 1,750 1,750 1,750 1,750 1,750 1,750 1,750 Saponification
degree of PVA 99.5 99.5 99.5 99.5 99.5 99.5 99.5 99.5 (mol %)
Spinning solution: the concentration of PVA (%) 17 17 17 17 17 18
18 17 the amount of boric acid 2.0 2.2 2.2 2.2 2.2 2.6 2.6 2.0
added (%) pH 4.3 4.1 4.1 4.1 4.1 4.0(1) 4.0(1) 4.3(2) Coagulation
bath: NaOH (g/l) 30 8 110 80 15 40 40 30 Na.sub.2 SO.sub.4 (g/l)
230 260 150 90 360 220 220 230 Neutralization bath: incapable of
H.sub.2 SO.sub.4 (g/l) 70 70 70 being spun 70 80 80 70 Na.sub.2
SO.sub.4 (g/l) 300 300 300 -- 300 320 320 300 Drawing: total
drawing ratio (%) 1,500 1,100(3) 1,200(4) -- 1,000(3) 1,500 1,200
1,100 roller drawing (%) 100 100 100 -- 100 100 100 100 wet-heat
drawing (%) 150 150 140 -- 150 150 140 150 dry-heat drawing (%) 220
140 192 -- 120 220 192 140
__________________________________________________________________________
Yarn Properties Amount of residue of boric acid (%) 0.45 0.51 0.52
-- 0.49 0.15 1.00 0.46 Tenacity (120.degree.C.) 9.3 6.2 7.0 -- 5.4
7.3 7.0 6.5 Initial modulus (120.degree.C.) (g/d) 135 72 82 -- 63
91 82 96 Creep (135.degree.C.) (%) 1.4 2.5 2.2 -- 3.1 2.3 2.4 2.3
__________________________________________________________________________
Note to Table 1:
In Example 1 to comparative Example 4, nitric acid is used to
adjust the pH.
1. tartatic acid used to adjust pH
2. acetic acid and sodium acetate used to adjust pH
3. sample exhibited poor drawability
4. sample exhibited poor spinnability
EXAMPLE 2
PVA fiber containing sodium borate and drawn to a total drawing
ratio of 1,500 percent is obtained in the same manner as in Example
1, except that sodium borate is employed in an amount of 1.5
percent by PVA in lieu of boric acid and tartaric acid is employed
in lieu of nitric acid for adjustment of pH. The product obtained
exhibits a yarn tenacity of 9.1 g/d at 120.degree. C., yarn initial
modulus of 127 g/d at 120.degree. C. and yarn creep of 1.5 percent
at 135.degree. C.
EXAMPLE 3
An aqueous PVA solution having a concentration of PVA of 15 weight
percent and containing 150g of PVA with a degree of polymerization
of 2,350 and a degree of saponification of 99.5 mole percent is
admixed with 30g of boric acid (2 percent by weight of PVA) and a
samll amount of acetic acid to prepare a spinning solution of pH of
4.5. The spinning solution is spun into a strongly alkaline
coagulating bath mainly of water containing 40 g/l of sodium
hydroxide and 250 g/l of sodium sulfate. After taking the spun
fibers out of the bath at a rate of 10 m/min., they are subjected
to roller drawing of 100 percent, neutralization, wet-heat drawing
of 150 percent, water-rinsing to adjust the amount of boric acid
residue to 0.4 percent by weight of PVA, dehydration and drying,
and dry-heat drawing of 200 percent. The product (1,200d/600f) is
thus drawn to a total drawing ratio of 1,400 percent. The product
thus obtained exhibits a yarn tenacity of 9.2 g/d at 120.degree.
C., yarn initial modulus of 131 g/d at 120.degree. C. and yarn
creep of 1.9 percent at 135.degree. C.; the product is superior in
its properties at high temperature.
EXAMPLE 4
An aqueous solution of PVA of 17 weight percent containing 100kg of
PVA with a degree of polymerization of 1,750 and a degree of
saponification of 99.9 mole percent is admixed with 2kg of boric
acid (2 weight percent of PVA) and 0.3kg of acetic acid (0.005g
equivalent to PVA 100g) to prepare a spinning solution. The pH is
maintained at 4.5.
The spinning solution is passed through nozzles of 1,000 holes in
number and 0.15mm in diameter into the coagulating bath containing
50 g/l of sodium hydroxide and 200 g/l of sodium sulfate. Then, the
fibers are taken out of the bath at a rate of 10 m/min. The
spinning condition is very stable in this case; during 2 weeks'
spinning, no difficulties such as clogging of the nozzles is
observed. The fiber thus spun is then subjected to the same
processing as in Example 3; i.e., roller drawing, neutralization,
wet-heat drawing, water-rinsing to adjust the amount of residual
boric acid to 0.5 percent by weight of PVA, dehydration drying, and
dry-heat drawing. The product (1,800d/1,000f) thus obtained is
drawn to a total drawing ratio of 1,400 percent. The product
exhibits a yarn tenacity of 9.3 g/d at 120.degree. C., yarn initial
modulus of 134 g/d at 120.degree. C. and yarn creep of 1.8 percent
at 135.degree. C.
EXAMPLE 5
1 Kg of an aqueous spinning solution containing 170g of PVA with a
degree of polymerization of 1,750 and degree of saponification of
99.5 mol percent, 5.95g of boric acid (3.5 weight percent on PVA)
and sulfuric acid sufficient to adjust the pH to 4 is prepared. The
spinning solution is passed through a nozzle into a coagulation
bath containing 15g/l of sodium hydroxide and 230g/l of sodium
sulfate. The resultant fiber is subjected to the same subsequent
treatment as in Example 1 to obtain PVA fiber containing 0.5 weight
percent of boric acid.
The product thus obtained exhibits excellent properties at
120.degree. C.
EXAMPLE 6
A PVA aqueous spinning solution containing 17 weight percent PVA
with a degree of polymerization of 1,700 and degree of
saponification of 99.5 mol percent, boric acid of 2 weight percent
on PVA and nitric acid of 0.2 weight percent on PVA to adjust the
pH to 4 is prepared.
The spinning solution is passed through a conventional nozzle
comprising 600 holes into a coagulation bath at 40.degree. C.
containing 20 g/l of sodium hydroxide and 250 g/l of sodium
sulfate. The resultant fiber is roller drawn and then subjected to
subsequent treatments such as; neutralization of sodium hydroxide
on the fiber with an acid, wet-heat drawing, water-rinsing of the
fiber to adjust the amount of boric acid in the fiber, drying and
dry-heat drawing to a total draw ratio of 1,300-1,500 percent.
In Table 2 below, the resultant PVA fibers containing various
amounts of boric acid are shown with their properties.
Table 2
__________________________________________________________________________
The amount of boric acid contained in 0 0.21 0.36 0.50 0.67 0.85
0.95 1.05 the fiber (%/PVA) Total drawing ratio (%) 1200 1500 1500
1500 1500 1400 1200 1140 denier/filament 1200/ 1200/ do. do. do.
1280/ 1480/ 1550/ 500 600 600 600 600 dry breaking tenacity (g/d)
9.7 11.2 11.6 11.7 11.5 10.1 9.8 9.3 20.degree.C. initial modulus
(g/d) 230 240 245 250 247 236 210 204 dry breaking tenacity (g/d)
7.0 8.0 8.5 8.7 8.6 8.5 7.4 7.3 120.degree.C. initial modulus (g/d)
70 101 115 120 127 122 96 95
__________________________________________________________________________
EXAMPLE 7
A PVA aqueous spinning solution containing 17 weight percent of PVA
with a degree of polymerization of 1,750 and a degree of
saponification of 99.9 mol percent, 2.8 weight percent on PVA of
boric acid and 0.24 weight percent on PVA of tartaric acid to
adjust the pH to 4 is prepared. The spinning solution is passed
through the same nozzle as in Example 1, into a coagulation bath at
45.degree. C. containing 30 g/l of sodium hydroxide and 225 g/l of
sodium sulfate. The resulting fiber is then subjected to subsequent
treatments such as; roller-drawing, neutralization of sodium
hydroxide on the fiber with an acid, wet-heat drawing,
water-rinsing of the fiber to adjust the amount of boric acid to
about 0.5 percent, drying and dry-heat drawing to a total draw
ratio of 1,200-1,500 percent.
The properties of the fibers thus obtained are shown in Table 3
below.
Table 3 ______________________________________ The amount of boric
acid contained in the fiber (%/PVA) 0.46 0.52 0.48 0.50 Total
drawing ratio (%) 1200 1350 1400 1500 denier/filament 1200/ do. do.
do. 600 dry breaking tenacity (g/d) 9.7 10.1 11.0 11.5 20.degree.C.
initial modulus (g/d) 232 230 245 260 dry breaking tenacity (g/d)
7.0 8.0 8.2 8.6 120.degree.C. initial modulus (g/d) 75 102 109 127
______________________________________
The PVA synthetic fibers of the present invention which exhibit
outstanding properties at high temperature find widespread
application, for example, they can be employed in the tension
member of V belts and for reinforcement of hoses. The high modulus
and low creep of the fibers of the present invention at high
temperature enables the manufacture of V belts exhibiting excellent
dimensional stability under the conditions of use. High pressure
hoses employed in oil pressurized machines and tools will be
greatly improved by the use of the PVA fibers of the present
invention because the expansion of the hose against the inner
pressure is kept very small by the high modulus of the present
fibers at high temperature. The excellent high temperature
properties of the PVA synthetic fibers produced in accordance with
the present invention are utilized to their fullest extent when the
PVA fibers are employed in the cord of a radial ply or a belted
bias-ply tire.
Although specific materials and conditions were set forth in the
above exemplary processes for preparing the outstanding polyvinyl
alcohol fibers of the present invention, these are merely intended
as illustrations of the present invention. Various other polyvinyl
alcohols, water-soluble borates and process conditions such as
those listed above may be substituted in the examples with similar
results.
Other modifications of the present invention will occur to those
skilled in the art upon a reading of the present disclosure. These
are intended to be included within the scope of this invention.
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