US3574812A - Process for producing polynosic fibers - Google Patents

Process for producing polynosic fibers Download PDF

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Publication number
US3574812A
US3574812A US59800A US3574812DA US3574812A US 3574812 A US3574812 A US 3574812A US 59800 A US59800 A US 59800A US 3574812D A US3574812D A US 3574812DA US 3574812 A US3574812 A US 3574812A
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United States
Prior art keywords
fibers
bath
sulfuric acid
filaments
formaldehyde
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US59800A
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English (en)
Inventor
Masaichi Kubota
Taro Yamamura
Atsushi Kawai
Takehiro Katsuyama
Masamichi Ikeda
Seiichi Omoto
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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Publication date
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Publication of US3574812A publication Critical patent/US3574812A/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • Y10T428/2909—Nonlinear [e.g., crimped, coiled, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2965—Cellulosic

Definitions

  • the obtained highly crimped polynosic fibers have an asymetric structure with the core-stainable layer positioned at the inside track of the crimp bend; the dye eX- haustion is at least 40%; wet modulus is 0.5 to 1.8 g./d. and crimps are more than 10/25 mm.
  • the present invention relates to improved highly crimped polynosic fibers and a process for producing the same.
  • the filaments which have drawn from the coagulation bath containing formaldehyde have high stretchability, and therefore when they are highly stretched in the second bath kept at a relatively high temperature, there are obtained fibers having high tenacity, high wet modulus and high resistance to water and alkali solution.
  • fibers obtained by use of a coagulation bath containing formaldehyde have many such excellent characteristics as mentioned above. On the other hand, however, they are not sufficient in elongation and dyeability and are not satisfactory in knot tenacity and the like.
  • aqueous solution containing an alkali metal salt of sulfuric acid, alkaline earth metal salt of sulfuric acid, ammonium salt of sulfuric acid or their mixture, said third aqueous bath being kept at a pH of 2.0 to 10.5 and 3,574,812 Patented Apr. 13, 1971 at a temperature of 30 to 70 C.
  • the third bath may be contained with a small amount of a sulfuric acid salt of zinc or cadmium.
  • the filaments which have been prepared by extruding a high 'y-value viscose into a coagulation bath containing sulfuric acid, sodium sulfate and formaldehyde and then stretching the resulting filaments in a second bath, are introduced into an aqueous solution of, for example, sodium sulfate, the filaments unexpectedly swell to a great extent and, they are sometimes dissolved with the lapse of time.
  • Such a phenomenon is observed not only in the case of sodium sulfate but also in the case of sulfuric acid salts of other alkali metals, alkaline earth metals or ammonium.
  • Such swelling action is greatly affected by the pH and temperatures of the salt solutions employed.
  • the pH and temperatures of the salt solutions to be used in the present invention should be within the ranges as described above. If the pH is less than 2.0, the diffusion of hydrogen ion into the fiber becomes marked, whereby the eifective swelling of fiber due to the salt employed is restrained. On the other hand, if the pH is more than 10.5, the fiber is swelled to a great extent and is markedly lowered in tenacity. Moreover, even when, in the above case, a sulfuric acid salt of zinc or cadmium is incorporated into the salt solution, the specific action described hereinafter cannot be displayed. As to the temperature, it may be said that the higher the temperature, the stronger the swelling action of the salt.
  • Preferable treatment temperature is within the range of 30 to 70 C. It has also been found that when an aqueous solution of a salt having a swelling action on fiber, as mentioned above, is incorporated with such a slight amount as less than 0.5 g./l. of a sulfuric acid salt of zinc or cadmium, the swelling of fiber is suitably controlled and the fiber properties are improved more effective y.
  • aqueous solution containing up to 50 g./l. of sodium sulfate and up to 1 g./l. of sulfuric acid.
  • the third bath is desirably incorporated, additionally, with up to 0.5 g./l. of zinc sulfate.
  • FIG. 1 is a graph which well expresses the above general relationship
  • FIG. 2 shows the cross section of the fibers obtained by treatment in accordance with the present invention.
  • FIGS. 3 and 4 show the side view of the present fiber and a conventional fiber.
  • the horizontal axis is graduated with the sodium sulfate concentration in the third bath, while the vertical axis with the dye exhaustion as a characteristic representing the swelling effect.
  • the solid line shows the case where a viscose containing 7% of cellulose and 4% of alkali and having a 'y-value of 80 and a viscosity of 260 poises is extruded into a coagulation bath containing 26 g./l. of sulfuric acid, g./l. of sodium sulfate, 0.1 g./l. of zinc sulfate and 7.5 g./-l.
  • Japanol Brilliant Blue 6BKX-0.3% o.w.f.
  • Sodium sulfate20% o.w.f.
  • black parts show the skin-stained layer.
  • fibers are stained using the following conditions, followed by washing through the alcohol series.
  • FIGS. 3 and 4 black parts show the core-stained layer.
  • fibers are stained using the following conditions, followed by washing with water and dehydration.
  • the 'y-value of the viscose employed is required to be at least 50, preferably at least 65 (corresponding to a salt point of at least 16). If the 'y-value is lower than said value, the effect of formaldehyde in the coagulation bath is not sufficient and no satisfactory crimps can be developed.
  • the formaldehyde concentration of the coagulation bath is preferably 4 to g./l. It is particularly desirable that the sulfuric acid concentration of the coagulation bath is within the range defined by the following equations:
  • concentration of sodium sulfate is preferably 20 to 250 g./l., and that of zinc sulfate, if it is to be incorporated, is desirably up to 0.3 g./l.
  • the filaments withdrawn from the coagulation bath are then stretched in the second bath.
  • the temperature of the bath and the tension applied to the filaments during stretching are the most important factors.
  • the temperature of the second bath is within the range of 45 to 75 C. If the bath temperature is out of said range, no excellent crimps can be developed.
  • the tension applied to the filaments during stretching should be less than 0.3 g./d. If the tension is more than 0.3 g./d., no highly crimped fibers can be obtained.
  • the second bath preferably contains a small amount of sulfuric acid, in view of the subsequent treatment.
  • the bath may also contain small amounts of salts and formaldehyde,
  • the filaments, which have been stretched in the above manner, are then relaxed, either as such or after cutting to staples, in a third bath comprising an aqueous salt solution, whereby the fibers undergo swelling action and, at the same time, develop markedly fine crimps.
  • the temperature of the third bath is 30 to 70 C. If the temperature is below 30 C., the swelling effect is low, while if the temperature is above 70 C, no excellent crimps are developed.
  • the fibers which have developed crimps are then transferred to a high temperature acidic bath to complete regeneration.
  • the fibers obtained according to the above-mentioned process have such characteristics as described below.
  • Cross section and side view of the fiber are in such a specific form as shown in FIGS. 2 and 3, respectively, and in the fibers, core-stainable layer is biassed.
  • the fibers have a heterogeneous structure as if it were conjugate fibers.
  • the crimp of the fibers is in a spiral form but, unlike in the case of conventional crimped staple fiber as shown in FIG. 4, the core-stainable layer is always positioned at the inside track of the crimp bend. In water, therefore, the crimp is straightened to a certain extent due to greater swelling of the core-stainable layer, but is completely restored on drying. That is, the fiber of the present invention has such a property as that of wool having so-called water reversible crimps.
  • the skin-stainable layer is always positioned at the inside track of the crimp bend.
  • the thicker side of the skin-stainable layer is positioned at the inside track of the crimp bend.
  • the fibers of the present invention are not only excellent in crimp properties but also are prominent in mechanical properties. Tenacity and wet modulus of the fibers are far higher than those of the conventional common crimped viscose staples. Particularly, the wet modulus at 5% elongation of the present fibers is, in general, 0.5 to 1.8 g./d. or more. Therefore, the fibers are excellent in dimensional stability and can withstand repeated washing. They are also high in knot tenacity and excellent in abrasion resistance.
  • the water retention of the fibers is equal to or somewhat higher than that of the recent polynosic fibers but the Water resistance and dimensional stability thereof are sufiiciently high. Excellence in dyeability is also a great characteristic of the fibers.
  • the fibers have a dye exhaustion of more than 40%, ordinarily in the range of 45 to a wet tenacity of 1.8 to 4 g./d., a wet modulus at 5% elongation of 0.5 to 1.8 g./d., and a crimp of more than 10/25 mm.
  • the fibers can be used in wide variety of fabrics with or without synthetic or cotton fibers. Fabrics converted from the fibers have comfortable hand, high slipresistance, high dimensional stability and superior mechanical properties.
  • EXAMPLE 1 A viscose containing 6.5% of cellulose and 4.5% of total alkali and having a viscosity of poises, a salt point of 21 and a 'y-value of 82 was extruded into a coagulation bath containing 35 g./l. of sulfuric acid, 75 g./l. of sodium sulfate and 7 g./l. of formaldehyde and kept at 25 C. The filaments withdrawn from the coagulation bath were immediately stretched to 300% the original length of the filaments under a tension of 0.05 g./d. in a second bath kept at 60 C. and containing 2 g./l. of sulfuric acid.
  • the filaments were relaxed in a third bath containing 5 g./l. of sodium sulfate and 0.1 g./l. of zinc sulfate and kept at 50 C. and at a pH of 6.8 to develop crimps.
  • the -values of the filaments just before entering the second and third baths were 65 and 57, respectively.
  • the regeneration of the filaments were completed in an aqueous bath containing g./l. of sulfuric acid and kept at 85 C. and were then scoured according to a conventional procedure. Fiber properties of the thus obtained fibers are shown in Table 1(A), and the cross section of the fiber after dyeing are shown in FIG. 2.
  • fibers (B) were produced in the same manner as above, except that the third bath contained no sulfates and was kept at 50 C. Fiber properties of these fibers are as shown in Table 1(B).
  • a process for producing improved highly crimped polynosic fibers characterized by extruding a viscose having a 'y-value of at least 50 into a coagulation bath containing sulfuric acid, 20 to 250 g./l. of sodium sulfate and more than 4 g./l. of formaldehyde, stretching the resulting filaments in a second bath kept at 45 to 75 C. under a tension of up to 0.3 g./d.
  • a third aqueous bath containing a salt selected from the group consisting of an alkali metal salt of sulfuric acid, an alkaline earth metal salt of sulfuric acid, an ammonium salt of sulfuric acid and mixtures thereof, said third aqueous bath being kept at a pH of from 2.0 to 10.5
  • a viscose containing 7% of cellulose and 4.5% of alkali and having .a viscosity of 320 poises, a salt point of 22 and a 'yvalue of 84 was extruded into a coagulation bath containing 37 g./l. of sulfuric acid, 80 g./l. of sodium sulfate and 8 g./l. of formaldehyde and kept at 23 C.
  • the filaments withdrawn from the coagulation bath were immediately stretched to 290% the original length of the filaments under a tension of 0.045 g./ d. in a second bath containing 1 g./l. of sulfuric acid and kept at 60 C.
  • the filaments were relaxed in a third bath containing 0.2 g./l. sulfuric acid, 10 g./l. of sodium sulfate and 0.1 g./l. of zinc sulfate, and kept at 50 C. at a pH of 3.4 to develop crimps. Subsequently, the regeneration of the filaments were completed in an aqueous bath containing 5 g./l. of sulfuric acid and kept at 85 C. The -values of the filaments just before entering the second and third baths were 66 and 59, respectively. Fiber properties of the thus obtained fibers are shown in Table 2(A).
  • fibers (B) were produced in the same manner as above, except that the third bath employed contained only 10 g./l. of sulfuric acid and kept at a pH of 1.4. Fiber properties of these fibers are shown in Table 2(B).
  • a process according to claim 2 wherein the third aqueous bath contains up to g./l. of sodium sulfate and up to 0.5 g./l. of zinc sulfate.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
US59800A 1966-09-22 1967-09-22 Process for producing polynosic fibers Expired - Lifetime US3574812A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6259566 1966-09-22
JP6701266 1966-10-12

Publications (1)

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US3574812A true US3574812A (en) 1971-04-13

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US59800A Expired - Lifetime US3574812A (en) 1966-09-22 1967-09-22 Process for producing polynosic fibers
US00067591A Expired - Lifetime US3741862A (en) 1966-09-22 1970-08-27 Highly crimped polynosic fibers

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US00067591A Expired - Lifetime US3741862A (en) 1966-09-22 1970-08-27 Highly crimped polynosic fibers

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US (2) US3574812A (enrdf_load_stackoverflow)
CH (1) CH477569A (enrdf_load_stackoverflow)
GB (1) GB1167555A (enrdf_load_stackoverflow)
NL (2) NL6712972A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632468A (en) * 1968-04-09 1972-01-04 Rayonier Inc High-crimp, high-strength rayon filaments and staple fibers and process for making same
US3689622A (en) * 1969-06-24 1972-09-05 Mitsubishi Rayon Co Method for producing highly crimped regenerated cellulose fibers by solvent stretching

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4245000A (en) * 1979-03-16 1981-01-13 Avtex Fibers Inc. Viscose rayon
USRE31457E (en) * 1979-03-16 1983-12-06 Avtex Fibers Inc. Viscose rayon
IT1129652B (it) * 1980-01-09 1986-06-11 Snia Viscosa Procedimento perfezionato per la filatura in continuo di rayon viscosa

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632468A (en) * 1968-04-09 1972-01-04 Rayonier Inc High-crimp, high-strength rayon filaments and staple fibers and process for making same
US3689622A (en) * 1969-06-24 1972-09-05 Mitsubishi Rayon Co Method for producing highly crimped regenerated cellulose fibers by solvent stretching

Also Published As

Publication number Publication date
GB1167555A (en) 1969-10-15
US3741862A (en) 1973-06-26
DE1669501B2 (de) 1975-06-05
NL6712972A (enrdf_load_stackoverflow) 1968-03-25
CH477569A (fr) 1969-08-31
NL137466C (enrdf_load_stackoverflow)
DE1669501A1 (de) 1970-07-30

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