US3734986A - Method for producing polyamide fiber having improved silky feel and lustre - Google Patents

Method for producing polyamide fiber having improved silky feel and lustre Download PDF

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US3734986A
US3734986A US00060029A US6002970A US3734986A US 3734986 A US3734986 A US 3734986A US 00060029 A US00060029 A US 00060029A US 6002970 A US6002970 A US 6002970A US 3734986 A US3734986 A US 3734986A
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polyamide
yarn
lustre
fiber
modifier
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T Kato
T Hidaka
C Okagawa
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Toray Industries Inc
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Toray Industries Inc
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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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/13—Cell size and distribution control while molding a foam
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/61—Processes of molding polyamide

Definitions

  • Polyamide fiber having improved silky lustre and silky touch is produced by melt-spinning modified polyamide pellets obtained by dispersing fine particles of polyalkylene ether into polyamide, continuously drawing the melt spun filaments until the birefringence of said filament reaches a specific pro-selected point, treating the drawn yarn with a solvent for polyalkylene ether and recovering the same.
  • the present invention relates to a method for producing a polyamide fiber having improved silky lustre and silky touch, and more particularly, to a method for producing such an improved polyamide fiber by meltspinning a polyamide fiber having polyalkylene ether incorporated therein.
  • Polyamide fiber has been used for textile products such as are used in clothing because it has excellent strength, high anti-abrasion, excellent dyeability, and high washand wearability. (It should be noted here that fiber is used to denote both filamentary fiber and multi-filament yarn.)
  • the conventional polyamide fiber has a waxy touch and appearance which are inherent disadvantages of the synthetic fiber, and which therefore restrict the applications thereof.
  • the cross sectional surface of the fiber is changed from circular into multilobal form. This eliminates the waxy touch of the synthetic fiber but the surface of the fiber glistens and the lustre of the synthetic fiber is completely different from that of silk.
  • the inventors of the present invention have found that the preferred properties of silk, in particular, silky lustre and touch can be obtained in a polyamide fiber by providing in the polyamide fiber voids of the appropriate size and volume and by appropriately making the surface of the fiber coarse.
  • polyalkylene ether is not dissolved into the polyamide, to say nothing of the low melting point and poor spinnability thereof, and therefore when polyamide and polyalkylene ether are merely mixed and the obtained mixture is melt-spun, the polymer melt is remarkably unstable as the polyalkylene ether of low melting point is separated from molten polyamide. As a result yarn breakage occurs and spinning becomes im possible.
  • the object of the present invention is to provide a method for producing polyamide fiber of excellent properties capable of smooth spinning by solving the various problems heretofore associated with the melt-spinning of polyamide fibers having polyalkylene ether blended therein.
  • Another object of the present invention is to provide a method for producing polyamide fiber having both silky lustre and silky touch by subjecting the modified polyamide obtained in accordance with the above mentioned method to an appropriate after-treatment.
  • Another object of the present invention is to provide a method for producing a polyamide fiber with a silky appearance and touch rather than the waxy touch and appearance peculiar to the usual polyamide fiber.
  • the present invention provides a method for producing polyamide fiber having improved silky lustre and silky touch, comprising the following steps;
  • the drawn polyamide yarn is then treated with a solvent for the modifier, to extract out a part or most of the modifier, thus producing voids in the fiber.
  • the polyalkylene ether is substantially insoluble in polyamide.
  • polyalkylene ether is low and it has poor spinnability. Therefore when polyalkylene ether is merely mixed with polyamide, it oozes out onto the surface of the polyamide pellets during the meltspinning process. This polyalkylene ether on the surface of the polyamide pellets acts as a lubricant causing the pellets to slip on the surface of the screw in the melt spinning apparatus making the feeding of pellets very difiicult. In addition to this, when the two components of the pellets are melted, the polyalkylene ether is separated from the polyamide. This causes yarn breakage at the spinneret, and substantially precludes melt-spinning.
  • polyalkylene ether is added before or during the polymerization of polyamide.
  • polyalkyene ether is blended with polyamide 4 pellets and thereafter the blended mixture is melt-mixed by a mixing extruder which pelletizes the mixture.
  • the dispersed state of the polyalkylene ether modifier can be determined by slicing the modified polyamide pellet with a microtome. The lateral cross section and longitudinal cross section thereof are then observed with a microscope.
  • the blend is re-melted and the kneading operation is repeated until pellets having modifier particles with more than 50% by weight of the proper particle size are produced.
  • the modifier particles discussed herein include not only spherical particles, but also other particle shapes, such as rotary ellipse (elongated spherical) particles, linear, long fusiform (agglomerated) particles, etc.
  • particle size generally refers to the diameter of a spherical particle, or the diameter at the longitudinal midsection of a rotary ellipse particle or for odd-shaped elongated particles, such as the linear fusiform, the smallest cross-section diameter perpendicular to the axis of the particle. Collectively these may be referred to as the diameter of the cross section of each particle.
  • the required amount thereof varies in accordance with the size of the particles, but as is described hereinafter, the range of the amount of the dispersed particles, wherein the desired properties are attained and the fiber processability is not degraded, is from 2 to 15% by weight. This range will be discussed in more detail hereinafter.
  • the second problem to be faced, in carrying out the melt-spinning and fiber shaping process with polyamide containing finely dispersed polyalkylene ether particles, is the mutual yarn-adhesion of fibers as they are taken up in the aqueous emulsion of spinning oil.
  • This yarn-adhesion remarkably increases the unwinding tension of the package, when the undrawn yarn is drawn, causing yarn breakage or unevenness of yarn properties. As a result, the production of drawn yarn is made practically impossible.
  • the yarn-adhesion is retained in the final product and a coarse hand, like plait yarn, is retained in the final product.
  • the above mentioned problem can be solved by continuously drawing the melt-spun undrawn yarn, prior to taking it up, until the birefringence of the yarn satisfies Formula 2.
  • the yarn-adhesion of the yarn or filament can be prevented as the modified polyamide containing polyalkylene ether is melt-spun, and has absorbed water content from the spinning oil or from the air.
  • the swelling elongation due to absorption of water content can be controlled by increasing the degree of orientation above some predetermined value.
  • FIG. 1 is a schematic illustration of a melt-spinning and drawing process as used in the present invention
  • FIG. 2 is a graph of modifier content versus birefringence of a drawn yarn with no yarn-adhesion in the present invention
  • FIG. 3 is a diagrammatic illustration of the process used for measuring certain optical properties of the fiber of the present invention.
  • FIG. 4 is a graph of certain optical properties used to determine quantitatively one important optical property of the fibers of the present invention.
  • FIG. 1 there is shown a diagram of an embodiment of the device for carrying out the method of this invention for producing polyamide fiber. More specifically there is shown polyamide fiber 1 extruded by spinning nozzle 2 from a melt of modified polyamide prepared by blending polyalkylene ether in polyamide. And then it is contacted with oil roller 3 where an oil finish is applied, and is then passed from draw feed rollers 4, to drawing rollers 5 revolving at higher peripheral velocity than that of draw feed rollers 4.
  • the degree of orientation required for controlling the yarn-adhesion of yarn or filament can be determined from the amount of the polyalkylene ether blended with polyamide, in accordance with Formula 2 given above. The reason for this is that the yarn-adhesive is mainly caused by polyalkylene ether. A plot of this relationship is given in FIG. 2, wherein the area bounded by the parameters given in Formulas 1 and 2 is shown by slant lines.
  • the amount of polyalkylene ether contained in l g. of polyamide is less than 0.2 mmol, the optical property of the fiber, with a part or all of the polyalkylene ether blended therein extracted therefrom, is not silky.
  • the amount of polyalkylene ether contained in 1 g. of polyamide is more than 3.5 mmol, yarn breakage or yarn-adhesion becomes excessive and spinning becomes very difficult even if the polyalkylene ether is finely dispersed in the polyamide.
  • the amount of polyalkylene ether is more than 3.5 mmol, yarn produced has no silky lustre but becomes chalky when the obtained yarn is washed and extracted.
  • the minimum birefringence is 40-45 1()- at maximum polyalkylene ether concentration. This birefringence is required for preventing yarn-adhesion when the polyamide which contains the possible maximum amount, i.e., 3.5 mmol/ g. of polyalkylene ether, is melt-spun. The minimum birefringence is close to that of the drawn yarn, as the amount of polyalkylene ether is lowered and the required birefringence for controlling yarn-adhesion is therefore also lowered.
  • the birefringence required for controlling yarn-adhesion has a tendency to be more or less changed in accordance with the structure of polyalkylene ether and the kind of the matrix polyamide, but the difference is not so great as the effect of the amount thereof to be added.
  • the birefringence can be determined substantially by the concentration of alkylene oxide radical in the polyamide.
  • a polyalkylene ether having a molecular weight from 600 to 60,000 may be used but a molecular weight of from 1000 to 20,000 is preferred.
  • polyalkylene ethers having a molecular weight within the above mentioned range greatly affects the properties of the yarn product and the melt-spinnability of the modified polyamide.
  • alkylene oxides upon which the modifiers used in the present invention eg the polyalkylene ethers or addition products thereof, are based, ethylene oxide or propylene oxide are preferred.
  • the polymer prepared by adding an alkylene oxide to organic compounds containing active hydrogen such as a homo-or-copolymer of propylene oxide, organic amines, alcohols, acids, and compounds Whose terminal hydroxyl radicals are confined, or mixtures of said compounds, can be used as the polyamide modifier.
  • organic compounds containing active hydrogen such as a homo-or-copolymer of propylene oxide, organic amines, alcohols, acids, and compounds Whose terminal hydroxyl radicals are confined, or mixtures of said compounds.
  • polyalkylene ether having high affinity for polyamides such as alkylene oxide adducts of polyamide oligomers or polyamide monomers containing amido radical in the molecule thereof are preferred.
  • the preferred compounds include ethylene or propylene oxide addition products of tetragonal through tridecagonal lactams, such as Z-piperidone, e-caprolactam, enantholactam, laurin lactam and other similar alkylene oxide addition products.
  • a phosphoric ester and/ or the metal salt thereof in order to prevent coloring of the polyamide caused by heat and the modifier blended therein, it is preferable to blend therewith a phosphoric ester and/ or the metal salt thereof.
  • the metal radical of the metal salt mention can be made of such, for example, as the alkali metals as Na and K, the alkaline earth metals as Mg, Ca, and Ba, the transition metals as Cr, Co, Cu, Zn, Sn, Mn, and Ni, and A1, of which the most convenient are the transition metals, particularly, Mn Cu, Co, and Ni.
  • phosphoric esters monoesters, diesters, triesters or mixtures thereof can be given.
  • meltspun and drawn modified polyamide containing polyalkylene ether be washed with a solvent which is inert against polyamide and active against the modifier blended therein so that a part or most of the modifier is extracted (from the fiber. It is also necessary that the appropriate amount of voids be formed in the fiber.
  • an organic solvent such as alcohol or benzene.
  • the extraction should be carried out in such a manner that the amount of voids in the fiber is within the range from 0.5-l3 vol percent.
  • Extraction can be carried out on yarn, but it can also be carried out on the textile product made from the yarn. Generally it is preferable to carry out extraction on the textile product from an industrial point of view.
  • textile product is a product knitted, woven, or otherwise made up of fibers such as those of the present invention.
  • fine white particles may be blended in the fiber forming material. This may also improve the processability of the fiber.
  • the diameters of circles circumscribed around these particles should not be above or more than /a of the diameter of the melt spun fiber.
  • the preferable size of these fine white particles is such that the diameters of circles circumscribed around the particles is from 0.1 to 4a.
  • a conventional method such as hydarulic elutriation, is appropriate.
  • a dispersing agent may be used when blending of the fine white particles is carried out during the polymerization of polyamide.
  • the commercially distributed inorganic or organic white pigments can be used.
  • the amount of fine white particles to be blended with the polyamide is more limited if the difference of the refractive index between the particle and the polyamide is too great.
  • C is the amount of fine white particles to be blended (weight percent); d is the absolute value of the difference of refractive index between the fine white particles and the polyamide).
  • the yarn product becomes chalky and the lustre, otherwise produced in accordance with the present invention, is not obtained.
  • Titanium oxide (2.50 or 2.75) Zinc sulfide (2.37)
  • polyamide refers to meltspinnable polymers of polymerizable 'monoaminomonocarboxylic acids, salts of diamine and dicarboxylic acid, or melt-spinnable fiber forming polyamides obtained from the amido forming derivatives thereof.
  • Copolymer of two or more of the foregoing can also be used.
  • the preferred polyamide used in this invention are polye capramide, polyhexamethylenedipamide, polyhexamethylenesebacamide.
  • Other aliphatic polyamides, polyamides having aromatic rings, aliphatic rings or heterocycles in the main chain can also be used.
  • Heat stabilizers, light stabilizers, dyes and homologues of the foregoing polyamide materials may also be blended in the polyamides used in this invention.
  • the improved polyamide fibers obtained in accordance with the present invention have from 0.5 to 13% by volume of finely dispersed voids in the fibers and have a surface lustre such that the ratio of the strength of scattered light (I/I as defined hereinafter) satisfies the Formula 4 below.
  • the lustre factor (a as defined hereinafter) satisfies the Formula 5 below.
  • the polyamide fiber of the present invention has high non-transparency.
  • the polyamide fiber having such lustre properties as mentioned above has a silky appearance, and is free of the waxy appearance peculiar to the usual synthetic fiber.
  • the reflectivity of the fiber is measured by the ratio of the strength of scattered light (I/I which is determined in the following manner, as illustrated in FIG. 3.
  • a test sample (S) is prepared by winding a test fiber on a non-reflective black panel in such a manner that the successive ends of test fiber lie in parallel and in contact with one another and there is no space between the respective adjacent test fiber ends.
  • the strength of reflected light (I of a standard white board of magnesium oxide (HS-Z 8722-1959) is measured under the same conditions.
  • N1 When the ratio of the strengths of scattered light, N1 is high, the whole fiber is made to shine brightly by incident light. When this value is low, the brightness of the whole fiber is lower.
  • the lustre factor (a) of the present invention is a measure of lustre quality, and it is obtained in the following manner.
  • the sample panel (S) is prepared by winding fibers in the same manner as described above.
  • the reflected light (I) strength in the direction of the light receiving angle 45 (the angle of reflection on a mirror surface) is continuously measured during rotation.
  • the strength of reflected light (I) is plotted against the angle of rotation of sample (S) rotating in the plane of sample (S), and a curve as is shown in FIG. 4 is obtained.
  • the lustre factor (a) is defined as the range (AB) of the angle of rotation in which the strength of reflected light exceeds the mean strength, which is the average value of the maximum strength of reflected light (I max.) and the minimum strength of reflected light (1 min.) of said curve in any half revolution of sample (S).
  • the lustre factor (a) shows the angular range in which the fiber looks brighter than the mean brightness of the fiber at the angle of mirror reflection thereof.
  • the fiber or bundles thereof look brighter when light is projected onto the fibers assembled in a textile product (wherein the axes of the fibers comprising the product are in various directions).
  • the only fibers which appear bright are those fibers aligned in a specific direction (wherein the axis of the fiber is parallel with the plane including the projected light direction). In such a case, the product appears to have low lustre.
  • optical properties of polyamide fibers produced in accordance with the present invention are compared by taking as examples the fibers as usually used for clothes (the unit filament size being 3 denier). This comparison is graphically illustrated in FIG. 4.
  • FIG. 4 shows the reflection pattern of silk (Curve 4) measured by the same instrument and in the same way used for polyamide fibers, as described herein.
  • the ratio of the strength of scattered light (I/I is high in the case of natural silk, and the lustre factor (a) is also high.
  • Conventional unmodified polyamide fiber (Curve 2), containing no titanium oxide, also has a high ratio of strength of scattered light. However, it has a very low lustre factor; accordingly the transparency of the conventional polyamide fiber is high and therefore when light is projected from a specific direction, it glistens and presents a waxy appearance and strong touch.
  • the improved polyamide fiber (Curve 1) of the present invention has high non-transparency, lustre factor (7) is high, and the ratio of strengths of reflected light (l/l is remarkably high. Generally, it presents a lustre similar to that of a natural silk. Therefore, when it is dyed, very brilliant colors can be obtained.
  • the ratio of the strength of scattered light (I/I is less than 1.5, the amount of the reflected light is very little as light is projected onto the fiber bundle, and the fiber bundle has insutficient brightness.
  • the fiber bundle sparkles only in a specific direction (generally in the direction parallel with the fiber axis) as light is projected onto the fiber, and it is not preferable.
  • Void size is determined from an electron microscopic photograph of a lateral cross section of the filament.
  • Fibers are associated into tow of 28,000 denier, and this tow is made into a blind the width of which is 2.5 cm.
  • This blind is set on a photoelectric photometer (produced by Nippon Precision Optical Co., Ltd., Model SEP-H), and the permeability or transparency (percent) with respect to white light of a tungsten lamp is measured.
  • the central portion of a pellet is cut into pieces (the thickness of the lateral cross sectional surface and longitudinal cross sectional surface of each piece being respectively 5 to 10p.) and the obtained pieces are observed with a microscope to determine the diameters of the dispersed particles and the number of particles in the pellet cross section.
  • Sulfuric acid relative viscosity (777) The relative viscosity of the solution prepared by dissolving 1.0 g. of dry polymer into cc. of 98% sulfuric acid. Viscosity is then measured using an Ostwalds viscometer.
  • Dynamic frictional coefiicient d The sample filament yarn is worked on a frictionless roller (whose diameter is 10 mm. and fixed to the frame), and the filament yarn is twisted to give three turns thereto. Then the tension before the roller is determined to be 5 g., and while running the yarn at the speed of 300 m./ min., the tension (T) after the roller is measured, and the value obtained in accordance with the following formula is the measure of the dynamic frictional coefiicient. 10
  • Example 1 obtained in accordance with Th l t l cross section of P ll t A was ob d the present invention, uniform extrusion was very exwith a microscope and the dispersed state of said modieehehtly Carried Further, there was 110 y breakage bomb was studied.
  • pellets B were dried under reduced 30 minutes and then pp into hOt W t r f r pressure in the same manner as in the case of Pellets A.
  • Voids wel'e Produced in the fibers- Pellets A and Pellets B were supplied respectively into The Void etlpaeity was about 33% y Volumeconventional melt-spinning hi d me1t spun at 45
  • the lateral cross section of fibers thus obtained was 250 C. Th re ft the spun yams were taken up at 800 observed with an electron microscope and as a result of m./min., and thereafter the yarns were draw o a the microscopic observation, it was found that the averond roller running at a peripheral speed of 2,800 m./min. age diameter of these Voids Was and the maximum Then they e tak up t producs drawn yarns f 70 diameter thereof was 1.5,u. Further, it was found that there d i 24 filaments was no void with a diameter of more than (about 2,)
  • the drawn yarn produced by using Pellets A was made bf the diameter of the fiber- Control 1, the drawn yarn produced by using Pellets B
  • the ratio of the Strength of Scattered o) and wa d E l 1 lustre factor (a) of the modified and unmodified nylon 6 A separate sample of yarn d d fr Pellets B fiber having been extracted as mentioned above, were was taken up as undrawn yarn at 800 m./min. in the same measured, and the results are given in Table manner as in the conventional spinning drawing process.
  • the modified hylbh 6 fiber of the Present invention had After havi b l ft o t overnight hi yam was drawn a ratio of the strength of scattered light and lustre factor four times by using a conventional draw-twister to prowhich satisfies both Formula 4 and Formula More du e drawn yarn, over, the modified nylon 6 fiber of this invention pre- Thi yarn a th m d C t l 2 sented a bright lustre and, in addition, very excellent non- Table 1 shows the melt-spinning state of all of these transparency and y and Warm touch Were obtahledyarns, the drawing state thereof, and the birefringence on the other hand, the unmodified nylon 6 had low of the drawn yarns. ratio of strength of diffused light, low lustre factor, and
  • Example 14 The modified polyamides of Examples 24, having no yarn-adhesion and excellent spinnability were washed under the same conditions as in Example 1 to extract the modifier. Thereafter the ratio of strength of diffused light and 0.13 part of acetic acid, as a viscosity stabilizer, were mixed, and water was added to the mixture to make 75% aqueous solution. With the modifier uniformly dissolved the solution was polymerized in accordance with a conventional method.
  • the modified poly-e-capramide (nylon 6) product was washed with large amounts of pure water (at 9095 C.) to remove unreacted lactam and oligomer, and then dried under a reduced pressure.
  • the concentration of modifier was 5.2% by weight, (the concentration of oxyethylene radical was 1.2 mmol/ g.) in the modified nylon 6, and the relative viscosity of the polymer was 2.45.
  • the modifier was very finely dispersed in the polymer and more than 80% by weight of fine spherical particles, with a particle size of 2p, was present.
  • This modified Nylon 6 was supplied to a conventional spinning machine and the melt spun yarn was taken up initially at a speed of 900 m./min. Then the speed of the drawing roller was changed and the yarn prior to being taken up was drawn under such a condition that various birefringence as shown in Table 3 were obtained.
  • the output of extruded polymer was changed in accordance with the drawing rate so as to produce 70 denier-24 filament drawn yarn.
  • the yarn-adhesion of the drawn yarn is shown in Table 3.
  • aqueous solution which was transparent and in which the modifier was uniformly dissolved was put into a polymerization vessel and heated under atmospheric pressure, while the reaction mixture was stirred with an efiicient stirrer provided with spiral blades. The stirring operation was initiated at the point in time when the modifier began to separate and the stirring operation was continued until the polymerization was terminated.
  • Examples of each of the remaining types of modified nylon 6 pellets were supplied to the screw type spinning machine, and were passed through the spinning nozzle pack, provided with a filter charged with 60 mesh and 200 mesh white Alundum, to melt-spin the modified nylon. Then the extruded fiber was taken up at a speed of 900 m./min. and thereafter it was continuously drawn.
  • the drawing operation was carried out on modified nylon 6 products containing Modifier No. 3 at several drawing speeds and substantially no yarn-adhesion was observed, no yarn breakage was brought about, and excellent drawn yarn was obtained.
  • nylon 6 fiber (whose elongation was from 35 to 40%) was prepared by blending 0.3 and 2.0% of titanium oxide along with unmodified nylon 6 and unmodified nylon 6 containing no modifier at all was obtained.
  • the above prepared modified polyamide fibers were wound in hank form and dipped into 40 C. hot water. Then they were shaken and stirred for about 30 minutes.
  • the amount of voids increases as the amount of modifier added increases. Along with the increase in the amount of voids, the transparency of the fibers is reduced, and the ratio of the strength of diffused light (U1 and lustre factor (a) are increased.
  • the modified polyamide fiber obtained in accordance with the method of the present invention when the modified polyamide fiber of Control 9, which contains 0.2 vol percent of voids, is taken as an example, the improvement of lustre is not sufficient, and the ratio of the strength of diffused light (U1 and lustre factor (a) are also close to those of the unmodified polyamide fiber of Control 6.
  • the fibers of Examples 58 which have a sufficiently high ratio of strength of diffused light (U1 and lustre factor (a), to satisfy the requirements of the present invention, are non-transparent and have a bright lustre.
  • Tricot weave of these fibers had a mild and silky lustre and, when compared with the product prepared by blending 0.3% by weight of titanium oxide, it had higher non-transparency, and presented a warmer and dryer touch.
  • the unmodified polyamide fiber of Control 6 had a lower ratio of strength of scattered light (U1 and lustre factor (a) and glistened only when observed from a specific direction. Further, it was remarkably transparent and had a waxy touch. Generally its appearance was harsher.
  • the polyamide fibers of Controls 7 and 8 prepared by blending titanium oxide had much lower ratios of strength of diffused light (U1 and the fibers generally presented a dull lustre. The appearances thereof was pastel colored.
  • the lustre of the polyamide fiber of the present invention is very close to that of natural silk as is apparent from Table 5.
  • the internal temperature of the autoclave was 300 C. and the pressure was controlled to be 18 kg./cm. Under these reaction conditions, 6 parts by weight (concentration of oxyethylene radical is 1.3 mmol/g. of lactam) of the molten ethylene oxide addition product of e-caprolactam mol ethylene oxide/mol of e-caprolactam was added thereto) was blended with the laurolactam, and the polymerization was terminated.
  • the modified nylon 12 pellets obtained by melt-spinning and cooling this reaction product had a sulfuric acid relative viscosity of 2.0.
  • unmodified nylon 12 (whose relative viscosity was 2.2) was prepared without blending modifier therein.
  • the modified nylon 12 was supplied into an extruder type spinning machine, and it was melt-spun at 280 C. and taken up at a speed of 800 m./min. Thereafter the yarn was drawn with a drawing roller running at a peripheral speed of 2400 m./min. by using the same device as in Examples 2-4, and then the drawn yarn 30 denier/ 6 filament was taken up.
  • the elongation of the drawn yarn was 40%, and the birefringence thereof was 41x10? Yarn-adhesion was not observed at all and no yarn breakage was observed.
  • the spinning operation was carried out very excellently.
  • This yarn was divided into four groups, and then the respective groups were wound on hanks, and the respective hanks were subjected to after-treatment.
  • the second hank was subjected to extraction by using boiling Water for 30 minutes and the hank thus treated was taken as Example 9.
  • the third hank was treated with 40 C. hot water for 30 minutes, and the yarn thus treated was taken as Example 10.
  • Example 11 The last hank was boiled in a mixture of methyl alcohol and benzene, mixed at a ratio of 1:1, for 30 minutes and the yarn thus treated was taken as Example 11.
  • the amount of voids in the case of the latter was remarkably greater than that of the former.
  • modified nylon 12 treated with boiling water, warm water or organic solvent presented a high ratio of strength of scattered light (I/I lustre factor, and excellent non-transparency and presented a silky lustre and a dry and desirable touch.
  • the modifier was separated from the nyon 6 and the modifier was finely dispersed in the form of spherical particles the average diameter of which was from 3 to 5
  • the modified nylon 6 pellets containing the above mentioned modifiers were then melt spun as in Examples 2-4.
  • the melt temperature was 265 C.
  • the take-up speed was 600 m./min.
  • the drawing speed was 1900 m./ min.
  • Drawn yarn 70 denier/24 filament was obtained.
  • the birefringence of the above modified nylon 6 products were about 45 10 and no yarn-adhesion was observed.
  • the yarn breakage of the molten polymer at the outlet of the spinning nozzle was different depending on the structure of the modifier. Remarkable yarn breakage was observed in the case of nylon '6 yarn prepared by blending the nonylphenol ethylene oxide addition product and, in addition, the modifier was separated from the a nylon 6. More specifically, it oozed out onto the surface of the pellets. This caused the supply of pellets to be very unsteady and irregular extrusion resulted.
  • the modifiers were uniformly dissolved in an aqueous lactam solution (85% aqueous solution). Microscopic observation of cross-sections of the pellets produced indicated that pellets prepared with the modifiers having the lower mole ratio of ethylene oxide in each of the pairs of addition products the nylon 6 yarns prepared by blending modifiers which dissolved into the nylon 6 (Controls 14, 15 and 16), and therefore they presented the same properties as the unmodified nylon 6.
  • the degree of extraction varies in accordance with the kind of the modifier used, the volume of voids produced by extraction may differ even though the proportion of blended modifier is the same. This of course results in differences in optical properties.
  • the respective monomer mixtures were then polymerized in autoclaves, while vigorously stirring the same, and then they were extruded into pellets.
  • the dispersed states of the modifiers in the pellets thus obtained were studied and it was found that more than 70% by weight of the modifiers were dispersed finely in the form of spherical particles the average diameter of which was less than 51.1..
  • the concentrations of oxyalkylene radicals contained in these polymers were 0.8, 0.8 and 0.9 mmol/ gram polymer, respectively.
  • the modified nylon 66 pellets thus obtained were meltspun in the same manner as in Examples 2-4, and the yarns were taken up at a speed of 900 m./min. and then drawn at a drawing speed of 3,000 m./min.
  • the respective yarns had excellent melt-spinning states, and no yarn breakage occurred. Further, no yarnadhesion of the drawn yarns was observed.
  • An aqueous solution was prepared by blending 5.2%, by weight, of this modifier with e-caprolactam.
  • metakaolin the refractive index of which is 1.60
  • a dispersing agent sodium pyrophosphate
  • This slurry was blended with the aqueous solution of e-caprolactam containing the above prepared modified in such a manner that a predetermined concentration of the slurry was obtained and then the mixture was sufiiciently stirred, heated and polymerized. Extraction of unpolymerized material were carried out in accordance with conventional methods and modified polycapramides containing 0.5% by weight and 1% by weight of metakaolin, and 4.8% by weight of modifier were obtained.
  • modified polycapramides containing 0.5 and 1.0% by weight of titanium oxide (the refractive index thereof being 2.52) and 4.8% by weight of modifier were obtained through hydraulic elutriation and polymerization as described.
  • polycapramides were melt-spun in accordance with the same spinning method as in Examples 24, and the yarn products were continuously drawn to produce polycapramide fibers (40 denier/10 filament) 22 mixture (dimer, trimer, and tetramer).
  • Ethylene oxide was added to this polyamide oligomer mixture in accordance with conventional methods, (average mole ratio/ ethylene oxide per mol oligomer 50 mol) and an ethylthe birefringence of which was respectively 45 l- 5 one oxide addition product (hereinafter referred to as the Now of the yarns had irregular extrusion problems and modifier) was obtained. no yarn breakage occurred during the drawin o eration.
  • iii-g g yams showed excellent processablhty charac- 5.8% by weight of modifier was dispersed in the pellets as fine spherical partlcles the average particle size of bleggehien :g1:mg3?0:1vt2? itilfiierzlvl'ilgledgglrlgglii 17:21: 'l iiesz e il ets were melt-s un in the same manner as mula 3 (Control 18), the frictional coefiicient was low.
  • EXAMPLES 22-23 60 white particles in amounts within the range of Formula Polycapramide obtained by polymerizing e-caprolactam was extracted with hot water, and the extracted product 3 presented a silky lustre and a very low dynamic frictional coelficient.
  • Method for producing polyamide fiber having improved silkyl lustre and silky touch comprising the steps of (1) blending a melt spinnable polyamide with a polyalkylene ether modifier which is substantially insoluble in said polyamide and has excellent thermal stability at the melting point of said polyamide, the proportion thereof, in millimol repeating alkylene oxide unit in said modifier per gram polyamide hereinafter referred to as a being in the range 3.5 to 0.2, (2) preparing from said blend modified polyamide pellets having said modifier finely dispersed therein as minute particles at least 50%, by weight, of which have an average axial diameter in their cross-section of below 20 (3) melt-spinning said modifier polyamide pellets to prodce filaments, (4) continuously drawing said filaments until the birefringence, An, of said spun filaments is not less than 49 log 32 wherein a stands for millimols (mmols) of the recurring alkyleneoxide unit in the polyalkylene ether modifier contained in 1 gram (g.) of the polyamide; and
  • polyalkylene ether modifier comprises an alkylene oxide addition product, said alkylene oxide having from 2 to 3 carbon atoms.
  • Method for producing polyamide fiber according to claim 1 wherein said blending step comprises uniformly dissolving said modifier in a polyamide monomer or polyamide monomer solution and polymerizing said monomer and wherein said modifier particles in said pellets formed therefrom have an average axial diameter in their crosssection of below 5.
  • Method for producing polyamide fiber according to claim 1 wherein fine white particles, having a refractive index of from 1.4 to 2.76 and a maximum diameter less than 10g and also less than the melt spun filament diameter, are blended into said polyamide along with said modifier, said blend proportion being within the range defined by the following formula:
  • fine white particles are selected from the group consisting of talc, kaolinite, titanium oxide and calcium carbonate.
  • polyalkylene ether modifier has a molecular weight in the range from 1,000 to 20,000.
  • amidoradical containing compound of said polyalkylene ether comprises ethylene or propylene oxide addition products of tetragonal through tridecagonal lactams.

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  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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US00060029A 1970-07-29 1970-07-31 Method for producing polyamide fiber having improved silky feel and lustre Expired - Lifetime US3734986A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917740A (en) * 1972-03-31 1975-11-04 Snia Viscosa Method for the production of polyamides by adding polyethyleneglycol having a low index of dispersion
US3929950A (en) * 1972-06-22 1975-12-30 Kureha Chemical Ind Co Ltd Process for producing porous synthetic resin film and sheet
US3962176A (en) * 1973-05-16 1976-06-08 Bayer Aktiengesellschaft Antistatic polyamide compositions which are stabilized against yellowing
US4100238A (en) * 1975-03-20 1978-07-11 Nippon Oil Company, Ltd. Process for producing permeable membranes
US4464435A (en) * 1978-10-25 1984-08-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same
US4963304A (en) * 1988-09-26 1990-10-16 The Dow Chemical Company Process for preparing microporous membranes
US20100047366A1 (en) * 2002-11-08 2010-02-25 Rhodianyl Articles with antibacterial and antifungal activity
WO2019116155A1 (en) * 2017-12-15 2019-06-20 3M Innovative Properties Company Fibers including an alkylene oxide-containing nonionic surfactant, articles, and methods
EP4624639A1 (en) * 2024-03-25 2025-10-01 Zeland Textech GmbH Method for producing colored yarns and/or colored fabrics in particular without or with only limited amount of wastewater discharge

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4525384A (en) * 1983-03-07 1985-06-25 Teijin Limited Process for producing wholly aromatic polyamide filaments heat-treated under tension

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917740A (en) * 1972-03-31 1975-11-04 Snia Viscosa Method for the production of polyamides by adding polyethyleneglycol having a low index of dispersion
US3929950A (en) * 1972-06-22 1975-12-30 Kureha Chemical Ind Co Ltd Process for producing porous synthetic resin film and sheet
US3962176A (en) * 1973-05-16 1976-06-08 Bayer Aktiengesellschaft Antistatic polyamide compositions which are stabilized against yellowing
US4100238A (en) * 1975-03-20 1978-07-11 Nippon Oil Company, Ltd. Process for producing permeable membranes
US4464435A (en) * 1978-10-25 1984-08-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same
US4963304A (en) * 1988-09-26 1990-10-16 The Dow Chemical Company Process for preparing microporous membranes
US20100047366A1 (en) * 2002-11-08 2010-02-25 Rhodianyl Articles with antibacterial and antifungal activity
US20110042845A1 (en) * 2002-11-08 2011-02-24 Rhodianyl Articles with Antibacterial and Antifungal Activity
WO2019116155A1 (en) * 2017-12-15 2019-06-20 3M Innovative Properties Company Fibers including an alkylene oxide-containing nonionic surfactant, articles, and methods
CN111465724A (zh) * 2017-12-15 2020-07-28 3M创新有限公司 包括含环氧烷的非离子表面活性剂的纤维、制品和方法
EP4624639A1 (en) * 2024-03-25 2025-10-01 Zeland Textech GmbH Method for producing colored yarns and/or colored fabrics in particular without or with only limited amount of wastewater discharge

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DE2039105B2 (de) 1973-06-20
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GB1300467A (en) 1972-12-20
NL7011263A (enExample) 1972-02-01
FR2102457A5 (enExample) 1972-04-07

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