US3642565A - Composite filaments having an elastic crimping property - Google Patents
Composite filaments having an elastic crimping property Download PDFInfo
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- US3642565A US3642565A US807863A US3642565DA US3642565A US 3642565 A US3642565 A US 3642565A US 807863 A US807863 A US 807863A US 3642565D A US3642565D A US 3642565DA US 3642565 A US3642565 A US 3642565A
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- polyamide
- composite filament
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- 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
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
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- 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
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
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- 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
- ABSTRACT Composite filament having an elastic crimping property, comr japan ,prised of at least two components disposed in an eccentric 1968 Japan "43/25756 sheath-core relation along the longitudinal axis of the filaapan ment, in which one component is composed of a polyester consisting mainly of polyethylene terephthalate and another [52] US.
- the core component may be con- UNITED STATES PATENTS stituted with a plurality number of cores. 3,540,080 1 l/ 1970 Goossens ..l8/8 18 Claims, 15 Drawing Figures Pmmmrmsmz 3.642.565
- the present invention relates to novel synthetic filaments, particularly to composite filaments having a high crimpability, an improved crimp elasticity and an excellent dyeability.
- the polyamide composite filament has poor crimp elasticity, resilient crimpability and crimp bulkiness. While, the polyester composite filament has excellent crimp elasticity, but has insufficient crimp durability because of its poor recovering properties for elongation, bending and compression.
- polyamide-polyester composite filaments wherein a homopolyester component is arranged in the core portion and a homopolyamide component is arranged in the sheath portion eccentrically to the core portion in order to compensate mutually the above-mentioned drawbacks in the polyamide composite filament and the polyester composite filament.
- the polyester component having poor recovering property for elongation is arranged in the inside portion of the crimps, the composite filament does not easily recover the original state, after applied mechanical stresses, such as repeating elongations, bendings, compressions, etc. Therefore, a desirable crimp durability cannot be obtained in the conventional sheath-core-type composite filament of polyamide-polyester.
- conventional composite filaments have only latent crimpability and do not develop spontaneous crimps even if the conjugate spun filaments are relaxed after drawing and they are linear as in usual monofilament and develop three-dimensional crimps only after they are subjected to shrinking treatments, such as hot water treatment and dry heat treatment.
- shrinking treatments such as hot water treatment and dry heat treatment.
- the composite filaments having the above-mentioned latent crimpability are knitted or woven into textures, such as stockings, socks, tricots and carpets, and then the resulting textures are directly subjected to a crimp developing treatment, tension and contact interference between mutual filaments in the texture suppress the crimp developability considerably and develop considerably nonuniform crimps to form unevenness on the surface of the texture.
- drawn composite filaments are generally subjected to a pretreatment, by which the drawn composite filaments are twisted or passed through a particular heater under tensionless state to develop preliminary crimps, and then led to various knitting or weaving steps.
- the object of the present invention is to provide a sheathcore-type composite filament of polyamide-polyester having a high crimp developability, which has never been attained in the conventional sheath-core-type composite filament, by using a highly shrinkable polyamide as the polyamide component to make a difference of shrinking percentage between the polyamide component and the polyester component larger, and further selecting the conjugate ratio of the polyester component and the degree of the eccentricity of core component corresponding to the shrinking percentage of the polyamide component.
- Another object of the present invention is to provide a composite filament having an excellent crimp elasticity and crimp recovering property, even when the filament is applied to mechanical stresses, such as repeating elongations, compressions and bendings, in said composite filament,, a polyamide component having an excellent recovering property for elongation being located in the inside portion of the crimps and a highly elastic polyester component being located in the out side portion of the crimps, when the composite filament is subjected to a shrinking treatment to develop crimps.
- Further object of the invention is to provide a composite filament having an excellent spontaneous crimpability which has never been seen in the conventional filament, that is, a novel composite filament capable of developing crimps spontaneously only by relaxing the drawn filament.
- the present invention provides a composite filament having an elastic crimping property.
- at least two different synthetic linear polymers are bonded in a sheath-core relation along the longitudinal direction of the unitary filament, characterized in that one polymer component is composed of a polyester consisting mainly of polyethylene terephthalate and another polymer component is composed of a highly shrinkable polyamide having a shrinking percentage in boiling water of at least l5 percent, that both the polymer components are arranged eccentrically in the cross section of the unitary filament, and that the core component occupies 1050 percent by weight in the unitary filament.
- the above-mentioned polyamide to be used in the present invention has a shrinking percentage in boiling water of l580 percent, preferably at least 20 percent.
- a shrinking percentage is less than 15 percent, a satisfactory crimp is formed with difficulty and the shrinking percentage is preferable to be higher, but when the shrinking percentage is more than percent, the commercial production cannot be effected.
- the shrinking percentage is determined by the following manner.
- the spun and drawn filaments are dipped in boiling water at C. for 15 minutes under a load of 0.5 mg./d. and are shrunk.
- the shrinking percentage is shown by the percentage of apparent loss of the length calculated by the following formula:
- lit- 1shrinking percentage X 100 wherein l designates the length of the shrunk filament and 1,, the length of the original filament.
- ordinary homopolyamides have a shrinking percentage in boiling water of less than l percent, but high molecular weight homopolyamides having an intrinsic viscosity [n] of more than 1.15 in m-cresol at 30 C. have a shrinking percentage in boiling water of more than percent, and can be used in the present invention.
- the most preferable highly shrinkable polyamides are copolyamide. That is, when the minor component of copolymerization in the copolyamide filament consisting of at least two polyamide-forming components is at least 5 percent by weight, the shrinking percentage in boiling water ofthe filament reaches usually more than percent.
- the amount of the minor component in the comonomers constituting the copolyamide component is extremely increased. Because, the melting point, crystallinity, heat resistance, strength, initial modulus, etc., of the copolyamide decrease.
- the amount of polyamide-forming minor component in the copolyamide should adopt such a value that the difference of the shrinking percentage from the polyester component is increased to the above necessary extent, within the range of at most percent by weight, preferably at most 20 percent by weight.
- FIG. I is a cross sectional view, in an enlarged scale, of a conventional side-by-side-type composite filament
- FIG. 2 is a cross-sectional view, in an enlarged scale, of a conventional concentric sheath-core-type composite filament
- FIG. 3 is a cross-sectional view, in an enlarged scale, of a monocore eccentric sheath-core-type composite filament according to the invention
- FIG. 4 is a cross-sectional view, in an enlarged scale, of an eccentric sheath-core-type composite filament according to the invention, wherein two separate cores are embedded eccentrically in the sheath,
- FIG. 5 is a cross-sectional view, in an enlarged scale, of an eccentric sheath-core-type composite filament according to the invention, wherein four cores are embedded eccentrically in the sheath,
- FIG. 6 is a cross-sectional view, in an enlarged scale, of a sheath-core-type composite filament according to the invention, wherein a core having a noncircular cross section is disposed eccentrically in the sheath,
- FIGS. 7 and 8 are cross-sectional views, in an enlarged scale, of sheath-core-type composite filaments according to the invention, wherein at least two cores having a noncircular cross section are disposed eccentrically in the sheath, and
- FIGS. 9-15 are cross-sectional views, in an enlarged scale, of embodiments of composite filaments according to the invention, which are composed of three different components.
- the present invention provides sheath-core-type composite filaments arranged highly shrinkable polyamide not used in the past and polyester eccentrically in the cross section of the unitary filament.
- Such composite filaments when merely relaxed after spinning and drawing, develop spontaneous crimps, the inside portion of which is located by the polyamide component having a high recovering property for elongation.
- the composite filaments having the abovementioned spontaneous crimps are subjected to a shrinking treatment, latent crimps are further developed remarkably along the crimp direction of the spontaneous crimps.
- the polyamide component having an excellent recovering property for elongation locates in the inside portion of the crimps and the polyester component having a high modulus of elasticity locates in the outside portion of the crimps, and consequently composite filaments having a high crimpability, improved crimp durability and crimp elasticity, which have never been obtained, can be easily obtained.
- the percentage of eccentricity b shows a measure of the degree of eccentricity of the core portion and is shown in the following way.
- the percentage of eccentricity is preferably at least 5.
- the percentage of eccentricity b is 0
- the number of cores in the cross section of the unitary filament is not always one, but may be plural as shown in FIGS. 4 and 5.
- the center of gravity (P) of the core components lies at the center of the straight line connecting the centers of gravity P1 and P2 of respective cores.
- the center of gravity (P) can be determined in the same manner.
- the cross-sectional shape of the core component is not always circular, but may be noncircular as shown in FIGS. 68.
- the amount occupied by the core component in the unitary filament is l050 percent by weight, preferably 20-40 percent.
- the amount is less than l0 percent by weight, it is difficult to obtain a composite filament having a desired crimpability and crimp elasticity.
- the percentage ofeccentricity of the core component in the cross section of unitary filament is too small, and it is difficult to obtain a highly crimpable composite filament.
- the composite filament according to the invention is particularly useful, when the shrinking percentage 0 of the polyamide component to be used, the percentage of eccentricity b of the core component and the percent by weight c ofthe core component in the unitary filament satisfy the relation shown by the above-mentioned formulae.
- the most useful composite filament in the present invention is multicore filaments, in which the core component locating in the cross section of the filament consists of two or more cores composed ofa polyester and the sheath component consists of a highly shrinkable polyamide, and further the abovementioned formulae l and the following formulas (2) E201 and 821.1 (2) mean of diameters of ratio of initial modulus and ratio of heat shrinkability of the polyamide based on the polyester respectively, are satisfied at the same time.
- the ratio E of initial modulus of the polyamide based on the polyester is less than and even if such composite filament is subjected to a crimp developing treatment, the crimp recovering property and crimp elasticity of the developed crimps are not satisfactory. While, in the case of the ratio of heat-shrinkability S being less than 1.1, even if the drawn filament is relaxed, the spontaneous crimpability is poor, and further the curliness after a crimp developing treatment is extremely low. Therefore, composite filaments having such a low crimpability are not suitable for the present invention.
- Another preferable composite filament capable of attaining the object of the present invention is one, wherein the highly shrinkable polyamide component composing the filament a homopolyamide component and a copolyamide component which form distinct filamentary components and are bonded along the filament axis, and further a core composed of a polyester component is embedded in said homopolyamide component without contacting with the above-mentioned copolyamide component.
- such a composite filament is characterized in that said core component is composed of a polyester consisting mainly of polyethylene terephthalate, and said sheath component is composed of at least two highly shrinkable polyamide components, a homopolyamide component having substantially homogeneous composition and a copolyamide component being arranged eccentrically in the cross section of the unitary filament, that said polyester component occupies l0-50 percent by weight in the unitary filament, and that said polyester component locates in said homopolyamide component without contacting with said copolyamide component said polyester component with the center of the filament and the other of which connects the center of gravity of said copolyamide component with the center ofthe filament, in the cross section of the unitary filament, is between 90 and 180.
- FIGS. 9-15 The bonding configuration of the above-mentioned three components, i.e., copolyamide, homopolyamide and polyester in the cross section of the composite filament of the present invention is shown, for example, by FIGS. 9-15, and the fundamental bonding configuration is shown by FIGS. 9 and 10.
- the copolyamide component (hereinafter referred to as component B) and the polyester component (hereinafter referred to as component C') are arranged in the core portion, and the homopolyamide component (hereinafter referred to as component A") is arranged in the sheath portion, and three components A, B and C are arranged eccentrically to each other.
- the component A and the component B are arranged in a side-by-side relation and the component C is arranged eccentrically to the component B as a core.
- the feature of the present invention lies in that the component C is surrounded by the component A in both the filaments shown in FlGS. 9 and 10.
- a composite filament having an excellent crimpability cannot be obtained. That is, when such a composite filament is subjected to a crimp developing treatment, the composite filament develops crimps, in which the polyester component locates in the inside portion of crimps as in the case of conventional polyesterpolyamide core-sheath composite filaments.
- the contribution of the modulus of elasticity of the polyester component to the total crimps is small, and further as the polyester component having poor recovering property for elongation locates in the inside portion of the crimps, such a filament is insufiicient in the crimp recovering properties and crimp durabilityities for mechanical stresses, such as repeating elongations, bendings and compressions.
- polyester component is arranged in a defined relation against the polyamide component. This defined arrangement will be explained with reference to drawings.
- the copolyamide and P 0 (the angle is hereinafter referred to as eccentric angle), one of which connects the center of gravity P, of the copolyamide component with the center 0 of the filament and the other of which connects the center of gravity P of the polyester component with the center 0 of the filament, is between and
- FIG. 12 shows an embodiment, wherein the polyester component forms one core and the copolyamide component forms two cores.
- the center of gravity (P) of the copolyamide component lies at the center of the straight lines P7 connecting respective centers of gravity P and P
- the eccentric angle a is exceeds the above-mentioned range, that is, a 5 90 the copolyamide component and the polyester component are too closely arranged, and it is difficult to attain the object of the invention.
- the cross-sectional configurations of the above-mentioned three components and the unitary filament of the composite filament of the present invention may be noncircular as shown in FlGS. 1 -15.
- the above-mentioned highly shrinkable polyamide components are composed of two components of a homopolyamide component and a at least 20-80 percent by weight, preferably 30-80 percent by weight, and the amount of the above-mentioned component is within the range of 8-70 percent by weight preferably 10-50 percent by weight.
- the homopolyamide component is less than 20 percent by weight, or the amount of the copolyamide component is percent by weight, the area occupied by the large, and various disadvantages owing to the use of copolyamide occur, and particularly, initial modulus, heat resistance and light resistance decrease. While, when the amount of the homopolyamide component is more than 80 percent by weight, the amount of the copolyamide component reduces considerably, and a composite filament having a desired crimpability cannot be obtained.
- the composite filament according to the present invention can be spun by means of conventional spinning process and apparatus.
- the drawing can be effected without the use of special process and apparatus, and effected by means of the exactly same process and apparatus as conventionally used.
- cold drawing at room temperature or hot drawing by means of a hot drawn pin or hot draw rollers heated at 60-1 80 C. can be used.
- copolyesters of main component of polyethylene terephthalate with other polyesters such as polyethylene isophthalate, polytetramethylene terephthalate, polyethylene oxybenzoate, polyethylene hexahydroterephthalate, etc.
- polyethylene isophthalate polytetramethylene terephthalate
- polyethylene oxybenzoate polyethylene hexahydroterephthalate
- amount of minor component of the copolymerization is preferably less than percent by weight, and when the amount of such minor component exceeds 5 percent by weight, the melting point, crystallinity and yarn property, particularly original length ofthe filament in the drawn state.
- the bundle of 30 drawn filaments having a length of 30 cm. is dipped in boiling water for 10 minutes under a load of 0.1
- Crimp elasticity decamethylenediamine, m-xylylenediamine, pxy-
- the crimp elasticity is shown by the load (mg./d.) required lylenediamine, bis-(p-aminocyclohexyl)methane and the like, is for stretching the length of the crimped composite filament with dicarboxylic acids, such as adipic acid, sebacic acid, bundle obtained in paragraph (2) (underaload of0.l mg./d.) dodecanedicarboxylic acid, isophthalic acid, hexto I percent. ahydroterephthalic acid and the like.
- dicarboxylic acids such as adipic acid, sebacic acid, bundle obtained in paragraph (2) (underaload of0.l mg./d.) dodecanedicarboxylic acid, isophthalic acid, hexto I percent. ahydroterephthalic acid and the like.
- the Crimp recovering percentage for elongation: highly shrinkable copolyamide component mention may be h length of the filament, when the crimped composite made of copolyamides obtained by copolymerizing at least 20 filament bundle in the above paragraph(2) is appliedaload of two conventional polyamide-forming components including .2 mg./d., is 1 an the g when a load of g-Idis the above-mentioned cyclic lactams and nylon salts, further added fOi one minute, i5 1 and then the length, 2
- the composite filament according to the present invention in after r e h load f -l g-/ 15. has a merit that when the filament is unwound from a bobbin C i recovering percentage f elongation and relaxed, it develops uniform spontaneous crimps having a 1 o spiral three-dimensional structure which have never been X 100 developed in the conventional composite filament.
- the composite filament is subjected to a crimp developing 40 Stiid iofid of 600 iS removed y t Position of the treatment the mamem develops crimps, in which the piston IS recovered naturally and after 5 mmutes the height is polyester component having an excellent elastic property read (the height 1 locates in the outside portion and the polyamide component
- the composite filament according to the invention can be Cooihassif Uiita Sky SE (manufactured y it in used in a wide field not only for garments but also for industri- 50 F- waist is PP i Of diawh iiiaiheht and of g al materials and interior ornaments in the form of continuous ciai acetic acid is added iheiieio- The, the assehihiy is heated mamems or Staple flb from room temperature to 95 C. in 30 minutes and main- The invention will be explained in more detail with talned at the same temperature for 30 minutes. The percentreference to lhe following exumples age of dye absorped shows the dyeability Crimping properties and dyeability shown in the following EXAMPLE I examples are determined as follows.
- Spontaneous curliness Polyethylene terephthalate having an intrinsic viscosity [n] The bundle of 30 drawn filaments having a length of 30 cm. of 0.63 in o-chlorophenol at 30 C. and polycaproamideis applied to a load of 0.1 mg./d.
- the spontaneous curliness is polyhexamethylene isophthalamide copolymer (hereinafter shown by the percentage of apparent loss of the length calcuabridged as 6/61) with a predetermined copolymerization ratio lated by the following equation. having an intrinsic viscosity [n] of l.02 in m-cresol at 30 C. were melted and conjugate spun at a temperature of 285 C.
- the obtained composite filament had a bonding configuration as shown in FIG. 7, in which two elliptical polyester core components existed in the eccentricity of 30 percent.
- copolyamide constituting the sheath portion of the composite filament was spun solely and the shrinking percentage of the resulting filament was measured and was 30 percent.
- the resultmg filaments were drawn times their the filaments Nos. 17, 18, 20 and 21,the polyamide located in original length at room temperature to obtain drawn comthe outside portion f the crimp Th f the polyester P monofilamems of component having poor recovering property for elongation Furthermorei the abov? descnbed copolyamlde Spun located mainly in the inside portion of the crimp, so that the solely and drawn to obtain a control filament, the shrinking 3O crimp recovering property ft elongation or compression Percenmge Ofwhlch was P was poor. On the other hand, in the composite filaments Nos.
- Crimp Properties of obtained composite filaments are 19 and 22-25 of the present invention containing high Show" in Table I shrinkable polyamidc in the core portion, the polyamidc comf"? from Table the filaments 13 havmg an ponent located in the inside of the crimp, so that the crimp eccentricity preferable for the present invention were ex- 35 recovering property was considerably high and crimpability tremely superior in crimpability, crimp elasticity and crimp was good recovering properties to the filament No. 12.
- EXAMPLE 5 Polyethylene terephthalate having an intrinsic viscosity of The same polyethylene terephthalate as used in Example I 0.65 in o-chlorophenol at 30 C. and nylon-6 having an intrinand three kinds of polyamides having various intrinsic viscosisic viscosity of 1.15 in m-cresol at 30 C.
- the H d 1.08 28.6 particularly preferable two-core composite filament according to the present invention develops crimps immediately when it TABLE 6 Crimp Crimp recovering recovering Spontapercentage percentage neous Total Crimp for elongafor com- I curliness curliness elasticity tion pression
- composite filament percent (percent) (mg./d.) (percent) (percent) Conventional composite filament 1 21 11 'I o 4 29 13 10
- the position of the C-component, polyester in the cross section of the filament was checked by a polarizing microscope, and as the result the polyester in the filament No. 35 located in the inside of the crimp, while the polyester in the filaments Nos. 36-38 located in the outside of the crimp. Accordingly, in the filament No. 35 the spontaneous crimp was somewhat poor, the total curliness after a shrinking treatment was considerably low, and the crimp elasticity and recovering percentage for elongation were poor. On the contrary, in the crimpdeveloped composite filaments Nos. 36-38 according to the present invention, the total curliness after a shrinking treatment was particularly high and the crimp elasticity and recovering percentage for elongation were excellent.
- the obtained composite filament had a bonding configuration as shown in FIG. 13, in which the B-component and the C-component were semicircular cores, and the eccentric angle a was Yarn quality, crimp property and dyeability of each composite filament are shown in Table 9.
- A-component polyhexamethylene adipamide-polyhexamethylene sebacamide copolymer having an intrinsic viscosity [n] of l.l2 and
- the obtained composite monofilament had a bonding configuration as shown in FIG. 10, in which C-component was arranged as a core component in A-component, A-component and B-component were bonded in a side-by-side relation, and an eccentric angle a between B- and C-components was 180.
- a composite filament having elastic crimping property comprising at least two components disposed in an eccentric sheath-core relation along the longitudinal axis of the filament, wherein a. the first component is the core component composed of a polyester consisting essentially of polyethylene terephthalate; and
- the second and any other components comprise the sheath of a highly shrinkable polyamide having a shrinking percentage of 15-85 percent; the percent by weight ofcore component in the filament being 5-50; and the following conditions (1) and (2) being present at the same time: (I) (i) 3.8 (l.4a X 5017+ 200 and (ii) B Z 5;
- b represents the percentage of eccentricity of the center of gravity (P) of the core component positioned in the cross section of the filament against the radius of the filament
- the composite filament as claimed in claim 1 wherein said percent by weight of the core or cores in the filament is 20 4.
- the composite filament as claimed in claim 1 which has at least two cores.
- polyamide is a copolyamide of more than 95 percent by weight of a polyamide-forming constituent and less than 5 percent by weight of another polyamide-forming constituent and having an intrinsic viscosity of at least 1.15.
- polyamide is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethyl'ene sebacamide).
- the sheath is constituted with two polyamide components disposed eccentrically to each other in distinct zone with intimate adherent surface extending along the filament axis, one of said components consists of a homopolyamide, the other of said components consists of a copolyamide and further the core composed of said polyester component is embedded in said homopolyamide component without contacting with said copolyamide component.
- copolyamide consists of less than percent by weight of a polyamide-forming constituent and more than 5 percent by weight of another polyamide-forming constituent.
- copolyamide component is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethylene sebacamide).
- polyethylene terephthalate comprises at least 95 percent of said first component (a).
Abstract
Composite filament having an elastic crimping property, comprised of at least two components disposed in an eccentric sheath-core relation along the longitudinal axis of the filament, in which one component is composed of a polyester consisting mainly of polyethylene terephthalate and another component or components comprise highly shrinkable polyamide having a shrinking percentage of 15-80 percent and the percent by weight of the core or cores in the filament is 5-50. It is preferable that the core component is composed of the polyester and the sheath component is composed of the polyamide. Furthermore, the eccentricity of the sheath-core relation is preferably at least 5. The core component may be constituted with a plurality number of cores.
Description
United States Patent Ogata et al. Feb. 15, 1972 [54] COMPOSITE FILAMENTS HAVING AN 2,932,079 4/1960 Dietzsch et al. ..161/ 175 ELASTIC CRIMPING PROPERTY 5,983,397 651361 Breen 161/173 ,03 35 6 1 62 Zimmerman 161/175 [721 lnvenmm Osaka; TSII- 3,459,846 8/1969 Matsui et al. ...264/17l iz f g g g f fi 3,488,251 6/1970 Etchells et al. ..161/l77 ira au, o apan 731 Assignees: Kanegaluchi Boseki Kabushiki Kaisha, FOREIGN PATENTS OR APPLICATIONS Tokyo, Japan; SNlA Vismsa Societa 43/ 16671 7/1968 Japan... ..264/D|G. 26 Nazionale lndustria pplicazioni Viscosa 43/22350 9/1968. Japan ..l6l/l75 S.p.A., Milan, Italy Primary Examiner-William J. Van Balen [22] Flled' 1969 AssistantExaminer-Raymond O. Linker, Jr. [21] Appl. No.: 807,863 Attorney-Stevens, Davis, Miller & Mosher 30 Foreign Application Priority Data [57] ABSTRACT Composite filament having an elastic crimping property, comr japan ,prised of at least two components disposed in an eccentric 1968 Japan "43/25756 sheath-core relation along the longitudinal axis of the filaapan ment, in which one component is composed of a polyester consisting mainly of polyethylene terephthalate and another [52] US. Cl ..l6l/l73, 161/175, 11/ 1 7 1, component or components comprise highly Shrinkable po]ya [51 1 Int Cl D01 d 5/28 mide having a shrinking percentage of 15-80 percent and the 58] Fieid 264/168 percent by weight of the core or cores in the filament is 5-50. a 2 DIG It is preferable that the core component is composed of the polyester and the sheath component is composed of the polyamide. Furthermore, the eccentricity of the sheath-core rela- [56] References Cited tion is preferably at least 5. The core component may be con- UNITED STATES PATENTS stituted with a plurality number of cores. 3,540,080 1 l/ 1970 Goossens ..l8/8 18 Claims, 15 Drawing Figures Pmmmrmsmz 3.642.565
' SHEET 2 or 2 Fig. /0 Fig. Fig. I?
' INVENT FLLNINRKO 06H H LTON NHRLLJE T Rn20 ITOH m 1,, 1/, BY L/ M I M 1., L
ATTORNEYS COMPOSITE FILAMENTS HAVING AN ELASTIC CRIMPING PROPERTY The present invention relates to novel synthetic filaments, particularly to composite filaments having a high crimpability, an improved crimp elasticity and an excellent dyeability.
lt has heretofore been well known that when different synthetic linear polymers are melted and conjugate spun simultaneously through common orifices in a sheath-core relation along the axial direction of the unitary filament, and the resulting filaments are drawn and subjected to shrinking treatment, then composite filaments having three-dimensional spiral crimps can be obtained.
Recently, a number of proposals have been made with respect to composite filaments having such three-dimensional crimp developability. For example, it has been known that as two polymer components constituting composite filaments, different homopolyamides, a homopolyamide and a copolyamide, different homopolyesters and a homopolyester and a copolyester are used in view of mutual adhesivity, conjugate spinnability and drawability, and the two polymers are bonded in a side-by-side relation as shown in FIG. 1, and composite filaments having a crimp developability are manufactured by the use of the difference between the shrinkabilities of both the polymers.
However, in these filaments, it is very difficult to improve properties other than crimping property, because two kinds of polymers constituting the composite filament have very similar chemical and physical properties.
.That is, the polyamide composite filament has poor crimp elasticity, resilient crimpability and crimp bulkiness. While, the polyester composite filament has excellent crimp elasticity, but has insufficient crimp durability because of its poor recovering properties for elongation, bending and compression.
Furthermore, polyamide-polyester composite filaments are known, wherein a homopolyester component is arranged in the core portion and a homopolyamide component is arranged in the sheath portion eccentrically to the core portion in order to compensate mutually the above-mentioned drawbacks in the polyamide composite filament and the polyester composite filament.
However, even when such composite filaments are subjected to a crimp developing treatment to develop threedimensional crimps, it is difficult to develop desired crimps, because the difference of shrinkability between the homopolyester component and the homopolyamide component constituting the composite filament is small, and they are arranged in a sheath-core relation. Moreover, when the sheath-core-type composite filaments of polyamide-polyester obtained by a conventional conjugate spinning process are subjected to a shrinking treatment to develop crimps, the ex cellent crimp elasticity of the polyester component cannot be developed fully on the whole filament, because the polyester component having elastic property is arranged in the inside portion of the crimps. Moreover, as the polyester component having poor recovering property for elongation is arranged in the inside portion of the crimps, the composite filament does not easily recover the original state, after applied mechanical stresses, such as repeating elongations, bendings, compressions, etc. Therefore, a desirable crimp durability cannot be obtained in the conventional sheath-core-type composite filament of polyamide-polyester.
Furthermore, conventional composite filaments have only latent crimpability and do not develop spontaneous crimps even if the conjugate spun filaments are relaxed after drawing and they are linear as in usual monofilament and develop three-dimensional crimps only after they are subjected to shrinking treatments, such as hot water treatment and dry heat treatment. Furthermore, when the composite filaments having the above-mentioned latent crimpability are knitted or woven into textures, such as stockings, socks, tricots and carpets, and then the resulting textures are directly subjected to a crimp developing treatment, tension and contact interference between mutual filaments in the texture suppress the crimp developability considerably and develop considerably nonuniform crimps to form unevenness on the surface of the texture. In order to obviate such disadvantages in the crimp developing treatment after knitting or weaving, drawn composite filaments are generally subjected to a pretreatment, by which the drawn composite filaments are twisted or passed through a particular heater under tensionless state to develop preliminary crimps, and then led to various knitting or weaving steps.
It has been now surprisingly found that by obeying to novel critical combination components and their nature, of physical characteristics of such components and of certain new relationship thereof in the structure of the composite filament, novel and useful composite filaments having latent crimpability and solved conventional various drawbacks completely can be obtained.
The object of the present invention is to provide a sheathcore-type composite filament of polyamide-polyester having a high crimp developability, which has never been attained in the conventional sheath-core-type composite filament, by using a highly shrinkable polyamide as the polyamide component to make a difference of shrinking percentage between the polyamide component and the polyester component larger, and further selecting the conjugate ratio of the polyester component and the degree of the eccentricity of core component corresponding to the shrinking percentage of the polyamide component.
Another object of the present invention is to provide a composite filament having an excellent crimp elasticity and crimp recovering property, even when the filament is applied to mechanical stresses, such as repeating elongations, compressions and bendings, in said composite filament,,a polyamide component having an excellent recovering property for elongation being located in the inside portion of the crimps and a highly elastic polyester component being located in the out side portion of the crimps, when the composite filament is subjected to a shrinking treatment to develop crimps.
Further object of the invention is to provide a composite filament having an excellent spontaneous crimpability which has never been seen in the conventional filament, that is, a novel composite filament capable of developing crimps spontaneously only by relaxing the drawn filament.
Other objects of the invention will be more apparent from the following description.
That is, the present invention provides a composite filament having an elastic crimping property. Wherein at least two different synthetic linear polymers are bonded in a sheath-core relation along the longitudinal direction of the unitary filament, characterized in that one polymer component is composed of a polyester consisting mainly of polyethylene terephthalate and another polymer component is composed of a highly shrinkable polyamide having a shrinking percentage in boiling water of at least l5 percent, that both the polymer components are arranged eccentrically in the cross section of the unitary filament, and that the core component occupies 1050 percent by weight in the unitary filament.
It is necessary that the above-mentioned polyamide to be used in the present invention has a shrinking percentage in boiling water of l580 percent, preferably at least 20 percent. When the shrinking percentage is less than 15 percent, a satisfactory crimp is formed with difficulty and the shrinking percentage is preferable to be higher, but when the shrinking percentage is more than percent, the commercial production cannot be effected.
The shrinking percentage is determined by the following manner.
The spun and drawn filaments are dipped in boiling water at C. for 15 minutes under a load of 0.5 mg./d. and are shrunk. The shrinking percentage is shown by the percentage of apparent loss of the length calculated by the following formula:
lit- 1 Shrinking percentage= X 100 wherein l designates the length of the shrunk filament and 1,, the length of the original filament.
Generally speaking, ordinary homopolyamides have a shrinking percentage in boiling water of less than l percent, but high molecular weight homopolyamides having an intrinsic viscosity [n] of more than 1.15 in m-cresol at 30 C. have a shrinking percentage in boiling water of more than percent, and can be used in the present invention.
The most preferable highly shrinkable polyamides are copolyamide. That is, when the minor component of copolymerization in the copolyamide filament consisting of at least two polyamide-forming components is at least 5 percent by weight, the shrinking percentage in boiling water ofthe filament reaches usually more than percent. While, when the major component of copolymerization is more than 95 percent by weight, it is preferable to increase the molecular weight of the copolyamide as in the case of the above-mentioned homopolyamides, otherwise in many cases the usual molecular weight of such copolyamides show the similar low shrinking percentage to conventional homopolyamides, such as polycaproamide or polyhexamethylene adipamide previously used and having an ordinary viscosityv Therefore, the difference of shrinking percentage in boiling water between the copolyamide component and the polyester component (usually 10-13 percent) is not sufficient, and it is difficult to obtain composite filaments having a desired crimpability. Furthermore, it is not preferable that for the purpose of increasing the difference of the shrinking percentage in boiling water between the copolyamide component and the polyester component, the amount of the minor component in the comonomers constituting the copolyamide component is extremely increased. Because, the melting point, crystallinity, heat resistance, strength, initial modulus, etc., of the copolyamide decrease. In general, the amount of polyamide-forming minor component in the copolyamide should adopt such a value that the difference of the shrinking percentage from the polyester component is increased to the above necessary extent, within the range of at most percent by weight, preferably at most 20 percent by weight.
For a better understanding of the invention, reference is taken to the accompanying drawings, wherein FIG. I is a cross sectional view, in an enlarged scale, of a conventional side-by-side-type composite filament,
FIG. 2 is a cross-sectional view, in an enlarged scale, of a conventional concentric sheath-core-type composite filament,
FIG. 3 is a cross-sectional view, in an enlarged scale, of a monocore eccentric sheath-core-type composite filament according to the invention,
FIG. 4 is a cross-sectional view, in an enlarged scale, of an eccentric sheath-core-type composite filament according to the invention, wherein two separate cores are embedded eccentrically in the sheath,
FIG. 5 is a cross-sectional view, in an enlarged scale, of an eccentric sheath-core-type composite filament according to the invention, wherein four cores are embedded eccentrically in the sheath,
FIG. 6 is a cross-sectional view, in an enlarged scale, of a sheath-core-type composite filament according to the invention, wherein a core having a noncircular cross section is disposed eccentrically in the sheath,
FIGS. 7 and 8 are cross-sectional views, in an enlarged scale, of sheath-core-type composite filaments according to the invention, wherein at least two cores having a noncircular cross section are disposed eccentrically in the sheath, and
FIGS. 9-15 are cross-sectional views, in an enlarged scale, of embodiments of composite filaments according to the invention, which are composed of three different components.
The present invention provides sheath-core-type composite filaments arranged highly shrinkable polyamide not used in the past and polyester eccentrically in the cross section of the unitary filament. Such composite filaments, when merely relaxed after spinning and drawing, develop spontaneous crimps, the inside portion of which is located by the polyamide component having a high recovering property for elongation. Moreover, when the composite filaments having the abovementioned spontaneous crimps are subjected to a shrinking treatment, latent crimps are further developed remarkably along the crimp direction of the spontaneous crimps. Furthermore, in these filaments, the polyamide component having an excellent recovering property for elongation locates in the inside portion of the crimps and the polyester component having a high modulus of elasticity locates in the outside portion of the crimps, and consequently composite filaments having a high crimpability, improved crimp durability and crimp elasticity, which have never been obtained, can be easily obtained.
In order to attain the object of the present invention, it is preferable to select the degree of eccentricity of the core component depending upon the shrinking percentage ofthe polyamide component to be used so as to satisfy the following formulae:
as; (1.4a 50b+ 200%) X 10*;10 :11; 15 and 10c50 wherein 0 represents a shrinking percentage of the polyamide component, b represents percentage of eccentricity of the center of gravity (P) of core component positioned in the cross section of the unitary filament against the radius of the unitary filament, and c represents percent by weight of the core component in the unitary filament, at the same time.
In the above formulae, the percentage of eccentricity b shows a measure of the degree of eccentricity of the core portion and is shown in the following way.
When the distance between the center (0) of the filament and the center of gravity (P) of the core component is OP in the unitary filament, and the radius of said unitary filament is r, then the percentage of eccentricity b is shown by the ratio of OP/r.
The percentage of eccentricity is preferably at least 5.
In the composite filament shown in FIG. 2, the percentage of eccentricity b is 0 In the composite filaments of the present invention, the number of cores in the cross section of the unitary filament is not always one, but may be plural as shown in FIGS. 4 and 5. In the filament shown in FIG. 4, the center of gravity (P) of the core components lies at the center of the straight line connecting the centers of gravity P1 and P2 of respective cores. In the filament shown in FIG. 5, the center of gravity (P) can be determined in the same manner. The cross-sectional shape of the core component is not always circular, but may be noncircular as shown in FIGS. 68.
In the present invention, the amount occupied by the core component in the unitary filament is l050 percent by weight, preferably 20-40 percent. When the amount is less than l0 percent by weight, it is difficult to obtain a composite filament having a desired crimpability and crimp elasticity. While, when the amount is more than 50 percent by weight, the percentage ofeccentricity of the core component in the cross section of unitary filament is too small, and it is difficult to obtain a highly crimpable composite filament.
The composite filament according to the invention is particularly useful, when the shrinking percentage 0 of the polyamide component to be used, the percentage of eccentricity b of the core component and the percent by weight c ofthe core component in the unitary filament satisfy the relation shown by the above-mentioned formulae.
The most useful composite filament in the present invention is multicore filaments, in which the core component locating in the cross section of the filament consists of two or more cores composed ofa polyester and the sheath component consists ofa highly shrinkable polyamide, and further the abovementioned formulae l and the following formulas (2) E201 and 821.1 (2) mean of diameters of ratio of initial modulus and ratio of heat shrinkability of the polyamide based on the polyester respectively, are satisfied at the same time.
In the above-mentioned formulas (2), N(D/R) represents a ratio (by weight) of the core component based on bonded total component. Furthermore, if theinitial moduli and heatshrinkabilities of the polyester and the polyamide are expressed by Ee, En, and Se, Sn, respectively, the ratio of initial modulus and the ratio of heat-shrinkability in the formulas (2) are shown by E=En/Ee and S=Sn/Se. For example, when the polyamide used has a low initial modulus, the ratio E of initial modulus of the polyamide based on the polyester is less than and even if such composite filament is subjected to a crimp developing treatment, the crimp recovering property and crimp elasticity of the developed crimps are not satisfactory. While, in the case of the ratio of heat-shrinkability S being less than 1.1, even if the drawn filament is relaxed, the spontaneous crimpability is poor, and further the curliness after a crimp developing treatment is extremely low. Therefore, composite filaments having such a low crimpability are not suitable for the present invention.
Another preferable composite filament capable of attaining the object of the present invention is one, wherein the highly shrinkable polyamide component composing the filament a homopolyamide component and a copolyamide component which form distinct filamentary components and are bonded along the filament axis, and further a core composed of a polyester component is embedded in said homopolyamide component without contacting with the above-mentioned copolyamide component.
That is, such a composite filament is characterized in that said core component is composed of a polyester consisting mainly of polyethylene terephthalate, and said sheath component is composed of at least two highly shrinkable polyamide components, a homopolyamide component having substantially homogeneous composition and a copolyamide component being arranged eccentrically in the cross section of the unitary filament, that said polyester component occupies l0-50 percent by weight in the unitary filament, and that said polyester component locates in said homopolyamide component without contacting with said copolyamide component said polyester component with the center of the filament and the other of which connects the center of gravity of said copolyamide component with the center ofthe filament, in the cross section of the unitary filament, is between 90 and 180.
The bonding configuration of the above-mentioned three components, i.e., copolyamide, homopolyamide and polyester in the cross section of the composite filament of the present invention is shown, for example, by FIGS. 9-15, and the fundamental bonding configuration is shown by FIGS. 9 and 10.
That is, in the filament shown in FIG. 9, the copolyamide component (hereinafter referred to as component B) and the polyester component (hereinafter referred to as component C') are arranged in the core portion, and the homopolyamide component (hereinafter referred to as component A") is arranged in the sheath portion, and three components A, B and C are arranged eccentrically to each other. Furthermore, in FIG. 10, the component A and the component B are arranged in a side-by-side relation and the component C is arranged eccentrically to the component B as a core. The feature of the present invention lies in that the component C is surrounded by the component A in both the filaments shown in FlGS. 9 and 10. However, when the component C is surrounded by the component B, a composite filament having an excellent crimpability cannot be obtained. That is, when such a composite filament is subjected to a crimp developing treatment, the composite filament develops crimps, in which the polyester component locates in the inside portion of crimps as in the case of conventional polyesterpolyamide core-sheath composite filaments. Consequently, the contribution of the modulus of elasticity of the polyester component to the total crimps is small, and further as the polyester component having poor recovering property for elongation locates in the inside portion of the crimps, such a filament is insufiicient in the crimp recovering properties and crimp durabilities for mechanical stresses, such as repeating elongations, bendings and compressions.
The most important characteristics of the present invention lie in that the polyester component is arranged in a defined relation against the polyamide component. This defined arrangement will be explained with reference to drawings.
As shown in FIG. 11, it is necessary that the copolyamide and P 0 (the angle is hereinafter referred to as eccentric angle), one of which connects the center of gravity P, of the copolyamide component with the center 0 of the filament and the other of which connects the center of gravity P of the polyester component with the center 0 of the filament, is between and The bonding configurations shown in FIGS. 9 and 10 have an eccentric angle 0f0z=l80.
FIG. 12 shows an embodiment, wherein the polyester component forms one core and the copolyamide component forms two cores. The center of gravity (P) of the copolyamide component lies at the center of the straight lines P7 connecting respective centers of gravity P and P When the eccentric angle a is exceeds the above-mentioned range, that is, a 5 90 the copolyamide component and the polyester component are too closely arranged, and it is difficult to attain the object of the invention. The cross-sectional configurations of the above-mentioned three components and the unitary filament of the composite filament of the present invention may be noncircular as shown in FlGS. 1 -15.
When the above-mentioned highly shrinkable polyamide components are composed of two components of a homopolyamide component and a at least 20-80 percent by weight, preferably 30-80 percent by weight, and the amount of the above-mentioned component is within the range of 8-70 percent by weight preferably 10-50 percent by weight. When the homopolyamide component is less than 20 percent by weight, or the amount of the copolyamide component is percent by weight, the area occupied by the large, and various disadvantages owing to the use of copolyamide occur, and particularly, initial modulus, heat resistance and light resistance decrease. While, when the amount of the homopolyamide component is more than 80 percent by weight, the amount of the copolyamide component reduces considerably, and a composite filament having a desired crimpability cannot be obtained.
The composite filament according to the present invention can be spun by means of conventional spinning process and apparatus.
Furthermore, the drawing can be effected without the use of special process and apparatus, and effected by means of the exactly same process and apparatus as conventionally used. For example, cold drawing at room temperature or hot drawing by means of a hot drawn pin or hot draw rollers heated at 60-1 80 C. can be used.
includes copolyesters of main component of polyethylene terephthalate with other polyesters, such as polyethylene isophthalate, polytetramethylene terephthalate, polyethylene oxybenzoate, polyethylene hexahydroterephthalate, etc. However, in the above-mentioned copolyester, the
amount of minor component of the copolymerization is preferably less than percent by weight, and when the amount of such minor component exceeds 5 percent by weight, the melting point, crystallinity and yarn property, particularly original length ofthe filament in the drawn state.
2. Total curliness:
The bundle of 30 drawn filaments having a length of 30 cm. is dipped in boiling water for 10 minutes under a load of 0.1
modulus of elasticity reduce due to the copolymerization and 5 mg./d. and then air-dried under the same load. The total curlifurther the crimpability decreases owing to the increase of after rimp de eloping treatment is Shown by the perheat-shrinkability. centage of apparent loss ofthe length calculated by the follow- As the homopolyamide component having substantially g equationlo la homogeneous composition to be used in the present invention, Total curliness= 0 X 100 mention may be made of homopolyamides obtained by 10 polymerizing cyclic lactams, such as caprolactam, enantholacwherein designates the length of the crimped filament and tam, lauryllactam and the like, or nylon salts of diamines, such l the original length ofthe filament in the drawn state. as tetramethylenediamine, hexamethylenediamine, un- 3. Crimp elasticity: decamethylenediamine, m-xylylenediamine, pxy- The crimp elasticity is shown by the load (mg./d.) required lylenediamine, bis-(p-aminocyclohexyl)methane and the like, is for stretching the length of the crimped composite filament with dicarboxylic acids, such as adipic acid, sebacic acid, bundle obtained in paragraph (2) (underaload of0.l mg./d.) dodecanedicarboxylic acid, isophthalic acid, hexto I percent. ahydroterephthalic acid and the like. Furthermore, as the Crimp recovering percentage for elongation: highly shrinkable copolyamide component, mention may be h length of the filament, when the crimped composite made of copolyamides obtained by copolymerizing at least 20 filament bundle in the above paragraph(2) is appliedaload of two conventional polyamide-forming components including .2 mg./d., is 1 an the g when a load of g-Idis the above-mentioned cyclic lactams and nylon salts, further added fOi one minute, i5 1 and then the length, 2
The composite filament according to the present invention in after r e h load f -l g-/ 15. has a merit that when the filament is unwound from a bobbin C i recovering percentage f elongation and relaxed, it develops uniform spontaneous crimps having a 1 o spiral three-dimensional structure which have never been X 100 developed in the conventional composite filament. Furtherli l more, when such spontaneously crimped filament is subjected imp r overing percentage for compression; to shrinking treatments, such as swelling, wetting and heating, The crimped composite filaments Obtained n the above latent crimps are added in addition to the spontaneous crimps P g p are Cut into a length w 20 of which are and extremely high crimps are formed. Therefore, when the introduced into a measuring cyiihdei' having a diameter of 5 composite filaments according to the invention are made into -v and a Piston of 200 weight moiihis the crimped various knitted goods, woven fabrics and pile articles, even if composite filaments and thereafter Said measuring cyiihder is the filaments obtained by conjugate spinning and drawing are siibleFted t a fine vibrtftioii and the eqtiiiihiihm Position of directly subjected to a knitting step or a weaving step without the Piston is read height 0)- pretreatment, which is necessary for the conventional filafi iofici of 9 is further l P to Said Piston and merits, crimped products having an extremely excellent qualithe equiiihiiiiihlioshioh of the Piston is read in the Same ty and peculiar properties can be obtained. Moreover, when ih'fihher as described above height is Thei'eaiiteiy the composite filament is subjected to a crimp developing 40 Stiid iofid of 600 iS removed y t Position of the treatment the mamem develops crimps, in which the piston IS recovered naturally and after 5 mmutes the height is polyester component having an excellent elastic property read (the height 1 locates in the outside portion and the polyamide component The crimp recovering percentage for cqmpression having an excellent recovering property for elongation locates L, l0 in the inside portion, and therefore a crimped filament having =FOX 100 an excellent crimp elasticity and crimp recovering property A, and further having a high bulkiness, stretchability and dura- Dyeabiiityi bility similar to those ofwool can b b i d into a dye bath prepared by dissolving 0.03 g. of acid dye, The composite filament according to the invention can be Cooihassif Uiita Sky SE (manufactured y it in used in a wide field not only for garments but also for industri- 50 F- waist is PP i Of diawh iiiaiheht and of g al materials and interior ornaments in the form of continuous ciai acetic acid is added iheiieio- The, the assehihiy is heated mamems or Staple flb from room temperature to 95 C. in 30 minutes and main- The invention will be explained in more detail with talned at the same temperature for 30 minutes. The percentreference to lhe following exumples age of dye absorped shows the dyeability Crimping properties and dyeability shown in the following EXAMPLE I examples are determined as follows.
i. Spontaneous curliness: Polyethylene terephthalate having an intrinsic viscosity [n] The bundle of 30 drawn filaments having a length of 30 cm. of 0.63 in o-chlorophenol at 30 C. and polycaproamideis applied to a load of 0.1 mg./d. The spontaneous curliness is polyhexamethylene isophthalamide copolymer (hereinafter shown by the percentage of apparent loss of the length calcuabridged as 6/61) with a predetermined copolymerization ratio lated by the following equation. having an intrinsic viscosity [n] of l.02 in m-cresol at 30 C. were melted and conjugate spun at a temperature of 285 C. in Spontaneous curl1ness= X 10D an eccentric sheath-core relation, in which polyethylene terephthalate formed a core and 6/6l copolymer formed a wherein I designates the length of the spontaneously 5 sheath, in a conjugate ratio (by weight) of 1:3 by means ofa crimped filament under the load of 0.l mg ld. and 1 the conventional conjugate spinning apparatus, and then the TABLE 1 Shrinking Copolymeripercentage zation ratio of mono- Elouga- Initial of 6/61 filament Stre th tion modulus Sample No. (by weight) Kind of composite filament (percent) (g. d.) (percent) (g./d.) 100/0 Conventional composite filament 12 4.8 82 35 99/1 Composite filament beyond the scope of the present invention 13 4.8 31 36 95/5 Composite filament oi the present invention 23 4. 7 34 34 90/10 d0 34 4.7 30 35 80/20 ...(10 50 4.4 35 31 /26 Composite filament beyond the scope of the present invention. 62 3.8 38 25 resulting filaments wcrc cold drawn 3.7 times their original length at room temperature to obtain drawn composite filaments of 70 d./l 8 f.
An enlarged cross section of this filament had a bonding configuration as shown in FIG. 3, in which an eccentricity b of polyethylene terephthalate of the core portion was 50 percent.
Yarn qualities of the composite filaments are shown in Table 1.
Furthermore, the results of crimp property measured with respect to the above-described composite filaments are shown 10 in Table 2.
h: yeability (percent) a Crimp Crimp recovering recovering percen e percent e for elonfor com gation pression D (percent) (percent) TABLE 2 Crimp Crimp l recovering recovering Sponts- Crimp percentage percentage neous Total elas-- for elonfor comcurllness curllness tlclty, gatlon presslon CHIDD elasticity (percent) (percent) mg./d. (percent) (percent) after king eatment (percent) Total curliness Initial shrin modulus tr Concerning the above-described crimped filaments Nos. l6, the position of polyethylene terephthalate of the core component in the cross section of the filament was checked by means of a polarizing microscope, and as the result polyethylene terephthalate in Nos. 1 and 2 located in the inside portion of the crimp, while the polyester in Nos. 3 to 6 located in the outside ofthe crimp. Filaments Nos. 1 and 2 did not develop spontaneous crimps, when they were drawn and relaxed, but filaments Nos. 3 to 5 developed spontaneous crimps when they were drawn and relaxed in crimped filaments thereof the total curliness was large, and the crimp elasticity and crimp recovering percentage were excellent. Filament No. 6 was poor in the yarn quality as shown in Table l and therefore had poor crimp elasticity and crimp recover- 4O ing properties, even though such a filament developed spontaneous crimps and had an excellent total curliness.
TABLE 3 Weight percentage of polyethylene Yarn quality terephthalate in mono- Elonfilament Stre th gation I (percent) (57d) (percent) 4. on 4. 4. 4. 4.
EXAMPLE 2 The same polyethylene terephthalate as used in Example 1 and polyhexamethylene adipamide-polycaproamide copolymer having an intrinsic viscosity [n] of H3 in m-cresol at 30 C. (copolymerization ratio of 66/6=90/l0) were melted and conjugate spun at a temperature of 285 C. in a predetermined conjugate ratio as shown in Table 3 by means ofa conventional sheath-core-type conjugate spinning apparatus, and then the resulting filaments were drawn 3.9 times their original length on a draw pin heated at 80 C. to obtain drawn composite filaments of 70 d./l 8 f.
The obtained composite filament had a bonding configuration as shown in FIG. 7, in which two elliptical polyester core components existed in the eccentricity of 30 percent.
On the other hand, copolyamide constituting the sheath portion of the composite filament was spun solely and the shrinking percentage of the resulting filament was measured and was 30 percent.
Yarn quality and crimp property of each composite filament i are shown in Table 3.
As seen from Table 3, in the filament No. 8 having a small content of polyethylene terephthalate (polyester component), a satisfactory crimp property was not obtained. On the contra- 5 ry, in the filaments Nos. 9 and 10, the content of the polyester E beyond thab""""""""' 9665i beyond the scope of the invention Kind of composite filament Composite filament [or control Composite filament Com osite fil component was within the scope of the present invention and all formulas to be applied to the present invention were satisfied, so that these filaments showed an excellent crimp property. In the filament No. ll, the content of the polyester component was larger than that of polyamide component, so that the dyeability for an acid dyestuff considerably lowered and such a filament was not used practically.
TABLE 4 Crimp Crimp recovering recovering Sponpercentage percentage Eccentaneous Total Crimp for elonfor com- Sample triclty curliness curliness elasticity gation pression No. Kind of composite filament (percent) (percent) (percent) (mg/ti.) (percent) (percent) opo oi the invention 7.1 60 invention 21 67 10. 7 79 7 EXAMPLE 3 means of the con ugate spinning apparatus of Example I, and
then the resulting filaments were drawn 4.2 times their original length on a draw pin heated at 90 C. to obtain drawn composite filaments of 70 d./l 8 f. respectively.
Enlarged cross sections of these composite filaments had respectively bonding configurations as shown in FIG. 3, in which the eccentricity b of the polyamide component of the core portion was 50 percent.
Crimp properties of the composite filaments thus obtained are shown in Table 6.
Concerning the crimped filaments Nos. 17 to after shrunk, the position of the polyamide component in the cross 25 section was checked by means of a polarizing microscope. In
The same polyethylene terephthalate as used in Example 1 and a copolyamide having an intrinsic viscosity [n] of 1.08 in l m-cresol at C. which was obtained by reacting caprolactam with a salt of N,N-bis(y-aminopropyl) piperazine and adipic acid in a weight ratio of 92/8, were conjugate spun in a sheath-core relation in which polyethylene terephthalate was a core component and copolyamide was a sheath component, at a temperature of 285 C. by means of the apparatus used in Example 1 in a conjugate ratio (by weight) of 30:70. In this case, the eccentricity of polyethylene terephthalate arranged in a form of circle in the core portion was changed variously.
the resultmg filaments were drawn times their the filaments Nos. 17, 18, 20 and 21,the polyamide located in original length at room temperature to obtain drawn comthe outside portion f the crimp Th f the polyester P monofilamems of component having poor recovering property for elongation Furthermorei the abov? descnbed copolyamlde Spun located mainly in the inside portion of the crimp, so that the solely and drawn to obtain a control filament, the shrinking 3O crimp recovering property ft elongation or compression Percenmge Ofwhlch was P was poor. On the other hand, in the composite filaments Nos.
Crimp Properties of obtained composite filaments are 19 and 22-25 of the present invention containing high Show" in Table I shrinkable polyamidc in the core portion, the polyamidc comf"? from Table the filaments 13 havmg an ponent located in the inside of the crimp, so that the crimp eccentricity preferable for the present invention were ex- 35 recovering property was considerably high and crimpability tremely superior in crimpability, crimp elasticity and crimp was good recovering properties to the filament No. 12.
EXAMPLE 5 EXAMPLE 4 Polyethylene terephthalate having an intrinsic viscosity of The same polyethylene terephthalate as used in Example I 0.65 in o-chlorophenol at 30 C. and nylon-6 having an intrinand three kinds of polyamides having various intrinsic viscosisic viscosity of 1.15 in m-cresol at 30 C. were melted and conties as shown in the following Table 5 were melted and conjujugate spun in an eccentric sheath-core relation, in which the gate spun in such a sheath-core relation that the polyester polyethylene terephthalate formed the core and the nylon-6 component was arranged in the sheath portion and the polyaformed the sheath, at a temperature of 285 C., the ratio mide component was arranged in the core portion, at a tem- N(D/R) of the core component to the total bonded comperature of 285 C. in a conjugate ratio (by weight) of 3:1 by ponents being 0.05, 0.10, 0.25, 0.40 and 0.5, and then the resulting filaments were cold drawn 3.79 times their original length to obtain drawn composite filaments of 70 d./l8 f., which had a cross section as shown in FIG. 4. in this case, the
Shrinking percentage of difference between heat shrinking percentages in both com TABLE 6 m ponents was 50 percent, i.e., S=l .5.
$3212; 5 32: Strength, elongation, dyeability and crimp property after Polyemide [1;] (percent) treatment for developing crimps in the obtained composite A 0.95 11.3 filaments are shown in Table 7. D 3 13,1 As seen from Table 7, when N(D/R) is less 0. l0 within the g- 6-5? :g-i scope of the present invention, the obtained composite fila- E. 1108 14:2 ment is extremely low in the curliness after developed crimps. g: d :32 Further, as seen from the spontaneous curliness in Table 7, the H d 1.08 28.6 particularly preferable two-core composite filament according to the present invention develops crimps immediately when it TABLE 6 Crimp Crimp recovering recovering Spontapercentage percentage neous Total Crimp for elongafor com- I curliness curliness elasticity tion pression Kind of composite filament (percent) (percent) (mg./d.) (percent) (percent) Conventional composite filament 1 21 11 'I o 4 29 13 10 Composite filament of the present inventio 18 43 16. 6 48 36 Composite filament beyond the scope of the i 2 16 12 d0 13 31 12.9 21 18 Conposite filament of the present invention 0 do TABLE 8 Crimp re- Sponta- Total covering per- Eccenneous curlcurliness Crimp eentage for Sample tric angle iness (percent) elasticity elongation No. a Kind of composite filament (percent) (0.1 mg./d.) (mg/d (percent) 70 Composite filament beyond the scope of the invention. 0. 6 21. 4 0.8 58
100 Composite filament of the invention. 13. 3 45. 6 1. 4 74 TABLE 10 Total Crimp Conjugate Spontacurliness recovering ratio Copolymerineous (percent) Crimp percentage (by weight) zation ratio curliness (0.1 elasticity for elongation Sample No. A :B:C oi 66/610 Kind of composite filament (percent) mg./d.) (mg./d.) (percent) 45 50:50:0 100/0 11.2 46" 50:50:0 97/3 25. 6 0.1 58 47 50:50:0 95/5 38. 4 0.3 61 48 50 50:0 00/10 57.1 0. 5 63 40 50 :50:0 80/20 70. 2 0.9 00 50 35:50:15 100/0 24. 7 0.5 56 51 35:50: 97/3 20. 6 0.0 67 52 65:50:15 05/5 42. 9 2. 5 70 53 35:50:15 00/10 67.8 3. 0 82 54 35:50:15 80/20 17. 6 80.8 5. 5 87 is drawn and relaxed and such a filament shows crimp property after developed crimps.
Moreover, the parts showing no numerical value in NS( D/R l+E) of Table 7 do not satisfy the range ofthe formula (2) according to the present invention.
an excellent EXAMPLE 6 Polyethylene terephthalate (C-component) having an intrinsic viscosity [n] of 0.65 in o-chlorophenol at 30 C., p0lycaprolactam-polyhexamethylene adipamide copolymer (copolymerization composition of 6/66=80/20 weight ratio, B-component) having an intrinsic viscosity [n] of l.05 in mcresol at 30 C. and polycaprolactam (A-component) having an intrinsic viscosity [n] of 1.0 in m-cresol at 30 C. were melted and conjugate spun in an eccentric sheath-core relation, wherein the B-component and the C-component formed the cores and the A-component formed sheath, in a conjugate ratio (by weight) ofA.-B.-C=80: l0: 10 at a temperature of 280 C. by means of a conventional conjugate spinning apparatus, and then the resulting filaments were cold drawn 3.8 times their original length to obtain drawn composite filaments of 70 d./l8 f.
An enlarged cross section of this filament had a bonding configuration as shown in FIG. 11, in which an eccentric angle a between the B-component and the C-component of core portions were changed variously.
Crimp properties of the composite filaments having said various eccentric angles were measured and the results are shown in Table 8.
Concerning the crimped filaments Nos. 3538, the position of the C-component, polyester in the cross section of the filament was checked by a polarizing microscope, and as the result the polyester in the filament No. 35 located in the inside of the crimp, while the polyester in the filaments Nos. 36-38 located in the outside of the crimp. Accordingly, in the filament No. 35 the spontaneous crimp was somewhat poor, the total curliness after a shrinking treatment was considerably low, and the crimp elasticity and recovering percentage for elongation were poor. On the contrary, in the crimpdeveloped composite filaments Nos. 36-38 according to the present invention, the total curliness after a shrinking treatment was particularly high and the crimp elasticity and recovering percentage for elongation were excellent.
EXAMPLE 7 Polyethylene terephthalate (C-component) and polycaprolactam (A-component) used in Example 6, and polycaprolactampolyhexamethylene isophthalamide copolymer (copolymerization composition of 6/6l=85/l5 weight ratio, B- component) having an intrinsic viscosity [n] of l.l3 in mcresol at 30 ture of 280 C. in a predetermined conjugate ratio as shown in Table 9 by means of a conventional sheath-core-type conjugate spinning apparatus, and then the resulting filaments were drawn 3.9 times their original length on a draw pin heated at C. to obtain drawn composite filaments of 70 d./l 8 f.
The obtained composite filament had a bonding configuration as shown in FIG. 13, in which the B-component and the C-component were semicircular cores, and the eccentric angle a was Yarn quality, crimp property and dyeability of each composite filament are shown in Table 9.
As seen from Table 9, in the filaments Nos. 41 to 44 containing more than 10 percent of polyester component (C-component) with high elasticity, splendid spiral spontaneous crimps were developed when they were drawn and relaxed, and when these drawn filaments were subjected to a shrinking treatment, a tension due to a contact interference between mutual filaments by the spontaneous crimp was small, so that the extremely excellent crimps were developed, and particularly crimp developability under a high load was excellent.
Furthermore, in the composite filaments Nos. 41-43 of the present invention, it was found that crimp elasticity and recovery for elongation were excellent. In the filament No. 44 containing 60 percent of polyester component (C-component), crimp property was fairly good, but had a fault in point of dyeability for acid dye.
EXAMPLE 8 Polyhexamethylene adipamide (A-component) having an intrinsic viscosity [n] of 1.02 in m-cresol at 30 C., polyhexamethylene adipamide-polyhexamethylene sebacamide copolymer (66/610, B-component) having an intrinsic viscosity [n] of l.l2 and polyethylene terephthalate used in Example 6 (C-component) were melted and conjugate spun in a conjugate ratio (by weight) of A:B:C=35:50: l 5: at a temperature of 290 C. by means of a conventional conjugate spinning apparatus for three-component system, and then the resulting filaments were hot drawn 4.l times their original length on a draw pin heated at 70 C. to obtain drawn composite monofilaments of 15 deniers.
The obtained composite monofilament had a bonding configuration as shown in FIG. 10, in which C-component was arranged as a core component in A-component, A-component and B-component were bonded in a side-by-side relation, and an eccentric angle a between B- and C-components was 180.
For a comparison, the above described A- and B-components were conjugate spun in a conjugate ratio (by weight) of lzl by means ofa conventional side-by-side-type conjugate spinning apparatus for two component system without using polyester of C-component and drawn under the same condi- C. were melted and conjugate spun at a temperations as described above to obtain drawn composite monofilament of 15 deniers having a bonding configuration as shown in FIG. 1.
Crimp properties of said composite filaments are shown in Table 10.
As seen from Table 10, conventional polyamide series composite filaments Nos. 45-49 did not develop spontaneous crimp at all and developed spiral latent crimps for the first time by a shrinking treatment. On the other hand, in the filaments Nos. 52-54 of the present invention containing high shrinkable copolyamide, spontaneous crimps were developed when such filaments were drawn and relaxed, and further the more excellent crimps were developed by a shrinking treatment, and also crimp elasticity and recovery for elongation were more excellent as compared with those of the conventional polyamide series composite filaments. In the filament No. 51, the shrinking percentage of B-component was not so high, so that the crimp property was poor as in the case of the filament No. 50.
What is claimed is:
1. A composite filament having elastic crimping property, comprising at least two components disposed in an eccentric sheath-core relation along the longitudinal axis of the filament, wherein a. the first component is the core component composed of a polyester consisting essentially of polyethylene terephthalate; and
b. the second and any other components comprise the sheath of a highly shrinkable polyamide having a shrinking percentage of 15-85 percent; the percent by weight ofcore component in the filament being 5-50; and the following conditions (1) and (2) being present at the same time: (I) (i) 3.8 (l.4a X 5017+ 200 and (ii) B Z 5;
wherein a represents said shrinking percentage of the sheath component,
b represents the percentage of eccentricity of the center of gravity (P) of the core component positioned in the cross section of the filament against the radius of the filament,
and
represents said percentage of the core component; and (2) (i) 1.2 X 1O NS(D/R) (l +1?) 5 10.1 X (NE 2);
(ii)E 5 0.1;and (iii) S e 1.1; wherein D is the arithmetic mean of diameters of each core, when the cores are circular, or when the cores are noncircular, is the arithmetic mean of diameters of circles, when said noncircular cores are calculated into circles, R is the diameter of the filament, N is the number ofcores, E is the ratio of initial modulus of the polyamide to the polyester, and S is the ratio of heat shrinkability of the polyamide to the polyester. 2. The composite filament as claimed in claim 1, wherein said shrinking percentage is at least percent.
3. The composite filament as claimed in claim 1, wherein said percent by weight of the core or cores in the filament is 20 4. The composite filament as claimed in claim 1 which has at least two cores.
5. The composite filament as claimed in claim 1, wherein said polyamide is a homopolyamide having an intrinsic viscosity ofat least 1.15.
6. The composite filament as claimed in claim 1, wherein said homopolyamide is nylon-6 or nylon-66.
7. The composite filament as claimed in claim 1, wherein said polyamide is a copolyamide of more than 95 percent by weight ofa polyamide-forming constituent and less than 5 percent by weight of another polyamide-forming constituent and having an intrinsic viscosity of at least 1.15.
8. The composite filament as claimed in claim 1, wherein said polyamide is a copolyamide of 95 70 percent by weight of a polyamide-forming constituent and 5 30 percent by weight of another polyamide-forming constituent.
9. The composite filament as claimed in claim 1, wherein said polyamide is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethyl'ene sebacamide).
10. The composite filament as claimed in claim 1, wherein the sheath is constituted with two polyamide components disposed eccentrically to each other in distinct zone with intimate adherent surface extending along the filament axis, one of said components consists of a homopolyamide, the other of said components consists of a copolyamide and further the core composed of said polyester component is embedded in said homopolyamide component without contacting with said copolyamide component.
11, The composite filament as claimed in claim 10, wherein the core and the copolyamide component of the sheath are arranged under such a condition that the lesser angle a formed by two straight lines, one of which connects the center of gravity of said core with the center of the filament and the other of which connects the center of gravity of said copolyamide component with the center of filament, in the cross section of the filament, is the range between and 180.
12. The composite filament as claimed in claim 10, wherein the shrinking percentage of the copolyamide component is at least 3 percent higher than that of the homopolyamide component.
13. The composite filament as claimed in claim 10, wherein said copolyamide consists of less than percent by weight of a polyamide-forming constituent and more than 5 percent by weight of another polyamide-forming constituent.
14. The composite filament as claimed in claim 10, wherein said homopolyamide component is of nylon-6 or nylon-66.
15. The composite filament as claimed in claim 10, wherein said copolyamide component is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethylene sebacamide).
16. The composite filament as claimed in claim 10, wherein said homopolyamide and said copolyamide are arranged in a side-by-side relation.
17. The composite filament as claimed in claim 10, wherein said homopolyamide and said copolyamide are arranged in an eccentric sheath-core relation.
18. The composite filament of claim 1, wherein polyethylene terephthalate comprises at least 95 percent of said first component (a).
Claims (17)
- 2. The composite filament as claimed in claim 1, wherein said shrinking percentage is at least 20 percent.
- 3. The composite filament as claimed in claim 1, wherein said percent by weight of the core or cores in the filament is 20 *40.
- 4. The composite filament as claimed in claim 1 which has at least two cores.
- 5. The composite filament as claimed in claim 1, wherein said polyamide is a homopolyamide having an intrinsic viscosity of at least 1.15.
- 6. The composite filament as claimed in claim 1, wherein said homopolyamide is nylon-6 or nylon-66.
- 7. The composite filament as claimed in claim 1, wherein said polyamide is a copolyamide of more than 95 percent by weight of a polyamide-forming constituent and less than 5 percent by weight of another polyamide-forming constituent and having an intrinsic viscosity of at least 1.15.
- 8. The composite filament as claimed in claim 1, wherein said polyamide is a copolyamide of 95 *70 percent by weight of a polyamide-forming constituent and 5 *30 percent by weight of another polyamide-forming constituent.
- 9. The composite filament as claimed in claim 1, wherein said polyamide is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethylene sebacamide).
- 10. The composite filament as claimed in claim 1, wherein the sheath is constituted with two polyamide components disposed eccentrically to each other in distinct zone with intimate adherent surface extending along the filament axis, one of said components consists of a homopolyamide, the other of said components consists of a copolyamide and further the core composed of said polyester component is embedded in said homopolyamide component without contacting with said copolyamide component.
- 11. The composite filament as claimed in claim 10, wherein the core and the copolyamide component of the sheath are arranged under such a condition that the lesser angle Alpha formed by two straight lines, one of which connects the center of gravity of said core with the center of the filament and the other of which connects the center of gravity of said copolyamide component with the center of filament, in the cross section of the filament, is the range between 90* and 180*.
- 12. The composite filament as claimed in claim 10, wherein the shrinking percentage of the copolyamide component is at least 3 percent higher than that of the homopolyamide component.
- 13. The composite filament as claimed in claim 10, wherein said copolyamide consists of less than 95 percent by weight of a polyamide-forming constituent and more than 5 percent by weight of another polyamide-forming constituent.
- 14. The composite filament as claimed in claim 10, wherein said homopolyamide component is of nylon-6 or nylon-66.
- 15. The composite filament as claimed in claim 10, wherein said copolyamide component is of poly(caproamide/hexamethylene adipamide), poly(caproamide/hexamethylene isophthalamide) or poly(hexamethylene adipamide/hexamethylene sebacamide).
- 16. The composite filament as claimed in claim 10, wherein said homopolyamide and said copolyamide are arranged in a side-by-side relation.
- 17. The composite filament as claimed in claim 10, wherein said homopolyamide and said copolyamide are arranged in an eccentric sheath-core relation.
- 18. The composite filament of claim 1, wherein polyethylene terephthalate comprises at least 95 percent of said first component (a).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1856568 | 1968-03-21 | ||
JP2575668 | 1968-04-17 | ||
JP2643468 | 1968-04-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3642565A true US3642565A (en) | 1972-02-15 |
Family
ID=27282266
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US807863A Expired - Lifetime US3642565A (en) | 1968-03-21 | 1969-03-17 | Composite filaments having an elastic crimping property |
Country Status (4)
Country | Link |
---|---|
US (1) | US3642565A (en) |
DE (1) | DE1914399A1 (en) |
FR (1) | FR2004427A1 (en) |
GB (1) | GB1234892A (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3901988A (en) * | 1973-12-03 | 1975-08-26 | Textron Inc | Inflatable trunk for air cushion supported vehicles |
US4707398A (en) * | 1986-10-15 | 1987-11-17 | Kimberly-Clark Corporation | Elastic polyetherester nonwoven web |
US4724184A (en) * | 1986-10-15 | 1988-02-09 | Kimberly-Clark Corporation | Elastomeric polyether block amide nonwoven web |
US4741949A (en) * | 1986-10-15 | 1988-05-03 | Kimberly-Clark Corporation | Elastic polyetherester nonwoven web |
US4756925A (en) * | 1986-03-31 | 1988-07-12 | Teijin Limited | Plasma and ion plating treatment of polymer fibers to improve adhesion to RFL rubber |
US4781966A (en) * | 1986-10-15 | 1988-11-01 | Kimberly-Clark Corporation | Spunlaced polyester-meltblown polyetherester laminate |
US4801482A (en) * | 1986-10-15 | 1989-01-31 | Kimberly-Clark Corporation | Elastic nonwoven pad |
US4820572A (en) * | 1986-10-15 | 1989-04-11 | Kimberly-Clark Corporation | Composite elastomeric polyether block amide nonwoven web |
US4923742A (en) * | 1986-10-15 | 1990-05-08 | Kimberly-Clark Corporation | Elastomeric polyether block amide nonwoven web |
US5906891A (en) * | 1995-12-26 | 1999-05-25 | Mitsubishi Gas Chemical Company, Inc. | Oriented polyamide fiber and process for producing same |
US6042592A (en) * | 1997-08-04 | 2000-03-28 | Meadox Medicals, Inc. | Thin soft tissue support mesh |
US20020138025A1 (en) * | 2001-03-09 | 2002-09-26 | Scimed Life Systems, Inc. | Medical slings |
US20060051578A1 (en) * | 2003-02-20 | 2006-03-09 | Motech Gmbh Technology & Systems | Multi-layer monofilament and process for manufacturing a multi-layer monofilament |
US20120231690A1 (en) * | 2005-06-24 | 2012-09-13 | North Carolina State University | Multicomponent fibers and microdenier fabrics prepared by fibrillation thereof |
CN106319648A (en) * | 2016-11-15 | 2017-01-11 | 上海理工大学 | Microfluid control spray head with parallel and coaxial parts arranged on one side, spinning device and spinning method |
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CN106591966B (en) * | 2016-11-21 | 2020-11-24 | 上海理工大学 | Electrohydrodynamic preparation method of silk particle parallel micro-nano structure |
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Also Published As
Publication number | Publication date |
---|---|
DE1914399A1 (en) | 1970-02-05 |
FR2004427A1 (en) | 1969-11-21 |
GB1234892A (en) | 1971-06-09 |
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