US2137235A - Shaped articles from polymeric materials - Google Patents

Shaped articles from polymeric materials Download PDF

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Publication number
US2137235A
US2137235A US125887A US12588737A US2137235A US 2137235 A US2137235 A US 2137235A US 125887 A US125887 A US 125887A US 12588737 A US12588737 A US 12588737A US 2137235 A US2137235 A US 2137235A
Authority
US
United States
Prior art keywords
filaments
polyamide
cold
filament
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US125887A
Other languages
English (en)
Inventor
Wallace H Carothers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US125887A priority Critical patent/US2137235A/en
Priority to US125926A priority patent/US2212772A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to DEP75583D priority patent/DE752536C/de
Priority to GB19921/37A priority patent/GB501197A/en
Priority to GB4634/39A priority patent/GB504344A/en
Priority to FR824548D priority patent/FR824548A/fr
Publication of US2137235A publication Critical patent/US2137235A/en
Application granted granted Critical
Priority to US273807A priority patent/US2238694A/en
Priority to US284065A priority patent/US2212770A/en
Priority to FR51149D priority patent/FR51149E/fr
Priority to DEI67338A priority patent/DE743508C/de
Priority to GB11623/40A priority patent/GB542509A/en
Priority to FR918711D priority patent/FR918711A/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
    • B02B1/00—Preparing grain for milling or like processes
    • 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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling drums
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62M—RIDER PROPULSION OF WHEELED VEHICLES OR SLEDGES; POWERED PROPULSION OF SLEDGES OR SINGLE-TRACK CYCLES; TRANSMISSIONS SPECIALLY ADAPTED FOR SUCH VEHICLES
    • B62M9/00—Transmissions characterised by use of an endless chain, belt, or the like
    • B62M9/04—Transmissions characterised by use of an endless chain, belt, or the like of changeable ratio
    • B62M9/06—Transmissions characterised by use of an endless chain, belt, or the like of changeable ratio using a single chain, belt, or the like
    • B62M9/10—Transmissions characterised by use of an endless chain, belt, or the like of changeable ratio using a single chain, belt, or the like involving different-sized wheels, e.g. rear sprocket chain wheels selectively engaged by the chain, belt, or the like
    • B62M9/12—Transmissions characterised by use of an endless chain, belt, or the like of changeable ratio using a single chain, belt, or the like involving different-sized wheels, e.g. rear sprocket chain wheels selectively engaged by the chain, belt, or the like the chain, belt, or the like being laterally shiftable, e.g. using a rear derailleur
    • B62M9/131—Front derailleurs
    • 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
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/221—Preliminary treatments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
    • D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • 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
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/61—Processes of molding polyamide
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • 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
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/268—Monolayer with structurally defined element
    • 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
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, 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
    • 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
    • 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
    • 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
    • Y10T428/2978—Surface characteristic
    • 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
    • Y10T428/298—Physical dimension
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31739—Nylon type

Definitions

  • This invention relates to fiber-forming synthetic polymers and more particularly to an improved method for cold drawing filaments derived from synthetic linear condensation polyamides.
  • fiber-forming polyamides are made by subjecting bifunctional polyamide-forming reactants, which may be either a polymerizable amino acid or a suitable mixture of diamine and dibasic acid, to polymerizing conditions until the polyamide formed is capable of being drawn into filaments which possess the unusual property of being capable of being cold drawn, that is drawn or elongated under application of stress inthe solid state, into fibers showing upon X-ray examination orientation along the fiber axis.
  • bifunctional polyamide-forming reactants which may be either a polymerizable amino acid or a suitable mixture of diamine and dibasic acid
  • the oriented fibers are for most purposes more useful than the unoriented filaments from which they are prepared because the oriented fibers are more pliable, tough, and elastic.
  • the force required todraw the large filaments at ordinary speeds of drawing is often sufiicient to break the filaments rather than cold draw them.
  • This invention is particularly concerned with a process by means of which the filaments may be cold drawn upon the application of considerably less dra'wing force, thus making possible the ready production of oriented large filaments such as the bristles mentioned in the first mentioned application without resorting to the use of extremely high viscosity polyamides or the use of organic plasticizers which decrease the softening temperature and affect the solubility of the bristle.
  • An object of this invention is to improve the properties of filaments derived from synthetic linear condensation polymers.
  • a further object is to provide an improved process for preparing oriented synthetic linear condensation polyamide filaments.
  • a further object is to improve the drawability of polyamide filaments.
  • a still further object is the manufacture of oriented large diameter filaments or bristles. Other objects will appear hereinafter.
  • filament refers to both the oriented and unoriented filaments or threads which are prepared from these polymers regardless of whether the filaments or threads are long (continuous) or short (staple), while the term fiber refers more specifically to the oriented filaments or threads.
  • the filaments refers to both the oriented and unoriented filaments or threads which are prepared from these polymers regardless of whether the filaments or threads are long (continuous) or short (staple), while the term fiber refers more specifically to the oriented filaments or threads.
  • the filaments refers to both the oriented and unoriented filaments or threads which are prepared from these polymers regardless of whether the filaments or threads are long (continuous) or short (staple), while the term fiber refers more specifically to the oriented filaments or threads.
  • the filaments refers to both the oriented and unoriented filaments or threads which are prepared from these polymers regardless of whether the filaments or threads are long (continuous) or short (staple), while the term fiber refers more specifically to the oriented
  • molten polymer may be prepared by the processes of dry or wet spinning or they may be prepared directly from the molten polymer.
  • the hydroxylated non-solvent with which the filaments are moistened or soaked before cold drawing is-preferably water but may be one of various other liquid non-solvents which contain an hydroxyl group.
  • the term nonsolvent as applied to these agents indicates that they do not dissolve the polyamide under the conditions of operation.
  • These liquid non-solvents include alcohols, particularly the lower aliphatic alcohols, glycols, hydroxy esters, hydroxy ketones, and the like. These liquids may be used alone, in admixture, or diluted with water. They may also be used with non-hydroxylated compounds such as acetone, dio-xan, ethyl acetate, and ether. Small amounts of polyamide solvents. e. g., phenols, and formic acids, may also be added.
  • the non-solvent em- .ployed may containforeign materials, such as wetting agents, salts, dyes, dye assistants, etc.
  • the most pronounced effects are obtained by treating the polyamide filament with the hydroxylated non-solvent until the latter has penetrated throughout the entire filament, i. e., until the filament is substantially saturated.
  • the time required for this purpose is dependent among other things upon the diameter of the filament and the nature of the liquid non-solvent.
  • the diameter of the final product (cold drawn fiber) wfll usually be in the neighborhood of 0.000l-0.00l5 inch, corresponding roughly to 0.1- denier, the time required for saturation is very short.
  • the desired effect can be obtained by spraying a filament with water and drawing immediately.
  • the soaking time can be shortened by using the liquid at a somewhat elevated temperature.
  • water at '75 to 100 C. acts more rapidly than cold water.
  • elevated temperatures it is desirable not to prolong the soaking after saturation has been attained.
  • the filament be drawn while wet. This does not mean that the filament must be drawn immediately upon removal from the liquid in which it has been soaked. If the filament is removed from the liquid and then kept in a moist atmosphere, 1. e., in air of high relative humidity, it can be kept almost indefinitely without losing its improved drawing qualities.
  • the drawing may also be applied while the filament is drying. It is within the scope of this invention to cold draw filaments which have been only partly saturated with the liquid medium. If desired, the filaments can be drawn while in the liquid medium.
  • the force required to draw the wet filaments is much less than that required to draw dry filaments, often A; to 7, less. That water should have such a remarkable effect on the drawing qualities of the polyamide filaments is very surprising, for water does not dissolve or noticeably swell. the filaments.
  • the amount of water absorbed on complete saturation is generally in the neighborhood of 6% based on the weight of the dry filaments.
  • marked improvements in drawing qualities are obtained even though the filament is not completely saturated.
  • the present invention as previously mentioned, is particularly advantageous in working with large filaments.
  • filaments having a diameter above 0.025 inch cannot generally be drawn at ordinary speeds due to breakage unless they have been penetrated with a liquid of the type described above.
  • the size of filaments which can be drawn without pretreatment is dependent among other things upon the method by which they are prepared and upon the nature of the polymer, particularly its intrinsic viscosity,
  • m is the viscosity of a dilute m-cresol solution of the polyamide divided by the viscosity of m-cresol in the same units and at the same temperature
  • C is the concentration in grams of polyamide per 100 cc. of solution.
  • the strength of the filaments increases with the intrinsic viscosity.
  • Polyamides having intrinsic viscosities above 0.8 are most suitable for the preparation of large filaments of the bristle type.
  • Filaments of diameter as high as 0.025 can be but seldom cold drawn without breakage unless pretreated with an hydroxylated non-solvent, and in the absence of this treatment filaments oi the mentioned diameter can be drawn only under aromas 4 especially favorable conditions, e. 3., when modified with plasticizers.
  • filaments having a diameter as low as 0.015 inch frequently give trouble in cold drawing unless they are pretreated with water. This fact is illustrated in Example III below.
  • Example I An undrawn filament of 0.024 inch diameter obtained from polyhexamethylene adipamide of intrinsic viscosity 0.83 was cut in samples 12 inches long. After soaking in various hydroxylated non-solvents for 36 hours at approximately 25 0., the samples were tested on a Scott tester with the results indicated below:
  • Example III A portion of a filament having a diameter of 0.016 inch prepared from polyhexamethylene adipamide of intrinsic viscosity 0.98 was soaked in cold water for 72 hours and then cold drawn with-the aid of a Scott tester. The force required to cold draw the filament was about 0.45 lb. Another sample of the same filament, which had been soaked in ethyl alcohol for 72 hours, was found to cold draw under a force of about 0.7 lb. 0n the other hand, untreated samples oi the same filament usually broke without drawing when subjected to stress in the Scott tester, generally at a force in the neighborhood of 1.5 lb.
  • This invention is not limited to the use of filaments, but is applicable broadly to shaped articles or products capable of undergoing cold drawing, regardless of whether the drawing is to be applied in one direction or in more than one direction.
  • additional examples of such products might ,be mentioned ribbons, bands, foils, and films.
  • cold drawing is facilitated by pretreating the products with water or some other hydroxylated non-solvent.
  • the oriented products in general have more desirable properties than the unoriented products I from which they are derived.
  • a valuable class of fiber-forming polyamides for the preparation of filaments, ribbons, bands, foils, and other products with which this invention is concerned are those derived from diamines of formula NH2CH2RCH2NH2 and dicarboxylic acids of formula HOOCCHzR'CHzCOOH or amids-forming derivatives thereof, in which R and R are divalent hydrocarbon radicals free from olefinic and acetylenic unsaturation and in which R has a chain length of at least two carbon atoms.
  • R is (CH2)s and R. is (CH2)v, wherein s and y are integers and x is at least two.
  • polystetramethylene adipamide examples of polyamides which fall within one or both of these groups might be mentioned in addition to polyhexamethylene adipamide cited in the foregoing examples, polytetramethylene adipamide, polytetramethylene suberamide, polytetramethylene sebacamide, polypentamethylene sebacamide, polyhexamethylene sebacamide, polyhexarnethylene ,s-methyl adipamide, polyoctamethylene adipamide, polydecamethylene adipamide; polydecamethylene pphenylenediacetamide, and poly-p-xylylene sebacamide.
  • this invention is applicable also to fiber-forming polyamides derived from polymerizable monoaminomonocarboxylic acids and their amideforming derivatives.
  • polyamides such polyamides might be mentioned the polymers derived from G-aminoc'aproic acid, 9-aminonoanoic acid, and ll-aminoundecanoic acid. It is also within the scope of this invention to draw wet filaments and the like derived from a mixture of fiber-forming polyamides or from interpolyamides, i. e polyamides prepared from a mixture of polyamide-forming reactants, e. g., a mixture of two or more diamines with one or more dicarboxylic acids, or a mixture of?1 dlamine, a. dicarboxyllc acid, and an amino ac
  • This invention is not limited to the cold draw ing of filaments, etc., consisting solely of synthetic w polymers. Other materials such as plasticizers,
  • a polyamide filament containing 3% titanium dioxide as delusterant is more readily drawn when wet than when dry.
  • the foreign material when present in moderate amounts, does not interfere with the cold drawing operation .or the beneficial effect of the water thereon.
  • this invention provides a simple and economical process for improving the drawing qualities of synthetic linear condensation polymer filaments, foils, ribbons, films, and the like. It is especially useful in the preparation of large oriented polyamide filaments, e. g., bristles, since such large filaments cannot ordinarily be cold drawn by the methods heretofore described.
  • An improved method for cold drawing shaped articles derived from fiber-forming synthetic polymers which comprises wetting the article with an hydroxylated non-solvent for the polymer, and then applying sufiicient stress to the article to effect cold drawing.
  • a process for manufacturing shaped articles which comprises forming such articles from fiberforming synthetic polyamides, substantially saturating the article with an hydroxylated non-solvent for the polyamide, and then applying sufiicient stress to the article to effect cold drawing.
  • a process for manufacturing artificial fibers which comprises forming a filament from a'fiberforming synthetic polyamide, wetting the filament with an hydroxylated non-solvent for the polyamide, and then cold drawing the filament.
  • a process for manufacturing artificial bristles which comprises forming from a fiber-form: 'ing synthetic polyamide a filament having a diameter such that when cold drawn the resulting diameter will be from 0.003 to 0.06 inch, substantially saturating the filament with an hydroxylated non-solvent for the polyamide, and then cold drawing the filament.
  • polyamide is the reaction product of a diamine and a substance of the class consisting-of dicarboxylic acids and amide-forming derivatives.
  • polyamide is obtainable from a diamine of the formula NHzCI-IzRCHzNI-Iz and a dicarboxylic acid of the formula HOOCCHsR'CHaCOOI-I, R and R being divalent hydrocarbon radicals free from oleflnic and acetylenlc unsaturation, and R having a chain length of at least two carbon atoms.
  • An improved method for cold drawing fiberforming synthetic linear condensation polyamides in the form of filaments, foils. ribbons, films and the like which comprises wetting said polyamide in such form with an hydroxylated non-solvent therefor and subjecting it to cold drawing.
  • a process for preparing fibers exhibiting orientation along the fiber axis which comprises cold drawing synthetic linear condensation polyamide filaments substantially saturated with water.

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Artificial Filaments (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Moulding By Coating Moulds (AREA)
US125887A 1937-02-15 1937-02-15 Shaped articles from polymeric materials Expired - Lifetime US2137235A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US125887A US2137235A (en) 1937-02-15 1937-02-15 Shaped articles from polymeric materials
US125926A US2212772A (en) 1937-02-15 1937-02-15 Synthetic polymers and shaped articles therefrom
DEP75583D DE752536C (de) 1937-02-15 1937-07-18 Verfahren zur Verbesserung der Eigenschaften faserbildender, durch Kondensation erhaeltlicher Linearpolymeren
GB19921/37A GB501197A (en) 1937-02-15 1937-07-19 Improvements in and relating to the production of artificial filaments, films and similar materials
GB4634/39A GB504344A (en) 1937-02-15 1937-07-19 Improvements in and relating to the production of artificial filaments, films and similar materials
FR824548D FR824548A (fr) 1937-02-15 1937-07-19 Perfectionnements aux matières artificielles
US273807A US2238694A (en) 1937-02-15 1939-05-15 Polymeric materials
US284065A US2212770A (en) 1937-02-15 1939-07-12 Process for forming films from synthetic linear polymers
FR51149D FR51149E (fr) 1937-02-15 1940-05-27 Perfectionnements aux matières artificielles
DEI67338A DE743508C (de) 1937-02-15 1940-07-04 Verfahren zur Herstellung von Filmen aus geschmolzenen linearen Polymeren, insbesondere Polyamiden
GB11623/40A GB542509A (en) 1937-02-15 1940-07-12 Transparent films of polymeric materials
FR918711D FR918711A (fr) 1937-02-15 1945-12-11 Substances polymères

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US125887A US2137235A (en) 1937-02-15 1937-02-15 Shaped articles from polymeric materials
US125926A US2212772A (en) 1937-02-15 1937-02-15 Synthetic polymers and shaped articles therefrom
US284065A US2212770A (en) 1937-02-15 1939-07-12 Process for forming films from synthetic linear polymers

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US273807A Expired - Lifetime US2238694A (en) 1937-02-15 1939-05-15 Polymeric materials
US284065A Expired - Lifetime US2212770A (en) 1937-02-15 1939-07-12 Process for forming films from synthetic linear polymers

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US273807A Expired - Lifetime US2238694A (en) 1937-02-15 1939-05-15 Polymeric materials
US284065A Expired - Lifetime US2212770A (en) 1937-02-15 1939-07-12 Process for forming films from synthetic linear polymers

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US2509740A (en) * 1942-11-03 1950-05-30 Du Pont Process for production of nylon of low thermoextensibility
US2509741A (en) * 1942-11-03 1950-05-30 Du Pont Production of filamentous structures
US2515175A (en) * 1946-01-19 1950-07-18 Fred Arbogast And Company Inc Leader for fishlines and method and apparatus for shaping the same
US2554564A (en) * 1947-06-24 1951-05-29 Celanese Corp Prestretching cellulose derivative yarns to increase tenacity
US2562373A (en) * 1945-09-19 1951-07-31 Orlan M Arnold Method of forming thin flexible polyamide articles
US2641081A (en) * 1950-11-14 1953-06-09 Francis M Boone Lure with improved weed guard
DE766120C (de) * 1941-06-19 1954-06-21 Ig Farbenindustrie Ag Verfahren zur Veredelung von Superpolyamiden aus ªÏ-Aminocarbonsaeuren
US2683101A (en) * 1950-10-07 1954-07-06 Atlas Powder Co Treated textiles
US2708805A (en) * 1952-12-19 1955-05-24 Hugh A Garvie Animated fish lures
DE935331C (de) * 1951-07-27 1955-11-17 Glanzstoff Ag Verfahren zur Polykondensation von Methylen-, Alkyliden- und Aralkyliden-bis-halogencarbonsaeureamiden
US2808622A (en) * 1955-09-23 1957-10-08 Polymer Corp Method of manufacturing nylon articles having improved dimensional stability
US3077004A (en) * 1956-03-23 1963-02-12 Du Pont Filament drawing
US3097415A (en) * 1959-02-20 1963-07-16 Acrylonitrile fiber and process for
US3102323A (en) * 1958-08-26 1963-09-03 Du Pont Textile
US3511677A (en) * 1963-02-28 1970-05-12 Du Pont Process for preparation of a sized zero-twist synthetic fiber yarn and product thereof
US4049766A (en) * 1974-12-09 1977-09-20 Akzona Incorporated Process for improving crystallinity in nylon 6
US20040253430A1 (en) * 1997-12-18 2004-12-16 Polk Dale E. Thermoplastic molding process and apparatus
US20130244047A1 (en) * 2010-06-23 2013-09-19 Dsm Ip Assets B.V. Film or plate
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same

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USRE23753E (en) * 1947-02-21 1953-12-15 Coated plastic products
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US2556666A (en) * 1948-03-23 1951-06-12 George H Snyder Hydraulic transmission
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US2627085A (en) * 1948-07-21 1953-02-03 Polymer Corp Apparatus for forming plastic strips
US2640817A (en) * 1948-07-26 1953-06-02 Nash Kelvinator Corp Antistatic coating for plastics
US2687673A (en) * 1949-04-04 1954-08-31 Boone Philip Textile material having oriented fibers
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US2690027A (en) * 1950-03-09 1954-09-28 John K Russell Floating tip for fishlines
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US2692182A (en) * 1951-04-14 1954-10-19 Rohm & Haas Durable, stiff finish for nylon and method for producing same
US2799133A (en) * 1951-05-24 1957-07-16 Clarence W Rose Drawable rope having pre-drawn segment and method for producing the same
US2770566A (en) * 1951-09-29 1956-11-13 Ritter Franz Method of bonding a polyamide layer to a polyvinyl chloride layer and products thus obtained
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US2728951A (en) * 1952-01-23 1956-01-03 Ici Ltd Process for quenching melt extruded film
US2736946A (en) * 1952-07-03 1956-03-06 Dow Chemical Co Polyacrylonitrile fibers having a scaly integument
US2728944A (en) * 1952-08-01 1956-01-03 Ici Ltd Production of artificial films
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US2801936A (en) * 1952-12-12 1957-08-06 American Motors Corp Acrylic resins bonded to polystyrene
US2821746A (en) * 1954-01-25 1958-02-04 Du Pont Apparatus for extruding films
DE1128970B (de) * 1954-02-02 1962-05-03 Du Pont Schlitzduese zur Herstellung von Folien mit Randwuelsten aus thermoplastischem Kunststoff
IT586979A (fr) * 1954-02-26 1900-01-01
US2774173A (en) * 1954-06-28 1956-12-18 Thienemann Heinz Tapered leader for fishing purposes from synthetic polymers
US2959570A (en) * 1954-06-30 1960-11-08 Onderzoekings Inst Res Process of extruding composition comprising a fiber forming linear condensation product and a thickening agent
DE1103877B (de) * 1955-02-02 1961-04-06 Goodyear Tire & Rubber Verfahren zur Herstellung eines Kordgewebes aus Polyamidfasergarn
DE1089307B (de) * 1955-02-03 1960-09-15 Walter Zehnder Hensler Vorrichtung zum Auftragen von Lack, insbesondere auf Moebelteile
DE1172164B (de) * 1955-05-24 1964-06-11 Bayer Ag Verfahren zum Herstellen von gut haftenden Schutzueberzuegen aus natuerlichem oder synthetischem Kautschuk auf Formteilen aus Polyamiden
NL208424A (fr) * 1955-06-30 1900-01-01
GB830442A (en) * 1955-06-30 1960-03-16 Du Pont Improvements in or relating to the production of shaped articles, particularly filaments, of synthetic polymers by melt extrusion processes
NL91295C (fr) * 1956-05-23
US3024081A (en) * 1956-05-28 1962-03-06 Dow Chemical Co Process for preparing coated synthetic fibers from normally crystalline polymers
US2936492A (en) * 1956-10-04 1960-05-17 Du Pont Method of casting crystalline polymer film
US2861319A (en) * 1956-12-21 1958-11-25 Du Pont Intermittent core filaments
DE1234974B (de) * 1957-01-11 1967-02-23 Mortimer Mark Marks Verfahren zur kontinuierlichen Herstellung von Kunststoffilmen und Vorrichtung zur Durchfuehrung des Verfahrens
DE1054233B (de) * 1957-04-27 1959-04-02 Basf Ag Verfahren zur beschleunigten Regelung des Feuchtigkeitsgehaltes von Polyamidformkoerpern
US3027602A (en) * 1957-12-16 1962-04-03 Du Pont Process for preparing glossy, transparent nylon films by melt extrusion of superpolyamide resins
US3083118A (en) * 1958-03-04 1963-03-26 Tee Pak Inc Method of depositing a polymer of olefinically unsaturated monomer within a polymeric material and the resulting product
DE1179354B (de) * 1958-06-19 1964-10-08 Ici Ltd Getriebe zum Antrieb von Giesstrommeln zur Herstellung von Filmen aus organischem thermoplastischem Kunststoff
US3121915A (en) * 1958-06-25 1964-02-25 Nat Distillers Chem Corp Art of extruding thermoplastic sheets
US3133138A (en) * 1958-12-19 1964-05-12 Du Pont Stretching and heat crystallization of poly(meta-phenylene isophthalamide) fibers
US3090076A (en) * 1959-05-20 1963-05-21 Nat Distillers Chem Corp Apparatus and process for high speed extrusion casting
BE602721A (fr) * 1960-04-19
US3078544A (en) * 1960-05-19 1963-02-26 Du Pont Crimpable synthetic filaments and process of manufacturing same
DE1177279B (de) * 1960-07-11 1964-09-03 Spinstofffabrik Zehlendorf Ag Verfahren zur Herstellung gefaerbter Spinnerzeugnisse aus Polyolefinen
US3079219A (en) * 1960-12-06 1963-02-26 Du Pont Process for wet spinning aromatic polyamides
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US3141194A (en) * 1962-02-09 1964-07-21 Avisun Corp Gas delivery nozzle for film casting apparatus
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE766120C (de) * 1941-06-19 1954-06-21 Ig Farbenindustrie Ag Verfahren zur Veredelung von Superpolyamiden aus ªÏ-Aminocarbonsaeuren
US2509740A (en) * 1942-11-03 1950-05-30 Du Pont Process for production of nylon of low thermoextensibility
US2509741A (en) * 1942-11-03 1950-05-30 Du Pont Production of filamentous structures
US2423182A (en) * 1943-04-29 1947-07-01 Du Pont Method of cold-drawing tapered filaments
US2562373A (en) * 1945-09-19 1951-07-31 Orlan M Arnold Method of forming thin flexible polyamide articles
US2515175A (en) * 1946-01-19 1950-07-18 Fred Arbogast And Company Inc Leader for fishlines and method and apparatus for shaping the same
US2554564A (en) * 1947-06-24 1951-05-29 Celanese Corp Prestretching cellulose derivative yarns to increase tenacity
US2683101A (en) * 1950-10-07 1954-07-06 Atlas Powder Co Treated textiles
US2641081A (en) * 1950-11-14 1953-06-09 Francis M Boone Lure with improved weed guard
DE935331C (de) * 1951-07-27 1955-11-17 Glanzstoff Ag Verfahren zur Polykondensation von Methylen-, Alkyliden- und Aralkyliden-bis-halogencarbonsaeureamiden
US2708805A (en) * 1952-12-19 1955-05-24 Hugh A Garvie Animated fish lures
US2808622A (en) * 1955-09-23 1957-10-08 Polymer Corp Method of manufacturing nylon articles having improved dimensional stability
US3077004A (en) * 1956-03-23 1963-02-12 Du Pont Filament drawing
US3102323A (en) * 1958-08-26 1963-09-03 Du Pont Textile
US3097415A (en) * 1959-02-20 1963-07-16 Acrylonitrile fiber and process for
US3511677A (en) * 1963-02-28 1970-05-12 Du Pont Process for preparation of a sized zero-twist synthetic fiber yarn and product thereof
US4049766A (en) * 1974-12-09 1977-09-20 Akzona Incorporated Process for improving crystallinity in nylon 6
US20040253430A1 (en) * 1997-12-18 2004-12-16 Polk Dale E. Thermoplastic molding process and apparatus
US20130244047A1 (en) * 2010-06-23 2013-09-19 Dsm Ip Assets B.V. Film or plate
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same
US10589474B2 (en) 2011-01-12 2020-03-17 Compagnie Chomarat Methods for manufacturing sublaminate modules and forming composite laminated structures from the same

Also Published As

Publication number Publication date
FR824548A (fr) 1938-02-10
US2212772A (en) 1940-08-27
GB542509A (en) 1942-01-13
FR51149E (fr) 1941-08-08
US2238694A (en) 1941-04-15
FR918711A (fr) 1947-02-17
GB504344A (en) 1939-04-19
DE743508C (de) 1943-12-28
GB501197A (en) 1939-02-20
US2212770A (en) 1940-08-27
DE752536C (de) 1963-08-20

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