Coated inorganic filaments and their preparation

Abstract

The present invention relates to a coated filament comprising an inorganic filament and a polymer composition comprising a thermoplastic polymer, wherein the polymer composition is in direct contact with the filament, and the coated filament has a length of 100 mm or more. In another embodiment, the present invention relates to a method for producing a coated filament, comprising the steps of: a. producing an uncoated inorganic filament, preferably an uncoated glass filament, from an inorganic melt; b. providing a melted polymer composition comprising a thermoplastic polymer; c. preferably applying the melted polymer composition to an uncoated inorganic filament using a roller die, a curtain coater die, or a slit die to solidify the melted polymer composition; d. obtaining a coated filament comprising an inorganic filament coated with a polymer composition, wherein the inorganic filament is in direct contact with the polymer composition; and e1. cutting the coated filament into pieces having a length of 100 mm or more, or e2 bundling a plurality of the coated filaments into a filament bundle or thread, and optionally cutting the filament bundle or thread into pieces having a length of 100 mm or more.

Description

[Background technology]

[0001] There are various processes for manufacturing inorganic fibers coated with organic materials as a base material, such as dip coating, predose coating, or curtain coating.

[0002] In the pre-dose coating process, the coating liquid is squeezed between the nozzle and the substrate. This causes shear forces acting on the substrate. During in-line filament coating, this can cause high-speed filament breakage.

[0003] In curtain coatings, the direction of the liquid flow and the movement of the fibers are not harmonized. This results in immediate changes in the direction of the liquid flow used for coating. Consequently, the Reynolds number increases, and therefore turbulence is generated. This turbulence does not coincide with the movement of the filaments and cannot be controlled, resulting in droplet formation in the liquid and the intrusion of air at the contact points.

[0004] The same applies to dip coating. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, the present invention is based on the objective of improving the above-mentioned problems. [Means for solving the problem]

[0006] The present invention is defined by the subject matter of the appended claims.

[0007] A coated filament is disclosed, comprising an inorganic filament and a polymer composition containing a thermoplastic polymer, wherein the polymer composition is in direct contact with the filament, and the coated filament has a length of 100 mm or more.

[0008] Because the polymer composition is in direct contact with the filament, this means that there are no components between the surface of the inorganic filament and the coating layer, and therefore, this means that there are no adhesion promoters, sizing agents, or similar compounds between the polymer composition and the inorganic filament. Typically, adhesion promoters or sizing agents are first applied to the inorganic filament before coating with the polymer composition.

[0009] The process described below eliminates the need for coating with an adhesion promoter or the like between the inorganic filament and the polymer composition.

[0010] Inorganic filaments are mineral materials, such as engineering glass (electric glass (E glass, aluminoborosilicate glass containing less than 1% by weight of alkali oxide); A glass (alkali-lime glass containing little to no boron oxide); AR glass; electro- / chemical resistant glass (E-CR glass, aluminoborosilicate glass containing less than 1% by weight of alkali oxide and having high acid resistance); C glass (alkali-lime glass with a high boron oxide content, also called T glass); D glass (borosilicate glass with a low dielectric constant); R Glass (aluminosilicate glass that does not contain MgO and CaO); S glass (aluminosilicate glass that does not contain CaO but has a high MgO content); M glass; or basalt; kaolin; alkaline earth silicates (combinations of AES, CaO, MgO, and SiO2); refractory ceramic fibers (RCF, also called aluminosilicate or ASW); polycrystalline wool (PCW, containing more than 70% alumina); alumina; metallic materials (steel alloys; aluminum alloys; copper alloys, platinum alloys, and pure platinum, especially alloys with rhodium).

[0011] Preferred inorganic filaments are glass fiber, E-glass, or E-CR glass.

[0012] The polymer composition includes, for example, at least 95% by weight, for example, at least 96% by weight, preferably at least 97% by weight, for example, at least 98.5% by weight, a thermoplastic polymer, and optionally, may contain, for example, 0.1 to 5.0% by weight of additives, based on the polymer composition.

[0013] Preferably, the polymer composition comprises at least 95% by weight of a thermoplastic polymer based on the polymer composition, and / or the thermoplastic polymer is selected from the group consisting of acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylate (ASA), polyethylene (PE), polyolefin elastomer (POE), polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride (PVC), polybutadiene (BR), ethylene propylene diene monomer (EPDM), polyamide (PA), thermoplastic polyurethane (TPU), and mixtures thereof, and preferably the thermoplastic polymer is polypropylene.

[0014] Thermoplastic polymers include acrylic polymers (acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polyisobutyl methacrylate (PiBMA), poly-n-butyl methacrylate (PnBMA), polyethyl methacrylate (PEMA), polymethyl methacrylate (PMMA)), cellulose acetate butyrate (CAB), fluorinated ethylene polypropylene (FEP), and other polymers soluble in trichloromethane, tetrachloromethane, or 1-bromonaphthalene, as well as polyamide 12 (polyamide Polyamides (PA) such as 12, PA-12), polycarbonates (PC) such as polybutadiene and bisphenol A polycarbonate, polyimides such as polychlorotrifluoroethylene (PCTFE) and polyetherimide (PEI), polysulfones such as polyethersulfone (PES), polyethylene (PE) such as UHMWPE, HMWPE, HDPE, LLDPE, LDPE, and polyethylene terephthalate (PET), polyisobutylene (PiB, butyl rubber), polyisoprene (PiP), polylactic acid (PLA), polyphenylene oxide (PPO), and polyphenylene sulfide (polyphenylene Polypropylene (PP), Atactic PP, Isotactic PP, Polystyrene (PS), Polysulfone (PSU), Polyurethane (PU), Polyvinyl acetate (polyvinylThe following materials may be selected from the group consisting of acetate (PVA), polyvinyl butyral, polyvinyl chloride (PVC), bromosoluble polymer, acrylic acid polymer, polyethyl methacrylate (PEMA), polymethyl methacrylate (PMMA), cellulose acetate (CA), cellulose acetate butyrate (CAThB), nitrocellulose (cellulose nitrate), polycarbonate (PC), bisphenol-A polycarbonate, polyphenylene oxide (PPO), polyurethane (PU), and polyvinyl acetate (PVA).

[0015] This composition is a grafted polypropylene which is A) grafted with C1) a side-chain compound capable of forming hydrogen bonds, and / or B) may include non-grafted polypropylene and C2) a compound capable of forming hydrogen bonds, and the total amount of A) and B) relative to the polypropylene composition is at least 70% by weight, and the polypropylene composition includes D) low molecular weight polyethylene having a maximum molecular weight of 5000 g / mol, for example, low molecular weight polyolefin, in an amount of less than 10% by weight relative to the polypropylene composition.

[0016] Adhesion between the polymer composition and inorganic fibers is improved by the use of adhesion promoters, preferably side-chain compounds capable of forming hydrogen bonds and / or compounds capable of forming hydrogen bonds in the polymer composition. Surprisingly, it has been found that it is possible to manufacture coated filaments in which the adhesion promoter is contained in the polymer composition itself rather than as an intermediate layer. This simplifies the manufacturing process.

[0017] A coated glass filament can take the form of a single glass filament with a coating layer. In this case, the coating layer may be provided on substantially all or part of the surface of the glass filament. A coated glass filament can also take the form of multiple glass filaments that are (partially) bundled together. In this case, the coating layer may not be present in the areas where the glass filaments are in contact with each other.

[0018] In some preferred embodiments, glass filaments with a coating layer are obtained by recycling polymer-coated glass filaments, such as epoxy-coated engraved glass filaments. To obtain uncoated glass filaments, the polymer, such as epoxy, can be removed from the polymer-coated glass filaments, for example, by burning the polymer. To obtain coated glass filaments, a coating of a polypropylene composition can be applied directly onto the thus obtained uncoated glass filaments. The use of recycled materials is highly desirable given the increasing awareness of sustainability.

[0019] The coated glass filament includes a coating layer of a polymer composition, preferably a polypropylene composition, directly applied to the glass filament. The absence of a sizing composition solves the problems associated with sizing compositions.

[0020] Preferably, the polypropylene composition used contains C1) a side chain compound capable of forming a hydrogen bond (as part of the grafted polypropylene) and / or C2) a compound capable of forming a hydrogen bond. The presence of C1) and / or C2) in the polypropylene composition improves the adhesion to glass fibers. Compounds C1) and C2) have a hydrogen atom or a functional group that can generate a hydrogen atom by (partial) hydrolysis of a group capable of forming a hydrogen bond with the glass filament. The hydrogen bond improves the adhesion of the polypropylene composition to the glass filaments. In some cases, in addition to forming a hydrogen bond, the condensation reaction between the silanol group on the glass surface and the hydrogen atom can create an ester or ether bond, and thus a covalent bond to the glass surface can occur.

[0021] A) Grafted polypropylene The polypropylene composition used may contain grafted polypropylene. Grafted polypropylene is polypropylene grafted with C1) a side chain compound capable of forming a hydrogen bond.

[0022] Suitable examples of C1) include anhydrides (e.g., maleic anhydride, itaconic anhydride), oligosilanes (e.g., vinyl-oligosilane, aminopropyl-oligosilane, acryloxy-oligosilane), epoxies, polyamides, and combinations thereof. The method of obtaining A) by grafting C1) onto polypropylene is known to those skilled in the art.

[0023] Preferably, C1) contains an anhydride (e.g., maleic anhydride, itaconic anhydride). Most preferably, C1) contains maleic anhydride. This results in good adhesion between the polypropylene composition and the glass filaments.

[0024] Preferably, the amount of C1) relative to the amount of A) is 0.5 to 10% by weight, for example, 0.6 to 5.0% by weight, 0.7 to 3.0% by weight, 0.8 to 2.0% by weight.

[0025] Compound capable of forming a hydrogen bond The polypropylene composition used may contain B) ungrafted polypropylene and C2) a compound capable of forming a hydrogen bond.

[0026] Preferable examples of C2) include oligosilanes (e.g., vinyl-oligosilane, aminopropyl-oligosilane, acryloxy-oligosilane), a copolymer of ethylene and 2-hydroxyethyl methacrylate (PE-HEMA), epoxy, polyamide, an organometallic compound having a pyrophosphate group, and combinations thereof.

[0027] Preferably, C2) is selected from the group consisting of oligosilanes (e.g., vinyl-oligosilane, aminopropyl-oligosilane, acryloxy-oligosilane), an organometallic compound having a pyrophosphate group, and combinations thereof. This provides good adhesion between the polypropylene composition and the glass filament.

[0028] Preferably, C2) contains vinyl-oligosilane or acryloxy-oligosilane, more preferably vinyl-oligosilane. This provides particularly good adhesion between the polypropylene composition and the glass filament.

[0029] It has been found that oligosilanes have a volatility low enough to react with polypropylene to achieve the desired effect.

[0030] Preferably, the polypropylene composition does not contain or substantially contains alkoxysilane compounds having a molecular weight of less than 300 (e.g., γ-aminopropyltriethoxysilane (APTES), γ-glycidoxypropyltrimethoxysilane (GPTMS), γ-methacryloxypropyltrimethoxysilane (MPTMS), vinyltriethoxysilane (VTES)). Preferably, the amount of such alkoxysilane compounds having a molecular weight of less than 300 relative to the polypropylene composition is less than 10% by weight, less than 5.0% by weight, less than 3.0% by weight, less than 1.0% by weight, less than 0.5% by weight, or 0% by weight.

[0031] Preferably, C2) includes an organometallic compound having a pyrophosphate group, preferably a titanate pyrophosphate compound or a zirconate pyrophosphate compound. This provides particularly good adhesion between the polypropylene composition and the glass filament. Suitable examples include neopentyl(diallyl)oxytri(dioctyl)pyrophosphate titanate, cyclo(di-octyl)pyrophosphate dioctyl titanate, dicyclo(dioctyl)pyrophosphate titanate, neopentyl(diallyl)oxytri(N-ethylenediamineo))ethyl titanate, cyclo[dineopentyl(diallyl)]pyrophosphate dineopentyl(diallyl)zirconate, di(dioctyl)pyrophosphate oxoethylene titanate, and 2-(N,N-dimethylamino)isobutanol adducts of di(dioctyl)pyrophosphate oxoethylene titanate.

[0032] Preferably, the amount of C2) relative to the total amount of B) and C2) is 0.2 to 10% by weight, for example, 0.3 to 5.0% by weight, 0.4 to 3.0% by weight, or 0.5 to 2.0% by weight.

[0033] D) Low molecular weight polyolefins Preferably, the polypropylene composition does not contain or substantially contains low molecular weight polyethylene having a number average molecular weight of up to 5000 g / mol. Preferably, the amount of such low molecular weight polyethylene, e.g., low molecular weight polyolefin, relative to the polypropylene composition is less than 10% by weight, less than 5.0% by weight, less than 3.0% by weight, less than 1.0% by weight, less than 0.5% by weight, or 0% by weight.

[0034] Preferably, the polypropylene composition does not contain, or substantially contains, low molecular weight polyolefins having a number average molecular weight of up to 5000 g / mol. For example, the total amount of such low molecular weight polyolefins (low molecular weight polyethylene having a number average molecular weight of up to 5000 g / mol and any other polyolefins having a number average molecular weight of up to 5000 g / mol) relative to the polypropylene composition is less than 10% by weight, less than 8.0% by weight, less than 5.0% by weight, less than 3.0% by weight, less than 1.0% by weight, less than 0.5% by weight, or 0% by weight.

[0035] additives Polymer compositions such as polypropylene compositions may further contain additives such as flame retardants, pigments, lubricants, slip agents, flow promoters, antistatic agents, processing stabilizers, long-term stabilizers, and / or UV stabilizers. The amount of additives may be, for example, 0.1 to 5.0% by weight.

[0036] Preferably, the total amount of A), B), C2), D), and the additives is 100% by weight relative to the polypropylene composition.

[0037] Preferred composition Preferably, the polypropylene composition has a melt viscosity of up to 25 Pa·s at the melting temperature of the polymer composition, preferably in the range of 1.0 to 25 Pa·s, more preferably in the range of 1.0 to 20 Pa·s, even more preferably in the range of 1.8 to 19.4 Pa·s, or in the range of 1.0 to 15 Pa·s, even more preferably in the range of 1.0 to 10 Pa·s, most preferably 1.0 to 5.0 Pa·s, the melting temperature of the polymer composition is determined for a 5 mg sample using differential scanning calorimetry on a second heating curve using heating and cooling rates of 10°C / min, and the melt viscosity is determined by applying vibration-shear to the molten sample with an angular frequency of 1 rad / s and a shear strain of 5% according to ISO 6721-10:2015.

[0038] In some preferred embodiments, the amount of A) relative to the polypropylene composition is at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or 100% by weight.

[0039] In some preferred embodiments, the total amount of B) and C2) relative to the polypropylene composition is at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or 100% by weight.

[0040] In some preferred embodiments, the polypropylene composition comprises A) and B). Preferably, the total amount of A) and B) relative to the polypropylene composition is at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 93% by weight, at least 95% by weight, at least 97% by weight, at least 99% by weight, or 100% by weight. Preferably, the amount of A) relative to the total amount of A) and B) is 1.0 to 30% by weight, for example, 2.0 to 25% by weight, 3.0 to 20% by weight, or 4.0 to 10% by weight.

[0041] In some preferred embodiments, the polypropylene composition comprises A), B), and C2). Preferably, the amount of B) relative to the total amount of A), B), and C2) is at least 65% by weight. Preferably, the amount of A) relative to the total amount of A) and B) is 1.0 to 30% by weight, for example 2.0 to 25% by weight, 3.0 to 20% by weight, or 4.0 to 10% by weight. Preferably, the amount of C2) relative to the total amount of B) and C2) is 0.2 to 10% by weight, for example 0.3 to 5.0% by weight, 0.4 to 3.0% by weight, or 0.5 to 2.0% by weight. In a particularly preferred embodiment, the amount of A) is 1.0 to 5.0% by weight, the amount of B) is 90 to 98% by weight, and the amount of C) is 1.0 to 5.0% by weight, relative to the total amount of A), B), and C).

[0042] In a particularly preferred embodiment in which the polypropylene composition comprises A), B), and C2), C1) is selected from the group consisting of anhydrides (e.g., maleic anhydride, itaconic anhydride), and C2) comprises an organometallic compound having a pyrophosphate group, preferably a titanate pyrophosphate compound or a zirconate pyrophosphate compound.

[0043] Further characteristics The present invention further provides a multifilament strand comprising a plurality of bundled coated glass filaments. The multifilament strand may further comprise uncoated glass filaments, but preferably, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, or at least 99% by weight of the multifilament strand are coated glass filaments.

[0044] The polymer composition may have a melt viscosity in the range of 1.0 to 25 Pas, preferably 1.8 to 19.4 Pas, at the melting temperature of the polymer composition. The melting temperature of the polymer composition is determined for a 5 mg sample using differential scanning calorimetry on a second heating curve with heating and cooling rates of 10°C / min. The melt viscosity is determined by applying vibration-shear to the molten sample with an angular frequency of 1 rad / s and a shear strain of 5%, in accordance with ISO 6721-10:2015.

[0045] Preferably, the polymer composition satisfies the following inequality 1, η≦(82×e^0.007×(ACTO))+_5 (Inequality 1) In the formula, η represents the melt viscosity in Pa·s measured at the melting temperature of the polymer composition, the melting temperature of the polymer composition was determined for a 5 mg sample using differential scanning calorimetry on a second heating curve with heating and cooling rates of 10°C / min, the melt viscosity was determined by applying vibration-shear to the melted sample with an angular frequency of 1 rad / s and a shear strain of 5% according to ISO 6721-10:2015, and ACTO represents the amount of reactive oxygen species in ppm in the polymer composition.

[0046] The reactive oxygen species content of a formulation is calculated based on the peroxide concentration and the reactive oxygen species content of the peroxide, which can be found in the supplier's technical data sheet.

[0047] The polymer composition can be applied to the glass filament in a molten state. The melt viscosity of the polymer composition at the application temperature (e.g., 250°C or 290°C) should not be too high.

[0048] Preferably, the polymer composition, such as a polypropylene composition, has a melt viscosity of up to 25 Pa·s at the melting temperature of the polymer composition, preferably in the range of 1.0 to 25 Pa·s, more preferably in the range of 1.0 to 20 Pa·s, even more preferably in the range of 1.8 to 19.4 Pa·s, or in the range of 1.0 to 15 Pa·s, even more preferably in the range of 1.0 to 10 Pa·s, most preferably in the range of 1.0 to 5.0 Pa·s, the melting temperature of the polymer composition is determined for a 5 mg sample using differential scanning calorimetry on a second heating curve using heating and cooling rates of 10°C / min, and the melt viscosity is determined by applying vibration-shear to the molten sample with an angular frequency of 1 rad / s and a shear strain of 5% according to ISO 6721-10:2015.

[0049] A polypropylene composition can be obtained by i) polymerizing monomers to obtain an intermediate polypropylene, and ii) sti-breaking the intermediate polypropylene.

[0050] For example, the intermediate polypropylene may have a melt flow index of 1.0 to 100 dg / min at 230°C and 2.16 kg, according to ISO 1133-1:2011.

[0051] Viscose breaking can be carried out by melt-mixing an intermediate polypropylene with at least one of a peroxide, a hydroxylamine ester, and a sulfur compound.

[0052] Preferably, the melt mixing is carried out at a temperature in the range of 160 to 300°C. If the melt mixing is carried out in the presence of a peroxide, it is preferably carried out at a temperature of 200 to 300°C, for example, 220 to 280°C or 240 to 260°C. If the melt mixing is carried out in the presence of a hydroxylamine ester, it is preferably carried out at a temperature in the range of 280 to 300°C.

[0053] When bis-breaking is performed in the presence of peroxides, the melting and mixing is carried out for a period of at least three times the half-life of the organic peroxide at the melting and mixing temperature, for example, 4 to 7 times or 5 to 6.5 times.

[0054] Preferably, the amount of peroxide in the bis-breaking step ii) is selected such that the polypropylene composition contains active oxygen at a concentration of at least 200 ppm, preferably 200 to 1000 ppm, relative to the polypropylene composition.

[0055] Preferably, the amount of peroxide in the bis-breaking step ii) is selected such that the polypropylene composition contains active oxygen at a concentration of at least 300 ppm, preferably at least 400 ppm, and more preferably at least 525 ppm relative to the polypropylene composition.

[0056] In some embodiments, the peroxide has a half-life of 1 hour at a first temperature of 120-145°C, preferably 125-140°C, more preferably 128-137°C. 1 / 2 It comprises a first peroxide having 1. An example of the first peroxide is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (e.g., Trigonox® 101 manufactured by AkzoNobel), which is 134°C T 1 / 2 It has 1.

[0057] Preferably, the first peroxide has a half-life of 0.1 hours at a temperature of 140 to 180°C, more preferably 150 to 170°C.

[0058] In some embodiments, the peroxide has a half-life of 1 hour at a second temperature greater than 145°C and up to 180°C, preferably up to 170°C, for example, greater than 145°C and up to 150°C, or at least 155°C and up to 170°C. 1 / 2 It contains a second peroxide having the following properties.

[0059] Furthermore, the second peroxide preferably has a half-life of 0.1 hours at a temperature of 165-188°C. An example of the second peroxide is T at 146°C. 1 / 2 3,6,9-triethyl-3,6,9-trimethyl-1,4,6-triperoxonane (e.g., Trigonox® 301 manufactured by Nouryon) having a half-life of 0.1 hours at temperatures of 2 and 170°C, and T 1 / 2 Examples include 3,3,5,7,7-pentamethyl-1,2,4-trioxepane (e.g., Trigonox® 311 manufactured by Nouryon) having a half-life of 0.1 hours at temperatures of 2 and 185°C.

[0060] In some embodiments, the peroxide is a first peroxide or a second peroxide.

[0061] In some embodiments, the peroxide includes a first peroxide and a second peroxide.

[0062] Preferably, the amount of peroxide relative to the intermediate polypropylene is 100 to 10,000 ppm.

[0063] Preferably, the amount of the first peroxide relative to the intermediate polypropylene is 100 to 2000 ppm.

[0064] Preferably, the amount of the second peroxide relative to the intermediate polypropylene is 100 to 8000 ppm, more preferably 1000 to 8000 ppm.

[0065] Preferably, the sulfur compound has the formula R1-SH, where R1 represents a C8-C18 alkyl group.

[0066] Polymer compositions with specific viscosities can be used particularly efficiently when coating inorganic filaments at high speeds.

[0067] The polymer composition coating can be either a speckle (spot) coating or a mantle coating. In the case of a speckle coating, the coating is distributed on the filament in the form of spaced speckles that cover 1-90%, 5-90%, and 10-90% of the fiber surface, rather than completely enclosing the filament. In the case of a mantle coating, the coating substantially completely encapsulates the filament while covering more than 90% of the fiber surface.

[0068] The filaments of the coated filament may have a diameter in the range of more than 2 μm to less than 50 μm, and / or the polymer composition layer may have a thickness in the range of more than 0.5 μm to less than 5 μm. The filaments of the coated filament may have a diameter in the range of more than 3 μm to less than 30 μm, preferably more than 8 μm to less than 10 μm. The polymer composition layer may have a thickness in the range of more than 0.02 μm to less than 3 μm, more than 0.1 μm to less than 3 μm, more than 0.2 μm to less than 3 μm, preferably more than 0.7 μm to less than 0.9 μm. Fibers (filament bundles) with various diameters can be manufactured from several filaments.

[0069] A filament bundle containing multiple of the above-mentioned coated filaments is also disclosed.

[0070] After coating with the polymer composition, the coated filaments can be immediately assembled or spun into filament bundles. Thus, the fluid polymer composition can still bind the filaments together. Consequently, the bonding within the filament bundles is particularly stable and can be further improved by adhesion promoters, especially in the case of speckle coatings, by the presence of compounds that can form hydrogen bonds in the polymer composition.

[0071] A single filament bundle may contain 2,000 to 5,000 coated filaments.

[0072] A filament bundle, or so-called thread, of the present invention is also disclosed.

[0073] A method for manufacturing coated filaments, a. A process for producing an uncoated inorganic filament, preferably an uncoated glass filament, from an inorganic melt; b. A step of providing a melted polymer composition containing a thermoplastic polymer, c. Preferably, a step of applying the molten polymer composition to an uncoated inorganic filament using a roller die, curtain coater die, or slit die, and solidifying the molten polymer composition. d. A step of obtaining a coated filament comprising an inorganic filament coated with a polymer composition, wherein the inorganic filament is in direct contact with the polymer composition, e1. A step of cutting the coated filament into pieces having a length of 100 mm or more, or e2 A method is also disclosed which includes the steps of gathering a plurality of the coated filaments into a filament bundle or thread, and optionally cutting the filament bundle or thread into pieces having a length of 100 mm or more.

[0074] Surprisingly, it was found that extremely high manufacturing speeds were possible by applying the process described in the claims.

[0075] In this process, the molten polymer composition may be distributed in the direction of gravity. In this process, the inorganic molten material and / or uncoated inorganic filament may be distributed in the direction of gravity.

[0076] Inorganic filaments are generally manufactured by drawing from an inorganic molten material. In the nozzle drawing process, glass pellets are weighed and melted in a nozzle box (bushing). The molten material exits the nozzle in the form of filaments and solidifies, so that individual filaments can be wound onto a drawing drum. For this purpose, the device may include, for example, a storage container for the glass pellets.

[0077] A coating device is present downstream of the nozzle, for example, a glass fiber bushing, from which a molten polymer composition is dispensed.

[0078] During application, the orientation of the uncoated inorganic filament and the polymer composition may be at an absolute angle of 45°, 25°, 10°, 5°, 1°, or 0° or less relative to each other at the point of contact.

[0079] In other words, the orientation of the uncoated inorganic filaments and the orientation of the polymer composition are substantially parallel to each other.

[0080] The angle is measured from the point where the polymer composition first wets the filament to the point where the polymer composition first passes over and makes direct contact with the filament (the first application point). The sides of the angle are the imaginary straight line through the filament between the wetting point and the first contact point and the straight line directly opposite on the surface of the polymer composition.

[0081] By specifying an angle or essentially parallelism, undesirable forces (warping forces, turbulence caused by changes in the direction of the polymer composition) are reduced, thus enabling rapid wetting of the filament.

[0082] When a polymer composition is applied to an uncoated inorganic filament, the rate at which the polymer composition moves may be 50% to 110%, 95% to 105%, or 99% to 101% of the rate at which the inorganic filament moves. Alternatively or additionally, the rate at which the inorganic filament moves may be 500 to 3000 m / min, 1250 to 1750 m / min, or 1450 to 1550 m / min.

[0083] Furthermore, by maintaining the speeds of the filament and polymer composition as equal as possible, the generation of undesirable forces (warping force, turbulence caused by changes in the direction of the polymer composition) can be reduced, enabling rapid wetting of the filament.

[0084] In particular, the combination of a low angle between the polymer composition and the filament at the application point, and the (almost) the same speed of the distributed polymer composition and filament, enables very high manufacturing speeds.

[0085] Inorganic melts and / or uncoated inorganic filaments may be electrostatically charged during manufacturing. Polymers may also be electrostatically charged.

[0086] Electrostatic charge can provide better adhesion of polymers to uncoated inorganic filaments, and vice versa.

[0087] Coated filaments may undergo further modification after being coated with a polymer composition. For example, adhesion promoters, crosslinking agents, lubricants, or film images can be applied to the coated filaments.

[0088] The polymer composition used in this method can be provided by mixing a thermoplastic polymer containing an adhesion promoter (e.g., a grafted polymer) with a thermoplastic polymer not containing an adhesion promoter (e.g., a non-grafted polymer). Each thermoplastic polymer may be provided in a solid or fluid form that results in a dry or wet blend, which can then be mixed. The solid polymer composition may be provided as pellets.

[0089] In this way, the ratio of thermoplastic polymers containing an adhesion promoter to thermoplastic polymers without an adhesion promoter can be suitably adjusted. The polymers can be mixed using an additional mixing device or an extruder.

[0090] After coating with the polymer composition, the coated filaments can be immediately assembled or spun into filament bundles. Thus, the fluid polymer composition can still bind the filaments together. Therefore, the bonding within the filament bundles is particularly stable, and can be further improved by the presence of adhesion promoters in the polymer composition, especially in the case of speckle coatings.

[0091] A coating apparatus for manufacturing coated filaments from uncoated inorganic filaments, in accordance with the above, a. A heating device for producing a fluid polymer composition, for example, a melted polymer composition containing a thermoplastic polymer. b. The nozzle is positioned to discharge the fluid polymer composition obtained from the heater in the direction of gravity, so that the fluid polymer composition meets the uncoated inorganic filament at the application point and begins to wet the uncoated inorganic filament at the wetting point. c. A supply line between the heater and the nozzle, d. A coating apparatus is also disclosed in which the nozzle is set such that the angle alpha between the application point and the wetting initiation point is 0° to 45°, 0° to 25°, 0° to 10°, or 0° to 1°, and the side of the nozzle is an imaginary straight line passing through the filament and an imaginary straight line passing through the polymer surface opposite the filament.

[0092] In other words, the orientation of the uncoated inorganic filaments and the orientation of the polymer composition are substantially parallel to each other.

[0093] For the purposes of this application, the terms "die" and "nozzle" are used interchangeably.

[0094] The coating apparatus can be configured to dispense the polymer composition through a nozzle under pressure. This can be achieved by an extruder, an additional pump, or a pressure vessel included in the device.

[0095] By specifying an angle or essentially parallelism, undesirable forces (warping forces, turbulence caused by changes in the direction of the polymer composition) are reduced, thus enabling rapid wetting of the filament.

[0096] The coating apparatus shall be arranged to distribute the molten polymer composition in the direction of gravity. The coating apparatus shall be arranged to distribute the inorganic molten material and / or uncoated inorganic filaments in the direction of gravity.

[0097] The nozzle configured to dispense the polymer composition may be a wide-slot nozzle, a curtain coater, or a roll coater. Preferably, the nozzle allows the molten polymer composition to be dispensed in a direction substantially parallel to the direction of the uncoated filament at the point of application.

[0098] A wide-slot nozzle has a front surface that includes the nozzle opening. The front surface is flat. Because the front surface is flat, the polymer composition, after leaving the nozzle, is driven by gravity to move across the entire lower part of the flat surface. This lower (and upper) part of the front surface is parallel to the fibers being guided through the coating apparatus.

[0099] The curtain coater also has a front surface that includes a nozzle opening. The front surface can be divided into an upper part above the nozzle opening and a lower part below the nozzle opening. The lower part is formed as a lip.

[0100] The lower section is configured to allow the polymer composition to move across the entire lower part of the flat surface after leaving the nozzle, and to be moved and driven by gravity. This lower part (lip section) of the front is at an angle with respect to the fibers guided through the coating device. The angle may be 5–45°, 10–40°, or about 30°. The upper part of the front is parallel to the fibers guided through the coating device. Thus, the upper and lip sections of the curtain coater are at angles of 5–45°, 10–40°, or about 30°.

[0101] Surprisingly, a curtain coater proved particularly useful because the application point is located at the lower front edge. Thus, the polymer composition is not trapped between the front and the fibers over extended periods of time or distance, thereby further reducing shear and other forces that would otherwise hinder the coating process.

[0102] While wide-slot nozzles can also be used, the application point of the polymer composition is directly at the nozzle opening. Therefore, the polymer composition is trapped between the front surface and the fibers for a certain period of time or distance.

[0103] Nozzles adapted for dispensing polymer compositions, particularly wide-slot nozzles, curtain coaters, or roll coaters, are adapted to distribute the molten polymer composition in the direction of gravity (for example, immediately before it hits an uncoated filament).

[0104] By specifying an angle or essentially parallelism, undesirable forces (shear forces, turbulence caused by changes in the direction of the polymer composition) are reduced, thus enabling rapid wetting of the filament.

[0105] The polymer composition may contain an adhesion promoter that improves the adhesion between the inorganic filament and the polymer composition. Therefore, the polymer composition may contain an adhesion promoter.

[0106] Surprisingly, in the process of the present invention, when an adhesion promoter is used, an inorganic fiber sizing agent is not required.

[0107] The polymer composition can be melted by a suitable heating device (e.g., a (uniscrew or twin-screw) extruder).

[0108] The coating device may also include a reservoir for polymer compositions containing an adhesion promoter and a reservoir for polymer compositions without an adhesion promoter.

[0109] In this way, the ratio of the polymer composition containing the adhesion promoter to the polymer composition without the adhesion promoter can be suitably adapted. The mixing of the polymer compositions can be carried out using additional mixing devices or extruders as discussed above. The polymers can be supplied in solid or fluid form (resulting in a dry or wet blend).

[0110] A device for producing filament bundles, a. A nozzle configured to produce uncoated inorganic filaments from an inorganic molten material. b. The above coating device, c. An apparatus comprising a fiber bundling device configured to produce a bundle of coated filaments from coated filaments is also disclosed.

[0111] The device for manufacturing filament bundles does not include a device for coating the uncoated inorganic filaments with, for example, an adhesion promoter, between a nozzle arranged to produce uncoated inorganic filaments from an inorganic melt and a coating device.

[0112] The apparatus may include multiple nozzles for dispensing uncoated inorganic filaments.

[0113] However, the device for manufacturing the filament bundle may also include devices immediately downstream of the coating device for further modification of the coated filaments (e.g., further coating devices, irradiation devices, heating devices, cooling devices, etc.).

[0114] The apparatus may also include, optionally downstream of the coating apparatus, a filament guide and a bobbin for receiving the filament bundle, for further modifying the coated filament. [Brief explanation of the drawing]

[0115] [Figure 1] A schematic front view of the apparatus for manufacturing filament bundles according to this disclosure is shown. [Figure 2] A schematic side view of the device from Figure 1 is shown. [Figure 3] This diagram schematically illustrates the process of coating uncoated inorganic filaments with a polymer composition. [Figure 4] This diagram schematically illustrates the process of coating uncoated inorganic filaments with a polymer composition using a wide-slot die. [Figure 5] This diagram schematically illustrates the process of coating uncoated inorganic filaments with a polymer composition using a curtain coater. [Figure 6]This diagram schematically illustrates the process of coating uncoated inorganic filaments with a polymer composition using a roll coater. [Modes for carrying out the invention]

[0116] Figures 1 and 2 show a front and side view of an apparatus for manufacturing a filament bundle according to the present disclosure. The same apparatus can be used to carry out the glass stretching process according to the present disclosure.

[0117] Pellets made of inorganic material (particularly gal) are supplied from a storage container melting furnace 1 (bushing). There, the inorganic material is metered and melted. The molten material flows out through nozzles between cooling fins (not shown) and thus solidifies. The inorganic material forms the core and the core of the polymer composition filament, and is also in the form of a filament. The uncoated inorganic filament 3 then passes through a coating device having nozzles for dispensing a fluid polymer composition, such as a molten polymer composition containing a thermoplastic polymer. The apparatus for producing filament bundles may further include a reservoir of adhesion promoter that supplies the molten polymer composition to the nozzles of the coating apparatus via a conduit.

[0118] The coated filaments can then pass through a modification device 17 (a sizing device equipped with post-sizing rollers and a sizing trough for applying additional aqueous solutions, preferably silane-containing solutions, such as sizing agents or coatings). Then, in the assembly device 6, filament bundles can be produced from the individual filaments. These bundles pass through a yarn guide 8 to a bobbin 9, where the fibers are wound and made available for further processing.

[0119] Figure 3 schematically shows, in a side view, the process of coating an uncoated inorganic filament 3 with a polymer composition 15 in a coating apparatus.

[0120] The uncoated inorganic filaments 3 are supplied through the coating device from the top to the bottom in the direction of gravity g. Thus, this is at a velocity V Fila as shown. The molten polymer composition 15 (for example, containing an adhesion promoter) is directed substantially parallel to the inorganic filaments 3. This is achieved by ultimately using dispensing nozzles (for example, 12, 13, 14) that also distribute the molten polymer composition 15 in the direction of gravity. The point at which the polymer composition is applied to the filaments is the application point 10. However, since the wetting process takes a certain amount of time, wetting has not yet occurred at this point. The point at which the polymer composition 15 wets the filaments, i.e., makes direct contact with them, is the point at which wetting 11 begins. After the start of wetting, the surface tension of the polymer composition causes the polymer composition to spread around the entire circumference of the filaments. Depending on the amount of polymer composition dispensed and / or the viscosity characteristics of the polymer composition, a speckle coating or a sheath coating of the polymer composition may appear on the filaments.

[0121] The angle alpha between the application point and the start point of wetting, whose sides are a straight imaginary line passing through the filament and a straight line on the opposite side of the filament passing through the surface of the polymer composition, can be 0° to 25°, 0° to 10°, or 0° to 1°.

[0122] The polymer composition 15 moves in the direction of gravity at a velocity V poly . V Poly and V Fila have essentially the same amount, so there is no undesirable force or influence between the polymer compositions on the filaments.

[0123] Figure 4 schematically shows the process of coating uncoated inorganic filaments with a polymer composition 15 using a wide slot die 12.

[0124] In the wide-slot die 12 as defined in this disclosure, the polymer composition 15 is distributed through a horizontal channel and flows vertically downward by gravity. The wide-slot nozzle 12 is arranged such that, as the polymer composition is distributed, the vertically discharged polymer composition meets the filament, and the vertically discharged polymer composition and filament have substantially the same velocity.

[0125] Figure 5 schematically illustrates the process of coating uncoated inorganic filaments 3 with a polymer composition 15 using a curtain coater 13.

[0126] In the curtain coater 13 as defined in this disclosure, the polymer composition 15 is distributed through horizontal channels, flows over the lip due to gravity, and is then discharged vertically. The curtain coater described herein has the advantage that no pressure from the polymer composition is applied to the filaments, which prevents high-speed fiber breakage.

[0127] Figure 6 schematically illustrates the process of coating an uncoated inorganic filament with a polymer composition using a roll coater 14.

[0128] In the roll coater 14 as defined herein, the polymer composition 15 is distributed through a horizontal channel and passes over the top of the roll. By rotating the roller, the polymer composition flows along the roller in the direction of the filament. Due to gravity, the polymer composition flows vertically. The roll coater 14 is arranged such that, as the polymer composition is distributed, the vertically discharged polymer composition collides with the filament, and the vertically discharged polymer composition and filament have substantially the same velocity. The spaced blades 16 on the roller and the tips to the roller between the discharge channel and the vertical discharge point of the polymer composition 15 can regulate the amount of polymer composition 15 discharged. The roll coater described herein has the advantage that no pressure from the polymer composition is applied to the filament, which prevents fiber breakage at high speeds.

[0129] Screening experiments to identify suitable thermoplastic polymers Samples of polymer compositions were prepared from the components listed in Table 1 as follows: When all components were solid, powder blends were prepared by mixing the powders in a plastic bag, and polymers in pellet form were powdered by low-temperature grinding. In the case of liquid additives, the additives were dissolved in a suitable solvent, spread on powdered polypropylene (PP), the solvent was evaporated overnight in a fume hood, and then the powder containing the additives was thoroughly mixed by shaking in a plastic bag.

[0130] The mixture thus formed was added at 300 g / hour via a loss-in-weight feeder to a Thermo Scientific Process 11 (P11) twin-screw co-rotating extruder with a diameter of 11 mm and an L / D of 45, which had a crew constructed with a transport element at a speed of 250 rpm and a kneading element with three sections, and a barrel with eight heating sections set to 40, 120, 180, 200, 200, 200, and 200°C, and a die set to 200°C. The extruded material was cooled in a water bath with flowing water and pelletized.

[0131] IFSS measurement (interfacial shear strength) Samples of coated glass filaments were prepared from pellets, and the interfacial shear strength was determined by the microbond test described in L. Yang & J. L. Thomason: Development and application of micromechanical techniques for characterizing interfacial shear strength (IFSS) in fiber-thermoplastic composites - Polymer Testing 31(2012)895-903). The pellets of the composition obtained above were melted, and filaments were drawn from the molten material. A loose knot was made from the filament, and one glass filament was placed inside the loose knot. The knot was tightened, and the excess PP filament was cut off, creating a small knot of PP filament around the glass filament. This was heated under nitrogen to melt the PP composition, forming droplets of the PP composition around the filament. After cooling, the droplets solidified. The glass filament was withdrawn, and the interfacial shear strength was measured.

[0132] In CE1, the polymer composition was applied to a glass filament equipped with an aminosilane sizing composition optimized for adhesion to PP. In CE2-CE4, E5, RE6-RE7, and E8-E19, the polymer composition was applied to a glass filament without using any sizing composition supplied by Fibrecoat GmbH.

[0133] material: A) C1) Type MAH: Exxelor PO1020 from Exxon Mobil, polypropylene grafted with maleic anhydride (0.9 wt% anhydride). C1) Type ITA: Polypropylene grafted with Scona TSPP8219GA from BYK Chemie GmbH, itaconic anhydride (2% by weight anhydride). C1) Type Epoxy: Polypropylene grafted with Scona TPPP8104FA from Chemie GmbH, glycidyl methacrylate (2.5 wt% glycidyl methacrylate) B) Propylene homopolymer PP595A from SABIC, with an MFR of 47 dg / min according to ISO 1133 at 230°C and 2.16 kg. C2) PA:Radipol S24HA, polyamide 6 from Radicii Group PE-HEMA: Poly(ethylene-hydroxyethyl methacrylate) containing 12% by weight of hydroxyethyl methacrylate. Vinyl-oligosilane: Silkquest G-170 from Momentive Performance Materials; Aminopropyl-oligosilane: Silkquest VX-225 from Momentive Performance Materials; Acrylicoxy-oligosilane: Silkquest A-274 from Momentive Performance Materials; Titanate pyrophosphate: Ken-React LICA38, neo-pentyl(diallyl)oxytri(dioctyl) pyrophosphate titanate from Kenrich Petrochemicals, Inc.

[0134] The compounds described above as C2) have hydrogen atoms capable of forming hydrogen bonds, or have a functional group that generates hydrogen atoms by (partial) hydrolysis of the group.

[0135] others EVA: Poly(ethylene-vinyl acetate) containing 10% by weight of vinyl acetate. Zirconate phosphate: Ken-React ZN12, isooctanolic acid zirconium complex from Kenrich Petrochemicals, Inc. Other compounds mentioned above do not have hydrogen atoms capable of forming hydrogen bonds, nor do they have functional groups that generate hydrogen atoms through (partial) hydrolysis of the group.

[0136] Other measurement methods Melting viscosity Melt viscosity was measured according to ISO 6721-10:2015 for either pellets or extruded pieces inserted into a plate-plate vibratory-shear rheometer. An Anton Paar MCR 502 rotational rheometer was used. The sample was melted inside a 25 mm diameter test shape at the measurement temperature (oven set to 250°C or 290°C), preheated in the oven for 1 minute to obtain a completely melted sample, trimmed to a 1 mm gap, and then vibratory-shear was applied at an angular frequency of 1 rad / s and a shear strain of 5%. During this test, melt viscosity was monitored as a function of time.

[0137] The rheometer was calibrated using standard linear propylene homopolymers (with different melt flow rates).

[0138] Melting temperature The melting temperature was determined by differential scanning calorimetry using a second heating curve, with a first heating rate of 10°C / min, a first cooling rate of 10°C / min, a second heating rate of 10°C / min, and a sample weight of 5 mg.

[0139] [Table 1]

[0140] In CE1, a glass filament containing a sizing composition coated with a composition containing polypropylene grafted with maleic anhydride exhibited high IFSS.

[0141] CE2 demonstrates that the application of polypropylene to glass filaments without sizing composition results in a low IFSS of less than 10 MPa.

[0142] A comparison of CE2 with CE3-CE4 demonstrates that the use of compounds that do not have hydrogen atoms capable of forming hydrogen bonds and that do not have functional groups that generate hydrogen atoms through (partial) hydrolysis of the group still results in a low IFSS of less than 10 MPa.

[0143] A comparison of CE2 with E5, RE6, RE7, and E8-E19 demonstrates that the use of compounds having hydrogen atoms capable of forming hydrogen bonds, or functional groups that generate hydrogen atoms through (partial) hydrolysis of the group, results in high IFSS exceeding 10 MPa.

[0144] The ILSS of bare glass filaments is very high (E5 and E11) compared to pure anhydrous grafted PP, and even higher than that of sized glass filaments containing PP / PP-g-MAH97 / 3 resin (CE1). Dilution of PP-g-MAH in PP homopolymer reduces the ILSS value (E13-E15), but even dilution to 3 wt% PP-g-MAH (E13) still results in a relatively high ILSS. The effect of epoxy grafted PP is lower than that of anhydrous grafted PP (E12 compared to E4 and E11).

[0145] The addition of oligosilanes to PP results in high ILSS (comparison of E8 and E10 with CE2). Comparing different types of oligosilanes, aminopropyl-oligosilane combined with PPMAH (E18) has the lowest effect. Acrylooxyoligosilane (E19) has a slightly higher effect, and vinyl oligosilane (E10) has a considerably higher effect. Increasing the vinyl-oligosilane level to 8% by weight resulted in a slight increase (E8).

[0146] The addition of both oligosilane and grafted PPMAH to PP does not have a significant effect on ILSS. The addition of both results in a lower ILSS than when either one is added separately (comparison between E17 and E10, and E17 and E13).

[0147] The addition of titanate pyrophosphate results in a high ILSS (comparison between E9 and CE2). The addition of both titanate pyrophosphate and grafted PPMAH to PP results in a significant increase in ILSS. The addition of both results in a higher ILSS than the addition of either one separately (comparison between E16 and E9, and comparison between E16 and E13).

[0148] Specific interactions via alcohol or amine / amide groups result in higher ILSS values, but are still at the lower end of RE6 and RE7 for all tested samples.

[0149] A composition for application onto freshly spun glass filaments was prepared as described below.

[0150] Composition Set 1: Blend Several blends of SABIC® 514M12 and SABIC® PP595A were prepared by extruding them in an ESDE 35mm 27L / D single-screw extruder, type ESE1-35-27, at barrel temperature settings of 150, 240, 290, 290, and 290°C. The extruder supplied the material to a melting pump and slitting die. The melting filter, melting pump, pipe to the die, and die temperature were all set to 290°C. Viscosity was also measured at 290°C. Table 1 shows the correlation between the content of SABIC® 514M12 material and melting viscosity.

[0151] [Table 2]

[0152] Composition Set 2: Screw-Breaking PP595A Screw breaking was performed on a Krauss-Maffei-Berstorff ZE25A 25mm co-rotating twin-screw extruder with a capacity of 48 L / D. The screw consists of a transport element with a kneading section. The barrel has 11 sections with set temperatures of 40, 120, 160, 190, 190, 190, 190, 190, 190, 190, and 190°C, and the die temperature was also set to 190°C. PP595A pellets were supplied by a loss-in-weight feeder. The peroxide mixture was dissolved in Linpar 10-13 oil and supplied to the extruder in barrel 4 by a liquid pump. The amounts of peroxide and active oxygen are shown in Table 2. The extruded material was cooled in a water bath with flowing water and pelletized. The melt viscosity was measured at 250°C.

[0153] [Table 3]

[0154] Composition Set 3: Screw-Breaking PP595A Viscobraking was performed on a larger scale using a peroxide masterbatch in a Krauss-Maffei-Berstorff ZE40A-UTX40mm co-rotating twin-screw extruder with a flow rate of 43 L / D. The screw consisted of a transport element with three kneading sections. Peroxide was added together with PP595A pellets as a 20 wt% masterbatch. The temperature profile setpoints were 20, 20, 30, 50, 100, 150, 230, 230, 230, 230, 235, 260, and 260°C. The samples were extruded at 175 rpm and 100 kg / hour. The amounts of peroxide and reactive oxygen species are shown in Table 3. Melt viscosity was measured at 250°C.

[0155] [Table 4]

[0156] The reactive oxygen species content of a formulation is calculated based on the peroxide concentration and the reactive oxygen species content of the peroxide, which can be found in the supplier's technical data sheet.

[0157] For example, sample 7 contains 1200 ppm of Trigonox 101 and 1000 ppm of Trigonox 301. The reactive oxygen species content of Trigonox 101 is 10.14%, and the reactive oxygen species content of Trigonox 301 is 7.4%. Therefore, the reactive oxygen species content of this sample is calculated to be 196 ppm. [Explanation of symbols]

[0158] List of reference symbols 1. Bushing (melting furnace) 2 nozzles 3. Uncoated inorganic filaments 4 Coating devices 5. Coated inorganic filaments 6 Assembly Devices 7 filament bundles 8 thread guide 9 coils 10 initial contact lines / points 11. Lines / points indicating the start of wetting 12 Wide Slot Nozzles 13 Curtain Coater 14 Roll Coater 15 Polymer Compositions 16 knives 17 Modification Devices Alpha: The angle between the polymer composition and the inorganic filament between the wetting point and the initial contact point. V Poly Speed ​​and direction of output of the melted polymer composition. V Fila Speed ​​and direction of the output inorganic filament.

Claims

1. A coated filament comprising an inorganic filament and a polymer composition containing a thermoplastic polymer, wherein the polymer composition is in direct contact with the filament, wherein the coated filament has a length of 100 mm or more.

2. The coated filament according to claim 1, wherein the polymer composition comprises an adhesion promoter.

3. The composition is a grafted polypropylene which is A) grafted with C1) a side-chain compound capable of forming hydrogen bonds, and / or B) Non-grafted polypropylene and C2) Compounds capable of forming hydrogen bonds, The coated filament according to claim 1 or the above, wherein the total amount of A) and B) relative to the polypropylene composition is at least 70% by weight, and the polypropylene composition contains D) low molecular weight polyethylene having a molecular weight of up to 5000 in an amount of less than 10% by weight relative to the polypropylene composition.

4. The coated filament according to any one of claims 1 to 3, wherein the polymer composition has a melt viscosity in the range of 1.0 to 25 Pas at the melting temperature of the polymer composition, the melting temperature of the polymer composition is determined for a 5 mg sample using differential scanning calorimetry on a second heating curve using heating and cooling rates of 10°C / min, and the melt viscosity is determined by applying vibration-shear to the melted sample with an angular frequency of 1 rad / s and a shear strain of 5% in accordance with ISO 6721-10:2015.

5. The coated filament according to any one of claims 1 to 4, wherein the coating is a spot coating or a mantle coating.

6. A filament bundle comprising a plurality of coated filaments as described in any one of claims 1 to 5.

7. A filament bundle, or so-called thread, according to claim 6.

8. A method for manufacturing coated filaments, a. A process for manufacturing an uncoated inorganic filament, preferably an uncoated glass filament, from an inorganic melt, b. A step of providing a melted polymer composition containing a thermoplastic polymer, c. Preferably, a step of applying the molten polymer composition to the uncoated inorganic filament using a roller die, a curtain coater die, or a slit die, and solidifying the molten polymer composition, d. A step of obtaining a coated filament comprising an inorganic filament coated with the polymer composition, wherein the inorganic filament is in direct contact with the polymer composition, e1. A step of cutting the coated filament into pieces having a length of 100 mm or more, or e2 A method comprising the steps of gathering a plurality of the coated filaments into a filament bundle or thread, and optionally cutting the filament bundle or thread into pieces having a length of 100 mm or more.

9. The method according to claim 8, wherein the polymer composition comprises an adhesion promoter.

10. The method according to claim 8 or 9, wherein during the application process, the polymer encounters the uncoated inorganic filament at an absolute angle of up to 45°, 10°, 5°, 1°, or 0°.

11. The method according to any one of claims 8 to 10, wherein when the polymer composition is applied to the uncoated inorganic filament, the rate at which the polymer is applied is 50% to 110%, 95% to 105%, or 99% to 101% of the rate at which the inorganic filament moves.

12. The method according to any one of claims 8 to 11, wherein the speed at which the inorganic filament moves is 500 to 3000 m / min, 1250 to 1750 m / min, or 1450 to 1550 m / min.

13. The method according to any one of claims 8 to 12, wherein the inorganic molten material and / or the uncoated inorganic filament is electrostatically charged during manufacturing.

14. The method according to any one of claims 8 to 13, wherein the polymer composition has a melt viscosity in the range of 1.0 to 25 Pas at the melting temperature of the polymer composition, the melting temperature of the polymer composition is determined for a 5 mg sample using differential scanning calorimetry on a second heating curve using heating and cooling rates of 10°C / min, and the melt viscosity is determined by applying vibration-shear to the melted sample with an angular frequency of 1 rad / s and a shear strain of 5% in accordance with ISO 6721-10:2015.

15. The method according to any one of claims 8 to 13, wherein the polymer is melted using a melting device, preferably an extruder.

16. A coated filament that can be obtained by the method described in any one of claims 8 to 14.

17. A filament bundle that can be obtained by the method described in any one of claims 8 to 14.

18. A coating device for manufacturing coated filaments from uncoated inorganic filaments, a. A heating device for producing a fluid polymer composition, for example, a melted polymer composition containing a thermoplastic polymer, b. A die is provided which the fluid polymer composition obtained from the heating device is discharged in the direction of gravity, thereby causing the fluid polymer composition to come into contact with an uncoated inorganic filament at the application point and to begin wetting the uncoated inorganic filament at the wetting point. c. A supply line between the heating device and the die, d. A coating device in which the die is set such that the angle alpha between the application point and the point where wetting begins is such that the side of the angle alpha is an imaginary straight line passing through the filament and an imaginary straight line passing through the surface of the polymer opposite to the filament, and the angle alpha is 0° to 45°, 0° to 10°, 0° to 5°, or 0° to 1°.

19. The coating device according to claim 18, further comprising a reservoir for an organic polymer containing an adhesion promoter and a reservoir for an organic polymer not containing an adhesion promoter.

20. The coating device according to claim 18 or 19, wherein the die arranged to discharge the polymer is a slot die, a curtain coater die, or a roller die.

21. A device for manufacturing filament bundles, a. A die arranged to manufacture uncoated inorganic filaments from an inorganic molten material, b. A coating device according to any one of claims 18 to 20, c. A device comprising a fiber focusing device arranged for producing a bundle of coated filaments from the coated filaments.

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