EP3631056B1 - Poil de filament plastique, brosse avec un tel poil et procede de fabrication d'un tel poil - Google Patents

Poil de filament plastique, brosse avec un tel poil et procede de fabrication d'un tel poil Download PDF

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Publication number
EP3631056B1
EP3631056B1 EP18728509.3A EP18728509A EP3631056B1 EP 3631056 B1 EP3631056 B1 EP 3631056B1 EP 18728509 A EP18728509 A EP 18728509A EP 3631056 B1 EP3631056 B1 EP 3631056B1
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EP
European Patent Office
Prior art keywords
mass
thermoplastic
bristle
spinning
polyphenylene
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.)
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EP18728509.3A
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German (de)
English (en)
Other versions
EP3631056A1 (fr
Inventor
Hans-Ulrich Pusch
Björn NEUER
Andreas Hilmar FISCHER
Pascal Heckenbenner
Benedikt NEUGIRG
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Perlon GmbH
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Perlon GmbH
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Priority to PL18728509T priority Critical patent/PL3631056T3/pl
Publication of EP3631056A1 publication Critical patent/EP3631056A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
    • 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
    • D01D5/082—Melt spinning methods of mixed yarn
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A46D1/02—Bristles details
    • A46D1/0207—Bristles characterised by the choice of material, e.g. metal
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

  • the invention relates to a bristle which is formed from a section of a plastic filament, a brush with at least one bristle carrier and a plurality of bristles attached to the bristle carrier, in particular in the form of a toothbrush, and a method for producing a bristle of the aforementioned type.
  • the bristles of which are made of monofilaments, so-called monofilaments, are made of plastic, which can be made relatively thin with a suitable material selection and also offer the possibility of structuring or profiling their outer surface in order to further improve the cleaning effect, especially in narrow gaps due to the scraping effect.
  • bristles of brushes formed from such filaments ensure additional properties, such as a certain coloring, stability against degradation through thermal stress or through chemical effects including enzymatic effects as a result of contact with saliva, the highest possible abrasion resistance, dimensional stability, flexural strength, flexural recovery and like that.
  • thermoplastic polymers For bristles of the generic type, synthetic threads made of melt-spinnable, thermoplastic polymers are usually used, with standard polymers that have been known for a long time, for example polyolefins such as polyethylene (PE) or polypropylene (PP), and polyamides such as polyamide 6 being used for reasons of cost (PA 6) or polyamide 6.6 (PA 6.6), or on polyester such as polybutylene terephthalate (PBT), provided that filaments made from these polymers can meet the desired requirements.
  • PE polyethylene
  • PP polypropylene
  • PA 6 polyamide 6
  • PA 6.6 polyamide 6.6
  • polyester such as polybutylene terephthalate (PBT)
  • the aforementioned polymers meet the physiological harmlessness requirements that are necessary in particular for use in toothbrushes.
  • bristles with a diameter between approximately 0.225 mm and 0.25 mm (“hard”), with a diameter in the range of approximately 0.2 mm (“medium”) or in the range between about 0.15 mm and about 0.18 mm (“soft”) are used.
  • hard a diameter between approximately 0.225 mm and 0.25 mm
  • medium a diameter in the range of approximately 0.2 mm
  • soft a diameter in the range between about 0.15 mm and about 0.18 mm
  • bristles made of polyamides tend to swell when they come into contact with water, which impairs their flexural rigidity.
  • bristles made of polyalkylene terephthalates such as polybutylene terephthalate (PBT), for example, prove to be less sensitive, but for the reasons mentioned above, a diameter of the bristles of significantly less than about 0.15 mm cannot be achieved with this either.
  • PBT polybutylene terephthalate
  • filaments made from thermoplastic, aliphatic polyketones are known from the prior art, for example the EP 0 310 171 A2 Describes melt-spun fibers made from ethylene / propylene / CO terpolymers, which have high tensile strengths and moduli of elasticity and are therefore proposed for use as tire cord or for the production of spunbonded fabrics, which are suitable for the production of roof underlays or as geotextiles.
  • melt and wet spinning processes are suitable for producing the filaments of generic bristles, with the dissolved polymer being spun into threads through a spinning capillary during wet spinning and the solvent being recovered as completely as possible and fed back into the production process. Nevertheless, it cannot be avoided that small amounts of the solvent used remain in the finished fiber, whereas it is desirable to provide a solvent-free fiber in order to minimize any potential safety risk, including a health hazard, caused by the presence of solvent residues in the fiber .
  • melt spinning processes in which higher degrees of crystallization can also be achieved, which can have an advantageous effect on the mechanical properties of the fiber.
  • processing by melt spinning often has to take place at significantly higher temperatures than wet spinning, which can lead to accelerated degradation or crosslinking reactions of the polymer and in turn have a detrimental effect on the properties of the fiber produced or lead to crosslinking reactions of the polymer, which can lead to Can limit processability in the extrusion process.
  • the invention is based on the object of proposing a bristle suitable for brushes, in particular toothbrushes, which can be produced easily and inexpensively while avoiding the aforementioned disadvantages as far as possible, and with a diameter that is as small as possible nevertheless sufficient flexural rigidity and durability having. It is also directed to a brush, in particular in the form of a toothbrush, with such bristles and to a method for producing such bristles.
  • a bristle of the type mentioned at the beginning which is formed from a section of a plastic filament, the polymer matrix of the plastic filament at least 70% by mass, based on the entire polymer matrix, of at least one thermoplastic, Contains aliphatic polyketone, which is composed of carbon monoxide units (CO units) and alkyl units, the polymer matrix of the plastic filament also contains at least one additive from the group of antioxidants and UV stabilizers, and the maximum diameter of the plastic filament between Is 0.01mm and 0.13mm.
  • the invention provides a brush with at least one bristle carrier and a plurality of bristles attached to the bristle carrier, in particular in the form of a toothbrush, to achieve this object, at least some of the bristles being of the aforementioned type.
  • the plastic filaments according to the invention which are primarily made from thermoplastic, aliphatic polyketones, which are built up from carbon monoxide units (CO units) and alkyl units, are characterized by a unique combination of properties that make them suitable for use as dental filaments, in particular for toothbrushes, opens up.
  • the polyketones according to the invention show a high mechanical, hydrolytic and chemical resistance, e.g. to weak acids or bases as well as to saliva.
  • plastic filament according to the invention with a very small diameter between about 0.01 mm and about 0.13 mm is able to optimally fulfill the cleaning effect intended for it.
  • the plastic filament based on the aforementioned polyketones benefits in particular from the high values when straightening up both in air and in water and their high flexural strength with simultaneous physiological harmlessness, so that the plastic filament has a very small diameter for dental care can be provided, but still achieves an equal or even better cleaning effect than conventional filaments based on polyamides or the like with larger diameters, which also cannot develop their cleaning effect in very narrow (tooth) spaces.
  • the plastic filaments according to the invention based on the thermoplastic, aliphatic polyketones mentioned are able to get deeper into (tooth) spaces or even into gingival pockets and also to clean these areas better than with filaments made of conventional materials according to the prior art technology is possible.
  • thermoplastic polyketones used as bristle materials according to the invention which are built up from carbon monoxide and alkyl units, are generally unsatisfactory Have oxidation resistance and a relatively poor resistance to electromagnetic radiation in the ultraviolet spectrum, which has proven to be intolerable for brushes in general and in particular for toothbrushes, which have to meet the highest requirements in terms of health safety and hygiene.
  • the invention counteracts this in that the polymer matrix of the plastic filament, from the sections of which the bristles according to the invention are formed, furthermore contains at least one additive from the group of antioxidants and UV stabilizers Physiologically harmless antioxidants and UV stabilizers described in more detail below have proven to be particularly suitable.
  • a brush such as a toothbrush, which contains the bristles according to the invention, be it exclusively or in particular partially, can be of any known shape, the bristles being arranged, for example, in bristle bundles.
  • the brush can have more bristles than is the case in the prior art, such as at least about 5000 bristles, in particular at least about 5500 bristles, preferably at least about 6000 bristles so that their cleaning effect can be further improved.
  • the bristles according to the invention are also particularly suitable for sonic and ultrasonic toothbrushes.
  • thermoplastic, aliphatic polyketone used for the plastic matrix of the bristles according to the invention consists in particular exclusively of carbon monoxide units or CO units and alkyl units, the aliphatic polyketones being copolymers or terpolymers with recurring structural units of the formula -R-CO-, which are mostly, if not necessarily exclusively, arranged alternately, but can also be arranged primarily statistically.
  • R is an alkyl radical, preferably a divalent aliphatic radical with two to six carbon atoms, ie a divalent ethyl, propyl, butyl, pentyl and / or hexyl group.
  • a spinning mass is initially selected which contains at least about 70% by mass of at least one such polyketone and, in particular, up to about 10% by mass of at least one additive the group of antioxidants and UV stabilizers.
  • This spinning mass is metered into an extruder for melting, which can be, for example, a single-screw extruder with a length to diameter ratio of about 20 to about 40, in particular from about 25 to about 30.
  • the screw of the extruder can advantageously be divided into three parts and have an area for drawing in the spinning mass and melting it, an adjoining area for compression and homogenization, and an area adjoining this in turn for ejecting the plasticized spinning compound.
  • the extruder can preferably comprise a plurality of zones for melting and homogenizing the spinning mass, with all zones essentially at the same temperature or with a falling or rising temperature profile or can also be operated with a temperature profile having temperature maxima and / or minima.
  • the plasticized spinning mass is then pressed in molten form through a nozzle plate, which can have one or more spinning capillaries, the diameter of which is a maximum of about 1.0 mm, in particular a maximum of about 0.8 mm, preferably a maximum of about 0.4 mm (in each case according to the Diameter of the bore on the exit side of the polymer mass), the temperature of the spinning mass on the exit side of the spinning capillary (s) in the range from about 190 ° C to about 300 ° C, in particular in the range from about 200 ° C to about 270 ° C , preferably in the range from about 220 ° C to about 260 ° C, for example in the range from about 220 ° C to about 250 ° C, such as in the range from about 237 ° C to about 242 ° C, (in each case when leaving the Spinning capillaries) is set.
  • the nozzle plate can usually be part of a spinning packet, which distributes the melt flow to the existing spinning capillaries and builds up the pressure necessary for spinning, and which advantageously has filter devices for the melted spinning mass, for example in the form of a metal net with a mesh size of about 10 mesh to about 350 mesh, in particular from about 80 mesh to about 250 mesh, as well as the downstream nozzle plate.
  • Additional filter devices can optionally consist of a further metal mesh of the type described, which is mounted in the melt channel of the extruder and preferably replaceable by means of a screen changer.
  • the temperature of the spinning mass should be selected in such a way that, on the one hand, adequate flowability of the spinning mass is ensured and, on the other hand, the thermal load on the spinning mass remains limited on the basis of the polyketones according to the invention, so that Cross-linking and degradation reactions as well as gel formation in the spinning mass are kept within limits or can even be suppressed entirely.
  • the melt can furthermore after the extrusion process by means of one or more spinning pumps, e.g.
  • nozzle plate in the form of gear pumps, at a pressure between about 5 bar and about 80 bar, in particular between about 45 bar and about 55 bar bar, are pressed through the nozzle plate, which can have, for example, between 1 and about 750 spinning capillaries with one of the aforementioned diameters.
  • a substantially vertical direction has been found to be the preferred flow direction of the melt, although not necessarily.
  • the filaments After the filaments have been shaped by means of the spinning capillaries, they can optionally be quenched, for example at a distance downstream of the spinning capillaries between about 0.1 cm and about 20 cm and, for example, in a water bath at a temperature between 5 ° C and about 95 ° C, in particular between about 25 ° C and about 30 ° C, or in air or in another gas or gas mixture at a temperature between about -100 ° C and about 200 ° C.
  • the resulting filament is then withdrawn from the spinning capillaries, for example by means of a suitable set of godets, with withdrawal speeds between about 1 m / min and about 200 m / min, in particular between about 1 m / min and about 120 m / min, preferably between about 5 m / min and about 50 m / min, for example in the range of about 20 m / min.
  • the take-off speed should preferably be selected in such a way that it differs from the exit speed of the spinning mass a degree of stretching greater than 1 results from the nozzle, which results in a higher crystallinity of the filament with improved mechanical stability, flexural strength and flexural recovery.
  • the degree of draw selected in this way improves the uniformity of the diameter of the filaments.
  • one or more filament drawing for example between different godet sets with a total drawing factor of expediently between about 1: 2 and about 1:15, in particular between about 1: 3 and about 1:15, preferably between about 1: 4 and about 1: 8, for example in the range between about 1: 4.8.
  • one or each stretching stage is followed by a relaxation or setting stage, in which tensions built up in the filament can be reduced while maintaining the corresponding tensile stress, resulting in a shrinkage factor, in particular between approximately 1: 0, 7 and about 1: 0.99 leads, for example in the range of about 1: 0.88 leads.
  • the individual steps of stretching and relaxation can be carried out, for example, with the aid of hot air or steam at temperatures of up to about 270.degree. C., in particular at temperatures of up to about 250.degree. C., for example in the range from about 180.degree. C. to about 220.degree , respectively.
  • lubricants, antistatic agents, thread closing agents and the like can optionally be applied to the filaments to improve their processability, a preferred method of application using a finishing roller at an adjustable speed, over which the filaments run in isolated or bundled form.
  • the filaments produced can then be fed to a suitable storage form, for example wound up, in order to be able to keep the filament in stock on a spool or reel, for example in a round, elongated or other shape.
  • the filament bundles produced can also be converted into a strand form.
  • a subsequent packaging e.g. by covering a tube or wrapping with e.g. paper or plastic.
  • a final fixation of the filaments for example in the form of heat setting at about 60 ° C to about 220 ° C in a tempering oven for about 5 minutes to about 30 hours or by means of a treatment in an autoclave for about 10 minutes to about 24 hours carried out, preferably before packaging.
  • Any crosslinking of the polymer matrix of the filaments can be suppressed by a combination of adapted process parameters such as temperature, shear, throughput, spinning draft, degree of stretching, fixation and dwell time.
  • the polymer matrix of the plastic filament is at least about 80% by mass, for example at least about 85% by mass, in particular at least about 90% by mass, for example at least about 95% by mass, preferably about 100%, based on the entire polymer matrix, of the at least one thermoplastic, aliphatic polyketone which is composed of carbon monoxide and alkyl units.
  • the at least one thermoplastic, aliphatic polyketone is a polyketone from the group of ethylene / CO copolymers, propylene / CO copolymers, ethylene / propylene / CO terpolymers and polymer Blends out of this.
  • the latter have the general structural formula where R is a monovalent methyl group (CH 3 group).
  • the ethyl-CO units and the propyl-CO units do not necessarily have to be arranged exclusively alternately and the monovalent methyl group "R" of the above propyl unit can also be bonded to the adjacent carbon atom of the above CH 2 group (- [CO-CH 2 -CHR-] n -), for example in a primarily statistical distribution in the molecule.
  • thermoplastic, aliphatic polyketone according to step (a) from the group of ethylene / CO copolymers, propylene / CO copolymers, ethylene / propylene / CO terpolymers and polymer blends thereof is selected.
  • the invention provides in particular the possibility of a very thin design of the bristles, whereby it can preferably be provided that the maximum diameter of the plastic filament is between about 0.01 mm and about 0.11 mm, in particular between about 0, 01 mm and about 0.08 mm, preferably between about 0.01 mm and about 0.06 mm, for example between about 0.02 mm and about 0.06 mm.
  • the polymer matrix of the plastic filament based on thermoplastic polyketones which are composed of carbon monoxide and alkyl units, can expediently be up to about 10% by mass, in particular up to about 5% by mass, preferably up to about 4% by mass, for example up to about 3% by mass or only up to about 2% by mass, each based on the entire polymer matrix, of the at least one additive from the group of antioxidants and UV stabilizers , in which in many cases it can also be sufficient if the polymer matrix contains up to about 1% by mass of at least one of the aforementioned additives.
  • the at least one additive from the group of antioxidants and UV stabilizers is at least one additive from the group of sterically hindered phenols, HALS (hindered amine light stabilizer) and which includes phosphites.
  • HALS hindered amine light stabilizer
  • antioxidants which the polymer matrix of the plastic filament, for example, with an advantageous proportion between about 0.1% by mass and about 5% by mass, preferably between about 0.5% by mass and about 3% by mass, can be added, sterically hindered phenols and / or HALS (hindered amine light stabilizer) and / or phosphites can be used according to the invention, which can optionally be combined with co-stabilizers.
  • HALS hindered amine light stabilizer
  • phosphites can be used according to the invention, which can optionally be combined with co-stabilizers.
  • antioxidants based on sterically hindered phenols include sterically hindered alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxyphenol, sterically hindered alkylthiomethylphenols, for example 2 , 4-Di-octylthiomethyl-6-tert-butylphenol, sterically hindered hydroxylated thiodiphenyl ethers, e.g.
  • phenols of the aforementioned type include 3,9-bis- [2,4-bis- (1-methyl-1-phenylethyl) phenoxy] -2,4,8,10-tetra-oxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10- tetraoxaspiro [5.5] undecane, p-tert-Amylphenolformaldehyde, ⁇ -diketones from the condensation of acetophenones and an ester of octadecanoic acid, bis [2- (tert-butyl-6 - [[3-tert-butyl-2-hydroxy-5-methylphenyl] methyl] - 4-methyl-phenyl] -1,4-benzenedicarboxylate and 1,2-bis [3,
  • co-stabilizers include, for example, organic phosphites and / or organic phosphonites, e.g. 5-butyl-5-ethyl-2- (2,4,6-tris-tert-butyl-phenoxy) -1,3-dioxa-2-phosphorinane, diethylphosphonoacetate or 2,2'-ethylidene bis- (4,6-di-tert-butylphenyl) fluorophosphonite, which are co-stabilizers for antioxidants known per se.
  • organic phosphites and / or organic phosphonites e.g. 5-butyl-5-ethyl-2- (2,4,6-tris-tert-butyl-phenoxy) -1,3-dioxa-2-phosphorinane, diethylphosphonoacetate or 2,2'-ethylidene bis- (4,6-di-tert-butylphenyl) fluorophosphonite, which
  • UV stabilizers examples include UV absorbing compounds such as benzophenones, e.g. 4-tert-butyl-2- (5-tert-butyl-2-oxo-3H-benzofuran-3-yl) phenyl-3,5- di-tert-butyl-4-hydroxybenzoate, and benzotriazoles, e.g.
  • a bristle according to the invention can of course provide that the polymer matrix of the plastic filament contains at least one additional additive from the group of pigments and dyes, fillers, matting agents, reinforcing agents, crystallization accelerators, lubricants and antistatic agents, which are in particular physiologically harmless and their proportion is based on the proportions usually added, which primarily depend on the type of additive in question.
  • the respectively desired amount of at least one further additive of the aforementioned type is added to the at least one thermoplastic, aliphatic polyketone according to step (a) or a master batch already contains the respective additive.
  • the additives from the group of antioxidants and UV stabilizers that are mandatory according to the invention.
  • colorants based on inorganic pigments or organic dyes can preferably be used, which can be added, for example, in the form of a masterbatch with a suitable carrier material during extrusion (step (b) of the process according to the invention).
  • suitable carrier material for example, in the form of a masterbatch with a suitable carrier material during extrusion (step (b) of the process according to the invention.
  • preferred pigments include carbon black, titanium dioxide or iron oxides.
  • preferred dyes include anionic dyes, acid dyes, metal complex dyes, cationic or basic dyes, and disperse dyes.
  • Examples of preferred fillers include carbonates such as chalk or dolomite, silicates such as talc, mica, Kaolin, or sulfates, such as barite, or oxides and hydroxides, such as quartz flour, crystalline silica, aluminum or magnesium hydroxides or magnesium, zinc or calcium oxides.
  • carbonates such as chalk or dolomite
  • silicates such as talc, mica, Kaolin
  • sulfates such as barite
  • oxides and hydroxides such as quartz flour, crystalline silica, aluminum or magnesium hydroxides or magnesium, zinc or calcium oxides.
  • An example of a preferred matting agent is titanium dioxide;
  • Examples of preferred crystallization accelerators include carboxylic acid esters.
  • lubricants examples include polyolefin waxes, fatty acids or their salts, fatty alcohols, fatty acid esters, silicones, polysiloxanes and, in particular, PMSQ, as described in US Pat EP 2 933 361 A1 are described.
  • Examples of preferred antistatic agents include carbon black, graphite, graphene, carbon nanotubes (CNT) or metal particles.
  • processing aids include waxes or longer-chain carboxylic acids including their salts, aliphatic, aromatic esters or ethers.
  • the individual polymer components can complement each other in a synergistic manner, with the plastic filaments being given excellent mechanical properties, such as a high modulus of elasticity, low modulus, for example Creep, low tendency to sag, etc., and thanks to the thermoplastic aliphatic polyketone, in particular, high flexural rigidity and increased abrasion resistance, so that the plastic filament can be made very thin.
  • the polymer matrix of the plastic filament is up to about 30% by mass, for example up to about 25% by mass, in particular up to 20% by mass, for example up to about 15% by mass. -%, preferably up to about 10% by mass, for example up to about 5% by mass, based on the entire polymer matrix, of at least one further thermoplastic polymer.
  • the at least one further thermoplastic polymer can preferably be selected from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyether sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, polyether imides, polyether ether ketones, the thermoplastic elastomers, in particular in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid-crystalline polymers, it being understood that several representatives of the aforementioned polymers can also be used.
  • These further polymers are primarily polymers known as such which are already used in the prior art for the production of filaments.
  • polyolefins examples include homo- or copolymers which are derived from ethylene and / or from propylene, optionally in combination with other ethylenically unsaturated aliphatic hydrocarbons, such as ⁇ -olefins having four to eight carbon atoms.
  • Polyethylene and polypropylene can be present in different densities and crystallinities.
  • polyesters include thermoplastic polymers which are derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as the alkyl esters, and from aliphatic, cycloaliphatic and / or aromatic dihydric alcohols, such as ethylene glycol, 1,3-propylene glycol and / or butylene glycol.
  • polyesters include thermoplastic-elastomeric polyesters (TPE-C), such as, for example, polyesters containing recurring butylene terephthalate structural units and containing recurring polybutylene glycol terephthalate structural units.
  • Aromatic-aliphatic polyester homopolymers or copolymers can preferably be used, such as, for example, polybutylene terephthalate homopolymers or copolymers containing butylene terephthalate units.
  • Such preferred polymers are therefore derived from butylene glycol and optionally further alcohols and from terephthalic acid or its polyester-forming derivatives, such as terephthalic acid esters or chlorides.
  • polyesters can contain structural units derived from other suitable dihydric alcohols, typical representatives of which are aliphatic and / or cycloaliphatic diols, for example 1,2-ethanediol, 1,3-propanediol, 1,2-cyclohexanedimethanol or mixtures thereof.
  • polyesters can contain structural units derived from other suitable dicarboxylic acids or their polyester-forming derivatives, typical representatives of which are aromatic and / or aliphatic and / or cycloaliphatic dicarboxylic acids, for example naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, cyclohexanedicarboxylic acid , Sebacic acid or mixtures thereof.
  • plastic filaments can also be produced which contain other polyesters, such as, for example, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate homopolymer or copolymers containing ethylene naphthalate units.
  • Components of thermoplastic copolyesters preferably include the above-mentioned diols and dicarboxylic acids, or correspondingly structured polyester-forming derivatives.
  • IV values solution viscosities
  • polyamides examples include thermoplastic polymers derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyamide-forming derivatives, such as their salts, and from aliphatic, cycloaliphatic and / or aromatic divalent amines, such as hexamethylenediamine.
  • polyamides include thermoplastic-elastomeric polyamides (TPE-A), for example polyamides containing recurring hexamethylene terephthalamide structural units and containing recurring polyethylene glycol terephthalamide structural units.
  • Polyamides used with preference include, in particular, partially crystalline aliphatic polyamides, which can be prepared from aliphatic diamines and aliphatic dicarboxylic acids and / or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids.
  • the starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropane, bis-aminomethylcyclohexane, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams are possible.
  • aliphatic dicarboxylic acids preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid
  • aliphatic diamines preferably 1,4-tetra
  • Copolyamides made from several of the monomers mentioned are included.
  • Caprolactams in particular ⁇ -caprolactam, can be used with particular preference.
  • the aliphatic homo- or copolyamides used according to the invention are also preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9 , Polyamide 10.9, polyamide 10.10, polyamide 11 or polyamide 12.
  • the polyesters and polyamides used according to the invention can also be derived from hydroxycarboxylic acids or from aminocarboxylic acids.
  • polyoxymethylenes examples include homo- or copolymers which contain recurring structural units of the formula -CH 2 -O-.
  • polyurethanes examples include homo- or copolymers which are derived from aromatic or (cyclo) aliphatic diisocyanates and from (cyclo) aliphatic or aromatic diols.
  • Polyurethanes contain, for example, repeating structural units of the formula -C 6 H 4 -NH-CO-OC 2 H 4 -O-CONH-.
  • Further examples of polyurethanes include thermoplastic-elastomeric polyurethanes (TPE-U).
  • polyphenylene sulfides include poly-p-phenylene sulfides, for example homopolymers or copolymers, which contain recurring structural units -para-C 6 H 4 -S-.
  • polyphenylene sulfones include poly-p-phenylene sulfones, for example homopolymers or copolymers, which contain recurring structural units —para — C 6 H 4 —SO x -, where x is a number between 1 and 2.
  • polyphenylene ethers examples include poly-p-phenylene ethers, for example homopolymers or copolymers, which contain recurring structural units -para-C 6 H 4 -O-.
  • polyphenylene ketones examples include poly-p-phenylene ketones, for example homopolymers or copolymers, which contain recurring structural units —para — C 6 H 4 —CO—.
  • polyphenylene ether ketones examples include poly-p-phenylene ether ketones, for example copolymers which contain recurring structural units -para-C 6 H 4 -CO- and recurring structural units -para-C 6 H 4 -O-.
  • liquid-crystalline polymers include liquid-crystalline aromatic polyesters, for example homo- or copolymers, which contain recurring structural units derived from para-hydroxybenzoic acid.
  • a bristle made of a plastic filament the polymer matrix of which contains at least one further thermoplastic polymer, such as one or more polymers of the above-mentioned type, in addition to the thermoplastic, aliphatic polyketone, which is composed of carbon monoxide and alkyl units that the polymer matrix of the plastic filament at least partially consists of a polymer blend of the at least one thermoplastic polyketone and the at least one further thermoplastic polymer is formed.
  • the at least one thermoplastic, aliphatic polyketone according to step (a) is up to about 30% by mass, in particular up to about 20% by mass, preferably up to about 10% by mass. -%, at least one further thermoplastic polymer, in particular from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyether sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, polyether imides, the Polyetheretherketones, to the thermoplastic elastomers, preferably in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid-crystalline polymers, are added.
  • a bristle made of a plastic filament the polymer matrix of which contains at least one further thermoplastic polymer in addition to the thermoplastic, aliphatic polyketone, which is composed of carbon monoxide and alkyl units, such as one or more polymers of the type mentioned above, can alternatively or additionally it can be provided that the plastic filament has a cross-section in which the at least one thermoplastic polyketone and the at least one further thermoplastic polymer are spatially separated, but connected to one another, in particular in a side-by-side and / or in a Core-sheath structure.
  • cross-sectional shape of the plastic filaments according to the invention does not necessarily have to be (circular) round, but has to be arbitrary. This can be, for example, regular or irregular cross-sections, point-symmetrical or axially symmetrical cross-sections, for example round, oval or n-angular cross-sections, where n is greater than or equal to 3, to tri- or multilobal cross-sections and the like.
  • the bristle according to the invention can also be mechanically and / or chemically tapered.
  • the toothbrush shown in the drawing comprises a bristle carrier 1 and a handle 2 (shown broken off), which in the present exemplary embodiment are designed in one piece and, for example, consist of one or more conventional, in particular thermoplastics, plastics are made.
  • a plurality of bristles 3 are fixed on the bristle carrier 1, which can be fixed in the bristle carrier 1 by means of extrusion coating and in the present case are arranged in several bristle bundles 4 arranged in rows and columns, for example in a matrix-like manner.
  • the bristles 3 each consist of a section of a plastic filament based on thermoplastic, aliphatic polyketones, as described in detail above.
  • the diameter of the bristles is advantageously less than about 0.08 mm, for example in the range between about 0.02 mm and about 0.05 mm, so that they can easily penetrate into interdental spaces and a very high number of them during normal use of the toothbrush

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Soie (3), laquelle est formée à partir d'une section d'un filament synthétique, la matrice polymère du filament synthétique contenant au moins 70 % en masse, par rapport à l'ensemble de la matrice polymère, d'au moins une polycétone aliphatique thermoplastique, laquelle est composée de motifs de monoxyde de carbone et d'alkyle, la matrice polymère du filament synthétique contenant également au moins un additif du groupe des antioxydants et des stabilisants UV, et le diamètre maximal du filament synthétique étant compris entre 0,01 mm et 0,13 mm.
  2. Soie selon la revendication 1, caractérisée en ce que la matrice polymère du filament synthétique contient au moins 80 % en masse, en particulier au moins 90 % en masse, de préférence environ 100 %, par rapport à l'ensemble de la matrice polymère, de l'au moins une polycétone aliphatique thermoplastique, laquelle est constituée de motifs de monoxyde de carbone et d'alkyle.
  3. Soie selon la revendication 1 ou 2, caractérisée en ce que l'au moins une polycétone aliphatique thermoplastique est une polycétone du groupe des copolymères éthylène/CO, des copolymères propylène/CO, des terpolymères éthylène/propylène/CO et des mélanges de polymères fabriqués à partir de ceux-ci.
  4. Soie selon l'une des revendications 1 à 3, caractérisée en ce que le diamètre maximal du filament synthétique est compris entre 0,01 mm et 0,11 mm, en particulier entre 0,01 mm et 0,08 mm, de préférence entre 0,01 mm et 0,06 mm.
  5. Soie selon l'une des revendications 1 à 4, caractérisée en ce que l'au moins une polycétone aliphatique thermoplastique présente au moins l'un des paramètres de matériau suivants :
    - une température de fusion comprise entre 180 °C et 250 °C, en particulier entre 190 °C et 230 °C ;
    - un indice de fluidité compris entre 1 et 350 g/10 min, en particulier entre 2 et 300 g/10 min, déterminé selon ASTM D1238 et ISO 1133 à 240 °C ;
    - une limite d'élasticité comprise entre 35 MPa et 70 MPa, en particulier entre 43 MPa et 63 MPa, déterminée selon ASTM D638 à 23 °C ; et
    - un module de flexion compris entre 450 MPa et 2 750 MPa, en particulier entre 650 MPa et 2 000 MPa, déterminé selon ASTM D790 à 23 °C.
  6. Soie selon l'une des revendications 1 à 5, caractérisée en ce que la matrice polymère du filament synthétique
    - contient jusqu'à 10 % en masse, en particulier jusqu'à 5 % en masse, par rapport à l'ensemble de la matrice polymère, de l'au moins un additif du groupe des antioxydants et des stabilisants UV, l'au moins un additif du groupe des antioxydants et des stabilisants UV comprenant en particulier au moins un additif du groupe des phénols à encombrement stérique, des HALS (hindered amine light stabilizer, photostabilisant de type amine encombrée) et des phosphites ; et/ou
    - contient au moins un autre additif du groupe des pigments et colorants, charges, agents de matage, agents de renforcement, accélérateurs de cristallisation, agents lubrifiants et antistatiques.
  7. Soie selon l'une des revendications 1 à 6, caractérisée en ce que la matrice polymère du filament synthétique contient jusqu'à 30 % en masse, en particulier jusqu'à 20 % en masse, de préférence jusqu'à 10 % en masse, par rapport à l'ensemble de la matrice polymère, d'au moins un autre polymère thermoplastique, l'au moins un autre polymère thermoplastique étant en particulier choisi dans le groupe des polyoléfines, polyesters, polyamides, polyoxyméthylènes, polyuréthanes, polyphénylènesulfures, polyphénylènesulfones, polyéthersulfones, polyphénylèneéthers, polyphénylènecétones, polyphénylèneéthercétones, polyétherimides, polyétheréthercétones, élastomères thermoplastiques, en particulier sous forme de polyuréthanes, polyesters et/ou polyamides thermoplastiques, et des polymères à cristaux liquides.
  8. Soie selon la revendication 7, caractérisée en ce que la matrice polymère du filament synthétique est au moins partiellement formée à partir d'un mélange de polymère d'au moins une polycétone thermoplastique et d'au moins un autre polymère thermoplastique.
  9. Soie selon la revendication 7 ou 8, caractérisée en ce que le filament synthétique présente une section transversale dans laquelle l'au moins une polycétone thermoplastique et l'au moins un autre polymère thermoplastique sont séparés spatialement, mais reliés l'un à l'autre de manière contiguë, en particulier dans une structure de type côté sur côté et/ou de type noyau-extérieur.
  10. Soie selon l'une des revendications 1 à 9, caractérisée en ce
    - que sa surface extérieure est pourvue d'un gaufrage ; et/ou
    - qu'elle est conçue pour être ondulée dans la direction longitudinale ; et/ou
    - qu'elle est effilée mécaniquement et/ou chimiquement.
  11. Brosse comportant au moins un porte-soies (1) et une pluralité de soies (3) fixées au porte-soies (1), en particulier sous la forme d'une brosse à dents, caractérisée en ce qu'au moins certains soies (3) sont conçues selon l'une des revendications 1 à 10.
  12. Procédé de fabrication d'une soie (3) selon l'une des revendications 1 à 10, comprenant les étapes suivantes :
    (a) fourniture d'une masse de filage qui contient au moins 70 % en masse d'au moins une polycétone aliphatique thermoplastique, laquelle est composée de motifs de monoxyde de carbone et d'alkyle, et l'au moins une polycétone aliphatique thermoplastique contenant, en particulier jusqu'à 10 % en masse, d'au moins un additif du groupe des antioxydants et des stabilisants UV ;
    (b) extrusion de la masse de filage selon l'étape (a) à travers au moins une plaque de buse au moyen d'un ou plusieurs capillaires de filage d'un diamètre maximal de 1,0 mm, en particulier d'un diamètre maximal de 0,8 mm, de préférence d'un diamètre maximal de 0,4 mm, la température de la masse de filage étant réglée, au niveau du côté de sortie (n) des capillaires de filage, dans la plage de 190 °C à 300 °C, en particulier dans la plage de 200 °C à 270 °C, de préférence dans la plage de 220 °C à 260 °C ;
    (c) décollage du filament formé à une vitesse de décollage comprise dans la plage de 1 à 200 m/min, en particulier de 5 à 50 m/min, de préférence en choisissant le rapport entre la vitesse de décollage et la vitesse de sortie de la masse de filage du capillaire de filage supérieur à 1 ;
    (d) étirage unique ou multiple du filament formé ;
    (e) enroulage éventuel du filament formé ; et
    (f) découpe du filament formé tout en préservant les soies (3).
  13. Procédé selon la revendication 12, caractérisé en ce
    - que l'au moins une polycétone aliphatique thermoplastique selon l'étape (a) est choisie dans le groupe des copolymères éthylène/CO, des copolymères propylène/CO, des terpolymères éthylène/propylène/CO et de mélanges de polymères de ceux-ci ; et/ou
    - que jusqu'à 30% en masse d'au moins un autre polymère thermoplastique, en particulier du groupe des polyoléfines, polyesters, polyamides, polyoxyméthylènes, polyuréthanes, polyphénylènesulfures, polyphénylènesulfones, polyéthersulfones, polyphénylèneéthers, polyphénylènecétones, polyphénylèneéthercétones, polyétherimides, polyétheréthercétones, élastomères thermoplastiques, de préférence sous forme de polyuréthanes, polyesters et/ou polyamides thermoplastiques, et des polymères à cristaux liquides, sont ajoutés à l'au moins une polycétone aliphatique thermoplastique selon l'étape (a).
  14. Procédé selon la revendication 12 ou 13, caractérisée en ce qu'au moins un autre additif du groupe des pigments et colorants, charges, agents de matage, agents de renforcement, accélérateurs de cristallisation, agents lubrifiants et antistatiques sont ajoutés à l'au moins une polycétone aliphatique thermoplastique selon l'étape (a).
  15. Procédé selon l'une des revendications 12 à 14, caractérisé par les étapes supplémentaires suivantes :
    (a2) fourniture d'une autre masse de filage qui contient au moins un autre polymère thermoplastique, en particulier du groupe des polyoléfines, polyesters, polyamides, polyoxyméthylènes, polyuréthanes, polyphénylènesulfures, polyphénylènesulfones, polyéthersulfones, polyphénylèneéthers, polyphénylènecétones, polyphénylèneéthercétones, polyétherimides, polyétheréthercétones, des élastomères thermoplastiques, en particulier sous forme de polyuréthanes, polyesters et/ou polyamides thermoplastiques, et des polymères à cristaux liquides ; et
    (b2) extrusion aussi bien de la masse de filage selon l'étape (a) que de l'autre masse de filage selon l'étape (a2) dans respectivement une extrudeuse au moyen d'au moins une plaque de buse comportant un ou plusieurs capillaires de filage, de sorte que chaque capillaire de filage est traversé aussi bien par la masse de filage selon l'étape (a) que par l'autre masse de filage selon l'étape (a2).
EP18728509.3A 2017-05-30 2018-05-18 Poil de filament plastique, brosse avec un tel poil et procede de fabrication d'un tel poil Active EP3631056B1 (fr)

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WO2016190596A2 (fr) 2015-05-27 2016-12-01 (주)효성 Produit de polycétone industriel comprenant des fibres de polycétone et son procédé de fabrication
WO2016190594A2 (fr) 2015-05-27 2016-12-01 (주)효성 Produit de polycétone industriel comprenant des fibres de polycétone et son procédé de fabrication
EP3520651B1 (fr) * 2016-09-29 2024-01-10 LG Household & Health Care Ltd. Poils de brosse à dents en polycétone, et brosse à dents les comprenant
CN106521704B (zh) * 2016-10-31 2019-03-08 江苏苏博特新材料股份有限公司 一种聚酮-聚甲醛复合纤维的制备方法

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DE202017002839U1 (de) 2018-08-31
EP3631056A1 (fr) 2020-04-08
EP3631057B1 (fr) 2024-01-17
US20200080236A1 (en) 2020-03-12
EP3631057A1 (fr) 2020-04-08
WO2018219495A1 (fr) 2018-12-06
MX2019014377A (es) 2020-01-23
ES2891998T3 (es) 2022-02-01
PL3631056T3 (pl) 2021-12-27
CN110678588A (zh) 2020-01-10
KR20200038427A (ko) 2020-04-13
WO2018219494A8 (fr) 2020-01-16
WO2018219494A1 (fr) 2018-12-06
JP2020521893A (ja) 2020-07-27
FI3631057T3 (fi) 2024-03-25
PT3631056T (pt) 2021-10-07

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