US2989798A - Filaments of improved dye-receptivity - Google Patents

Filaments of improved dye-receptivity Download PDF

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Publication number
US2989798A
US2989798A US519033A US51903355A US2989798A US 2989798 A US2989798 A US 2989798A US 519033 A US519033 A US 519033A US 51903355 A US51903355 A US 51903355A US 2989798 A US2989798 A US 2989798A
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United States
Prior art keywords
amine
polymer
sheath
groups
core
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Expired - Lifetime
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US519033A
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English (en)
Inventor
Douglas G Bannerman
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EIDP Inc
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EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority to NL113790D priority Critical patent/NL113790C/xx
Priority to NL208424D priority patent/NL208424A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US519033A priority patent/US2989798A/en
Priority to FR1154279D priority patent/FR1154279A/fr
Application granted granted Critical
Publication of US2989798A publication Critical patent/US2989798A/en
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Expired - Lifetime legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/26—Composite fibers made of two or more materials
    • 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]
    • 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

Definitions

  • a primary object of the present invention is provision of nylon filaments of improved dyeability.
  • An object is provision of multicomponent filaments containing readily dyeable polyamide composition.
  • FIGURE 1 is an axial longitudinal section of a spinneret assembly designed according to this invention for extrusion of multicomponent filaments.
  • FIGURE 2 is a transverse cross section of the apparatus of FIGURE 1 taken at 22 thereof and showing the plan of the front or bottom spinneret plate.
  • FIGURE 3 is a transverse cross section taken at 3--3 of FIGURE 1 to show the plan of the top or back plate thereof.
  • FIGURE 4 is a transverse cross section of a filamentary product of the apparatus of FIGURE 1.
  • the objects of the present invention are accomplished by simultaneous extrusion of more than one polymeric substance, including one that is characterized by amine end-groups, as a core, and one that is essentially free of amine end-groups, as a surrounding sheath.
  • This is done by extruding the polymers, of which at least one has fiber-forming characteristics, simultaneously, after having surrounded a stream of the polymer having amine end-groups with a fluid layer of the polymer relatively free of amine end-groups.
  • the invention comprehends particularly a polyamide filamentary structure characterized by dyeability with acid dyes. and formed by simultaneous extrusion of a first polyamide having acid-receptive amine end-groups and constituting the core of the structure and a second polyamide essentially lacking such amine end-groups and constituting a surrounding sheath.
  • Polyamides having an intrinsic viscosity of at least about 0.4 can be converted into self-supporting filaments by extrusion of the molten polymer through fine orifices (melt-spinning), tenacity and other properties of the product being enhanced subsequently by cold-drawing it to increased length.
  • melt-spinning fine orifices
  • tenacity and other properties of the product being enhanced subsequently by cold-drawing it to increased length.
  • an excess of one or the other of the polymerizing reactants is employed in the polymerization of diamines and dicarboxylic acids or their amide-forming derivatives, or some other viscosity stabilizer is used with these reactants or in the polymerization of aminocarboxylic acids, with the objective of terminating growth of the polymer molecules.
  • polymer having fewer than about 50 amine equivalents per 10 grams of polymer is considered essentially free of amine end-groups because at that content melt-spinning of the polymer is commercially feasible, despite degradation (attributable to amine content) that occurs upon exposure of the polymer to the atmosphere.
  • Spinning of polymer containing more than this amount has not been commercial, and a content of 10 equivalents of amine end-groups per 10 grams of polymer is termed high in degradable amine.
  • the usual terminal amine group is primary, secondary and tertiary amine groups are included also. Filaments of high average amine endgroup content are dyeable to deep fast colors with acid dyes.
  • FIGURE 1 shows in axial section a spinneret assembly useful for this purpose.
  • Front or bottom plate 1 with orifices 2 is recessed at the back about plateau-like protrusions 4.
  • Back or top plate 7 is sealed against and spaced from the front plate by gasket 6 and shim 16, the former being ring-shaped and located near the periphery of the opposing faces of the two plates and the latter being disc-shaped and located concentric with the two plates.
  • Relatively unconstricted region 12 between the two plates is interrupted at intervals by constricted regions 15 between the opposing face of the back plate and plateaus 5 of the protrusions from the front plate.
  • the back plate is partitioned on top by outer wall 19 and inner wall 29 into annular chamber 8 and central chamber 9.
  • the annular chamber communicates with the constricted regions between the two plates through counterbored apertures 10, and the central chamber communicates with the intervening relatively unconstricted region through holes 11.
  • the two plates are retained in place by cap 18 threaded onto the end of the back plate.
  • the upper part of the housing (not shown) receives suitable piping or other supply means for separate connection to the two chambers, which may constitute distribution or filtering spaces as desired.
  • Pin 14 through cylindrical openings (opening 25 in the front plate and opening 26 in the back plate) near one edge of the plates ensures concentricity of the two plates.
  • FIGURE 2 shows the plan of the front plate. Appearing in this view are eight plateaus, each concentric with an extrusion orifice and uniformly spaced about a circle inside the outer gasket. As shown in this view and in FIGURE 1, each orifice consists of capillary 21 at the exit end and larger counterbore 22 extending to the capillary from the plateau. Also visible, supported in a shallow annular groove, is gasket 6, the opposing face of the back plate being similarly grooved to ensure a good seal between the two plates. The apertures in the top plate opposite the orifices of the bottom plate are similarly constructed, each being composed of terminal capillary 23 and introductory counterbore 24.
  • FIGURE 3 shows the appearance of the back plate sectioned as indicated on FIGURE 1. Visible are the concentric outer and inner walls, the capillaries and counterbores of eight apertures spaced uniformly on a circle between the two walls, and four openings located within the central chamber defined by the inner wall.
  • the back plate Upon emerging from the spinneret orifices, the core-forming component is protected from the atmosphere by a uniform cover of the sheath-forming component.
  • a polyamide is formed by reacting 10,523 grams of hexarnethylenediammonium adipate (40.1 moles), 93.7 grams of hexamethylene diamine (0.808 mole), and gram of acetic acid (0 mole), under the conditions taught by Carothers in Patent 2,130,948, September 20, 1938.
  • a solution of 5.5 grams of the polymer in 50 ml. of 90% formic acid has a relative viscosity of 31.4 at 25 C. and contains 26 and 135 equivalents of carboxyl and amine end-groups, respectively per grams of polymer.
  • This polymer is spun as the core of a two-component fiber simultaneously with a polyhexamethylene adipamide of 41 relative viscosity having 43 and 74 equivalents of amine and carboxyl end-groups, respectively, per 10 grams of polymer as the sheath component.
  • the pump speeds for the two components are adjusted to give a sheath-core weight ratio of 30/70.
  • the polymers are spun at 285 C. and the resultant yarn wound up at 1206 yards per minute. Good spinning ensues for a period of five hours, at which time the spin is discontinued. with no spinneret drips having occurred.
  • the yarn is drawn 3.22X over a cold pin to give a final yarn with a total denier of 95.
  • the yarn has a tenacity of 4.7 grams per denier and an elongation at break of 24.3%.
  • the yarn is of uniform denier and shows uniform concentric sheath/ core relationships from filament to filament.
  • Tubings knit from the two-component yarn prepared as above and from a single-component yarn prepared under similar conditions but using only the low-amine polyhexamethylene adipamide used for the sheath above were dyed separately at the boil for one hour (ratio of bath: tubing of of 50:1) in an acid dye bath having the following composition: 0.5% 1-amino-4-anilino-2-anthraquinone sodium sulfonate, 3% acetic acid, and 2% sodium lauryl sulfate. From saturation dyeings the high-amine two-component tubing picked up 3.4 weight percent of dye as contrasted with 1.8 percent dye takeup by the tubing made of the one-component, low-amine yarn. When both tubings were dyed to the same shade and then submitted to repeated launderings, the tubing made of the two-component yarn retained 91% of the dye in contrast to the low-amine yarn tubing which retained only 78% of the dye.
  • a polyhexamethylene adipamide is made by reacting hexamethylenediammonium adipate with hexamethylene diamine equivalent to 1.14 mol percent of the salt and with acetic acid equivalent to 0.182 mol percent of the salt as above.
  • the final polyamide has a relative viscosity of 36 and contains and 44 equivalents of amine and carboxyl end-groups, respectively, per 10 grams of polymer.
  • This polymer is mixed with 1.9% of its weight of titanium dioxide and 0.56% of its weight of the sodium salt of phenyl phosphinic acid (as disclosed by Gray in Patent 2,510,777), in order to reduce the atmospheric degradation of the polymers at the spinning temperature and spun at 800 yards per minute. The frequency of spinneret drips is one per six hours in spite of the added stabilizer.
  • the yarn is cold-drawn to give a delustered yarn (hereinafter designated as control 2) with a total denier of 72.
  • Another high-amine polyamide is made by reacting hexamethylenediamrnonium adipate with 1.94 mol percent of hexamethylene diamine under conditions as given above.
  • the resulting polymer has a relative viscosity of 41 and contains 146 and 22 equivalents of amine and carboxyl end-groups, respectively, per 10 grams of polymer.
  • This polymer is mixed with 2.4% of its weight of titanium dioxide and spun as the core of a two-component yarn; and a polymer as used for control 1, but without titanium oxide is used for the sheath of the yarn.
  • the spinning pumps for the two-component melts are adjusted to give a ratio of sheath/ core of 15/85.
  • the polymers spin well and no spinneret drips occur in 44 hours, at which time the run is stopped.
  • the filaments are drawn over a cold pin to give a delustered yarn with a total denier of 71, total TiO content of 1.9%, and an over-all amine content of 12x10 equivalents per gram. Representative transverse cross sections of these filaments appear in FIGURE 4, the dyeing of the core being represented by stippling.
  • sheath-core yarn exemplified here spun much better than the single-component high-amine yarn (more than 44 hours versus 6 hours for the same drip frequency) even though it contained more amine groups but also that the two-component yarns with a bright sheath, i.e., with no delusterant present, spun much better than control 1, which contained pigment but less than 0.3 as many amine groups as the core of the two-component fiber (more than 44 hours per drip as compared to 20 hours).
  • the three yarns had physical properties given in Table I below.
  • Knit tubings were made of the three yarns and dyed competitively in the dye bath of Example I. Control 1 gave the lightest shades, control 2 gave an intermediate shade and the sheath-core yarn gave the darkest blue shades. Similar results were obtained for 2, 5, and 15- minute dyeing. Fabrics were also woven of the three yarns and dyed separately under equivalent conditions in the dye bath of Example I to similar shades. The fabric woven of the sheath-core yarn with the high-amine core showed the greatest wash-fastness, with control 2 being intermediate between it and control 1. Similarly, the dyed fabric Woven of the sheath-core yarn showed the greatest light-fastness as determined by 20' hours exposure in a fadeometer instrument, with control 2 being intermediate. Similar dyeing results were obtained with the acid dye Cl. 430.
  • polyhexamethylene adipamide Although this invention has been illustrated with polyhexamethylene adipamide because of its recognized commercial importance, it is applicable also to other polyamides, including copolymers, whether prepared by the reaction of diarnines and dibasic acids, and their derivatives, amino acids, or other compounds (e.g., caprolactam, which yields a polyamide under proper reaction conditions).
  • the invention is applicable similarly to other fiber-forming polymers that may contain amine groups, including polyureas derived, for example, from a diisocyanate and a diamine, as shown by Rinke et al. in Patent 2,511,544; polyurethanes; polythioureas; polythioamides; polysulfonamides, as taught by Jones et al.
  • Copolyesteramides also can be used.
  • the amine content of the core polymer may arise from a blend of a polymer containing amine groups and another polymer with few or no amine groups as, for example, a blend of a polyamide and a polyester, such as polyethyleneterephthalate.
  • an N-amino-alkyl morpholine can be used as a viscosity stabilizer in the preparation of polyamides, as taught by Watson in Patent 2,585,199, in order to obtain polymers with tertiary amine end-groups having increased dyeability with 'acid dyes.
  • Other means of forming amine end-groups by polymerization or after-treatment of a polymer will be obvious to those skilled in the art.
  • this invention is of value when spinning polyamides containing from about 4 to 400 equivalents of amine group per grams of polymer.
  • the invention affords a process for the commercial spinning of any polymers containing any finite concentration of amine groups.
  • the over-all amine concentration in the two-component filament should be between and 400 equivalents per 10 grams of polymer and preferably between and 200. This can be obtained by balancing the amine content of the core and sheath and their relative thickness.
  • the products of this invention can be dyed with that class of dyes containing acid groups known as acid or direct dyes, including those with the following color index numbers: 176, 161, 1088, 365, 589, 594, and 5 83.
  • the sheath and core of a filament need not be composed of the same type of polymer.
  • a polyester sheath can be spun over polyamide core having a high content of amine endgroups. In this manner the acid-dyeing characteristics of one polymer can be combined with the surface properties of a second polymer.
  • This invention is of value in that it provides two-component filaments that can be dyed to deep, uniform shades that are washand light-fast.
  • this invention has been illustrated with filaments containing the sheath and core components in a concentric relation, any eccentric arrangement can be used and, furthermore, the shape can be as desired, e.g., cruciform, ribbon, Y-shape, as well as circular. Regardless of shape, the dyed products display greater fastness to laundering and light than single-component filaments dyed to the same shade. The products are eminently suitable for all manner of textile applications.
  • a filament of improved dye receptivity and retention comprising a sheath-core filament having comprising as a core a polymeric substance containing at least 10 equivalents of amine end-groups per 10 grams of polymer and as a sheath a polymeric substance having fewer than about 50 amine equivalents per 10 grams of polymer.
  • a filament of improved dye receptivity and retention comprising a sheath-core filament having as a core a fiber-forming polyamide containing at least 10 equivalents of amine end groups per 10 grams of polymer, and as a sheath a fiber-forming polyamide having fewer than about 50 amine equivalents per 10 grams of polymer.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Multicomponent Fibers (AREA)
  • Artificial Filaments (AREA)
US519033A 1955-06-30 1955-06-30 Filaments of improved dye-receptivity Expired - Lifetime US2989798A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NL113790D NL113790C (fr) 1955-06-30
NL208424D NL208424A (fr) 1955-06-30
US519033A US2989798A (en) 1955-06-30 1955-06-30 Filaments of improved dye-receptivity
FR1154279D FR1154279A (fr) 1955-06-30 1956-06-26 Procédé d'extrusion de composition fibrogènes

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US519033A US2989798A (en) 1955-06-30 1955-06-30 Filaments of improved dye-receptivity

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Cited By (56)

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US3251913A (en) * 1960-06-03 1966-05-17 Ici Ltd Production of a sheath-core polyester filament of enhanced dyeability
US3386967A (en) * 1965-01-19 1968-06-04 Allied Chem Polycaproamide having excess number of carboxyl end groups over amino end groups
US3477899A (en) * 1964-06-25 1969-11-11 Bayer Ag Bifilar polyamide yarns and filaments
US3505165A (en) * 1964-05-15 1970-04-07 Bayer Ag Bifilar polyamide yarns and filaments
US3511815A (en) * 1968-05-08 1970-05-12 Ahmet Nuri Sayin Deep dyeing polycarbonamide filament
US3541198A (en) * 1963-12-07 1970-11-17 Keizo Ueda Process for manufacturing composite filaments
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US4251200A (en) * 1978-11-30 1981-02-17 Imperial Chemical Industries Limited Apparatus for spinning bicomponent filaments
DE3036931A1 (de) * 1979-10-04 1981-04-23 Viscosuisse S.A., Emmenbrücke Antistatischer zweikomponenten-faden und verfahren sowie vorrichtung zu seiner herstellung
US4309476A (en) * 1979-04-24 1982-01-05 Teijin Limited Core-in-sheath type aromatic polyamide fiber and process for producing the same
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US5888651A (en) * 1997-08-25 1999-03-30 Basf Corporation Colored bicomponent fibers
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US20070054104A1 (en) * 2005-03-25 2007-03-08 Ittel Steven D Spin-printing of electronic and display components
US20080153973A1 (en) * 2004-09-28 2008-06-26 Steven Dale Ittel Spin-Printing of Electronic and Display Components
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WO2018187192A1 (fr) 2017-04-03 2018-10-11 Georgia-Pacific Nonwovens LLC Structures absorbantes unitaires multicouches
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FR1154279A (fr) 1958-04-04
NL208424A (fr) 1900-01-01

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