US3751547A - Process for producing high modulus polyvinyl alcohol synthetic fibers - Google Patents

Process for producing high modulus polyvinyl alcohol synthetic fibers Download PDF

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Publication number
US3751547A
US3751547A US00157246A US3751547DA US3751547A US 3751547 A US3751547 A US 3751547A US 00157246 A US00157246 A US 00157246A US 3751547D A US3751547D A US 3751547DA US 3751547 A US3751547 A US 3751547A
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Prior art keywords
fibers
hot
pva
hot drawing
ratio
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US00157246A
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H Kawakami
K Kawabata
K Kimura
H Satoh
A Miyoshi
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Unitika Ltd
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Unitika Ltd
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Priority claimed from JP5623970A external-priority patent/JPS4832624B1/ja
Priority claimed from JP5623870A external-priority patent/JPS4832623B1/ja
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/228—Stretching in two or more steps, with or without intermediate steps
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for producing high modulus polyvinyl alcohol synthetic fibers which comprises spin-drawing polyvinyl alcohol synthetic fibers having a homogeneous section and then carrying out a multistage hot drawing. Polyvinyl alcohol synthetic fibers are produced by such a process.
  • the present invention relates to a process for producing polyvinyl alcohol (hereinafter called PVA) synthetic fibers having a high modulus and particularly excellent dynamic modulus, high strength and low elongation, and to PVA synthetic fibers produced by such a process, and particularly relates to providing PVA synthetic fibers which are useful as cord elements for radial tires.
  • PVA polyvinyl alcohol
  • fiber cord materials used for radial tires have a high modulus, that is, a high Youngs modulus, and especially a dynamic modulus which does not decrease at high temperatures.
  • PVA synthetic fibers have the highest Youngs modulus or dynamic modulus among various kinds of synthetic fibers.
  • PVA synthetic fibers cannot be used satisfactorily as radial tire cord materials though they are promising, because the high Youngs modulus and the dynamic modulus thereof decrease greatly at high temperatures. Consequently, they have not yet been practically used.
  • the present invention relates to a process for producing PVA fibers which have a high modulus, especially a high dynamic modulus at a high temperature, high strength and low elongation, which is characterized by carrying out the spin drawing of PVA fibers having a homogeneous section and then carrying out multistage hot drawing, and is also characterized by afiording, if desired, 20-50% moisture to the fibers at the second and/or subsequent stages of the hot drawing, and PVA fibers produced by the same process.
  • FIG. 1 is a graph showing the relationship between the spin drawing ratio and the dynamic modulus of the resulting fibers when applying the present invention.
  • FIG. 2 is a graph showing the relationship between the draw ratio at the first hot drawing and the dynamic modulus of the resulting fibers.
  • the PVA synthetic fibers having a homogeneous section produced by a wet spinning process used in the present invention there are fibers which are prepared by spinning a PVA solution using a coagulation bath which contains caustic alkali as the main ingredient, and fibers which are prepared by spinning a PVA solution containing boric acid or borax using an alkaline coagulation bath which contains dehydrating salts.
  • the spin-drawing in the present invention is carried out by taking out coagulated fibers obtained by the common spinning method from the coagulation bath, in air, by means of a first godet roll and drawing the fibers in air using guides or rolls, or drawing the fibers in an aqueous solution of salts at a high temperature, or applying both of the abovernentioned treatments.
  • the multistage hot drawing of the PVA synthetic fibers is carried out by conducting the first hot drawing at a temperature above C. and below the melting point of the fibers and conducting the second and subsequent stage hot drawing at a temperature above C., in which the later the stage is, the higher the temperature which is used at said hot drawing.
  • the first hot drawing it is preferable to conduct the first hot drawing at a draw ratio as high as possible, preferably more than 3 times. In general, 3-5 times of the draw ratio is adopted.
  • the second hot drawing is generally carried out at a 1.1-1.4 draw ratio.
  • the present invention it has been found that it is preferable to afiord moisture after the first hot drawing in order to improve the drawability, because the drawability of the PVA synthetic fibers after the second and subsequent hot drawing is largely improved by afiording moisture using water or an aqueous emulsion of oils.
  • the amount of moisture is preferably 20-50% based on the fiber.
  • the first hot drawing is carried out at more than 3 times the draw ratio and that the total draw ratio including the spindrawing ratio is at least 10 times so as to prevent the rise of nap and the break of yarns upon the addition of moisture at the second hot drawing.
  • the fibers drawn by the first hot drawing are then subjected to the second hot drawing after afiording 20-50% moisture without drying.
  • the moisture may be added by spraying, dropping or dipping in water or an aqueous emulsion of oils such as mineral oils. If the amount of the moisture is less than 20%, it becomes diificult to carry out drawing to a high degree because of partial super-heating in a hot drawing oven at the subsequent hot drawing. If the amount of the moisture is more than 50%, a temperature in the hot drawing oven lowers by heat of vaporization of the excess moisture on the surface of fibers, and it becomes difficult to carry out the drawing.
  • the second hot drawing it is preferable to carry out the second hot drawing at a slightly higher temperature, that is, more than 180 C., than the first hot drawing temperature and at more than 1.1 of the hot draw ratio.
  • a slightly higher temperature that is, more than 180 C.
  • the first hot drawing temperature and at more than 1.1 of the hot draw ratio it is possible to repeatedly carry out the addition of moisture for the hot drawing after the second hot drawing, such as a third hot drawing and a fourth hot drawing, etc.
  • the third and fourth hot drawings are not required.
  • PVA fibers are subjected to spin drawing at 4 times or so of a draw ratio in the preparation of PVA fibers by a wet spinning process, washing with water, drying and hot drawing.
  • hot drawing is carried out only one time. If PVA fibers having a homogeneous section are subjected to spin-drawing by the prior art at the same draw ratio as in the present invention, the resulting fibers have a poor drawability and a poor dynamic modulus.
  • hot drawability is improved remarkably when affording 20-5 moisture to the PVA synthetic fibers having the homogeneous section produced by a wet spinning process.
  • the reasons why the hot drawability is improved by affording the moisture to fibers after the first hot drawing are not yet clear, it is supported as follows. Namely, when the PVA synthetic fibers which are oriented and crystallized in some degree by the first hot drawing are subjected to additional hot drawing, it is necessary to weaken the firm hydrogen bond between the molecules of PVA. Water functions as the plasticizer which weakens the binding of the molecules of PVA and makes rearrangement of the molecules easy. Accordingly, by affording moisture before the second and subsequent hot drawings, it becomes possible to draw highly, above 20 times of the total draw ratio, which is impossible to obtain by the prior art methods, and the modulus of the fibers is improved remarkably.
  • FIG. 1 is a graph which shows the relationship between the dynamic moduli at 20 C. and 100 C. and the spindrawing ratio of fibers which are obtained by spinning a 15% aqueous solution of PVA having an average degree of polymerization of 1700 as the spinning solution using an aqueous solution of 400 g./l. of caustic soda as the coagulation bath, drawing with changing the spindraw ratio, neutralizing with a bath of 300 g./l. of Glaubers salt and 50 g./l. of sulfuric acid at room temperature, treating with a bath of 300 g./l. of Glaubers salt and 30 g./l. of sulfuric acid at 90 C., washing with water and drying, conducting the first hot drawing at 225 C.
  • FIG. 2 is a graph showing the relationship between the dynamic moduli at 20 C. and 100 C. and the first hot draw ratio of fibers obtained by spinning using the same spinning solution and coagulation bath as above, conducting the spin-drawing at a 4 times draw ratio, conducting the first hot drawing of the dryed fibers by changing the drawing ratio at 225 C., affording 30% Water,
  • the dynamic modulus is measured in the air by means of a dynamic modulus measurement device at the following conditions: length of sample: 3 cm.; initial tension: 0.2 g./d.; frequency: cps.; dynamic strain: 0.6%; and rate of heating: 1.5 C./min.
  • the fibers were then neutralized with a bath of 300 g./l. of Glaubers salt and 50 g./l. of sulfuric acid at room temperature and then treated with a bath having the same composition at 85 C.
  • the resulting fibers having a homogeneous section were subjected to a first hot drawing at 230 C., a second hot drawing at 240 C. and a third hot drawing at 245 C. in a hot drawing oven.
  • the fibers were either dipped in water and squeezed to aflford 30% moisture or not dipped in water.
  • the hot draw ratio of each stage was 80% of the maximum hot draw ratio at breaking.
  • fibers having a 2-layer structure were produced by the same procedure using a 15% aqueous solution of PVA having a 1700 degree of polymerization as the spinning solution and a saturated Glaubers salt solution as the coagulation bath.
  • the draw ratios and properties of each fiber are shown in Tables 1 and 2.
  • the hot drawing property is remarkably improved by carrying out the multistage hot drawing of fibers having a homogeneous section which are produced by spinning, using a caustic alkali solution as the coagulation bath, and that fibers having a high strength, a low elongation and a good dynamic modulus can be obtained.
  • These fibers are suitable for use as reinforcing elements for reinforced plastics and as tire cords for radial tires.
  • drawability is further improved by repeating addition of moisture and hot drawing after the first hot drawing, and the drawn filament does not fiuif.
  • fibers having a Z-layer structure consisting of a skin layer and a core layer which are produced by spinning in a Glaubers salt solution cannot be subjected to such drawing, even though affording moisture, and the fibers are nappy.
  • the denier of the filament yarn used in the process of the present invention is preferabzy less than 10,000 deniers so as not to cause disorder of the fibers at the addition of moisture, and so as to heat uniformly at hot drawing.
  • Example 1 Fibers were produced by spinning a 15% aqueous solution of PVA having an average degree of polymerization of 2500 as the spinning solution using an aqueous solution containing 350 g./l. of caustic soda as the coagulation bath. After removal from the coagulation bath, the fibers were subjected to spin-drawing at a draw ratio of 4.5 times. After neutralizing with a bath of 280 g./l. of Glaubers salt and 50 g./l. of sulfuric acid at room temperature and treating in a bath of 250 g./l. of Glaubers salt and 30 g./l. of sulfuric acid at 80 C., the fibers were washed with water and dried.
  • the fibers were then subjected to a first hot drawing at 230 C. at a ratio of 3.6 times and a second hot drawing at 245 C. at a ratio of 1.23 times, by which the total draw ratio became times.
  • the dynamic moduli and Youngs moduli of the treated filament yarn (1200 d., 500 f.) at 20 C. and 100 C. were 39x10 dyne/cmP, 2.9 10 dyne/crnF, and 4140 kg./mm. 2110 kg./mm. respectively.
  • Example 2 Dried fibers obtained by the process of Example 1 were subjected to a first hot drawing at 230 C. in a ratio of 3.6 times followed by dipping in water and squeezing to afford 40% moisture. The fibers were then subjected to a second hot drawing so as to increase the total draw ratio to 21.8 times. The fibers had a 15.6 g./d. strength, a 5% elongation and a dynamic moduli at 20 C. and 100 C. of 41x10 dyne/cm. and 3.0)(10 dyne/cmfi, respectively.
  • Example 3 Fibers were produced by spinning a 15 .5% aqueous solution of PVA having an average degree of polymerization of 1700 (to which 1% boric acid based on the weight of PVA was added) as the spinning solution into a coagulation bath consisting of 15 g./l. of caustic soda and 360 g./l. of Glaubers salt. After taking the fibers out, they were subjected to spin-drawing in a ratio of 4 times, neutralized in a bath of 300 g./l. of Glaubers salt and 30 g./1. of sulfuric acid at room temperature and then treated with a bath having the same composition at C. After washing with water and drying, the fibers were subjected to a first hot drawing in hot air at 235 C.
  • PVA having an average degree of polymerization of 1700 (to which 1% boric acid based on the weight of PVA was added) as the spinning solution into a coagulation bath consisting of 15 g./l. of caustic soda and 360
  • the resulting filament yarn (2000 d., 750 f.) had a 14.6 g./d. strength and a 5.7% elongation, and a dynamic modulus and a Youngs modulus at 20 C. of 36x10 dyne/cmP, and 4280 kg./mm. and at C. of 2.5 10 dyne/cm. and 2310 kg./mm.
  • the fibers which were subjected to hot drawing without the second hot drawing had a 12.0 g/d. strength, a 6.6% elongation and a dynamic modulus and a Youngs modulus at 20 C. of 2.6)(10 dyne/cm. and 3160 kgJmrn. and at 100 C. of 1.7 10 dyne/crn. and 1560 kgJmmP. These values were inferior to those of the fibers of the present invention.
  • Example 4 The fibers were produced by spinning using the same procedure as in Example 3. After being subjected to spindrawing at a spin-draw ratio of 3.5 times, the fibers were subjected to a first hot drawing at 238 C. at a ratio of 4 times and a second hot drawing at 245 C. at a ratio of 1.26 times, followed by dipping in an emulsion containing mineral oil as the main ingredient and squeezing the fibers to afford 30% moisture. Then, a third hot drawing treatment was carried out at a ratio of 1.25 times, by which the total draw ratio became 22 times.
  • the dynamic modulus and the Youngs modulus at 20 C. were 4.0 10 dyne/cm. and 4630 kg./mm. and at 100 C. were 3.1 10 dyne/rnm. and 2390 kg./mm. respectively.
  • Example 5 Fibers were produced by spinning a 15.5% aqueous solution of PVA having an average degree of polymerization of (to which 2% boric acid based on the weight of PVA was added) as the spinning solution into a co agulation bath which consisted of a saturated Glaubers salt solution containing 15 g./l. of caustic soda. After taking the fibers out, they were subjected to spin-drawing in a ratio of 4 times followed by neutralizing with a bath containing 300 g./l. of Glaubers salt and 30 g./l. of sulfuric acid at room tempertaure and then treated with a bath having the same composition at 90 C.
  • the fibers were subjected to a three-stage hot drawing at the following conditions: 235 C. for 10 seconds at a ratio of 3.5 times; 238 C., for 10 seconds at a ratio of 1.15 times; and 240 C. for 10 seconds at a ratio of 1.15 times, by which the total drawing ratio became 22.5 times.
  • the resulting filaments had a 15.8 g./d. strength and a 4.5% elongation.
  • Dynamic moduli at 20 C. and C. were 3.8)(10 dyne/crn. and 3.O 10 dyne/cmP, respectively.
  • Example 6 Fibers were produced by spinning a 14% aqueous solution of PVA having an average degree of polymerization of 2500 (to which 2.0% boric acid based on the weight of PVA was added to make the pH 4) as the spinning solution using a saturated Glaubers salt solution containing 10 g./l. of caustic soda as the coagulation bath. After taking out the fibers, they were subjected to spin-drawing in a ratio of 4.5 times, neutralized with 300 g./1. Glaubers salt and 30 g./l. of sulfuric acid at room temperature and then treated with a bath having the same composition at 90 C. After washing with water and drying, the fibers were subjected to a first hot drawing at 230 C.
  • the fibers were then dipped in water for 5 seconds and squeezed by rolls. The fibers were then subjected to a second hot draw ing at 245 C. for 8 seconds in a ratio of 1.2 times, by which the total draw ratio became 21.6 times.
  • the result- 7 ing filament yarn (1200 d., 500 f.) had a 16.2 g./d. strength and a elongation.
  • the dynamic modulus at 20 C. was 3.7 dyne/cm. and at 120 C. was 3.1 10 dyne/cmfi. The fibers did not fluff as compared to the fibers obtained by the same treatment but not affording moisture at the hot drawing treatment.
  • Example 7 Fibers were produced by spinning an 11% aqueous solution of PVA having an average degree of polymerizatiion of 3500 (to which 1.5% boric acid based on the weight of PVA was added) as the spinning solution with a coagulation bath having the same composition as in Example 6.
  • the fibers Were subjected to spin-drawing in a ratio of 5 times, followed by the treatment as in Example 6. After drying, the fibers were subjected to the first hot drawing at 230 C. in a ratio of 3.0 times.
  • the fibers were then dipped into an emulsion containing mineral oil as the main component and squeezed to remove the liquid to afford 30% moisture.
  • the fibers were then subjected to a second hot drawing at 240 C. at a ratio of 1.3 times.
  • the fibers were subjected to a third hot drawing at 250 C. in a ratio of 1.15 times.
  • the resulting filament yarn (1400 d., 500 f.) had a 17.2 g./d. strength and a 4% elongation.
  • the dynamic modulus at 20 C. was 3.8 10 dyne/cm. and at 120 C. was 3.2 10 dyne/cmfi.
  • Example 8 Fibers were produced by spinning a %3 aqueous solution of PVA having an average degree of polymerization of 2500 as the spinning solution using an aqueous solution of 380 g./l. of caustic soda as the coagulation bath. After taking out the fibers, they were subjected to spindrawing at a ratio of 4.5 times. After treating with a bath of 250 g./l. of Glaubers salt and g./l. of sulfuric acid at 80 C., the fibers were washed with water and dried. The dry fibers were subjected to a first hot drawing at 225 C. in a ratio of 3.0 times, followed by spraying thereon an emulsion containing a vegetable oil as the main component to afford 40% moisture.
  • the fibers were then subjected to second drawing at 235 C. in a ratio of 1.2 times, by which the total draw ratio became 21.1 times.
  • the filament yarn (1800 d., 750 f.) had a 16.3 g./d. strength and a 4% elongation.
  • the dynamic modulus was 3.7 10 dynelcmfi.
  • the fibers had a 14.0 g./d. strength, a 5.5% elongation and a 3.1)(10 dyne/cm. dynamic modulus.
  • said coagulating bath comprises a Glaubers salt solution.
  • steps (8) and (9) are repeated once and wherein the third hot-drawing operation is conducted at a draw ratio of 1.05 to 1.20 and at a temperature of from 240 to 250 C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
US00157246A 1970-06-27 1971-06-28 Process for producing high modulus polyvinyl alcohol synthetic fibers Expired - Lifetime US3751547A (en)

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JP5623970A JPS4832624B1 (de) 1970-06-27 1970-06-27
JP5623870A JPS4832623B1 (de) 1970-06-27 1970-06-27

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US (1) US3751547A (de)
CA (1) CA987875A (de)
DE (1) DE2132055C2 (de)
FR (1) FR2100001A5 (de)
GB (1) GB1314000A (de)
IT (1) IT942125B (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852402A (en) * 1969-11-25 1974-12-03 S Tanaka Process for the preparation of polyvinyl alcohol fibers
US4199366A (en) * 1977-11-21 1980-04-22 Inventa Ag Fur Forschung Und Patentverwertung Fiber-reinforced cement-like material
JPS59130314A (ja) * 1982-09-30 1984-07-26 アライド・コ−ポレ−シヨン 高強度および高モジュラスのポリビニルアルコール繊維およびその製造法
US4599267A (en) * 1982-09-30 1986-07-08 Allied Corporation High strength and modulus polyvinyl alcohol fibers and method of their preparation
US4698194A (en) * 1983-12-12 1987-10-06 Toray Industries, Inc. Process for producing ultra-high-tenacity polyvinyl alcohol fiber
US5093063A (en) * 1986-12-27 1992-03-03 Unitika Ltd. Method of producing polyvinyl alcohol fibers
US20100059155A1 (en) * 2008-09-09 2010-03-11 Walter Kevin Westgate Pneumatic tire having a high strength/high modulus polyvinyl alcohol carcass ply
CN103380236A (zh) * 2011-02-24 2013-10-30 帝斯曼知识产权资产管理有限公司 用于拉伸聚合的细长物体的多级拉伸方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2101522B (en) * 1981-01-26 1984-05-31 Showa Denko Kk Producing high tenacity monofilaments
JPH0343265Y2 (de) * 1985-06-11 1991-09-10
NL8502315A (nl) * 1985-08-23 1987-03-16 Stamicarbon Voorwerpen uit polyvinylalcohol met hoge sterkte en modulus, alsmede werkwijze voor het vervaardigen hiervan.

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3032385A (en) * 1958-04-12 1962-05-01 Air Reduction Process of wet spinning polyvinyl alcohol
GB917355A (en) * 1960-02-23 1963-02-06 Kurashiki Rayon Kk Method of manufacturing synthetic fibres of polyvinyl alcohol

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852402A (en) * 1969-11-25 1974-12-03 S Tanaka Process for the preparation of polyvinyl alcohol fibers
US4199366A (en) * 1977-11-21 1980-04-22 Inventa Ag Fur Forschung Und Patentverwertung Fiber-reinforced cement-like material
JPS59130314A (ja) * 1982-09-30 1984-07-26 アライド・コ−ポレ−シヨン 高強度および高モジュラスのポリビニルアルコール繊維およびその製造法
US4599267A (en) * 1982-09-30 1986-07-08 Allied Corporation High strength and modulus polyvinyl alcohol fibers and method of their preparation
JPH0375644B2 (de) * 1982-09-30 1991-12-02 Allied Signal Inc
US4698194A (en) * 1983-12-12 1987-10-06 Toray Industries, Inc. Process for producing ultra-high-tenacity polyvinyl alcohol fiber
US5093063A (en) * 1986-12-27 1992-03-03 Unitika Ltd. Method of producing polyvinyl alcohol fibers
US20100059155A1 (en) * 2008-09-09 2010-03-11 Walter Kevin Westgate Pneumatic tire having a high strength/high modulus polyvinyl alcohol carcass ply
CN103380236A (zh) * 2011-02-24 2013-10-30 帝斯曼知识产权资产管理有限公司 用于拉伸聚合的细长物体的多级拉伸方法
US20150038663A1 (en) * 2011-02-24 2015-02-05 Dsm Ip Assets B.V. Multistage drawing process for drawing polymeric elongated objects
US9428599B2 (en) * 2011-02-24 2016-08-30 Dsm Ip Assets B.V. Multistage drawing process for drawing polymeric elongated objects

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DE2132055C2 (de) 1984-09-06
CA987875A (en) 1976-04-27
GB1314000A (en) 1973-04-18
DE2132055A1 (de) 1972-01-05
IT942125B (it) 1973-03-20
FR2100001A5 (de) 1972-03-17

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