EP3146095A1 - Fil à âme et enveloppe, procédé de production d'un fil à âme et enveloppe, produit médical et trousse médicale - Google Patents

Fil à âme et enveloppe, procédé de production d'un fil à âme et enveloppe, produit médical et trousse médicale

Info

Publication number
EP3146095A1
EP3146095A1 EP15722186.2A EP15722186A EP3146095A1 EP 3146095 A1 EP3146095 A1 EP 3146095A1 EP 15722186 A EP15722186 A EP 15722186A EP 3146095 A1 EP3146095 A1 EP 3146095A1
Authority
EP
European Patent Office
Prior art keywords
thread
core
core diameter
diameter
thickness
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.)
Withdrawn
Application number
EP15722186.2A
Other languages
German (de)
English (en)
Inventor
Martin Dauner
Erhard Müller
Sven Oberhoffner
Martin Hoss
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.)
ITV DENKENDORF PRODUKTSERVICE GmbH
Original Assignee
ITV DENKENDORF PRODUKTSERVICE GmbH
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
Application filed by ITV DENKENDORF PRODUKTSERVICE GmbH filed Critical ITV DENKENDORF PRODUKTSERVICE GmbH
Publication of EP3146095A1 publication Critical patent/EP3146095A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods
    • A61B17/04—Surgical instruments, devices or methods for suturing wounds; Holders or packages for needles or suture materials
    • A61B17/06—Needles ; Sutures; Needle-suture combinations; Holders or packages for needles or suture materials
    • A61B17/06166—Sutures
    • 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
    • D01D5/20—Formation of filaments, threads, or the like with varying denier along their length
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods
    • A61B2017/00831—Material properties
    • A61B2017/00964—Material properties composite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods
    • A61B17/04—Surgical instruments, devices or methods for suturing wounds; Holders or packages for needles or suture materials
    • A61B17/06—Needles ; Sutures; Needle-suture combinations; Holders or packages for needles or suture materials
    • A61B17/06004—Means for attaching suture to needle
    • A61B2017/06028—Means for attaching suture to needle by means of a cylindrical longitudinal blind bore machined at the suture-receiving end of the needle, e.g. opposite to needle tip
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods
    • A61B17/04—Surgical instruments, devices or methods for suturing wounds; Holders or packages for needles or suture materials
    • A61B17/06—Needles ; Sutures; Needle-suture combinations; Holders or packages for needles or suture materials
    • A61B17/06166—Sutures
    • A61B2017/06176—Sutures with protrusions, e.g. barbs

Definitions

  • the invention relates to a core-sheath thread, a method for producing such a thread and a medical product and a medical kit.
  • melt-blow nonwovens are known as coalescers, wherein the nonwoven fabric is formed from meltblown polymer fibers, the diameter of individual fibers varying along their length such that a single fiber has different diameters at different points along its length Length.
  • the typical diameter of the individual filaments in melt-blow nonwovens is 1 ⁇ and ⁇ ⁇ .
  • WO 99/15470 A1 are optical fibers of silicon dioxide, which have a varying diameter due to the use of different drawing rates during the manufacturing process.
  • US 4,631,162 relates to irregular multifilament hollow fibers which have sinusoidal filament constituents.
  • GB 535,263 discloses the production of tapered filaments for bristles and fishing lines. To produce the filaments, the filament material throughput and the take-off speed of the resulting filaments are varied.
  • the publications GB 990,780 and GB 813,857 each show multifilaments each having a diameter varying in the longitudinal direction.
  • jet nozzles of variable diameter GB 990,780
  • guide elements which change the way from the nozzle to the winding in the short term (GB 813,857) are used.
  • the subject of EP 0 270 019 A2 is a multifilament yarn which consists of two ribbon-shaped, filament-like constituents, at least one filamentous core constituent and, in some cases, at least two middle, filamentous components is composed.
  • the core component extends sinusoidally along the longitudinal axis of the filament.
  • US 2012/0010656 A1 relates to a surgical suture having suture portions that differ in diameter.
  • the US 2013/0101844 A1 relates to profiled individual filaments which are glued together by means of a spinning process in a stochastic, so random manner, whereby different overall cross-sectional structures can be formed.
  • the invention proposes a thread with a thread core and a sheath surrounding the thread core, i. a so-called core-sheath thread (thread with a core-sheath structure or with a core-sheath structure) before.
  • the thread core may be partially, in particular only partially, or completely, i. full surface or continuous, be surrounded by the mantle.
  • the thread according to the invention is characterized in particular in that it has at least one thread longitudinal section, along which the thread core has a longitudinal axis of the thread. dens varying (changing) diameter and / or the sheath have a varying in the longitudinal direction of the thread (changing) thickness.
  • the thread is characterized in particular by the fact that it has at least one thread longitudinal section, along which the thread core diameter and / or the jacket thickness vary (change).
  • the at least one thread longitudinal section with the varying thread core diameter and / or the varying jacket thickness as a result represents a gradient region extending in the longitudinal direction of the thread in relation to the thread core diameter and / or the jacket thickness.
  • the invention is based, in particular, on the surprising finding that core-sheath threads having a varying ratio of thread core diameter to sheath thickness, in particular core-sheath threads having at least one gradient region extending in the longitudinal direction of the thread, both with respect to the thread core diameter and in terms on the jacket thickness, various uses, both in the technical and medical field, which will be discussed in more detail below.
  • the thread has at least one thread longitudinal section along which both the thread core diameter and the jacket thickness vary in the longitudinal direction of the thread.
  • At least one thread longitudinal section generally means in the sense of the present invention a thread longitudinal section or a plurality of thread longitudinal sections, ie two or more thread longitudinal sections has a plurality of corresponding thread longitudinal sections.
  • the thread core diameter and / or the jacket thickness can in a further embodiment, continuously, in particular linear or substantially linear, or discontinuous, in particular stepwise, vary, preferably increase or decrease.
  • a linear or substantially linear increase or decrease in the thread core diameter and / or the jacket thickness are particularly preferred according to the invention.
  • the increase or decrease in the thread core diameter and / or the jacket thickness along the at least one thread longitudinal section in an unstretched access is subject to stood the thread of an absolute slope of 20 mm / cm to 0.01 mm / cm, in particular 15 mm / cm to 0.02 mm / cm, preferably 10 mm / cm to 0.02 mm / cm.
  • absolute slope is understood to mean the absolute measure, that is to say independent of the sign, of the steepness of a straight line or a curve which characterizes the variation of the thread diameter.
  • the absolute slope values can be much smaller.
  • the at least one thread longitudinal section may have a length fraction of 1% to 50%, in particular 1% to 30%, preferably 1% to 20%, based on the total length of the thread.
  • the length portions described in this paragraph are particularly advantageous for medical uses of the thread.
  • the at least one thread longitudinal section has a length fraction of 50% to 99%, in particular 70% to 99%, preferably 80% to 99%, based on the total length of the thread.
  • the thread also has at least one thread longitudinal section, along which the thread core diameter is continuous and / or the jacket thickness is constant or substantially constant throughout.
  • the at least one longitudinal thread section may have a length fraction of 50% to 99%, in particular 70% to 99%, preferably 80% to 99%, and for non-medical uses of the thread a length fraction of 1% to 50%, in particular 1% to 30%, preferably 1% to 20%, in each case based on the total length of the thread.
  • the thread may further comprise at least one longitudinal thread section, along which the thread core diameter and the jacket thickness are respectively constant or substantially constant throughout, the thread core diameter having its maximum and the shell thickness having its minimum.
  • the thread may further comprise at least one longitudinal thread section, along which the thread core diameter and the jacket thickness are each continuously constant or substantially constant, wherein the thread core diameter is greater than the shell thickness.
  • the thread may further comprise at least one thread longitudinal section, along which the thread core diameter and the jacket thickness are respectively constant or substantially constant throughout, the thread core diameter having its minimum and the jacket thickness having its maximum.
  • the thread may further comprise at least one longitudinal thread section, along which the thread core diameter and the jacket thickness are each continuously constant or substantially constant, wherein the thread core diameter is smaller than the shell thickness.
  • the thread may further comprise at least one longitudinal thread section along which the thread core is exposed, i. the thread has no thread core.
  • the core-sheath structure of the thread is not formed continuously over the entire thread length.
  • the thread has a multiplicity of thread longitudinal sections, along which the thread core diameter and / or the jacket thickness, preferably the thread core diameter and the jacket thickness, vary, and preferably a multiplicity of thread longitudinal sections, along which the thread core diameter and / or the jacket thickness, preferably the thread core diameter Thread core diameter and the shell thickness (each) are constant or substantially constant throughout, and optionally a plurality of thread longitudinal sections, along which exposes the string core, on.
  • the thread longitudinal sections described in the previous paragraph may occur singly or periodically along the thread.
  • the thread preferably has an alternating sequence of thread longitudinal sections, along which the thread core diameter and / or the jacket thickness, preferably the thread core diameter and the jacket thickness, vary, and of thread longitudinal sections, along which the thread core diameter and / or the jacket thickness, preferably the thread core diameter and the jacket thickness , (each) are continuously constant or substantially constant.
  • the thread has a preferably recurring sequence of the following thread longitudinal sections in the sequence a) - d): a) thread longitudinal section, along which the thread core diameter and the jacket thickness are each constant or substantially constant, the thread core diameter has its maximum and the shell thickness has its minimum, preferably the thread core diameter is greater than the shell thickness, b) thread longitudinal section, along which the thread core diameter decreases and preferably the coat thickness increases correspondingly; c) the thread longitudinal section along which the thread core diameter and the jacket thickness are respectively constant or substantially constant, the thread core diameter having its minimum and the jacket thickness having its maximum, preferably the thread core diameter being smaller than the jacket thickness, and d ) Thread longitudinal section, along which the thread core diameter increases and the jacket thickness preferably decreases accordingly.
  • the total length of the sequence of the thread longitudinal sections a) - d) in the unstretched state of the thread can be ⁇ 50 cm, in particular ⁇ 35 cm, preferably ⁇ 20 cm. These overall lengths are particularly advantageous in medical uses of the thread.
  • the thread may in principle have a circular cross-section or a non-circular cross-section, in particular an oval, ellipsoidal or polygonal, such as triangular, rectangular, square, rhombic, pentagonal, hexagonal or star-shaped cross-section.
  • the thread in particular the thread core diameter and / or the jacket thickness, may in principle comprise a resorbable, partially absorbable or non-resorbable polymer or a corresponding polymer blend (blend) or be formed from such a polymer or such a polymer blend.
  • the polymer may be a homo- and / or copolymer.
  • the copolymer may in turn be selected from the group comprising random copolymer, segmented copolymer (block copolymer), graft copolymer and mixtures (blends) thereof.
  • block copolymer segmented copolymer
  • graft copolymer graft copolymer and mixtures (blends) thereof.
  • the term "copolymer” is to be understood as meaning a polymer which is composed of at least two recurring monomer units.
  • the term "copolymer” is understood as meaning, for example, bipolymers, ie polymers which are composed of two recurring monomer units, and terpolymers, ie, polymers composed of three repeating monomer units.
  • the thread comprises at least one polymer or is formed from at least one polymer which is selected from the group comprising polyolefins, polyamides, polyesters, polycarbonates, polyurethanes, in particular thermoplastic polyurethanes, polyhydroxyalkanoates, copolymers thereof, salts thereof, stereoisomers thereof and Mixtures (blends) thereof.
  • the thread may comprise at least one polymer or be formed from at least one polymer selected from the group consisting of polyethylene, low density polyethylene, high density polyethylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polypropylene, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, nylon 6, Nylon 6-6, nylon 6-12, nylon 12, polytetrafluoroethylene, polyvinylidene difluoride, polytetrafluoropropylene, polyhexafluoropropylene, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, polyglycolic acid, polylactic acid, polydioxanone, poly-3-hydroxybutyric acid, poly-4 hydroxybutyric acid, polytrimethylene carbonate, poly- ⁇ -caprolactone, copolymers thereof, salts thereof, stereoisomers thereof and mixtures (blends) thereof.
  • polyethylene low density polyethylene
  • a preferred terpolymer for the thread is composed for example of recurring glycolide, ⁇ -caprolactone and Trimethylencarbonatumbleen and commercially available under the name Monosyn ® .
  • both the thread core and the sheath are formed from a resorbable polymer, wherein the polymers for the thread core and the sheath differ in terms of their degradation rate.
  • the thread according to the invention can thus have a degradation gradient formed in the longitudinal direction of the thread.
  • the thread has over the thread length preferably continuously constant or substantially constant overall diameter.
  • total diameter is to be understood as the diameter which results from the sum of the thread core diameter and the jacket thickness.
  • the thread in particular the thread core and / or the jacket, is provided with at least one additive.
  • either only the thread core or only the jacket is provided with at least one additive. That way you can form with particular advantage additive gradients, which extend in the longitudinal direction of the thread. According to the statements made so far, such a gradient may vary continuously, preferably linearly or substantially linearly, or discontinuously, in particular stepwise, preferably increase or decrease.
  • the at least one additive can be incorporated into the thread, in particular the thread core and / or the sheath.
  • the at least one additive may for example be part of a polymer compound which is used for producing the thread, in particular the thread core and / or the shell thickness.
  • the at least one additive can coat the thread or be part of a thread coating.
  • the at least one additive is in particular selected from the group consisting of antimicrobial, in particular antibiotic, active ingredients, anti-inflammatory agents, disinfecting agents, analgesic agents, scar-reducing agents, cytostatics, pore-forming substances / foaming agents (chemical or physical), plasticizers, lubricants, dyes, Pigments, radioactive substances, radiopaque substances, nucleating agents, matting agents, density-influencing substances, conductive substances, refractive substances, magnetizable substances and mixtures thereof.
  • antimicrobial in particular antibiotic, active ingredients, anti-inflammatory agents, disinfecting agents, analgesic agents, scar-reducing agents, cytostatics, pore-forming substances / foaming agents (chemical or physical), plasticizers, lubricants, dyes, Pigments, radioactive substances, radiopaque substances, nucleating agents, matting agents, density-influencing substances, conductive substances, refractive substances, magnetizable substances and mixtures thereof.
  • resistance gradients can be formed by an additive with conductive substances, which can be used, for example, for the production of so-called "smart textiles".
  • Additive dyeing allows the production of effect threads, in particular surgical threads with tinning effects. This is especially true in cases where the ratio of thread core diameter varies to coat thickness and in particular the thread core and the coat are colored differently.
  • the thread has anchoring structures.
  • the anchoring structures are preferably intended for anchoring in biological, in particular human and / or animal, tissues.
  • the anchoring structures preferably protrude from the thread surface.
  • the anchoring structures are preferably formed by means of incisions in the thread.
  • the anchoring structures can be formed by means of a cutting depth that is greater than the jacket thickness, so that the thread core is also incised.
  • the anchoring structures can be formed in thread longitudinal sections with a minimum thread core diameter by means of a depth of cut, which corresponds at most to the shell thickness, preferably smaller than the shell thickness.
  • the thread core is not incised in this case, which can be realized with particular advantage greater differences in the stiffness of the anchoring structures.
  • the anchoring structures can in principle be formed in at least one row-shaped arrangement, staggered arrangement, zigzag arrangement, spiral arrangement, randomized arrangement or in combinations thereof in the longitudinal and / or transverse direction, preferably in the longitudinal direction, on the thread surface.
  • the anchoring structures can furthermore have a unidirectional and / or multidirectional, in particular bidirectional, arrangement on the thread surface.
  • the arrangement of the anchoring structures can in this case in particular in the longitudinal and / or transverse direction of the thread, preferably in the longitudinal direction of the thread, be formed.
  • Unidirectionally arranged anchoring structures are characterized in the sense of the present invention in that they are oriented only in one direction of the thread.
  • Bidirectionally arranged anchoring structures are characterized in the sense of the present invention, however, by the fact that a part of the anchoring structures are oriented in one direction and another part of the anchoring structures in a direction opposite thereto.
  • a part of the anchoring structures can be oriented along a first thread longitudinal section in the direction of a second thread longitudinal section, while another part of the anchoring structures can be oriented along the second thread longitudinal section in the direction of the first thread longitudinal section.
  • a unidirectional or bidirectional design of the anchoring structures in the longitudinal direction of the thread is preferred.
  • the thread has on its surface two rows of bidirectionally arranged anchoring structures, which are each arranged offset in the longitudinal direction of the thread and in particular in its circumferential direction by 180 degrees.
  • the anchoring structures barb, coat of arms, shield, dandruff, wedge, thorn, especially rosendornen-, sting, arrow, V, and / or W-shaped.
  • the anchoring structures are in the form of barbs.
  • the anchoring structures are each formed pointed or pointed at their protruding from the thread surface ends.
  • the anchoring structures are formed only on one or more thread longitudinal sections whose thread core diameter is greater than its shell thickness.
  • the anchoring structures may in particular be formed on one or more thread longitudinal sections, along which the thread core diameter and the jacket thickness are respectively constant or substantially constant, with its thread core diameter being greater than its shell thickness.
  • the anchoring structures may be formed on a section of one or more filament longitudinal sections along which the filament core diameter and / or the jacket thickness, preferably the filament core diameter and the jacket thickness, vary.
  • the thread can basically be stretched or unstretched.
  • the thread may be a monofilament or multifilament, in particular a braided multifilament.
  • the thread can furthermore be in the form of an endless thread, in particular continuous monofilament, or of a cut-to-length thread.
  • the thread of the invention may further be a solid thread, i. around a thread without lumen, act.
  • the thread of the invention may be a hollow thread, i. a thread with a lumen, preferably with a lumen extending in the longitudinal direction of the thread act.
  • the lumen is usually formed within the thread core.
  • the thread core is only partially surrounded by the jacket.
  • the thread can have thread longitudinal sections without a jacket, so-called stripped thread longitudinal sections.
  • the thread at least at one end of the thread, in particular at both ends of the thread, one or possibly more stripped thread longitudinal sections.
  • the thread according to the invention opens up manifold fields of application, both in the technical and in the medical field.
  • the thread is generally suitable for the production of technical textiles, in particular in the form of woven, knitted, knitted, laid or nonwoven fabrics.
  • the thread according to the invention is suitable, for example, for the production of textiles with light-optical effects which can be used, for example, as automotive textiles, home textiles and / or for the decoration of furniture and rooms.
  • the thread is particularly preferably intended for use as a medical, in particular surgical, thread (suture).
  • the thread is preferably a medical, in particular surgical, thread (medical, in particular surgical, suture material). Further medical uses will be explained in more detail below.
  • the invention relates to a method for producing a thread, in particular a thread according to the first aspect of the invention.
  • a thread core component and a sheath component are formed from a shaping outlet opening of an extrusion apparatus to form a thread having a thread core and a sheath surrounding the thread core, ie, forming a thread having a core-sheath structure. coextruded.
  • the method according to the invention is characterized in particular by the fact that the mass throughput of the thread core component and / or the shell component varies in order to form a varying (changing) thread core diameter in the longitudinal direction of the thread and / or to form a (varying) shell thickness varying in the longitudinal direction of the thread / or the thread is withdrawn after exiting the outlet opening at a varying (varying) speed.
  • the sheath may in principle partially, in particular only partially, or completely, that is to say in the thread core. completely or continuously, surrounded.
  • longitudinal thread segments can be formed, along which the thread core has a thickness varying in the longitudinal direction of the thread and / or the jacket has a varying thickness in the longitudinal direction of the thread ,
  • the diameter of the thread core component and / or the shell component may vary continuously, in particular linearly or substantially linearly, or discontinuously, in particular stepwise, preferably increase or decrease.
  • the total mass flow rate ie the sum of the mass flow rate of the thread core component and the mass flow rate of the shell component, is kept constant or substantially constant.
  • the thread preferably has at least one thread longitudinal section, along which the thread core diameter and / or the jacket thickness, preferably the thread core core diameter and the cladding thickness, vary in the longitudinal direction of the thread, and preferably at least one thread longitudinal section, along which the thread core diameter and / or the jacket thickness, preferably the thread core diameter and the shell thickness (each) are continuously constant or substantially constant on.
  • the mass flow rate of the thread core component and the mass flow rate of the sheath component can be varied, for example, in a contrasting manner, so that the total mass flow rate composed of the two partial mass flow rates remains constant or essentially constant at any time.
  • a lesser mass throughput of the thread core component can be compensated by a correspondingly higher mass throughput of the shell component, and vice versa.
  • the mass flow rate of the thread core component and / or the mass flow rate of the shell component can be varied periodically or occasionally.
  • the mass flow rate of the thread core component and / or the sheath component can be kept constant and varied or vice versa.
  • the inventively provided extrusion device usually includes an extruder for the thread core component and an extruder for the shell component. Both extruders can each be operated with their own spinning pump. Furthermore, the extrusion device expediently has a first melt channel for the thread core component and a second melt channel for the jacket component, which as a rule concentrically surrounds the first melt channel in the region of the spinneret. The first and the second melt channel expediently open into a common outlet opening of the extrusion device.
  • the extrusion device has a further melt channel, which is generally surrounded concentrically in the region of the spinneret by the first melt channel.
  • the additional melt channel is preferably run with a liquid or gaseous support medium, for example nitrogen.
  • the speed of a spinning pump responsible for the extrusion of the thread core component and / or the speed of a spinning pump responsible for the extrusion of the shell component are varied in a preferred embodiment.
  • the rotational speed of the spinning pump responsible for the extrusion of the yarn core component or the rotational speed of the spinning pump responsible for the extrusion of the sheath component is reduced. If, on the other hand, the mass throughput of the filament core component or sheath component is to be increased, the rotational speed of the spinning pump responsible for the extrusion of the filament core component or the rotational speed of the spinning pump responsible for the extrusion of the sheath component is increased.
  • the rotational speed of the spin pump responsible for the extrusion of the filament core component may be decreased from 10 revolutions / min. To 5 revolutions / min and, accordingly, the rotational speed of the spinning pump responsible for the extrusion of the shell component of FIG. 5 Revolutions / min increased to 10 revolutions / min.
  • the mass flow rate of the thread core component and / or the jacket component can be varied by controlling the mass flow rate within the aforementioned melt channels, for example by means of controllable switches which reduce or close the cross-sectional area of the melt channels and, if necessary, increase or open again, or by means of an adjustable bypass becomes.
  • the rotational speed of a godet responsible for the withdrawal of the yarn is varied.
  • the withdrawal speed of the thread can be varied periodically or occasionally.
  • the withdrawal speed of the thread in alternating sequence (substantially) can be kept constant and varied or vice versa.
  • the draw-off speed of the thread is increased while the mass throughput of the thread core component is lowered.
  • the drawing speed of the thread can be lowered while increasing the mass flow rate of the thread core component.
  • the at least one additive is added to the thread core component or sheath component, wherein the thread core and the sheath component can be formed either from the same polymer or from different polymers.
  • it can also be provided to form an additive gradient by adding at least one additive in varying amounts to the thread core component and / or sheath component.
  • the core component and / or the sheath component may in principle comprise a resorbable, partially absorbable or non-resorbable polymer or a corresponding polymer mixture (blend) or be formed from such a polymer or such a polymer mixture.
  • a resorbable, partially absorbable or non-resorbable polymer or a corresponding polymer mixture (blend) or be formed from such a polymer or such a polymer mixture.
  • the thread core component and / or the sheath component comprise at least one polymer or are formed from at least one polymer which is selected from the group comprising polyolefins, polyamides, polyesters, polycarbonates, polyurethanes, in particular thermoplastic polyurethanes, polyhydroxyalkanoates, copolymers thereof, salts thereof, Stereoisomers thereof and mixtures (blends) thereof.
  • the thread core component and / or the sheath component may comprise at least one polymer or be formed from at least one polymer which is selected from the group consisting of polyethylene, low density polyethylene, high density polyethylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polypropylene, polyethylene terephthalate, Polypropylene terephthalate, polybutylene terephthalate, nylon 6, nylon 6-6, nylon 6-12, nylon 12, polytetrafluoroethylene, polyvinylidene difluoride, polytetrafluoropropylene, polyhexafluoropropylene, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, polyglycolic acid, polylactic acid, polydioxanone, poly-3-hydroxybutyric acid, poly-4- hydroxybutyric acid, polytrimethylene carbonate, poly-e-caprolactone, copolymers thereof, salts thereof, stereoisomers thereof, and mixture
  • the thread can be left in an unstretched state.
  • the thread is drawn.
  • a stretching of the thread is preferably carried out under heat, in particular in a temperature range of 20 ° C to 140 ° C.
  • heat for example, infrared rays, electrically heated continuous furnaces, tempered water baths or chambers with steam can be used.
  • the thread can be guided over a roll or godet system, a so-called draw line.
  • the rollers or godets can in this case have different speeds of rotation.
  • each successive roll or godet has a higher rotational speed than the preceding roll or godet of the draw line.
  • the last roll or galette of such stretch line may be up to 15% slower than the penultimate roll or godet of the draw line, thereby relaxing with an increase in the elasticity of the thread.
  • the thread can be clamped between the clamping jaws of a tensioning device and then stretched under the effect of temperature.
  • the drawing of the thread can generally be carried out with a draw ratio of 1 .5 to 12, in particular 2.5 to 10, preferably 3 to 8.
  • anchoring structures in particular anchoring structures projecting from the thread surface, are produced.
  • the anchoring structures are preferably intended for anchoring in biological, in particular human and / or animal, tissues.
  • the anchoring structures can be produced in particular in the form of barbs on the thread surface.
  • the anchoring structures are preferably produced by means of incisions in the thread.
  • the thread for forming the anchoring structures can be cut so deeply that the thread core is also cut.
  • only the jacket can be cut in order to produce the anchoring structures.
  • the anchoring structures are preferably produced only on one or more thread longitudinal sections of the thread whose thread core diameter is greater than its shell thickness. In this way, comparatively small cutting depths are sufficient to ensure a cutting of the thread core. In addition, the mechanical stability, in particular the linear tensile strength, of the resulting yarn is greater.
  • the anchoring structures can basically be generated thermally, for example by means of a laser, and / or mechanically, for example by means of a corresponding cutting device.
  • Suitable cutting devices suitably comprise a cutting bed, at least one cutting blade and holding devices for the thread to be cut.
  • a cutting bed can be used with a groove for the mechanical cutting of the anchoring structures, wherein the groove is provided for receiving the thread to be cut.
  • the anchoring structures can basically be produced in a stretched or unstretched state of the thread.
  • the anchoring structures can be produced before or after a stretching of the thread.
  • the thread is cut before or after stretching to create the anchoring structures.
  • anchoring structures projecting from the thread surface can be produced by means of a subsequent stretching, in particular with formation of special geometries as a function of the cutting distance, cutting depth and cutting angle.
  • projecting anchoring structures can be produced from the thread surface.
  • the thread is partially stripped, ie the mantle of the thread is partially removed.
  • the removal of the jacket is preferably carried out at one or both ends of the thread. In principle, the jacket can be removed before or after a stretching of the thread.
  • the thread to be produced may be an endless thread, in particular an endless monofilament, or a cut thread, in particular a cut monofilament.
  • the thread is subjected to a post-treatment, a so-called "post-treatment.”
  • post-treatment a so-called "post-treatment.”
  • the thread is usually tempered in vacuo, which can increase the crystallinity of the thread and, in particular, lower the residual monomer content of the thread , which can be achieved by such a treatment, consists in a reduced susceptibility of the thread to shrinkage.
  • the invention relates to a thread which can be obtained or produced by a method according to the second aspect of the invention.
  • the thread is preferably a medical, in particular surgical, thread (medical, in particular surgical, suture material).
  • the invention relates to a technical textile which comprises at least one thread according to the invention, preferably a plurality of threads according to the invention.
  • the technical textile can basically have a textile structure or consist of such a structure, which is selected from the group comprising woven, knitted, knitted, braided, laid, fleece and combinations thereof.
  • the technical textile may in particular have a network or be in the form of a network.
  • the technical textile may have a textile fabric or be in the form of such a fabric.
  • the technical textile may furthermore have a hollow body structure, in particular a tubular structure, or be present in the form of such a structure.
  • the invention relates to a medical product which comprises at least one thread according to the invention, preferably a plurality of threads according to the invention.
  • the medical product may in principle have a textile structure or consist of such a structure which is selected from the group comprising woven, knitted, knitted, braided, laid, fleece and combinations thereof.
  • the medical product may in particular have a network or be made as a network.
  • the medical product may have a textile fabric or be in the form of such a fabric.
  • the medical product may further comprise a hollow body structure, in particular a tubular structure, or be in the form of such a structure.
  • the medical product is preferably a surgical implant, particularly preferably a medical, in particular surgical, thread (medical, in particular surgical, suture material).
  • the medical product is selected from the group comprising hernia mesh, prolapse mesh, wound dressing, hemostyptic, venous patch, implant for dura mater replacement, vascular prosthesis, in particular arterial vascular prosthesis, stent graft, stent and occluder.
  • the medical product is intended for use as a nerve guide rail.
  • the invention relates to a kit, in particular in the form of a needle-thread combination, comprising at least one surgical needle, in particular two surgical needles, and at least one thread according to the invention, in particular a thread according to the invention or a plurality of threads according to the invention, i. two or more threads of the invention, or a medical product according to the invention.
  • the at least one needle as well as the at least one thread or the medical product may be spatially separated from each other. Alternatively, the at least one thread or medical product may already be needled.
  • a longitudinal section of the at least one thread or the medical product is preferably completely received by a fastening device of the at least one surgical needle.
  • the sheath component can be removed beforehand either mechanically, thermally, by means of solvent and / or by decomposition in the section of the thread or medical product accommodated by the needle.
  • the resulting tapered portion of the suture or medical product thus permits the use of a needle, in particular an atraumatic needle, having a drilled hole for suture receiving, of smaller diameter.
  • a needling is preferably carried out at both ends of the thread.
  • a needling is preferably carried out at the thread end, which is opposite to the orientation (direction) of the anchoring structures.
  • the other end of the thread is preferably formed either as a loop, stopper or cable tie-like structure, whereby a fixation of the thread in biological, especially human and / or animal, tissues is made possible as a starting point for a continuous seam.
  • the at least one needle may be formed either straight or curved.
  • the at least one needle may be formed at its expediently pointed end either cutting or provided with a round tip.
  • the at least one needle in another embodiment has at its tip end a borehole into which the at least one thread or medical product is inserted and subsequently fixed to the at least one needle, for example by squeezing can be.
  • the invention relates to the use of a thread according to the invention for producing a thread without core-shell structure, i. without core-shell construction whose diameter varies (changes) in the thread length direction.
  • the thread diameter may vary continuously, in particular linearly or substantially linearly, or discontinuously, in particular stepwise, preferably increase or decrease.
  • the jacket can be removed by dissolving in a solvent in which the thread core of a thread according to the invention is insoluble.
  • the shell can be removed by means of a chemical or enzymatic reaction, such as, for example, hydrolysis, in particular ester hydrolysis. If the melting point of the sheath is lower than the melting point of the thread core, a suitable physical method for removing the sheath is to melt the sheath by means of heat supply and drain from the thread core.
  • the jacket can be removed by means of a drawing of a thread according to the invention by breaking the jacket apart during the drawing process and detach from the thread core, in particular detach mechanically, leaves.
  • FIG. 2a shows a cross section of the thread longitudinal section Ui
  • FIG. 2b shows a cross section of the thread longitudinal section u 2 )
  • FIG. 3a shows a further embodiment of a thread according to the invention in the unstretched state
  • FIG. 3b shows an enlarged illustration of anchoring structures with different flexural rigidity after stretching of the thread shown in FIG. 3a
  • FIG. 4 shows a further embodiment of a needle thread according to the invention
  • Figure 5 the course of the thread core diameter of a manufactured according to Example 3.
  • FIG. 6 shows the course of the lumen size, the thread core layer and the jacket layer in the case of a hollow thread according to the invention.
  • FIG. 1 shows a longitudinal section of a drawn thread 100 according to the invention.
  • the thread 100 has a thread core 1 10 and a sheath 120 surrounding the thread core 1 10.
  • the thread 100 has a core-shell structure.
  • the thread 100 has a (substantially) constant total diameter d.
  • the thread 100 can be further subdivided into the thread longitudinal sections Ui), u 2 ), u 3 ) and u 4 ) described below.
  • the thread longitudinal sections Ui) and u 3 ) each have a constant shell thickness and a constant thread core diameter. While the cladding thickness of the thread longitudinal sections Ui) is smaller than the cladding thickness of the thread longitudinal sections u 3 ), the thread core diameter is reversed, ie the thread core diameter of the thread longitudinal sections Ui) is greater than the thread core diameter of the thread longitudinal sections u 3 ).
  • both the jacket thickness and the thread core diameter vary.
  • the jacket thickness along the thread longitudinal sections u 2 ) increases linearly and the thread core diameter accordingly decreases linearly.
  • the thread core diameter along the thread longitudinal sections u 4 increases linearly, whereas the shell thickness of the thread longitudinal sections u 4 ) decreases correspondingly linear.
  • the thread 100 has in the longitudinal direction a preferably recurring sequence of the thread longitudinal sections Ui), u 2 ), u 3 ) and u 4 ).
  • FIG. 2 a schematically shows a cross section of the yarn longitudinal section U 1) shown in FIG. 1 and illustrates that in the yarn shown in FIG. 1 the diameter of the thread core 1 10 along this yarn longitudinal section is greater than the thickness of the jacket 120.
  • Figure 2b shows schematically a cross section of the yarn longitudinal section shown in Figure 1 u 3 ).
  • the thickness of the shell 120 along the yarn longitudinal section u 3 ) is greater than the diameter of the thread core 1 10.
  • FIG. 3 a shows a further embodiment of a thread 100 according to the invention in the unstretched state.
  • the thread 100 has on its surface two rows of bidirectionally arranged anchoring structures 128 ', which are spaced apart via incisions 1 18'.
  • the anchoring structures 128 ' are arranged offset in the circumferential direction of the thread 100 by 180 degrees to each other.
  • the depth of the cuts 1 18 ' is adjusted so that they penetrate along the yarn longitudinal sections Ui), u 2 ) and u 4 ) in the thread core 1 10, along the yarn longitudinal section u 3 ), however, only in the casing 120.
  • anchoring structures 128 ' can be transferred into anchoring structures 128 projecting from the thread surface, as shown in FIG. 3b.
  • the depth of cut as shown in Figure 3a, may be greater than the shell thickness, ie the thread core can be cut 1 10, can be realized in this way along the thread longitudinal sections with varying thread core diameter and varying shell thickness anchoring structures with different flexural stiffness, especially if
  • the jacket 120 is formed from a stiffer polymer than the thread core 1 10.
  • the left, shown in Figure 3b anchoring structure on a cutting of the thread longitudinal section Ui) the average, shown in Figure 3b anchoring structure to a cutting of the thread longitudinal section u 2 ) or u 4
  • the hatched area indicates the proportion of the jacket and the unshaded area the proportion of the thread core at the respective anchoring structure.
  • FIG. 4 shows a further embodiment of a stretched thread 100 according to the invention.
  • the thread 100 was cut to length about 0.5 cm from the beginning of the thread longitudinal section u 3 ). Subsequently, in the yarn longitudinal section of u 3 ), the sheath component was removed, so that over about 0.5 cm of the thin filament core of the yarn longitudinal section u 3 ) was exposed.
  • an atraumatic needle 130 which had a hole for receiving the thread.
  • a small diameter needle could be chosen for this purpose, so that the outer needle diameter substantially coincided with the total thread diameter. In general, such small needle thread diameter ratios of less than 1.3, preferably ⁇ 1..1 and more preferably ⁇ 1.0, can be realized.
  • the sheath polymer can serve as a thread coating for improving the knot run and the knot security and contain antimicrobial and / or antibacterial and / or disinfecting and / or analgesic and / or scar-reducing agents. example part
  • Example 1 Preparation of a core-shell monofilament having a poly-p-dioxanone (PDO) thread core and an alternating core-sheath ratio poly-e-caprolactone (PCL) sheath
  • PDO poly-p-dioxanone
  • PCL poly-e-caprolactone
  • the core-sheath monofilament was produced on a bicomponent monofilament extrusion line consisting of a single-screw extruder with two heating zones (core component, polydioxanone (PDO) violet with 0.08% by weight D & C Violet 2) and a co-rotating twin-screw extruder with 6 heating zones (sheath, Polycaprolactone (PCL) undyed) and a dosing station for relined driving of the extruder.
  • core component polydioxanone (PDO) violet with 0.08% by weight D & C Violet 2
  • PCL Polycaprolactone
  • the nozzles had a diameter of 1, 5 mm at the outlet opening.
  • the core component was supplied via a centric capillary, which ends in front of the nozzle outlet opening, while the jacket component annularly surrounded the central capillary.
  • the control of the bicomponent equipment was modified to allow it to be separated for the spinning polymer of the core polymer and for the spinning polymer of the jacket polymer, in each case a starting value for the spinning pump speed [rpm] and a range ( ⁇ rpm) within which the spinning pump speeds were varied.
  • the spinning pump speed variation was inverse: by the time the spinning pump speed of the core polymer increased, the spinning polymer spinning speed of the sheath polymer was reduced.
  • a holding time t H was set for both spinning pumps together, during which the spinning pump speeds were kept constant at their maximum or minimum, and a ramp time t R during which the spinning pump speed either increased from minimum to maximum or dropped from maximum to minimum.
  • the length of the constant regions Ui) and u 3 ) thus resulted from the holding time, multiplied by the withdrawal speed, the length of the varying regions from the ramp time, multiplied by the withdrawal speed.
  • the parameterization was as follows: Holding time t H : 2 s
  • Temperature profile core extruder 140 ° C / 160 ° C
  • Temperature profile jacket extruder all zones 190 ° C
  • the diameter of the bicomponent monofilament was essentially constant at 1, 196 mm ⁇ 0.025 mm over its entire duration.
  • Example 2 Drawing, Cutting, Parting and Needling of the Core-Sheath Monofilament of Example 1 as Stitch-Channel Closing Suture
  • the thread was needled with a needle (length 26 mm, needle diameter 0.58 mm, drill channel diameter 0.33 mm, taper-point) by means of a Quicky Tach III needling machine.
  • the needle to thread diameter ratio was 1, 07, while this is usually located in commercial threads of this thread thickness between 1, 8 and 3.5.
  • a stretched PDO monofilament with a constant over the entire thread length diameter of 0.49 mm with a needle was needled. This resulted in a needle-to-thread ratio of 2.0. It should be noted that the needles used were typical needles for thread sizes USP 3-0 and USP 1.
  • the puncture channel bleeding is a major problem. It results from the large, formed by the needle diameter puncture channel, which can not be nearly filled in suture materials on the market by the smaller thread diameter.
  • the ratios of the cross-sectional area of the needle to the cross-sectional area of the thread must be used. In Example 2 according to the invention, this ratio was 1.14, while the comparative example of starch USP 1 had a ratio of 4.0.
  • a standing cylinder filled with water was closed with a latex film, through which the thread according to the invention was pulled in previously by means of the surgical needle and in a further experiment the comparative suture material.
  • the thread according to the invention was pulled in so far that the thread longitudinal section Ui) was in the region of the stitch channel of the latex film. Now the cylinder was turned over so that the water column stood on the membrane. The leaked water through the branch channel was collected in a second vessel over a period of 1 minute. While the thread according to the invention exited only 1 ml in the observed period, the comparative thread was 18 ml.
  • the thread according to the invention thus reduces the extent of the puncture channel bleeding in an efficient manner. In a needling with cutting needles even an even greater difference is to be expected, since the membrane is not only displaced as a "vessel wall", but is cut by means of the cutting of the needle, whereby an effectively larger channel is formed.
  • Example 3 Preparation of a core-sheath monofilament with a core of one thread
  • the core-sheath monofilament was prepared essentially analogous to Example 1, with the GTCL block terpolymer dyed with the D & C Violet 2 dye forming the thread core and processed on the single-screw extruder, while the amorphous and uncolored LDL7030 formed the sheath produced by the Twin-screw extruder was fed.
  • a stretched strand of the GTCL copolymer has a flexural modulus of 580 N / mm 2
  • the LDL7030 has a flexural modulus of 5430 N / mm 2 and thus is much more rigid and harder than the GTCL polymer.
  • Temperature profile core extruder 190 ° C / 210 ° C
  • Temperature profile shell extruder 80/100/120/140/160/180/200 ° C
  • Spinning head temperature 210 ° C
  • the diameter of the bicomponent monofilament was essentially constant at 1, 193 mm ⁇ 0.020 mm over the entire run time.
  • the LDL7030 jacket was removed by inserting a piece of thread in acetone.
  • the filament core polymer is insoluble in acetone.
  • the filament core diameter di on the average 0.96 mm, which gave the shell thickness MDi to 0.1 17 mm and thus 9.8% of the total diameter.
  • the core diameter d 2 averaged 0.83 mm and the jacket thickness MD 2 thus 0.182 mm, which corresponded to 15.3% of the total diameter.
  • the length of the regions Ui) and u 3 ) in the unstretched state averaged 4.6 cm, while the regions u 2 ) and u 4 ) (ie the regions of varying core-shell portions) were on average 2.3 cm long.
  • Example 4 Surgical suture with unidirectional anchoring structures, formed by cutting into the core-sheath thread produced according to Example 3, with subsequent drawing and needling
  • the core-sheath monofilament from Example 3 pretreated beforehand to increase the crystallization of the thread core was cut to 25 cm so that the middle of the thread longitudinal section Ui) lay in the middle of the thread.
  • the incisions for creating the anchoring structures were made on an automated plant with control of the individual process steps, which consisted essentially of the following elements:
  • a cutting abutment in the form of a groove in which the clamped thread is guided under tension was about 60% of the thread diameter (40% of the thread diameter looked up out of the groove) and the groove width about 120% of the thread diameter, so that the thread could be rotated freely in the groove after each individual incision.
  • the cutting device itself which consisted of a fast linear motor handling (simplified axis) and at the lower end of a blade holder was mounted with clamped blade.
  • the axis allowed an accuracy of the cut length of 20 ⁇ .
  • the plant included two oppositely positioned cutting devices.
  • a cutting device was sufficient to make a bi-directional thread (the barb tip of both barb sections looked towards the center of the thread) both cutters were needed.
  • the macroscope was used to adjust the cutting depth and to check the cutting distance and the cutting angle.
  • the thread was examined microscopically following the cutting. As expected, it was found that in the area of Ui) the incisions went into the core component whereas in the area of u 3 ) only the cladding was cut.
  • the jacket was removed over a length of 0.5 cm by means of a puller heated to 80 ° C.
  • the remaining core diameter here was 0.43 mm, while the total diameter of the thread outside the anchoring structures was 0.61 mm.
  • a cutting needle having a radius of 180 °, a length of 26 mm and a needle diameter of 0.73 mm was mounted at a bore diameter of 0.47 mm.
  • the needle-thread diameter ratio was thus 1.55.
  • both the pulling power and the pull-out force in pork belly for the areas Ui) and u 3 ) were measured.
  • the needle was attached almost at right angles to the surface of the tissue and pulled through the tissue according to their radius and their length, so that a semicircular puncture channel formed.
  • the thread was then pulled through the fabric and determines the pulling power for both longitudinal sections. Due to the higher stiffness of the anchoring structures in the range of u 3 ), the pulling force was here at 1, 8 N compared to only 1.2 N in the range of Ui).
  • the end opposite the needle was then clamped in the tensile testing machine and the thread moved in the anchoring direction.
  • Example 5 Hollow thread with degradation gradient and substantially constant diameter and lumen for use as a nerve guide
  • the bicomponent system was therefore combined with a three-fluid nozzle, with the inner opening to produce the lumen was driven with a precisely metered volume of nitrogen (supporting gas).
  • the spinning head temperature was 140 ° C.
  • the hollow fiber thus formed had a substantially constant outer diameter of 1.98 mm and a substantially constant lumen of 1.48 mm.
  • the hollow thread each had about 1, 5 cm long dark colored and very bright spots, which were separated by each about 5 cm long areas with varying color depth. From the varying longitudinal areas and the adjacent areas of dark and light color, cross sections were taken at a distance of 0.5 cm and examined microscopically.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Molecular Biology (AREA)
  • Medical Informatics (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Biomedical Technology (AREA)
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  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un fil pourvu d'une âme et d'une enveloppe entourant l'âme, le fil comportant au moins une partie longitudinale le long de laquelle l'âme a un diamètre qui varie dans la direction longitudinale du fil et/ou l'enveloppe a une épaisseur qui varie dans la direction longitudinale du fil. L'invention concerne en outre un procédé de production d'un fil dans lequel un composant formant âme et un composant formant enveloppe sont co-extrudés d'un orifice de sortie d'un dispositif d'extrusion qui effectue une mise en forme lors de laquelle une fibre est formée avec une âme et une enveloppe entourant l'âme. Pour avoir un diamètre d'âme qui varie dans la direction longitudinale du fil et/ou une épaisseur d'enveloppe qui varie dans la direction longitudinale du fil, on fait varier le débit massique du composant formant âme et/ou du composant formant enveloppe et/ou on tire le fil après sa sortie de l'orifice de sortie à une vitesse variable. L'invention concerne en outre un fil qui peut être obtenu ou produit selon le procédé, un textile technique, un produit médical, une trousse, en particulier sous la forme d'une combinaison aiguille-fil, ainsi que l'utilisation du fil pour produire un fil, sans une structure âme-enveloppe, dont le diamètre varie dans la direction longitudinale du fil.
EP15722186.2A 2014-05-20 2015-05-12 Fil à âme et enveloppe, procédé de production d'un fil à âme et enveloppe, produit médical et trousse médicale Withdrawn EP3146095A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014209601.4A DE102014209601A1 (de) 2014-05-20 2014-05-20 Kern-Mantel-Faden, Herstellungsverfahren für einen Kern-Mantel-Faden, medizinisches Produkt sowie medizinisches Kit
PCT/EP2015/060430 WO2015176993A1 (fr) 2014-05-20 2015-05-12 Fil à âme et enveloppe, procédé de production d'un fil à âme et enveloppe, produit médical et trousse médicale

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US20240115282A1 (en) * 2022-10-11 2024-04-11 Covidien Lp Surgical constricting devices and surgical methods utilizing same

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WO2010052005A1 (fr) * 2008-11-06 2010-05-14 Itv Denkendorf Produktservice Gmbh Fil chirurgical à âme gainée

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US2932850A (en) 1955-08-01 1960-04-19 Celanese Corp Production of filaments of uneven denier
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