US3786125A - Process for producing acrylic synthetic fibers of noncircular cross-section and with improved sparkle - Google Patents

Process for producing acrylic synthetic fibers of noncircular cross-section and with improved sparkle Download PDF

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Publication number
US3786125A
US3786125A US00279625A US3786125DA US3786125A US 3786125 A US3786125 A US 3786125A US 00279625 A US00279625 A US 00279625A US 3786125D A US3786125D A US 3786125DA US 3786125 A US3786125 A US 3786125A
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United States
Prior art keywords
spinning
sparkle
fiber
section
synthetic fibers
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Expired - Lifetime
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US00279625A
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English (en)
Inventor
K Shimoda
I Obama
T Kusunose
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • D01F6/18—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 nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • 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
    • Y10T428/2973—Particular cross section

Definitions

  • This invention relates to a process for producing acrylic synthetic fibers of a noncircular cross-section, improved in sparkle, from a spinning solution prepared by dissolving an acrylic polymer in an inorganic solvent. More particularly the present invention relates to a process for producing acrylic synthetic fibers of a noncircular crosssection improved in the sparkle by wet-spinning a spinning solution prepared by dissolving an acrylic polymer in an inorganic solvent, through a spinnerette made of a synthetic resin and having a particular spinning orifice shape and thermal conductivity, while maintaining a predetermined jet stretching ratio.
  • Synthetic fibers having a noncircular cross-section are known as to be peculiar with respect to physical properties as brightness, bulkiness and covering power as compared with synthetic fibers having the usual circular crosssection, and therefore various means for their industrial production have already been developed.
  • acrylic synthetic fibers having a noncircular cross-section from a spinning solution prepared by dissolving an acrylic polymer in an inorganic solvent by the wet-spinning process, it is necessary to increase the jet stretching ratio which is represented as a ratio of the coagulated filament pulling out velocity/ the average flowing velocity of the spinning solution through the sipnning orifice.
  • a spinnerette made of a metal is generally high in the thermal conductivity so that the reduction of the temperature of the spinning solution near the spinning orifice is great and it is very difiicult to maintain the above mentioned jet stretching ratio at a predetermined level, Therefore, unless spinning orifices in which the ratio of the long diameter/the short diameter is extremely large are used, it has been difiicult to form any desired noncircular cross-section from spun fibers.
  • a principal object of the present invention is to pro vide a novel industrial method of forming acrylic synthetic fiber of a noncircular cross-section, improved in sparkle, by a wet-spinning process.
  • Another object of the present invention is to deter- United States Patent mine a spinning orifice shape and jet stretching ratio favorable to the production of acrylic synthetic fibers of a noncircular cross-section by using a spinnerette device made of a synthetic resin material.
  • Such objects of the present invention can be attained by extruding a spinning solution prepared by dissolving an acrylic polymer in an inorganic solvent into a coagulating bath through a spinnerette whose thermal conductivity does not exceed 5 10- cal. cmf 'secr -deg.” and in which are formed spinning orifices each having a dimensional ratio defined by the following relative Formulae 1 and 2:
  • a is the smallest width of the spinning orifice
  • b is the largest width of the spinning orifice measured in the same direction as of a
  • c is the long diameter of the spinning orifice measured in the direction at right angles with the above mentioned a or b, and narrowed in the central part so as to be formed into a fiber filament and taking the filament out of said coagulating bath while maintaining the jet stretching ratio (represented as a ratio of a cogulated filament pulling out velocity/ average flowing velocity of the spinning solution through the spinning orifice) of less than 0.6.
  • FIG. 1 exemplifies spinning orifice shapes suitable to work the present invention
  • FIG. 2 shows a spinning orifice shape of a spinnerette to melt-spun synthetic fiber filaments to be used as a spinning orifice forming material in making a spinnerette device by a synthetic resin pouring and molding process;
  • FIG. 3 shows photographs of cross-section of acrylic synthetic fibers obtained by wet-spinning by varying the spinning orifice shape
  • FIG. 4 shows photographs of side surfaces of acrylic synthetic fibers obtained by varying the jet stretching ratio
  • FIG. 5 is a block diagram of a contrast index measuring apparatus
  • FIG. 6 is a plan view of the apparatus showing the formation of the essential part in FIG. 5;
  • FIG. 7 is a view for explaining the shape of the peak in the recording paper representing the high light of a tested sample.
  • the present invention is directed to the production of acrylic synthetic fibers of a noncircular cross-section having a characteristic sparkle by selecting a material much lower in thermal conductivity than any metal material as spinnerette forming material and specifying the spinning orifice shape and a range of the jet stretching ratio in wet-spinning acrylic synthetic fibers.
  • an acrylic fiber with a cross-sectional shape having a narrow portion in the central part and with improved brightness in acrylic synthetic fibers by adopting the above mentioned requirements as integrally combined. Therefore, even in case of a partial deviation from the above described peculiar spinning conditions, not only the cross-sectional shape of the finally obtained acrylic synthetic fibers but also the level of the sparkle will fluctuate more than a negligible amount.
  • the cross-sectional shape of the finally obtained acrylic synthetic fiber will substantially approach to a circular shape and the level of the sparkle will be considerably reduced.
  • the jet stretching ratio is set in a range exceeding 0.6, not only the macroscopic form peculiarity but also the surface form of the microscopic order of the finally obtained fiber of noncircular cross-section will vary and the luster itself will qualitatively vary.
  • the present invention has its fundamental basis in the fact that a peculiar spinning orifice shape, narrow at the center, is effective to improve the sparkle in the spun fiber even under the state in which the jet stretching ratio is substantially reduced. This was discovered by noting the fact that, when the jet stretching ratio is reduced with a view to smoothing the surface form of the finally obtained acrylic synthetic fiber of a concircular cross-section, the cross-sectional shape of the spun fiber will approach a circular shape substantially in proportion to the reduction of the jet stretching ratio.
  • thermosetting synthetic resin material in which the thermodeformation temperature defined in ASTM (The American Society for Testing Materials) D648 is above 70 C. and the bending strength defined in ASTM D790 is not less than 700 kg./cm. such as a polyether resin, polycarbonate resin, phenol resin or epoxy resin.
  • Spinning orifice shapes preferable in working the present invention are exemplified in FIG. 1 in which a represents the smallest width of the spinning orifice, b represents the largest width of the spinning orifice measured in the same direction as a, and 0 represents the long diameter of the spinning orifice measured in the direction at right angles with the above mentioned a or b.
  • a represents the smallest width of the spinning orifice
  • b represents the largest width of the spinning orifice measured in the same direction as a
  • 0 represents the long diameter of the spinning orifice measured in the direction at right angles with the above mentioned a or b.
  • a boring tool of the same cross-sectional shape as of the spinning orifice is used as seen in the ordinary spinnerette device made of a metal.
  • it can be formed by synthetic resin casting by the embedding technique mentioned in Japanese patent 'publication No.
  • a is the smallest width of the spinning orifice
  • b is the largest Width of the spinning orifice measured in the same direction as a
  • c' is the long diameter of the spinning orifice measured in the direction at right angles with the above mentioned a or b.
  • acrylic polymer as used in the present in- 'vention is a fiber-forming polymer having acrylonitrile as a main component and means inclusively a polyacrylonitrile, a copolymer of more than 70% by weight acrylonitrile with another vinylic monomer copolymerizable with acrylonitrile or a polymer blend of such polymer with another polymer.
  • inorganic solvents which can be used in the present invention for dissolving such acrylic polymer to prepare a spinning solution, there can be enumerated concentrated aqueous solutions of such thiocyanates as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and calcium thiocyanate, mixtures of these thiocyanates, concentrated aqueous solutions of such inorganic salts as zinc chloride and lithium chloride and concentrated aqueous solutions of such inorganic acids as sulfuric acid and nitric acid.
  • concentrated aqueous solutions of such inorganic salts as zinc chloride and lithium chloride
  • concentrated aqueous solutions of such inorganic acids as sulfuric acid and nitric acid.
  • water or an aqueous solution of the above mentioned inorganic salt or inorganic acid of a concentration less than 35% there can be used for the 00- agulating bath.
  • the acrylic synthetic fiber having a noncircular crosssection and wet-spun by the method of the present invention can be subjected to the usual after-treatment such as washing, stretching, compacting, drying and heat-relaxing in the ordinary manner after the fiber formation in the coagulating bath.
  • a contrast index and 60-degree mirror surface luster (G5 are adopted as scales for quantitatively evaluating the sparkle of the finally obtained acrylic synthetic fiber of a noncircular crosssection.
  • 60-degree mirror surface luster (G A fiber tow to be measured has the crimps stretched under tension while being heated, is pulled and arranged in parallel and is fixed at both ends on a cardboard to prepare a rectangular test piece of 6 cm. X 4.5 cm.
  • a luster meter Model GM-S manufactured by Murakami Coloring Technical Laboratory
  • the fibers are measured by irradiating them with rays so that a plane including incident rays and reflected rays may be made to coincide with the axes of the fibers and the angle of incidence of the irradiating rays may be 60 degrees with the direction of pulling and arranging the fibers.
  • the contrast index can be determined by measuring a sample S by using a scanning type microscopic luster meter consisting of a current source stabilizer ST, voltage stabilizer EST, light source L, magnifying lens optical system El, movable photoelectric multiplying tube R, amplifier A and register system REC shown in the block diagram in FIG. 5.
  • a scanning type microscopic luster meter consisting of a current source stabilizer ST, voltage stabilizer EST, light source L, magnifying lens optical system El, movable photoelectric multiplying tube R, amplifier A and register system REC shown in the block diagram in FIG. 5.
  • the fiber tow to be measured is pulled and arranged in parallel and is pasted to a cardboard to prepare a sample plate 27.
  • the sample plate 27 is positioned on a disk-shaped sample stand 28 so that the pulling and arranging direction of the fiber two may be vertical to the horizontal plane of the diskshaped sample stand 28.
  • a light source 29 is of such optical system that irradiating rays may proceed in parallel with the horizontal plane of the disk-shaped sample stand 28 and their angle of incidence may be 45 degrees with the fiber two to be tested.
  • the optical axis of a photoelectric multiplying tube 21 movable in parallel with the horizontal plane of the disk-shaped sample stand 28 is provided to coincide with a. normal erected on the sample surface at the point of incidence, and a magnifying lens optical system EL consisting of an objective 26 of a magnification of 11.1 times, lens barrel 25 and camera 24 is provided between the sample fiber two and photoelectric multiplying tube 21 so that the image of the sample may be focused on a frosted glass plate 23 fixed to the camera 24.
  • a rectangular slit 22 which is 1.0 mm.
  • the electric output of the photoelectric multiplying tube 21 is fed to such register REC having a full scale width of 0 to 5- mv. as, for example, a register Model LER-12A manufactured by Yokokawa Electric Machinery Manufactory, Ltd. through an amplifier A in which the fed voltage is made constant in advance by a high voltage controller EST and low voltage controller ST and is recorded on a recording paper sheet moving by maintaining a constant velocity of 60 mm. per minute in said part.
  • Contrast index log n The larger the contrast index of the fiber two, the clearer and stronger the microscopic spot light pencil reflected ttrom the sample surface and the more remarkable the visible sparkle.
  • EXAMPLE 1 An acrylic polymer of a molecular weight of 58,000 made by copolymerizing 91% acrylonitrile and 9% methyl acrylate was dissolved in an aqueous solution of sodium thiocyanate of a concentration of 46% to prepare. a spinning solution of a polymer concentration of 11%. The spinning solution was heated to 70 C. and was extruded into a coagulated bath consisting of an aqueous solution of sodium thiocyanate of a concentration of at a temperature of 3 C. by using a spinnerette (of a thermal conductivity of 4X10 cal. -sec.- 'cm.- 'deg. having spinning orifices shown in A in FIG.
  • the cross-sectional shape maintains the jet stretching ratio at 0.5 but is close to a circular shape and the sparkle represented by the 60-degree mirror surface luster or contrast index is evidently reduced.
  • EXAMPLE 2 An acrylic polymer of a molecular weight of 58,000 made by copolymerizing 89% acrylonitrile and 11% methyl acrylate was dissolved in an aqueous solution of sodium thiocyanate of a concentration of 46% to prepare a spinning solution of a polymer concentration of 12%. The spinning solution was heated to 70 C., and extruded into an aqueous solution of sodium thiocyanate of a concentration of 10% at a temperature of 3 C.
  • the same spinning solution was spun, stretched, dried to be compacted and heat-relaxed under the same spinning conditions as in the above mentioned Example 2, except that the material of the spinnerette was changed to a metal having platinum as a main component from the epoxy resin in the above mentioned Example 2, to make an acrylic synthetic fiber of a monofilament fineness of 15 deniers.
  • the crosssection was close to a circular shape and the sparkle was insufficient.
  • the 60-degree mirror surface luster of the acrylic synthetic fiber spun by setting the jet stretching ratio at each of 1.00 and 0.23 is shown in Table 3.
  • a process for producing acrylic synthetic fibers of a noncircular cross-section improved in sparkle characterized by extruding a spinning solution prepared by dissolving an acrylic polymer in an inorganic solvent into a coagulating bath through a spinnerette whose thermal conductivity does not exceed 5X10" cal. cmr sec.- deg.-
  • a is the smallest width of the spinning orifice
  • b is the largest width of the spinning orifice measured in the same direction as of a
  • c is the long diameter of the spinning orifice measured in the direction at right angles with the above mentioned a or b and narrowed in the central part so as to be formed into a fiber filament and taking the filament out of said coagulating bath while maintaining the jet stretching ratio, which is defined as the ratio of coagulated filament pulling out velocity/ average flowing velocity of the spinning solution through the spinning orifice, between 0.23 and 0.6.
  • the acrylic polymer is an acrylic copolymer consisting of not less than 70% by weight of acrylonitrile and the remainder being one or more vinyl monomers copolymerizable with acrylonitrile.
  • thermodeformation temperature above 70 C. and a bending strength not less than 700 kg./cm.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
US00279625A 1971-08-12 1972-08-10 Process for producing acrylic synthetic fibers of noncircular cross-section and with improved sparkle Expired - Lifetime US3786125A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP46061202A JPS5146169B2 (enrdf_load_stackoverflow) 1971-08-12 1971-08-12

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US3786125A true US3786125A (en) 1974-01-15

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US00279625A Expired - Lifetime US3786125A (en) 1971-08-12 1972-08-10 Process for producing acrylic synthetic fibers of noncircular cross-section and with improved sparkle

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US (1) US3786125A (enrdf_load_stackoverflow)
JP (1) JPS5146169B2 (enrdf_load_stackoverflow)
CA (1) CA972915A (enrdf_load_stackoverflow)
DE (1) DE2239683A1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006057A (en) * 1988-02-16 1991-04-09 Eastman Kodak Company Modified grooved polyester fibers and spinneret for production thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182606A (en) * 1975-11-20 1980-01-08 Fiber Industries, Inc. Slit extrusion die
JPS57167411A (en) * 1981-04-03 1982-10-15 Mitsubishi Rayon Co Ltd Acrylic synthetic fiber and its production
JPS5860011A (ja) * 1981-10-02 1983-04-09 Asahi Chem Ind Co Ltd アクリル系扁平モノフィラメントの製造方法
JPS61138714A (ja) * 1984-12-11 1986-06-26 Kanegafuchi Chem Ind Co Ltd 獣毛状光沢を有するアクリル系繊維及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006057A (en) * 1988-02-16 1991-04-09 Eastman Kodak Company Modified grooved polyester fibers and spinneret for production thereof

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Publication number Publication date
JPS5146169B2 (enrdf_load_stackoverflow) 1976-12-07
CA972915A (en) 1975-08-19
JPS4827019A (enrdf_load_stackoverflow) 1973-04-10
DE2239683A1 (de) 1973-02-22
AU4533172A (en) 1974-02-14

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