WO2018219495A1

WO2018219495A1 - Bristle made of a plastic filament, brush comprising bristles of this kind, and method for producing bristles of this kind

Info

Publication number: WO2018219495A1
Application number: PCT/EP2018/000266
Authority: WO
Inventors: Hans-Ulrich Pusch; Björn NEUER; Andreas Hilmar FISCHER; Pascal Heckenbenner; Benedikt NEUGIRG
Original assignee: Perlon Gmbh
Priority date: 2017-05-30
Filing date: 2018-05-18
Publication date: 2018-12-06
Also published as: US20200080236A1; KR20200038427A; EP3631057A1; WO2018219494A8; WO2018219494A1; ES2891998T3; JP2020521893A; PL3631056T3; PT3631056T; FI3631057T3; EP3631056A1; DE202017002839U1; EP3631057B1; CN110678588A; EP3631056B1; MX2019014377A

Abstract

The invention relates to a bristle which is formed from a portion of a plastic filament. In order to still provide good material properties, such as a high flexural resistance and good longevity, in spite of a very thin design of the bristle, the invention proposes that the polymer matrix of the plastic filament contains at least 70 mass % of at least one thermoplastic, aliphatic polyketone in relation to the total polymer matrix, which polyketone is built from carbon monoxide and alkylene units, wherein the polymer matrix of the plastic filament also contains at least one additive from the group of antioxidants and UV stabilisers, and wherein the maximum diameter of the plastic filament is between 0.01 mm and 0.13 mm. The invention also relates to a brush comprising bristles of this kind, in particular in the form of a toothbrush, and to a method for producing the filaments of bristles of this kind by means of melt spinning.

Description

Bristle made of a plastic filament, brush with such bristles and method for producing such bristles

The invention relates to a bristle which is formed from a section of a plastic filament, a brush having at least one bristle carrier and a plurality of bristles fixed to the bristle carrier, in particular in the form of a toothbrush, and a method for producing a bristle of the aforementioned type.

The cleaning action of brushes, in particular - though not exclusively - of toothbrushes, is decisively dependent, on the one hand, on the geometry of the individual bristles, and, on the other hand, on their material, with the frequent need to design the bristles with the smallest possible diameter, so that they can even in very narrow columns, eg in narrow interdental spaces, to be able to develop their cleaning effect. At the same time, however, the bristles must nevertheless have a certain flexural rigidity and durability for this purpose.

In practice, therefore, brushes have proven their bristles of monofilaments, so-called monofilaments, are made of plastic, which can be made relatively thin with a suitable choice of material and also provide the opportunity to structure their lateral surface or profile to further improve the cleaning effect, especially in narrow gaps due Schabwirkung. In addition, bristles of brushes formed from such filaments provide additional properties, such as a certain coloration, resistance to degradation by thermal stress, or chemical action including enzymatic

Action due to contact with saliva, the highest possible abrasion resistance, dimensional stability, bending strength, bending recovery and the like. Synthetic filaments of melt-spinnable thermoplastic polymers are usually used for generic bristles, where, for reasons of cost, generally long-known standard polymers are used, for example polyolefins, such as polyethylene (PE) or polypropylene (PP), on polyamides, such as polyamide 6 (PA 6) or polyamide 6.6 (PA 6.6), or on polyesters, such as polybutylene terephthalate (PBT), if filaments of these polymers can meet the desired requirements. In addition, the above-mentioned polymers fulfill the physiological safety requirements, in particular for use in toothbrushes.

However, the mechanical properties and thus the smallest possible diameter of such bristles are limited, which is why in known toothbrushes usually bristles having a diameter between about 0.225 mm and 0.25 mm ("hard"), with a diameter in the range of about 0.2 mm ("medium") or in the range between about 0.15 mm and about 0.18 mm ("soft") use find. For example, polyamide bristles tend to swell on contact with water, which impairs flexural rigidity. Although, for example, bristles made of polyalkylene terephthalates, such as, for example, polybutylene terephthalate (PBT), are less sensitive, for the abovementioned reasons no diameter of the bristles of significantly less than about 0.15 mm can be achieved here as well. In addition, filaments of thermoplastic, aliphatic polyketones are known from the prior art, for example, EP 0 310 171 A2 describes melt-spun fibers of ethylene / propylene / CO terpolymers, which have high tensile strengths and moduli of elasticity and therefore for use as Tire cord or for the production of spunbonded nonwovens, which are suitable for the production of roof underlays or as geotextiles.

WO 2016/190594 A2 and WO 2016/190596 A2 likewise disclose wet-spun fibers of ethylene / propylene /

CO terpolymers are known, which have excellent strength and elongation values and are also distinguished by high water and heat resistance and by good thermal conductivity. Applications for these fibers include various uses, such as the manufacture of ropes, hoses, nets, spunbonded fabrics, airbags or protective clothing, and geotextile applications, as reinforcing fibers in composites, as belts, safety nets, conveyor belts, fishing lines or tennis strings , For the production of the filaments of generic bristles are basically melt and wet spinning process, wherein in wet spinning, the dissolved polymer by a

Spinning capillary spun into threads and the solvent is recovered as completely as possible and returned to the manufacturing process. Nevertheless, it is unavoidable that small amounts of the solvent used remain in the finished fiber, whereas it is desirable to provide a solvent-free fiber to minimize any potential safety hazard, including a health hazard, caused by the presence of solvent residues in the fiber ,

In practice, therefore, one resorts primarily to melt spinning processes in which higher degrees of crystallization can be achieved, which can have an advantageous effect on the mechanical properties of the fiber. However, melt spinning processing often requires significantly higher temperatures than wet spinning, which can lead to accelerated degradation or crosslinking reactions of the polymer and, in turn, adversely affect the properties of the fiber being produced or can lead to crosslinking reactions of the polymer Can limit processability in the extrusion process.

The object of the invention is to propose a bristle which is suitable for brushes, in particular for toothbrushes and which can be produced simply and inexpensively while at least minimizing the aforementioned disadvantages and nevertheless provides sufficient bending stiffness and durability at the smallest possible diameter. having activity. 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.

In terms of product technology, this object is achieved with a bristle of the type mentioned at the outset, which is formed from a section of a plastic filament, the polymer matrix of the plastic filament being at least 70 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, wherein the polymer matrix of the plastic filament further contains at least one additive from the group of antioxidants and UV stabilizers, and wherein the maximum diameter of the plastic Filamentes between 0.01 mm and 0.13 mm.

Further, the invention provides for solving this problem, a brush with at least one bristle carrier and a plurality of fixed to the bristle carrier bristles, in particular in the form of a toothbrush, before, at least in some bristles is those of the aforementioned type.

Finally, in order to achieve this object, the invention provides a process for the production of such a bristle comprising the following steps:

(A) providing a spinning mass, which at least

70 wt .-% of at least one thermoplastic aliphatic polyketone contains, consisting of carbon monoxide units (CO units) and alkyl moieties is constructed, and wherein the at least one thermoplastic aliphatic polyketone, in particular up to

10% by mass, containing at least one additive from the group of antioxidants and UV stabilizers;

(b) extruding the dope according to step (a)

at least one nozzle plate having one or more spinning capillaries with a diameter of at most 1.0 mm, in particular of at most 0.8 mm, preferably of at most 0.4 mm, wherein the temperature of the spinning mass on the outlet side of the spinning capillary (s) in the range of 190 ° C to 300 ° C, in particular in the range of 200 ° C to 270 ° C, preferably in the range of 220 ° C to 260 ° C is set;

(c) stripping off the filament formed at a take-off speed in the range from 1 to 200 m / min, in particular from 5 to 50 m / min, preferably by selecting the ratio of draw speed to exit speed of the spinning mass from the spinning capillary of greater than 1;

(d) single or multiple stretching of the formed filament;

(e) optionally spooling the formed filament; and

(f) cutting the formed filament to obtain the

Bristles.

The plastic filaments according to the invention, which are manufactured primarily from thermoplastic, aliphatic polyketones which are composed of carbon monoxide units (CO units) and alkyl units, are distinguished by a unique combination of properties which make them suitable for use as dental filaments, in particular for toothbrushes, opens. Thus, the polyketones of the invention show a high mechanical, hydrolytic and chemical resistance, eg to weak acids or bases as well as to saliva. They also have a pronounced balance between stiffness and toughness of the material as well as an extraordinary abrasion resistance, whereby even in the moist state a comparatively small change of the mechanical material properties, such as the bending and tensile strength, occurs, so that the plastics material according to the invention Filament with a very small diameter between about 0.01 mm and about 0.13 mm is able to fulfill its intended cleaning effect optimally. The plastic filament based on the abovementioned polyketones, in particular, benefits from the high levels of recovery both in air and in water and their high flexural strength combined with physiological safety, so that the plastic filament for dental care has a very high resistance low

Diameter can be provided, but still achieves a level or even better cleaning effect than conventional filaments based on polyamides or the like with larger diameters, which also can not develop their cleaning effect in very narrow (tooth) spaces. Consequently, the plastic filaments of the invention based on said thermoplastic aliphatic polyketones are able to penetrate deeper into interdental spaces or even in periodontal pockets and also to clean these areas better than filaments made of conventional materials according to the prior art the technology is possible. However, there is a disadvantage of the invention as

Bristles used thermoplastic polyketones, which are composed of carbon monoxide and alkyl moieties, in that they usually a not satisfactory oxidation resistance and relatively poor resistance to electromagnetic

Have radiation in the ultraviolet spectrum, which has been found to be intolerable for brushes in general and in particular for toothbrushes, which must meet the highest standards of health safety and hygiene, intolerable. This is counteracted by the invention 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, in particular in the case of toothbrushes Bristles which have been described in detail below, physiologically harmless antioxidants and UV stabilizers have been found to be particularly suitable.

A brush, such as A toothbrush containing the bristles according to the invention, be it exclusively or in particular in part, may be of any known form, wherein the bristles may be arranged, for example, in bristle bundles. However, due to the very small diameter of its bristles of at most about 0.13 mm, the brush can have more bristles than is the case in the prior art, for example 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. In addition, it has been found that the bristles according to the invention are also particularly suitable for sonic and ultrasonic toothbrushes.

The thermoplastic aliphatic polyketone used for the plastic matrix of the bristles according to the invention comprises in particular exclusively consists of carbon monoxide units or CO units and alkyl units, the aliphatic polyketones being co- or terpolymers with recurring structural units of the formula

-R-CO- is, which usually, though not notwendi ^¬ gerweise are exclusively, alternately arranged, but may also be arranged randomly mainly. In this case, "R" is an alkyl radical, preferably a divalent aliphatic radical having two to six carbon atoms, ie a divalent ethyl, propyl, butyl, pentyl and / or hexyl group.

In the melt spinning process according to the invention for the production of plastic filaments based on thermoplastic, aliphatic polyketones is first a

A dope containing at least about 70% by weight of at least one such polyketone and, more preferably, up to about 10% by weight of at least one additive selected from the group consisting of antioxidants and UV stabilizers. This dope is dosed to melt into an extruder, which may be, for example, a single screw extruder having a length to diameter ratio of from about 20 to about 40, more preferably from about 25 to about 30. The screw of the extruder can advantageously be divided into three parts and have a region for the collection of the spinning mass and for melting the same, a subsequent region for compaction and homogenization and in turn a subsequent region for ejecting the plasticized dope. The extruder may preferably comprise a plurality of zones for melting and homogenizing the dope, wherein all zones substantially at the same temperature or with decreasing or increasing temperature profile or can also be operated with a temperature profile showing temperature maxima and / or minima.

The plasticized dope is then pressed in molten form through a die plate, which may have one or more spinning capillaries whose diameter is at most about 1.0 mm, in particular at most about 0.8 mm, preferably at most about 0.4 mm (each corresponding to the Diameter of the bore at the exit side of the polymer mass), wherein the temperature of the spinning mass on the exit side of the spinning capillary (s) in the range of about 190 ° C to about 300 ° C, in particular in the range of about 200 ° C to about 270 ° C. , preferably in the range of about 220 ° C to about 260 ° C, for example in the range of about 220 ° C to about 250 ° C, such as in the range of about 237 ° C to about 242 ° C, (each at the exit from the spinning capillaries) is set. As a rule, the nozzle plate can be part of a spin pack which distributes the melt stream to the existing spinning capillaries and builds up the pressure necessary for spinning, and which advantageously comprises filter means for the molten spinning mass, e.g. in the form of a metal mesh with a mesh size of about 10 mesh to about 350 mesh, in particular of about

80 mesh to about 250 mesh, and may include the downstream nozzle plate. Additional filtering devices may optionally be in another, in the melt channel of the extruder mounted and preferably exchangeable by means of a screen changer metal mesh of the type described. The temperature of the spinning mass should be chosen such that on the one hand sufficient fluidity of the spinning mass is ensured, on the other hand, the thermal load of the spinning mass on the basis of the polyketones according to the invention remains limited, so that Crosslinking and degradation reactions and gel formation in the dope can be kept within limits or even completely suppressed. In order to spin the melt into the filaments, the melt can also, after the extrusion process by means of one or more spin pumps, for example 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, are pressed through the nozzle plate, which may have, for example, between 1 and about 750 spinning capillaries with one of the aforementioned diameters. As the preferred direction of flow of the melt, a substantially vertical direction has been found, although not necessarily.

After shaping the filaments by means of the spinning capillaries, optionally a quenching thereof may be provided, which for example take place at a distance downstream of the spinning capillaries between about 0.1 cm and about 20 cm, and e.g. 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 can take place.

The resulting filament is then stripped from the spinning capillaries, for example by means of a suitable set of godets, expediently take-off speeds of between about 1 m / min and about 200 m / min, in particular between about 1 m / min and about 120 m / min, preferably be set 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 such that in relation to the exit speed of the spinning mass results in a draw ratio of greater than 1 from the die, resulting in a higher crystallinity of the filament with improved mechanical stability, flexural strength and flexural recovery. In addition, the so selected degree of stretching improves the diameter uniformity of the filaments.

Immediately thereafter, one or more filament stretches, e.g. between different godet sets with a total draw factor of preferably 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, e.g. in the range between about 1: 4,8. Advantageously, it can be provided in this context that adjoining one or each stretching stage is a relaxation or fixing stage in which stresses 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, eg in the range of about 1: 0.88. 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 ° C., in particular at temperatures of up to about 250 ° C., e.g. in the range of about 180 ° C to about 220 ° C, take place.

Then, optionally, an application of lubricants, antistatic agents, thread-locking agents and the like to the filaments to improve their processability can be performed, whereby a preferred application mode can be made by means of an adjustable roller speeding roller over which the filaments run in isolated or bundled form. Subsequently, the filaments produced can be supplied to a suitable storage form, for example, wound up, in order to be able to keep the filament on a spool or reel, for example in a round, oblong or other form, in stock. Optionally, a transfer of the filament bundles produced can be made into a strand form. In any case, a subsequent packaging, for example by means of coating a tube or wrapping done with eg paper or plastic. Optionally, a final fixation of the filaments, for example in the form of a thermofixation at about 60 ° C. to about 220 ° C. in an annealing oven for about 5 minutes to about 30 hours or by means of a treatment in an autoclave for about 10 minutes be carried out until about 24 h, preferably before packaging.

Finally, the filaments are produced in one

Cutting device tailored to the bristles.

By a combination of adapted process parameters, such as temperature, shear, throughput, spinning delay, degree of twist, fixation and residence time, any possible crosslinking of the polymer matrix of the filaments can be suppressed. In an advantageous embodiment, it can be provided that the polymer matrix of the plastic filament is at least about 80% by weight, for example at least about 85% by weight, in particular at least about 90% by weight, for example at least about 95% by weight, preferably about 100%, based on the total polymer matrix, containing at least one thermoplastic aliphatic polyketone, which is composed of carbon monoxide and alkyl moieties. In a further advantageous embodiment, the at least one thermoplastic, aliphatic polyketone is a polyketone from the group of the ethylene / CO copolymers, the propylene / CO copolymers, the ethylene / propylene / CO terpolymers and Polymer blends from this. Last ^¬ re have the general structural formula

where R is a monovalent methyl group (CH ₃ group). However, as already mentioned, the ethyl-CO units and the propyl-CO units need not necessarily be arranged exclusively alternately, and the monovalent methyl group "R" of the above propyl moiety may be further bonded to the adjacent carbon atom of the above CH ₂ group (- [CO-CH ₂ -CHR-] _n -), eg in predominantly random distribution in the molecule.

In procedural terms, it can therefore be provided in this connection that the at least one thermoplastic aliphatic polyketone according to step (a) is selected from the group consisting of the ethylene / CO copolymers, the propylene / CO copolymers, the ethylene / propylene / CO- erpolymere and polymer blends thereof is selected.

As already mentioned, the invention gives, in particular, the possibility of a very thin design of the

Bristles, wherein it can be preferably provided that the maximum diameter of the plastic filament 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.

Moreover, it can be advantageously provided in a bristle according to the invention that the at least one thermoplastic, aliphatic polyketone has at least one of the following material parameters:

a melting temperature between about 180 ° C and about

250 ° C, especially between 190 and 230 ° C, preferably between about 197 ° C and about 223 ° C;

a melt flow index (MFI) between about 1 g / 10 min and about 350 g / 10 min, in particular between about 2 g / 10 min and about 300 g / 10 min, preferably between about 6 g / 10 min and about 60 g / 10 min, determined according to ASTM D1238 and ISO 1133 at a temperature of 240 ° C and 21.6 N;

a tensile strength at yield of between about 35 MPa and about 70 MPa, in particular between about 43 MPa and about 63 MPa, determined according to ASTM D638 at 23 ° C; and

a flexural modulus between about 450 MPa and about 2750 MPa, in particular between about 650 MPa and about 2350 MPa, preferably between about 650 MPa and about 2000 MPa, determined according to ASTM D790 at 23 ° C. As already indicated, the polymer matrix of the plastic filament based on thermoplastic poly ketones, which are composed of carbon monoxide and alkyl units, expediently up to about 10 Mass .-%, in particular up to about 5 Mass .-%, preferably up to about 4% by weight, for example up to about 3% by weight or even up to about 2% by weight, in each case based on the entire polymer matrix, of the at least one additive from the group of the antioxidants and UV stabilizers contain, wherein in many cases it may also be sufficient if the polymer matrix contains up to about 1% by weight of at least one of the abovementioned additives. With regard to such additives, it may be preferable for the reasons given above for the at least one additive from the group of the antioxidants and the UV stabilizers to contain at least one additive from the group of sterically hindered phenols, the HALS (hindered amine light stabilizer) and comprising phosphites.

As antioxidants, which of the polymer matrix of the plastic filament, for example, with an advantageous part to about 0.1 wt .-% and about 5 Mass .-%, preferably between about 0.5 wt .-% and about 3 mass .-%, may be used according to the invention, in particular Ste hischgehindererte phenols and / or HALS (hindered amine light stabilizer) and / or phosphites can be used, which optionally combined with co-stabilizers who can. Advantageous antioxidants based on sterically hindered phenols include sterically hindered alkylated monophenols, eg, 2, 6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxyphenol, sterically hindered Alkylthiomethylphenole , eg 2,4-dioctylthio methyl-6-tert-butylphenol, sterically hindered hydroxylated thiodiphenyl ethers, eg 2, 2 * -thio-bis (6-tert-butyl-4-methylphenol), 4,4 '- Thio-bis (6-tert-butyl-3-methylphenol) 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di -sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxy-phenyl) disulphide, sterically hindered alkylidene-bisphenols, eg 2, 2'-methylene-bis- (6-tert-butyl) butyl-4-methylphenol, sterically hindered benzylphenols, eg 3, 5, 3 ', 5 ¹ -tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, hindered hyd crude benzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate or bis (1,2,2,6,6-pentamethyl-4-piperidyl ) - [[3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylmalonate, sterically hindered hydroxybenzyl aromatics, eg, 1, 3, 5-tris (3, 5-di tert-butyl) -4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5, 6 -tetramethylbenzene, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol, sterically hindered phenolic triazine compounds, e.g. B. 2, 4-bis-octylmercapto- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2,4-bis [[4- (2-ethylhexyloxy ) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1, 3, 5-triazine or 2- (4,6-bis (2, -dimethylphenyl) -1, 3, 5-triazine 2-yl-5- (3- ((2-ethylhexyl) oxy) -2-hydroxypropoxy-phenol, sterically hindered phenolic benzylphosphonates, eg, dimethyl-2, 5-di-tert-butyl-4 hydroxybenzylphosphonate, N- (3, 5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid alkyl ester, ester of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with one or more valent alcohols, esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, esters of ß- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with a or polyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , such as N, N'-bis (3, 5-d i-tert-butyl-4-hydroxy-phenylpropionyl) -hexamethylenediamine, Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine or N, N ¹ -bis ( 3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine. Further examples of 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-dimethyl- ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, p-tert-amylphenolformaldehyde, β-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-methylphenyl] -1, benzene dicarboxylate and 1, 2-bis [3, 3-bis-

(3-tert-butyl-4-hydroxyphenyl) butanoate] ethylene. Advantageous co-stabilizers include e.g. organic phosphites and / or organic phosphonites, e.g. 5-butyl-5-ethyl-2-

(2,4,6-tris-tert-butylphenoxy) -1,3-dioxa-2-phosphorinane, diethylphosphonoacetic acid ethyl ester or 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphonite, which are known as such co-stabilizers for antioxidants. Examples of preferred UV stabilizers include UV-absorbing compounds, for example benzophenones, for example 4-tert-butyl-2- (5-tert-butyl-2-oxo-3H-benzofuran-3-yl) -phenyl-3, 5-di-tert-butyl-4-hydroxybenzoate, and benzotriazoles, eg, 2 (2'-hydroxy-5'-methylphenyl) benzotriazoles, 7,9-alkyl-3- [3- (2H-benzotriazole-2-one yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl] propionates, 2- (4, 6-diphenyl-l, 3, 5-triazin-2-yl) -5-hexyloxy) phenol or 3, 5 Di-tert-butyl-4-hydroxy-3-phenylpropionic acid ester of the 1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,8- (1H, 3H, 5H) -trione, triazines, in particular hydroxyphenyltriazines, for example 2,4-bis [[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine or 2- (4 , 6-bis- (2,4-dimethylphenyl) -1,3,5-triazin-2-yl-5- (3- ((2-ethylhexyl) oxy) -2-hydroxypropoxy-phenol, as well as compounds of the HALS type ("hindered amine light stabilizer"), eg bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -1, 10-decane diacid, N, N ¹ -propane-1,3-diyl-bis- (3,5-di-tert-butyl-4-hydroxy-3-phenyl-propionamide) or the like. In addition, it can of course be provided in a bristle according to the invention that the polymer matrix of the plastic filament contains at least one further additive from the group of pigments and dyes, fillers, matting agents, reinforcing agents, crystallization accelerators, lubricants and antistatic agents are physiologically harmless in particular and their proportion is based on the amounts usually added, which depend primarily on the type of the respective additive. In terms of process engineering, it may be provided in this context that the at least one thermoplastic aliphatic polyketone according to step (a) is added to the respective desired amount of at least one further additive of the aforementioned type or a master batch already contains the particular additive. The same applies, of course, to the additives compulsorily provided according to the invention from the group of antioxidants and UV stabilizers. For the purpose of coloring the plastic

Filaments may preferably be used on the basis of inorganic pigments or organic dyes, which may be e.g. in the form of a masterbatch with a suitable carrier material during extrusion

(Step (b) of the method according to the invention) can be metered. Examples of preferred pigments include carbon black, titanium dioxide or iron oxides. Examples of 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 barytes, or oxides and hydroxides, such as quartz flour, crystalline silica, Alumi ^¬ nium- or magnesium hydroxides or magnesium, zinc or calcium.

An example of a preferred matting agent is titanium dioxide; Examples of preferred crystallization accelerators include carboxylic esters. Examples of preferred lubricants include polyolefin waxes, fatty acids or their salts, fatty alcohols, fatty acid esters, silicones, polysiloxanes and in particular PMSQ, as described in EP 2,933,361 AI. Examples of preferred antistatic agents include carbon blacks, graphite, graphene, carbon nanotubes (CNTs), or metal particles.

Examples of preferred processing aids include waxes or longer chain carboxylic acids including their salts, aliphatic, aromatic esters or ethers.

As already indicated, in combinations of the thermoplastic aliphatic polyketones with selected other thermoplastic polymers, the individual polymer components complement each other in a synergistic manner, wherein the plastic filaments can be given excellent mechanical properties, such as a high modulus of elasticity, by the other polymers Creep, low Kröpfungsneigung etc., and by the thermoplastic aliphatic polyketone in particular a high flexural strength and increased abrasion resistance in order to make the plastic filament very thin. According to a According to a further development of a bristle according to the invention, the polymer matrix of the plastic filament can be up to about 30% by weight, for example up to about 25% by weight, in particular up to 20% by weight, 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 total polymer matrix, of at least one further thermoplastic polymer. The at least one further thermoplastic polymer may preferably be chosen from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyether sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, polyetherimides , Polyetheretherketone, the thermoplastic elastomers, in particular in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid crystalline polymers may be selected, of course, several representatives of the aforementioned polymers can be used. These other polymers are primarily known as such polymers, which are already used in the prior art for the production of filaments.

Examples of polyolefins include homo- or copolymers derived from ethylene and / or from propylene, optionally in combination with other ethylenically unsaturated aliphatic hydrocarbons, such as 4 to 8 carbon olefins. Polyethylene and polypropylene can be present in different densities and crystallinities. Examples of polyesters include thermoplastic polymers derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as the alkyl esters, and aliphatic, cycloaliphatic and / or aromatic dihydric alcohols, such as ethylene glycol, 1, 3-propylene glycol and / or butylene glycol. Other examples of poly ^¬ ester include thermoplastic elastomeric polyester (TPE C), such as polyester comprising recurring butylene terephthalate repeating units and comprising recurring polybutylene glycol terephthalate structural units. Aromatic-aliphatic polyester homopolymers or copolymers, such as, for example, polybutylene terephthalate homopolymers or copolymers comprising butylene terephthalate units, may be used. Such preferred polymers are thus derived from butylene glycol and optionally further alcohols and terephthalic acid or its polyester-forming derivatives, such as terephthalic acid esters or chlorides, from. In addition to or instead of 1,4-butanediol, such polyesters may contain structural units derived from other suitable dihydric alcohols, typical representatives of which include aliphatic and / or cycloaliphatic diols, for example 1,2-ethanediol, 1,3-propanediol, 1,2 Cyclohexanedimethanol or mixtures thereof. In addition to or instead of terephthalic acid or its polyester-forming derivatives, such polyesters may 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, adipic acid , Sebacic acid or mixtures thereof. It can follow It is also possible to produce plastic filaments which contain other polyesters, for example polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate homopolymer or copolymers comprising ethylene naphthalate units. Building blocks of thermoplastic copolyesters preferably comprise the abovementioned diols and dicarboxylic acids, or correspondingly constructed polyester-forming derivatives. Preference is given to using polyesters whose solution viscosities (IV values) are at least about 0.60 dl / g, in particular between about 0.80 dl / g to about 1.05 dl / g, preferably between about 0.80 dl / g and about 0.95 dl / g, each measured at 25 ° C in dichloroacetic acid (DCE)). Examples of polyamides 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. Other examples of polyamides include thermoplastic-elastomeric polyamides (TPE-A), for example polyamides containing repeating hexamethylene terephthalamide structural units and containing repeating polyethylene glycol terephthalamide structural units. Preferably used polyamides comprise in particular partially crystalline aliphatic polyamides which can be prepared starting from aliphatic diamines and aliphatic dicarboxylic acids and / or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids. Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,, -trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably 1-tetramethylene diamine, 1,6-hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisamino-methylcyclohexane, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams into consideration. Copolyamides of several of the monomers mentioned are included. Caprolactams, in particular ε-caprolactam, can be used with particular preference. The aliphatic homo- or copolyamides used according to the invention are furthermore 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. Furthermore, the polyesters and polyamides used according to the invention can also be derived from hydroxycarboxylic acids or from aminocarboxylic acids.

Examples of polyoxymethylenes include homopolymers or copolymers which contain repeating structural units of the formula -CH ₂ -O-.

Examples of polyurethanes include homo- or copolymers 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-O-C ₂ H ₄ -O-CONH-. Further examples of polyurethanes include thermoplastic-elastomeric polyurethanes (TPE-U).

Examples of polyphenylene sulfides include poly-p-phenylene sulfides, for example homopolymers or copolymers which contain repeating structural units -para-C ₆ H ₄ -S-. Examples of polyphenylene sulfones include poly-p-phenylene sulfone, for example, homopolymers or copolymers containing as structural units ^¬ derkehrende -p-C ₆ H ₄ -SO _x - contain, in WO x is a number between 1 and 2 is.

Examples of polyphenylene ethers include poly-p-phenylene ethers, for example homopolymers or copolymers which contain repeating structural units -para-C ₆ H ₄ -O-.

Examples of polyphenylene ketones include poly-p-phenylene ketones, for example homopolymers or copolymers which contain repeating structural units -para-C ₆ H ₄ -CO-. Examples of polyphenylene ether ketones include poly-p-phenylene ether ketones, for example, copolymers containing repeating structural units -para-CgH ₄ -CO- and recurring structural units -para-C ₆ H ₄ -O-. Examples of liquid-crystalline polymers include liquid-crystalline aromatic polyesters, for example homopolymers or copolymers, which contain repeating structural units derived from para-hydroxybenzoic acid. According to one embodiment of a plastic filament bristle, the polymer matrix of which comprises 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 above type in 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.

In terms of process engineering, it can therefore be provided in this connection that the at least one thermoplastic aliphatic polyketone according to step (a) is up to about 30% by mass, in particular up to about

20 at .-%, preferably up to about 10 Mass .-%, of at least one further thermoplastic polymer, in particular from the group of polyolefins, the polyester, the polyamides, the polyoxymethylene, the polyurethanes, the polyphenylene sulfides, the polyphenylene sulfone, the Polyethersulfone, the polyphenylene ether, the polyphenylene ketones, the polyphenylene ether ketones, the polyetherimides, the Polyetheretherketo- ne, the thermoplastic elastomers, preferably in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid crystalline polymers added. According to a further embodiment of a plastic filament bristle, the polymer matrix of which, in addition to the thermoplastic aliphatic polyketone, which is composed of carbon monoxide and alkyl units, contains at least one further thermoplastic polymer, such as one or more polymers of the abovementioned type, may alternatively or additionally 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 arranged together, in particular in a side-by-side and / or or a core-shell structure. From a procedural point of view, it can therefore be provided in this context that the method comprises the following additional steps:

(a2) providing another dope which

at least one further thermoplastic polymer, in particular from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyethersulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, polyetherimides, polyetheretherketones containing thermoplastic elastomers, in particular in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid-crystalline polymers; and

(b2) extruding both the spinning mass according to step (a) and the other spinning mass according to step (a2) in an extruder through at least one nozzle plate with one or more spinning capillaries, so that each spinning capillary of both the spinning mass according to step

(A) and by the further dope according to step (a2) is flowed through.

Such coextrusion of various thermoplastic polymers for producing filaments is known as such from the prior art.

It should be noted at this point that the cross-sectional shape of the plastic filaments according to the invention does not necessarily have to be (circular) round, but to be arbitrary. For example, these may be regular or irregular cross-sections, point- or axis-symmetrical cross-sections, for example round, oval or n-cornered cross-sections, where n is greater than or equal to 3, to tri or multilobal cross sections and the like.

In addition, to improve the cleaning effect of the bristles of the invention may be provided that

- Its lateral surface is provided with an embossing;

and or

- It is designed corrugated in the longitudinal direction.

Thus, in the plastic filament, for example by means of a stamping mill, a corrugation with any amplitude and / or wavelength can be pressed in, or it can be applied to the outer surface of the plastic filament, e.g. another embossing are applied, which is advantageously carried out before the filaments are cut to length according to step (f).

If desired, the bristle of the invention may also be taped mechanically and / or chemically. Further features and advantages of the invention will become apparent from the following description of an embodiment with reference to the drawing. The single FIGURE shows a schematic detail view of an embodiment of a toothbrush with thin bristles formed from sections of a plastic filament based on thermoplastic, aliphatic polyketones.

The graphically reproduced toothbrush comprises a bristle carrier 1 and a handle 2 (shown broken off), which in the present embodiment is a formed lumpy and are made for example of one or more conventional, especially thermoplastic, plastics. On the bristle carrier 1, a plurality of bristles 3 is fixed, which may be fixed in the bristle carrier 1 by means of encapsulation, for example, and in the present case are arranged in a plurality of bristle bundles 4 arranged in rows and columns, for example in matrix-like fashion. The bristles 3 each consist of a section of a thermoplastic 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 during the intended use of the toothbrush and a very high number For example, bristles of between about 5,000 and about 7,000, such as about 6,000, can accommodate bristle carriers to provide a very efficient cleaning action.

Claims

claims

1. bristle (3), which is formed from a portion of a plastic filament, wherein the polymer matrix of the plastic filament at least 70 Mass .-%, based on the total polymer matrix, of at least one thermoplastic aliphatic polyketone containing Carbon monoxide and alkyl units is constructed, wherein the polymer matrix of the plastic filament further contains at least one additive from the group of antioxidants and UV stabilizers, and wherein the maximum diameter of the plastic filament is between 0.01 mm and 0.13 mm ,

2. Bristle according to claim 1, characterized in that the polymer matrix of the plastic filament at least 80 Mass .-%, in particular at least 90 Mass .-%, preferably about 100%, based on the total polymer matrix, of the at least one thermoplastic, aliphatic polyketone contains, which is composed of carbon monoxide and alkyl moieties.

3. bristle according to claim 1 or 2, characterized in that it is the at least one thermoplastic, aliphatic polyketone to a polyketone from the Group of ethylene / CO copolymers, the propylene / CO copolymers, the ethylene / propylene / CO terpolymers and polymer blends thereof.

Bristle according to one of claims 1 to 3, characterized in that the maximum diameter of the plastic filament between 0.01 mm and 0.11 mm, in particular between 0.01 mm and 0.08 mm, preferably between 0.01 mm and 0.06 mm.

Bristle according to one of claims 1 to 4, characterized in that the at least one thermoplastic, aliphatic polyketone has at least one of the following material parameters:

a melting temperature between 180 ° C and 250 ° C, in particular between 190 ° C and 230 ° C;

a melt flow index between 1 and 350 g / 10 min, especially between 2 and 300 g / 10 min, determined according to ASTM D1238 and ISO 1133 at 240 ° C;

a yield stress between 35 MPa and 70 MPa, in particular between 43 MPa and 63 MPa, determined according to ASTM D638 at 23 ° C; and

a flexural modulus between 450 MPa and 2750 MPa, in particular between 650 MPa and 2000 MPa, determined according to ASTM D790 at 23 ° C.

Bristle according to one of claims 1 to 5, characterized in that the polymer matrix of the plastic filament up to 10 mass .-%, in particular up to 5 mass .-%, based on the total polymer matrix, of we least one additive from the group containing antioxidants and UV stabilizers. Bristle according to one of claims 1 to 6, characterized in that the at least one additive from the group of antioxidants and UV stabilizers we least one additive from the group of sterically hindered phenols, the HALS (hindered amine light stabili zer) and comprising phosphites.

Bristle according to one of claims 1 to 7, characterized in that the polymer matrix of the plastic filament at least one further additive from the group of pigments and dyes, the fillers, de Mattierungsmittel, reinforcing agents, the crystallization lisationsbeschleuniger, the lubricant and the anti-static contains statika.

Bristle according to one of claims 1 to 8, characterized in that the polymer matrix of the plastic filament up to 30% by mass, in particular up to 20% by mass, preferably up to 10% by mass, based on the total polymer matrix, contains at least one other thermoplastic polymer.

Bristle according to claim 9, characterized in that the at least one further thermoplastic polymer from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyether sulfones, polyphenylene ethers, polyphenylene lenketone, the polyphenylene ether ketones, the polyether imides, the polyetheretherketones, the thermoplastic elastomers, in particular in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid crystalline polymers is selected.

Bristle according to claim 9 or 10, characterized in that the polymer matrix of the plastic filament is at least partially formed from a polymer blend of the at least one thermoplastic polyketone and the at least one further thermoplastic polymer. 12. Bristle according to one of claims 9 to 11, characterized in that the plastic filament has a cross section in which the at least one thermoplastic polyketone and the at least one further thermoplastic polymer spatially separated, but are arranged together, in particular in one side on-side and / or a core-shell structure.

13. Bristle according to one of claims 1 to 12, characterized in that

- Its lateral surface is provided with an embossing; and or

- It is designed corrugated in the longitudinal direction.

Bristle according to one of claims 1 to 13, characterized in that it is mechanically and / or chemically tufted.

Brush with at least one bristle carrier (1) and a plurality of bristles (3) fixed to the bristle carrier (1), in particular in the form of a toothbrush, characterized in that at least some bristles (3) are those according to one of claims 1 until 14 acts.

Brush according to claim 15, characterized in that

- The bristles (3) arranged in bristle bundles (4)

are; and or

- The brush at least 5000 bristles (3), in particular at least 5500 bristles (3).

A method of making a bristle (3) according to any one of claims 1 to 14, comprising the following steps:

(a) providing a spinning dope containing at least 70% by weight of at least one thermoplastic aliphatic polyketone which is composed of carbon monoxide and alkyl units, and wherein the at least one thermoplastic aliphatic polyketone, in particular up to 10% by weight, contains at least one additive from the group of antioxidants and UV stabilizers;

(B) extruding the spinning mass according to step (a) by at least one nozzle plate with one or more spin capillaries having a diameter of not more than 1.0 mm, in particular not more than 0.8 mm, preferably not more than 0.4 mm, the temperature of Dope is adjusted at the exit side of the spinning capillary (s) in the range of 190 ° C to 300 ° C, in particular in the range of 200 ° C to 270 ° C, preferably in the range of 220 ° C to 260 ° C;

(c) stripping the filament formed at a take-off speed in the range from 1 to 200 m / min, in particular from 5 to 50 m / min, preferably with a choice of the ratio of take-off speed to exit speed of the spinning mass from the Spinning capillary greater than 1;

(d) single or multiple stretching of the formed

filament;

(e) optionally spooling the formed filament; and

(f) cutting the filament formed to obtain the bristles (3).

18. The method according to claim 17, characterized

that

- The selected at least one thermoplastic aliphatic polyketone according to step (a) from the group of ethylene / CO copolymers, the propylene / CO copolymers, the ethylene / propylene / CO terpolymers and polymer blends thereof becomes; and or

- The at least one thermoplastic, aliphatic polyketone according to step (a) up to 30 Mass .-% of at least one other thermoplastic polymer, in particular from the group of polyolefins, the polyester, the polyamides, the polyoxymethylene, the

Polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyethersulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, polyetherimides, polyetheretherketones, thermoplastic elastomers, preferably in

Form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid crystalline polymers may be added. 19. The method according to claim 17 or 18, characterized in that the at least one thermoplastic aliphatic polyketone according to step (a) at least one further additive from the group of pigments and Dyes added to fillers, dulling agents, reinforcing agents, crystallization accelerators, lubricants and antistatic agents.

Method according to one of claims 17 to 19, characterized by the following additional steps:

(a2) providing a further dope comprising at least one further thermoplastic polymer, in particular from the group of polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyethersulfones, polyphenylene ethers, polyphenylene ketones; Polyphenylene ether ketones, the polyetherimides, the polyetheretherketones, the thermoplastic

Elastomers, in particular in the form of thermoplastic polyurethanes, polyesters and / or polyamides, and the liquid-crystalline polymers; and

(b2) extruding both the dope according to step

(A) as well as the further spinning mass according to step (a2) in each case an extruder through at least one nozzle plate with one or more spin capillaries, so that each spin capillary of both the spinning mass according to step (a) and the other dope according to step (a2 ) is flowed through.