Classifications

• • 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
  • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2929—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.]
• • 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

Definitions

• Composite yarns based on a homopolyamide and a binary copolyamide containing at most 20 percent by weight of nonisomorphous polymer units derived from specific diacids and diamines, the remainder consisting of the same unit as that of the homopolyamide have also been proposed.
• the melting points of the two polymers are closer together and the spinning difficulties are considerably reduced.
• the present invention provides a composite yarn which comprises as its polymer components (a) polyhexamethyleneadipamide and (b) a ternary copolyamide prepared from hexamethylenediammonium adipate, 5-25 percent (based on the total weight of the salts) of hexamethylenediammonium terephthalate, and 5-20 percent (on the same basis) of an additional salt derived from an aliphatic dicarboxylic acid containing six to 12 carbon atoms in the molecule and (i) an unsubstituted or C alkyl-substituted hexamethylenediarnine or (ii) a cycloalkane diamine of the formula:
• R represents (CH2) m (CH2) n R1 R, Ill! or Q I'ti L wherein m is an integer from 1 to 4, n and n are or integers from 1 to 4, p is an integer from 1 to 6, R is H, CH or C H and R is H, CH C H or cyclohexyl.
• cycloalkane diamines exsist as structural isomers, they can be used in the pure form or as an isomer mixture as desired.
• Suitable diamine components of the additional salt include hexamethylenediamine, trimethylhexamethylenediamine, 3- aminomethyl-3,5 ,S-trimethyl-cyclohexylaminel di( 4-aminocyclohexyl)methane and 2,2-bis(4-aminocyclohexyl propane. Trimethylhexamethylenediamine is particularly valuable as a substituted hexamethylenediamine.
• aliphatic dicarboxylic acid components of the additional salt adipic, sebacic and dodecanedioic acids may be particularly mentioned, though if the diamine used is hexamethylenediamine the diacid must obviously be other than adipic acid.
• the ternary copolyamides can be made by general methods which are well known in the art, as can the monomers from which they are made,
• the polyhexamethylene adipamide and the ternary copolyamide are preferably present in the yarn in substantially equal proportions by weight.
• This new type of yarn has several substantial advantages due to the presence of terephthalate units as one of the constituents in the ternary copolyamide.
• a ternary copolyamide containing hexamethylene adipamide units, units derived from hexamethylenediammonium terephthalate, and units derived from an additional monomer salt which confers nonisomorphous properties on the final copolyamide, as described above, can have a higher melting point than a binary copolyamide produced from hexamethylenediammonium adipate and an identical proportion of the same additional monomer salt.
• melt viscosity resulting from the presence of these additional monomer units also helps to improve the spinning of the yarn, especially permitting to put the bundle under greater tension.
• This increased melt viscosity also makes it possible to use a higher viscosity polyhexamethylene adipamide as the other constituent.
• the composite yarns of improved strength may be obtained.
• the units derived from hexamethylene diammonium terephthalate in the ternary copolyamide enable copolyamides with a high crystallization peak to be obtained and thus the stretching of the yarn to be carried out under more severe conditions.
• the crystallization peak and the melting peak are measured by differential enthalpy analysis, under nitrogen using a temperature rise of 8 C per minute, of a previously melted and quenched sample.
• the temperatures corresponding to the start, the maximum and the end of the crystallization and melting peaks can thus be observed.
• the area of the peak, which is proportional to the degree of crystallization, is given in the Examples for a weight of polymer of 10 mg.
• the latent crimp of the yarns of this invention is greater than that of comparable yarns obtained from binary copolyamides containing no terephthalamide units.
• the latent crimp can be developed by heating to rather high temperatures, but the crimp obtained is more stable to possible temperature variations to which the yarn may be subsequently subjected.
• the percentage of hexamethylenediammonium terephthalate in the copolyamide required to confer these properties on the copolymer varies within the range of 5 to 25 percent by weight.
• the advantages obtained using copolyamides prepared from less than 5 percent by weight are negligible while using amounts greater than 25 percent by weight it is difficult to obtain a copolyamide having a melt viscosity similar to that of the polyhexamethylene adipamide. [Considerable differences between the melt viscosities of the two constituents of the yarn gives rise to difficulties in spinning].
• 10 to 15 percent by weight of hexamethylenediammonium terephthalate are used in the preparation of the eopolyamide.
• the proportion of units derived from the additional monomer salt in the eopolyamide varies within the range of 5 to 20 percent by weight depending on the desired crimp and on the nature of the additional monomer salt which leads to the non-isomorphous copolymer used.
• the yarns can be obtained by a conventional melt spinning process by simultaneous extrusion of two polymers, alongside one another or in the form of a non-concentric core and sheath, through the same holes of a spinneret, the ratio of the throughputs rates is preferably substantially 1:1 but can be as low as 1/3, to give a ratio of polyhexamethylene adipamide to eopolyamide of 1:3 by weight or as great as 3:1.
• the yarns so formed are stretched, as by passing them under tension round a snubbing pin, which may be heated, without bringing the yarn to a temperature which would cause appreciable crystallization of the copolymer, and the crimp is subsequently developed by heat treatment, for example treatment of the yarn in the tension free state or of an article produced from the yarn with boiling water.
• heat treatment for example treatment of the yarn in the tension free state or of an article produced from the yarn with boiling water.
• the crimp obtained is characterized by the extensibility of the yarn and by the half-decrimping and half-recrimping forces.
• the springiness of the crimp and hence its resistance to decrimping is, for a given extensibility, directly dependent on the magnitude of these forces. This resistance to decrimping is important during handling or use of the yarn.
• the extensibility is given by the formula:
• L is the length of the decrimped yarn under a load of 225 mg/dtex and l is the length of the crimped yarn in a tension-free state.
• the measurements may be carried out using an INSTRON tensometer, the crimp being pulled out and then allowed to return. Graphs are drawn for the range I to L and the extensibility is read off as the abcissa and the half-decrimping and half-recrimping forces as the ordinate.
• the composite yarns obtained from these ternary eopolyamides and polyhexamethyleneadipamide may with particular advantage be used in hosiery because of their elasticity and strength and because they impart to the article an attractive appearance and an agreeable feel. They may also be used in the manufacture of other knitted fabrics and woven fabrics and carpets.
• EXAMPLE 1 Polyhexamethylene adipamide and a eopolyamide produced from hexamethylenediammonium adipate, hexamethylene-diammonium terephthalate and hexamethylenediammonium sebacate in proportions of 67/17/16 by weight are extruded alongside one another at 290 C, simultaneously in a 1:1 weight ratio and at the same throughput, through the same holes of a hole spinneret using a conventional melt spinning device.
• the monofilament yarns On issuing from the spinneret the monofilament yarns travel through an atmosphere of a cooling gas and are then wound up at 420 m/minute.
• the yarns are then stretched at ambient temperature in a ratio of 4.12 by being passed at a speed of 540 m/minute over a stretching rod 8 mm in diameter.
• the crimp is developed in boiling water, the yarns being kept in a tension-free state.
• the yarns then possess the following properties:
• EXAMPLE 2 A composite yarn is prepared by the method of Example 1 except that the hexamethylenediammonium sebacate is replaced by di(4-aminocyc1ohexyl)methane adipate and also the proportions of the constituents of the eopolyamide being 65/ 1 5/20 by weight.
• the two polymers are simultaneously extruded at 292 C through the holes of a 30 hole spinneret, the ratio of the throughputs of the homopolyamide and of the eopolyamide being 60/40.
• the resulting yarns are wound up at 300 m/rninute.
• the yarns After treatment in the tension-free state with boiling water, the yarns possess the following properties:
• EXAMPLE 3 Composite yarns are prepared by the procedure of Example 1 except that the hexamethylenediammonium sebacate is replaced by di(4-aminocyclohexyl)methane sebacate, the proportions of the constituents in the eopolyamide then being 70/15/15 by weight.
• the two polymers are extruded at 290 C simultaneously in a 1:1 weight ratio and at the same throughput through the holes of a spinneret possessing three series of 10 holes and the composite yarns obtained are wound up at a speed of 600 m/minute.
• the yarns in the tension-free state are dipped in boiling water to develop the crimp. They then possess the following properties:
• the yarns are used for the manufacture of very elastic stockings and have an attractive appearance on the leg.
• EXAMPLE 4 Composite yarns are prepared as in Example 1 except that the hexamethylenediammonium sebacate is replaced by 3- amin0methyl-3,5,5-trimethyl-cyclohexylamine-l adipate, the proportions of the constituents of the eopolyamide being 75/ 10/15 by weight.
• the two polyamides are extruded simultaneously in a 1:1 weight ratio and at the same throughput at 292 C through the same holes of a spinneret having two series of 24 holes, and the yams obtained are wound up at a speed of 600 m/minute.
• the yarns obtained After being stretched at ambient temperature to a ratio of 3.95 by being passed at a speed of 520 m/minute over a rod 6 mm in diameter, the yarns obtained are dipped in the tensionfree state into boiling water to develop the crimp. They then have the following properties:
• Composite yarns are prepared under the same conditions as described in Example 4, using polyhexamethylene adipamide and a copolyamide produced from hexamethylenediammonium adipate, hexamethylenediammonium terephthalate and di(4-aminocyclohexyl)methane adipate, in the proportions of 65/15/20 by weight.
• the yarns After being stretched and treated with boiling water, the yarns have the following properties:
• the yarns On issuing from the spinneret the yarns travel through an atmosphere of a cooling gas and are then wound up at the rate of 600 m/minute.
• the crimp is developed by treating the yarns with boiling water, the yams being kept in a tension-free state.
• the resulting yarns have the following properties:
• EXAMPLE 7 A composite yarn is produced under the same conditions as described in Example 6 except that the 2,2-bis(4-aminocyclohexyl)propane dodecanoate is replaced by 3- aminomethyl-3,5,5-trimethyl-cyclohexylamine-1 adipate, the ratio of the constituents being 75/15/10 by weight.
• This crimped yarn is of good quality, free of filaments which are stuck together and the crimp is very regular.
• Example 6 are prepared as described in Example 6 from polyhexamethylene adipamide and a copolyamide produced from hexamethylenediammonium adipate, hexamethylenediammonium terephthalate and a salt of a diacid having six or 10 carbon atoms and an aliphatic or cycloaliphatic diamine.
• a composite yarn whose constituent filament or filaments have a side-by-side or non-concentric sheath core structure which consists essentially of as its polymer components (a) polyhexamethylene adipamide and (b) a ternary copolyamide prepared from hexamethylenediammonium adipate, 5 to 25 percent (based on the total weight of the salts) of hexamethylenediammonium terephthalate, and 5 to 20 percent (on the same basis) of an additional salt derived from an aliphatic dicarboxylic acid containing six to 12 carbon atoms in the molecule and a diamine selected from the group consisting of unsubstituted hexamethylenediamines, C alkyl-sub stituted hexamethylene diamines and cycloalkane diamines of the fonnula:
• R is selected from the group consisting of (R )n and 1 1 R, l 'l l l R1 J.
• n and n are integers from 0 to 4
• p is an integer from 1 to 6
• R is selected from the group consisting of H, CH and C H and R is selected from the group consisting of H, CH ,C H and cyclohexyl.
• a yarn according to claim 1, wherein the additional salt is selected from the group consisting of hexamethylenediammonium sebacate, di(4-aminocyclohexyl)methane adipate, di(4-aminocyclohexyl)methane sebacate, S-aminomethyl- 3,5,S-trimethylcyclohexylarnine-l adipate, and 2,2-bis(4- aminocyclohexyl )propane dodecanoate.
• a yarn according to claim 1 containing substantially equal proportions by weight of the polyhexamethylene adipamide and the ternary copolyamide.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Multicomponent Fibers (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

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Citations (3)

• 1969
  • 1969-11-17 NL NLAANVRAGE6917260,A patent/NL169204C/xx active
  • 1969-11-24 BE BE742144D patent/BE742144A/xx unknown
  • 1969-11-24 JP JP44094186A patent/JPS4910613B1/ja active Pending
  • 1969-11-24 GB GB57472/69A patent/GB1287305A/en not_active Expired
  • 1969-11-24 US US879594A patent/US3664917A/en not_active Expired - Lifetime
  • 1969-11-24 CH CH1748069A patent/CH508751A/fr not_active IP Right Cessation
  • 1969-11-24 LU LU59868D patent/LU59868A1/xx unknown
  • 1969-11-25 DE DE19691959150 patent/DE1959150A1/de active Granted

Patent Citations (3)

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