Reabsorbable glass fibers coated with a sizing agent and method for preparing the same

Abstract

The present invention relates to a resorbable, biocompatible, preferably bioactive, glass fiber coated with a sizing agent, the sizing agent comprising a thermoplastic, resorbable and biocompatible compatibilizer, and the polyester is covalently bonded to the glass fiber through a coupling agent having at least one silane moiety. The fiber is preferably produced via a process in which a volatile amine is present as a temporary processing aid. The present invention further relates to a method for coating resorbable, biocompatible glass fibers, a kit for coating glass fibers, a composite comprising the coated glass fiber, and a medical device comprising the composite.

Description

Technical Field

[0001] The present invention relates to resorbable and biocompatible glass fibers coated with a sizing agent. The present invention further relates to a method for coating resorbable and biocompatible glass fibers and to a component kit suitable for use therewith.

Background Art

[0002] Glass fibers are high-performance materials used in many technical fields that require excellent mechanical properties and relatively low weight, such as aerospace, automotive, marine, energy, sports equipment, household goods, and medical implants. They are often used in composites where fibers, such as carbon fibers or glass fibers, are embedded in a matrix of another dissimilar material, such as a polymeric material.

[0003] Composites containing glass fibers embedded in a polymer matrix are considered to be very useful for medical applications, particularly for orthopedic implants for the repair of bone and cartilage. The composites can be manufactured to be biocompatible and resorbable, meaning that when implanted, they degrade and are resorbed in the body of a mammal (e.g., a human) at a controlled rate. This allows for the production of implants that do not need to be removed from the body and thus do not require re-surgery.

[0004] The performance of these composites generally depends on many factors, such as the amount, type, length, thickness, and arrangement of the glass fibers, the content and properties of the matrix material, and the quality of the interfacial bond between the polymer matrix material and the glass fibers. One way to improve the quality of the interfacial bond between the polymer matrix material and the glass fibers is the application of a sizing agent.

[0005] Glass fiber sizing agents contain components with different functions. The main components are film forming agents (also called compatibilizers) and coupling agents.

[0006] The film-forming agent forms a thin film on glass fibers and performs several functions. In particular, it improves the processability of the glass fibers and the performance of the final product. Above all, it protects and lubricates the fibers and holds them together during the manufacturing of the composite. In addition, perhaps counterintuitively, it also helps to spread the glass fibers during the wet impregnation process of the composite manufacturing. When the glass fibers are to be used in a composite in combination with a polymer matrix, the film-forming agent in the sizing agent is usually chemically similar to the polymer matrix of the composite. This improves the adhesion between the polymer matrix and the glass fibers. It also ensures good wetting of the sized glass fibers by the matrix polymer by reducing the surface energy. In this context, it should be noted that the surface of the glass fibers is generally hydrophilic, while the polymer matrix often has hydrophobic characteristics.

[0007] In sizing agents compatible with thermoplastic polymer matrices, it is ideal that the film former is covalently bonded, i.e., grafted, to the glass fiber surface via a coupling agent, such as silane. A graft-type film former chemically similar to the hydrophobic matrix polymer can provide a strong interface between the matrix polymer and the glass fibers through adhesion and chain entanglement. This type of entanglement helps to efficiently transfer load from the matrix polymer to the reinforcing fibers, thus providing high initial mechanical strength and strength retention in vitro or in vivo.

[0008] For sizing to be effective, it is naturally necessary that the sizing agent remains on the glass during processing. According to JLThomason, Glass fiber sizing: A review, Composites Part A 127 (2019) 105619, it is known that up to 80% of the sizing agent on glass fibers can be removed by extraction with acetone. This suggests that some of the film forming agent, and possibly other components, may not be chemically bonded to the glass fibers but instead be physically adsorbed onto the surface. High levels of physically adsorbed sizing agent will limit the strength of the resulting composite and will have an undesirable impact on the strength retention of glass-reinforced composites, implants, or devices in vivo. [Overview of the project] [Problems that the invention aims to solve]

[0009] Therefore, there is a need for stronger, biocompatible, and reabsorbable composites, as well as a need for simpler methods to manufacture such products. There is also a need for better sizing materials and methods for applying such sizing materials to reabsorbable and biocompatible glass fibers. [Means for solving the problem]

[0010] The present invention relates to a reabsorbable and biocompatible glass fiber coated with a sizing agent, wherein the sizing agent comprises a thermoplastic, reabsorbable, and biocompatible compatibilizer covalently bonded to the glass fiber through a coupling agent having at least one silane moiety, and the coated glass fiber has an apparent interfacial shear strength with respect to a reference matrix polymer determined by a single fiber pullout test, wherein the apparent interfacial shear strength is at least 10% higher than the apparent interfacial shear strength of a bare glass fiber with respect to the same reference matrix polymer.

[0011] The present invention further provides a method for providing a sizing agent for reabsorbable and biocompatible glass fibers, a) Glass fiber, A coupling agent having at least one epoxy moiety and at least one silanol group in a liquid medium, and In a liquid medium, a reaction product is obtained from the reaction of a compatibilizer with a volatile tertiary amine, wherein the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups. By bringing the glass fiber into contact with the sizing composition, b) subject the coated glass fiber to a drying process, c) subject the dried coated glass fibers to a curing process at an elevated temperature. d) The cured coated glass fiber is subjected to a process to evaporate the volatile tertiary amine. The above methods include

[0012] The sizing composition used in the method according to the present invention is preferably aqueous. It comprises a reaction product of a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups, i.e., a compatibilizer, and a volatile tertiary amine. While not wishing to be bound by theory, it is thought that this product contains ionic clusters (e.g., in the form of alkylammonium carboxylate salts) that act as ionic emulsifiers, which preferentially occupy the interface between the dispersed compatibilizer and the surrounding water, resulting in a microdispersion or nanodispersion. Thus, the volatile tertiary amine acts to promote the dispersion of the compatibilizer in water. In addition, in some embodiments, it also catalyzes the reaction between the compatibilizer and a silane coupling agent.

[0013] A drying step is performed when a dispersed compatibilizer and a silane coupling agent are applied to glass fibers in a liquid medium. During this drying step, the liquid medium is removed. Furthermore, the silanol groups of the coupling agent react with the glass fibers, and the resulting reaction water is also removed. Subsequently, while the glass fibers harden, the alkylammonium carboxylate salt decomposes, regenerating the carboxylic acid functional group, which then reacts with the epoxy group of the coupling agent. Depending on the selection of a volatile tertiary amine, this reaction may be catalyzed by a tertiary amine also released in the decomposition of the alkylammonium carboxylate salt. The tertiary amine can be removed, for example, by evaporation through the application of a vacuum or an inert gas flow. In one embodiment, the process is controlled so that a sufficient amount of tertiary amine is present in the system to catalyze the reaction between the carboxylic acid group and the epoxy group derived from the silane coupling agent.

[0014] As described above, the compatibilizer is designed to function as a transiently reactive surfactant by using a volatile tertiary amine, thereby promoting dispersion in (aqueous) emulsions and suspensions without the need for additional, and possibly harmful, surfactants. Furthermore, because the compatibilizer is designed to react with the epoxy group of the silane coupling agent, it results in high grafting efficiency onto glass, thereby promoting adhesion and physical interaction with the matrix polymer.

[0015] The present invention further relates to a component kit for carrying out the method of the present invention to obtain the coated glass fibers of the present invention. The present invention also relates to a composite comprising uniformly sized glass fibers, and a medical device comprising the composite. [Modes for carrying out the invention]

[0016] The present invention relates to a reabsorbable and biocompatible glass fiber coated with a sizing agent containing a thermoplastic, reabsorbable, and biocompatible compatibilizer, wherein the sizing agent is covalently bonded to the glass fiber through a coupling agent having at least one silane moiety. The sizing agent or size is understood herein to mean a coating on the glass fiber containing a coupling agent covalently bonded to the glass and covalently bonded to the compatibilizer. The glass fiber has an apparent interfacial shear strength with respect to a reference matrix polymer, as determined by a single-fiber pulp test, which is at least 10% higher than the apparent interfacial shear strength of a bare glass fiber with respect to the same reference matrix polymer.

[0017] A coupling agent is a compound that can provide a chemical bond between two dissimilar materials. Typically, these are molecules having functional groups that can bond with organic materials (e.g., polymers, e.g., polyesters), and molecules having functional groups that can bond with inorganic materials (e.g., glass, e.g., glass fibers). The coupling agent of the present invention comprises at least one silane moiety, where silane is understood to mean a (functional) group or molecule having four bonds with a central silicon atom. An example of a silane is silane tetrahydride, which is a silicon atom surrounded by four hydrogen atoms. The coupling agent will be described in detail below.

[0018] The compatibilizer is a low molecular weight polymer that is miscible with the polymer matrix of the composite in which the glass fibers are to be incorporated. The reaction product of the volatile tertiary amine and the compatibilizer in this invention is preferably designed to function as a transient processing aid that promotes the dispersibility of the compatibilizer in aqueous emulsions and suspensions without the need for additional surfactants. It is preferable not to add additional surfactants because they may have adverse effects, such as leaching from the product during manufacturing or final use. The compatibilizer is designed to react with a coupling agent so that it has high grafting efficiency on glass, thereby promoting adhesion and physical interaction, such as entanglements, between the compatibilizer and the matrix polymer of the composite in which uniformly sized glass fibers may be used. The compatibilizer is described in detail below.

[0019] Preferably, the dry weight of the sizing is at least 0.1% by weight of the coated glass fibers, more preferably at least 0.2% by weight of the coated glass fibers, particularly 0.3% by weight of the coated glass fibers, more preferably at least 0.4% by weight of the coated glass fibers, more preferably at least 0.5% by weight of the coated glass fibers, and even more preferably at least 0.6% by weight of the coated glass fibers. Preferably, the dry weight of the covalently bonded sizing agent is 5% by weight or less, particularly 3% by weight or less, more particularly 1.2% by weight or less of the coated glass fibers, more preferably 1.0% by weight or less of the coated glass fibers, even more preferably 0.8% by weight or less of the coated glass fibers, and even more preferably 0.6% by weight or less of the coated glass fibers. Lower values, for example, 0.3% by weight or less, are also possible. Here, the coated glass fibers are understood to mean glass fibers containing a covalently bonded sizing agent, i.e., glass fibers containing a coupling agent and a compatibilizer.

[0020] Throughout this entire text, references to glass fibers are to be understood as referring to coated glass fibers, unless it is specified otherwise or it is not clear from the description that this is not the case.

[0021] Volatile tertiary amines are used in the method of the present invention and are removed through evaporation. It is preferred that the volatile tertiary amines are substantially removed, more preferably completely removed. Preferably, the amount of volatile tertiary amines in the coated glass fibers after drying and curing is less than 10 ppm, or less than the detection limit of gas chromatography - mass spectrometry (GC - MS). Here, it is understood that a tertiary amine refers to a compound having a nitrogen atom, a lone pair of electrons, and three organic substituents. Even after the evaporation step, there is a possibility that volatile tertiary amines remain in the glass fibers. Therefore, in some embodiments, the coated glass fibers of the present invention contain at least 0.1 ppm, in some embodiments at least 0.2 ppm, or at least 0.3 ppm, of tertiary amines. As indicated above, the amount of volatile tertiary amines in the coated glass fibers after drying and curing is preferably less than 10 ppm.

[0022] The thickness of the sizing applied is preferably 200 nm or less, more preferably 150 nm or less, more preferably 120 nm or less, more preferably 100 nm or less, still more preferably 75 nm or less. It is understood that a thinner sizing layer can be beneficial, particularly for glass fibers having a diameter less than 6 μm.

[0023] A sizing agent containing a thermoplastic, resorbable, and biocompatible polyester covalently bonded to the glass fiber through a coupling agent having at least one silane moiety increases the strength of the interfacial bond between the glass fiber and the polymer matrix surrounding the glass fiber after being incorporated into the composite material. This effect can be quantitatively determined using a single fiber pull-out test. In this test method, a single sized glass fiber is embedded in a molten polymer using a suitable apparatus. Subsequently, the fiber is pulled out using a suitable apparatus, and the apparent interfacial shear strength is calculated. This method is described in detail below. The experiment can also be performed on fibers not coated with a compatibilizer. By comparing the results of fibers with and without a compatibilizer coating, the effect of the compatibilizer coating on the peel force from the polymer matrix can be quantified.

[0024] In the present invention, the coated glass fiber has an apparent interfacial shear strength by a reference matrix polymer determined in a single fiber pull-out test, and the apparent interfacial shear strength is at least 10% higher than the apparent interfacial shear strength of the bare glass fiber by the same reference matrix polymer as above.

[0025] In the context of this definition, the reference matrix polymer is a matrix polymer having a chemical composition corresponding to the chemical composition of the compatibilizer. For example, if the compatibilizer is polycaprolactone, then for this definition, the corresponding reference matrix polymer is polycaprolactone. Thus, this parameter makes it possible to quantify the quality of adhesion of the sizing to the glass fiber relative to a standard matrix material, i.e., a polymer with the same composition as the compatibilizer. In the context of this definition, the bare glass fiber is a coated glass fiber that has been fired at 500°C for 2 hours in the presence of oxygen (usually air). This process removes the compatibilizer. The effect of the sizing agent in the reference matrix can be determined by comparing the apparent interfacial shear strength values ​​obtained for the coated glass fiber and the bare glass fiber with those of the standard matrix.

[0026] Preferably, the coated glass fiber has an apparent interfacial shear strength with respect to the reference matrix polymer that is at least 20%, and particularly at least 30%, higher than the apparent interfacial shear strength of bare glass fiber with respect to the same reference matrix polymer, as determined in a single fiber pulp test.

[0027] In one embodiment, the coated glass fiber has an apparent interfacial shear strength of at least 10 MPa, particularly at least 15 MPa, and more particularly at least 20 MPa, when determined by a single fiber pulp test, compared to the reference matrix polymer. The apparent interfacial shear strength compared to the reference matrix polymer, when determined by the single fiber pulp test, is preferably at least 30 MPa, more preferably at least 40 MPa, and even more preferably at least 50 MPa.

[0028] It should be noted that when the coated glass fibers are incorporated into other matrix materials, different values ​​may be obtained in single-fiber pulping tests depending on the matrix-compatibility agent combination.

[0029] The (uncoated) glass fibers used in the present invention preferably have a diameter of less than 30 μm, particularly less than 25 μm, more particularly less than 20 μm, less than 15 μm in some embodiments, or even less than 10 μm, as determined according to ASTM D 1577-01C. Preferably, the diameter is at least 3 μm, particularly at least 5 μm, particularly at least 6 μm, or at least 8 μm. In one embodiment, the glass fibers originate from a glass fiber bundle, and the coefficient of variation of the diameter of the glass fibers in the glass fiber bundle is 15% or less, particularly 10% or less. The coefficient of variation may be 8% or less, or 6% or less. In some embodiments, it has been found that the coefficient of variation may be 3% or less, which is a measure of very uniform diameter. The coefficient of variation is determined as follows: the diameter is determined for 30 glass fibers from the glass fiber bundle. The mean diameter and standard deviation are calculated. The coefficient of variation is obtained by dividing the standard deviation by the mean diameter, and is expressed as a percentage.

[0030] The glass fiber bundles used in the present invention preferably have at least 50 fibers, preferably at least 100 fibers, more preferably at least 150 fibers, and even more preferably at least 200 fibers. Maximum values ​​may include 5000 fibers, and more particularly 3000 fibers. The glass fiber bundles used in the present invention preferably have a linear density of 20 to 1300 tex, particularly 50 to 500 tex, and preferably 70 to 300 tex, when measured according to ASTM D1577-01 A. The term "linear density" corresponds to the weight of a certain length of the glass fiber bundle, and the unit tex corresponds to the weight in grams per 1000 meters of fiber.

[0031] Glass is always composed of various components. These are often divided into three categories: 1) network formers, 2) network modifiers, and 3) intermediates. Network formers are the main components of glass and form a highly cross-linked skeletal network that gives most of the glass its properties. Network modifiers are a class of components that are added to fine-tune the physical properties of the glass to meet certain specifications. Network modifiers usually reduce the glass network connectivity. There are also components that are involved in the glass network and from which the glass properties can be fine-tuned. These components belong to the intermediate class.

[0032] The glass fibers used in the present invention preferably have a composition comprising a network-forming agent and a network-modifying agent, wherein the molar ratio of the network-forming agent to the network-modifying agent is 1 to 4, preferably 1.5 to 3.5, and more preferably 2 to 3. It has been observed that ratios following such a range, particularly one of the preferred ranges, result in good glass quality, especially suitable for fiber formation.

[0033] In a preferred embodiment, the glass fiber is a bioactive glass fiber. Bioactive glass fibers are known in the art and are designed to induce or modulate bioactivity. Bioactive materials are often surface-active materials that can interact with mammalian tissues. The bioactive glass may be further designed to elute ions or other chemicals that result in osteoconductive, osteoinductive, anti-infective, and / or angiogenic benefits.

[0034] The glass fibers are preferably silicon oxides, such as silica (SiO2), boron oxides, such as diboron trioxide (B2O3) and boron trioxide (B6O), and phosphorus oxides, such as phosphorus trioxide (P2O3) and phosphorus pentoxide (P2O5 or P4O). 10 The glass fibers are preferably sodium oxides, for example, Na2O or Na2O 2、 The glass fiber comprises a network modifier selected from magnesium oxide, such as MgO, and calcium oxide, such as CaO. More preferably, the glass fiber comprises several network-forming agents and several network modifiers.

[0035] The glass fiber is preferably, 50-75% by weight of SiO2, especially 55-75% by weight, more especially 60-75% by weight, 0-15% by weight of B2O3, 0.5-5% by weight of P2O5, especially 0.5-4% by weight, and more specifically 0.5-3% by weight. 5-20% by weight of Na2O, 0-25% by weight of CaO, especially 2-25% by weight, and more specifically 5-25% by weight. 0-10% by weight of MgO, 0-1% by weight of Li2O, 0-15% by weight of K2O, especially 0-10% by weight, and more specifically 0-4% by weight. 0-4% by weight of SrO, 0-5% by weight of Al2O3, 0-5% by weight of Fe2O3 The composition contains (the sizing agent is not included in the calculation).

[0036] In one embodiment, the glass fiber has a composition comprising 60-75% by weight of SiO2, 0-15% by weight of B2O3, 0.5-3% by weight of P2O5, 5-20% by weight of Na2O, 5-25% by weight of CaO, 0-10% by weight of MgO, 0-1% by weight of Li2O, 0-4% by weight of K2O, 0-4% by weight of SrO, 0-5% by weight of Al2O3, and 0-5% by weight of Fe2O3 (excluding the sizing agent).

[0037] In one embodiment, the glass composition contains less than 10% by weight, particularly less than 5% by weight, of B2O3. In one embodiment, the glass composition contains 7 to 20% by weight of Na2O. In one embodiment, the glass composition contains 2 to 8% by weight of MgO. In one embodiment, the glass composition contains 5 to 15% by weight of CaO.

[0038] The glass fibers used in this invention are preferably radiopaque, meaning they are not transparent to X-rays. X-rays are understood to be high-energy radiation with wavelengths of approximately 10 pm to 10 nm. The use of radiopaque glass fibers is particularly attractive in composites for implantable medical devices because it allows for in-vivo monitoring of composite degradation through X-rays.

[0039] The glass fiber preferably has a tensile strength of 1000 to 3000 MPa, preferably 1200 to 2500 MPa, and more preferably 1400 to 2200 MPa, as measured by a tensile test in accordance with DIN EN ISO 5079.

[0040] The glass fiber preferably has an elastic modulus of 20 to 100 GPa, preferably 35 to 85 GPa, and more preferably 50 to 70 GPa, as measured by a tensile test in accordance with DIN EN ISO 5079 "Determination of breaking force and elongation at break of individual fibers" (ISO 5079:2020).

[0041] Attractive glass fibers and glass fiber bundles for use in the present invention are described in a patent application with the same filing date and priority date as this application, titled "Resorbable and biocompatible glass fiber bundle having a well-defined diameter and process for making such," the full text of which is incorporated herein by reference.

[0042] The present invention also relates to a composite comprising a plurality of coated glass fibers according to the present invention, wherein the plurality of coated glass fibers are embedded in a reabsorbable polymer matrix. The reabsorbable polymer matrix can be any suitable reabsorbable polymer matrix known in the art. Preferably, the reabsorbable polymer matrix is ​​polylactic acid. Further examples will be given below.

[0043] The present invention further relates to medical devices comprising coated glass fibers or composites of the present invention. Examples of medical devices are typically medical implants, which include bone fixation devices, intramedullary nails, joint (hip, knee, elbow) implants, spinal implants, and other devices for such applications, such as fracture fixation, tendon reattachment, or spinal fixation.

[0044] Examples of bone fixation devices include screws, plates, rods, tapes, nails, wires, pins, tapes, anchors, cables, ties, or wire ties, plate and screw systems, and external fixators.

[0045] The coated glass fibers or composites of the present invention can also be used in tissue engineering, such as in woven and nonwoven fabrics, and in scaffolding.

[0046] The present invention further provides a method for providing reabsorbable and biocompatible glass fibers coated with a sizing agent, a) Glass fiber, A coupling agent having at least one epoxy moiety and at least one silanol group in a liquid medium, and In a liquid medium, a reaction product is obtained from the reaction of a compatibilizer with a volatile tertiary amine, wherein the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups. By bringing the glass fiber into contact with the sizing composition, b) subject the coated glass fiber to a drying process, c) subject the dried coated glass fibers to a curing process at an elevated temperature. d) The cured coated glass fiber is subjected to a process to evaporate the volatile tertiary amine. The above method includes the following steps.

[0047] In this specification, a reaction product of a compatibilizer and a volatile tertiary amine, wherein the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups, may be referred to as a "neutralized compatibilizer." The term "neutralized" means the presence of an ionic cluster containing a negatively charged carboxylic acid group and a positively charged amine group.

[0048] In step a) of the method according to the present invention, the glass fibers are coated with a sizing composition by contacting them with a coupling agent in a liquid medium and a neutralized compatibilizer in a liquid medium. In one embodiment, the coupling agent and the neutralized compatibilizer are present in a single liquid medium. In this case, step a) is performed by reacting the compatibilizer (the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups) with a volatile tertiary amine and the coupling agent (the coupling agent having at least one epoxy moiety and at least one silanol group) , in a liquid medium, Glass fiber sizing formulation He was This includes covering. In another embodiment, the coupling agent and the neutralized compatibilizer are provided in separate liquid media in separate steps. In this case, the glass fibers are generally first brought into contact with the liquid media containing the coupling agent, and then into contact with the liquid media containing the neutralized compatibilizer. Optionally, an intermediate drying step and an optional intermediate curing step may be performed. The contact step can be carried out, as is known in the art, for example, by passing the fibers, for example, in bundle form, through a bath of the liquid media.

[0049] The liquid medium is preferably an aqueous medium. In this case, the neutralized compatibilizer exists in the form of a dispersion, particularly a microdispersion, or even a nanodispersion. This dispersion may be formed by providing a compatibilizer containing a certain amount of a thermoplastic, reabsorbable, and biocompatible polymer containing a carboxylic acid moiety, neutralizing at least a portion of the carboxylic acid moiety of the compatibilizer with a predetermined amount of a tertiary amine, and then dispersing the neutralized compatibilizer in a liquid medium, particularly an aqueous liquid medium. The compatibilizer may be provided, for example, in the form of a melt or in the form of a solution in a suitable solvent.

[0050] The tertiary amine used in the method of the present invention is selected to be volatile. In the context of this specification, the term "volatile" refers to a sizing agent. The treatment was performed This means that the amine can be evaporated from the glass fibers. In addition, the tertiary amine used in this method is preferably selected so that it can act as a catalyst for the reaction between the coupling agent and the compatibilizer. Therefore, preferably, the tertiary amine used in this method can act as a catalyst for the reaction between at least one epoxy moiety of the coupling agent and the carboxylic acid moiety of the compatibilizer.

[0051] The sizing composition is applied to the glass fibers. GrantSubsequently, the coated glass fibers are subjected to a drying process, either in one or two steps, with or without intermediate drying and / or curing as described above. In the drying process, the liquid medium, preferably water, is removed. Furthermore, if this has not been done in the two steps described above, the silanol groups of the coupling agent react with the glass fibers, and the resulting reaction water is also removed. The drying process is generally carried out under relatively mild conditions. This is attractive because it ensures the preservation of some of the tertiary amine that acts as a catalyst for the reaction between the terminal acid groups of the compatibilizer and the epoxy groups on the silane coupling agent. Preferred reaction conditions include temperatures in the range of 0 to 50°C. Preferably, water is removed under reduced pressure (i.e., below 100 kPa, preferably below 50 kPa) at about room temperature (i.e., 15 to 25°C).

[0052] The silane portion of the coupling agent forms hydrogen bonds with the -OH groups present on the surface of the glass fibers. These bonds eventually transform into covalent bonds with the glass fibers after losing water molecules during the curing process. Therefore, the reaction between the epoxy portion of the coupling agent and the glass is considered a solid-state reaction that results in silane grafting into the solid glass via silanol bonds.

[0053] The dried coated glass fibers are subjected to a curing process at an elevated temperature. As described above, in the curing process, the reaction between the silane portion of the coupling agent and the -OH groups on the glass fiber surface is completed to form silanol bonds, and the reaction between the epoxy portion of the coupling agent and the neutralized compatibilizer takes place. This preferably occurs above the glass transition temperature of the compatibilizer. Therefore, the reaction between the epoxy portion and the neutralized compatibilizer preferably takes place at a temperature of at least 70°C, more preferably at least 80°C, more preferably at least 90°C, and even more preferably at least 100°C. In order to prevent thermal oxidative damage to the coupling agent and / or compatibilizer, it may also be preferable to limit the temperature to a maximum of 140°C, more preferably at a maximum of 120°C. Therefore, it is understood that the reaction between the epoxy portion and the neutralized compatibilizer preferably takes place at a temperature of 80-140°C, more preferably 100-120°C.

[0054] The coupling agent comprises an epoxy (i.e., glycidyl) group for bonding to the carboxylic acid moiety. The coupling agent further comprises a silanol group for bonding to the glass. In one embodiment, the silanol group is formed by reacting a compound having an alkoxysilane group with (a limited amount of) water to convert the alkoxysilane group to a silanol group. Preferred compounds having an alkoxysilane group are compounds selected from the group including 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, (3-glycidoxypropyl)triethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 1-(3-glycidoxypropyl)-1,1,3,3,3-pentaethoxy-1,3-disilapropane, and 8-glycidoxyoctyltrimethoxysilane.

[0055] Preferably, the (neutralized) compatibilizer is dispersed in water as a nanodispersion. The nanodispersion is understood here to be a dispersion in which the droplets of compatibilizer in the continuous phase are on the nanometer scale, i.e., a dispersion in which the D90 of the droplets of compatibilizer in the liquid medium, measured using dynamic light scattering (e.g., using Malvern and ASTM E3247), is 350 nm or less, preferably 250 nm or less, more preferably 100 nm or less, even more preferably 50 nm or less, and even more preferably 10 nm or less. In one embodiment, the average particle size (z-mean) of the neutralized compatibilizer in the liquid medium is 350 nm or less, preferably 250 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less.

[0056] Furthermore, it has been observed that the presence of the tertiary amine successfully promotes the dispersion of the compatibilizer. This process is presumed to function by converting a portion of the compatibilizer into a transient ionic surfactant that promotes dispersion by preferentially positioning itself at the interface between water and the polymer.

[0057] Preferably, the molar ratio of the tertiary amine to the carboxylic acid portion is 0.4 to 2.0, more preferably 0.5 to 1.0, and more preferably 0.6 to 0.8.

[0058] The compatibilizer is preferably polylactide (PLA), poly-L-lactide (PLLA), poly-DL-lactide (PDLA), L-lactide / DL-lactide copolymer (PLDLA), polyglycolide (PGA), poly(ε-caprolactone) (PCL), glycolide copolymer, ε-caprolactone copolymer, lactide copolymer, glycolide / trimethylene carbonate copolymer (PGA / TMC), lactide / tetramethylglycolide copolymer, lactide / trimethylene carbonate copolymer, lactide / δ-valerolactone copolymer, lactide / ε-caprolactone copolymer, glycolide / lactide copolymer (PGLA), lactide / glycol Lido / trimethylene carbonate terpolymer, lactide / glycolide / ε-caprolactone terpolymer, PLA / polyethylene oxide copolymer, asymmetric 3,6-substituted poly-1,4-dioxan-2,5-dione, polyhydroxybutyrate (PHB), PHB / β-hydroxyvalerate copolymer (PHB / PHV), poly-β-hydroxypropionate (PHPA), poly-p-dioxanone (PPD), poly-δ-valerolactone-poly-ε-caprolactone, poly(ε-caprolactone-DL-lactide) copolymer, oxalic acid polyester, poly-β-malic acid (PMLA), poly-β-alkanoic acid, and mixtures thereof are selected from the group. Additionally or alternatively, the compatibilizer has a number average molecular weight (M) of 50 kg / mol or less, preferably 35 kg / mol or less, more preferably 30 kg / mol or less, and even more preferably 25 kg / mol or less. nThe compatibilizer has a molecular weight of at least 2.0 kg / mol, and more particularly at least 3.0 kg / mol. The appropriate weight of the compatibilizer in each individual case also depends on the properties of the compatibilizer. The molecular weights of these polymers were measured via relative GPC analysis using polystyrene calibration, as described in detail in the examples. The compatibilizer is preferably selected from the group of polylactide, poly(lactide-co-glycolide), poly(lactide-co-ε-caprolactone), polyglycolide (PGA) and poly(ε-caprolactone) (PCL). More preferred compatibilizers include hydrophilic polyester copolymers based on polyethylene glycol monomers, particularly copolymers of polyethylene glycol with lactide, glycolide and / or caprolactone.

[0059] The tertiary amine is preferably selected from the group comprising trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldimethylamine, methyldiethylamine, dimethylethanolamine, diethylethanolamine, N'-methylmorpholine, N'-ethylmorpholine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2,6-lutidine.

[0060] Preferably, at least a portion of the tertiary amine is removed under reduced pressure (i.e., less than 100 kPa, preferably less than 50 kPa) and at a high temperature (80-140°C).

[0061] Preferably, the compatibilizer is in a molten state or dissolved in an organic solvent when combined with a tertiary amine to form a dispersion of the neutralized compatibilizer in a liquid medium.

[0062] It is preferable that the compatibilizer comprises a carboxylic acid moiety by converting the alcohol moiety of a thermoplastic, reabsorbable, and biocompatible polymer to a carboxylic acid moiety through a ring-opening reaction with an anhydride, and / or by synthesizing the polymer from a suitable cyclic ester monomer (or a suitable mixture of several such monomers) and an α-hydroxy acid initiator. Alternatively, compatibilizers having an acid group may be prepared by polycondensation of a diacid and a diol using a small excess of acid, according to methods described in the field of polymer chemistry.

[0063] Preferably, the molar ratio of the coupling agent to the amount of the carboxylic acid moiety is at least 0.5. In other words, preferably, at least two carboxylic acid moieties are provided for each silane moiety. The greater the number of carboxylic acid moieties, the higher the likelihood that the carboxylic acid moieties will reach the glass fiber and chemically bond.

[0064] The present invention further relates to a component kit for coating reabsorbable and biocompatible glass fibers, Compatibilizer containing a certain amount of a thermoplastic, reabsorbable and biocompatible polymer, including a carboxylic acid moiety. Volatile tertiary amines, and, A coupling agent having at least one epoxy moiety and at least one silane moiety. Regarding the above parts kit, which includes the above.

[0065] Preferably, the kit is a medical kit, in which case it is understood to be intended and suitable for manufacturing a medical device.

[0066] Preferably, the kit further comprises reabsorbable, biocompatible, and preferably bioactive, glass fibers. The component kit may further include instructions for carrying out a method according to the present invention.

[0067] As described above, the present invention also relates to a composite comprising the coated glass fibers of the present invention and a reabsorbable and biocompatible polymer matrix. Examples of suitable reabsorbable and biocompatible polymer matrix materials include polylactide (PLA), poly-L-lactide (PLLA), poly-DL-lactide (PDLA), L-lactide / DL-lactide copolymer (PLDLA), polyglycolide (PGA), poly(ε-caprolactone) (PCL), glycolide copolymer, ε-caprolactone copolymer, lactide copolymer, glycolide / trimethylene carbonate copolymer (PGA / TMC), lactide / tetramethylglycolide copolymer, lactide / trimethylene carbonate copolymer, lactide / δ-valerolactone copolymer, lactide / ε-caprolactone copolymer, glycolide / lactide copolymer (PGLA), lactide / trimethylene carbonate copolymer, lactide / δ-valerolactone copolymer, lactide / ε-caprolactone copolymer, and lactide / lactide copolymer (PGLA). The group includes polymers selected from the following: tide / glycolide / trimethylene carbonate terpolymers, lactide / glycolide / ε-caprolactone terpolymers, PLA / polyethylene oxide copolymers, asymmetric 3,6-substituted poly-1,4-dioxane-2,5-dione, polyhydroxybutyrate (PHB), PHB / β-hydroxyvalerate copolymer (PHB / PHV), poly-β-hydroxypropionate (PHPA), poly-p-dioxanone (PDO), poly-δ-valerolactone-poly-ε-caprolactone, poly(ε-caprolactone-DL-lactide) copolymers, oxalic acid polyesters, poly-β-malic acid (PMLA), poly-β-alkanoic acid, and mixtures thereof. With respect to the compatibilizer, the polymer matrix is ​​preferably selected from the group consisting of polylactide, poly(lactide-co-glycolide), poly(lactide-co-ε-caprolactone), polyglycolide (PGA), and poly(ε-caprolactone) (PCL).

[0068] In one embodiment, the compatibilizer and the polymer matrix are constructed from the same type of monomer, and more particularly, in the same ratio. This ensures good compatibility between the coated glass fiber and the matrix.

[0069] In one embodiment, at least 10% of the structural units of the compatibilizer are identical to the structural units of the matrix polymer. This is one way to ensure good compatibility between the glass fibers and the matrix material. In one embodiment, at least 20%, at least 40%, or at least 60% of the structural units of the compatibilizer are identical to the structural units of the matrix polymer. In one embodiment, both the compatibilizer and the matrix polymer contain at least 20% by weight, particularly at least 30% by weight, of lactide units. In one embodiment, both the compatibilizer and the matrix polymer contain at least 20% by weight, particularly at least 30% by weight, of caprolactone units. In another embodiment, both the compatibilizer and the matrix polymer contain at least 20% by weight, particularly at least 30% by weight, of glycolide units.

[0070] Preferably, the intrinsic viscosity of the matrix polymer in the composite material is 1.5 to 4.0 dL / g, preferably 1.8 to 3.0 dL / g, and more preferably 2.0 to 3.0 dL / g.

[0071] Generally, the polymer composite material has a Young's modulus (tested by ASTM D7264 / D7264M) higher than that of the matrix polymer, preferably 110% to 1000%, more preferably 200% to 600%, and most preferably 300% to 500% compared to the matrix polymer.

[0072] Preferably, the glass-reinforced polymer composite material has a mechanical strength according to a three-point bend test (tested according to ASTM D7264 / D7264M) that is higher than the strength of the matrix polymer, preferably at least 110% compared to the matrix polymer, preferably at least 200% compared to the matrix polymer, and most preferably at least 400% compared to the matrix polymer when the applied force is perpendicular to the reinforcing fibers.

[0073] Preferably, the composite has a glass fiber content of 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 80% by weight, even more preferably 20 to 70% by weight, and most preferably 30 to 60% by weight, calculated from the total of glass and polymer. Alternatively, the composite preferably has a glass fiber content of at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, and even more preferably at least 90% by weight.

[0074] The composite according to the present invention may contain, in addition to glass fibers and polymers, further components in amounts of, for example, 30% by weight or less, 20% by weight or less, or 10% by weight or less. Examples of further components may be hydroxyapatite and calcium phosphate, such as tricalcium phosphate (TCP), such as β-TCP. The composite may preferably contain additives embedded within it, such as active pharmaceutical ingredients (APIs) or mineral components.

[0075] The present invention also relates to a medical device comprising a polymer matrix coated with glass fibers according to the present invention or a composite according to the present invention. An attractive composite and a method for obtaining the same is described in a patent application filed by the same applicant, inventor and date as this application, entitled "Biocompatible and resorbable polymer composite material and method for obtaining such", the text of which is incorporated herein by reference in its entirety.

[0076] As those skilled in the art know, glass fibers are generally manufactured in the form of fiber bundles, where several individual fibers, often also referred to as filaments, are obtained as bundles from the glass manufacturing process. These fiber bundles may also be referred to as yarn or strand. The present invention relates to coated glass fibers and methods for coating glass fibers. This coating procedure can often be applied to the glass fibers in the fiber bundle, but by properly dispersing the fibers, it will be ensured that the coating is applied to individual fibers. The coated glass fibers can be incorporated into a composite. In the composite, the glass fibers or fiber bundles may exist as continuous fibers and / or chopped fibers. When chopped fibers are used, they generally have lengths in the range of 1 mm to 50 mm, particularly 1 mm to 25 mm, more particularly 1 mm to 20 mm, even more particularly 2 mm to 10 mm, and most particularly less than 4 mm and greater than 1 mm.

[0077] In one embodiment, the medical device comprises a unidirectional composite tape. Glass fiber-based tapes are known in the art. They comprise a biodegradable polymer and a plurality of unidirectionally aligned continuous glass fibers, where the fibers are aligned along the length of the tape. The tape generally has a width of at least twice, particularly at least five times, and more particularly at least ten times, the thickness of the tape. The length of the tape is generally at least ten times, particularly at least 100 times, the width of the tape. The thickness of the tape is preferably less than 0.3 mm, more preferably less than 0.2 mm, and even more preferably less than 0.15 mm. The length of the tape is preferably at least 1 m, more preferably at least 5 m, and even more preferably at least 10 m. The third dimension (i.e., width) is preferably 0.5 to 10 cm, more preferably 0.8 to 5 cm, and even more preferably 1 to 2.5 cm. Composite tapes can be obtained, for example, by spreading out a bundle of glass fibers, bringing the glass fibers into contact with a polymer matrix in a liquid phase, and then solidifying the matrix. Unidirectional composite tapes preferably have a matrix content of 2 to 40% by weight, more particularly 5 to 30% by weight, more particularly 5 to 25% by weight, and in certain embodiments 10 to 20% by weight. The properties of the matrix and the glass fibers are as described elsewhere and apply herein.

[0078] In one embodiment, the medical device comprises a plurality of layers, where one or more layers comprise one or more composite tapes.

[0079] Accordingly, in one embodiment, the composite is molded in the form of a unidirectional composite tape, as described above. In an alternative embodiment, the composite is molded as strands, (cannula-like) rods, tubes, pellets, or granules. Strands / rods are preferably round-shaped fiber-reinforced polymers having a diameter of 5 to 50 mm. Pellets are small cross-sections along the length of rods with a diameter of about 5 to about 50 mm, and granules are small particles having a diameter of about 1 to about 10 mm. The dimensions of the pellets or granules may be adapted to match the dimensions of a feed screw used in polymer processing techniques, such as injection molding.

[0080] As will be apparent to those skilled in the art, different embodiments of the present invention can be combined insofar as they are not mutually exclusive. Preferred embodiments relating to the properties and various components of the glass fiber sizing can also be applied to the above-mentioned component kit, the above-mentioned composite, and the above-mentioned medical device.

[0081] All percentages used herein are weight percentages unless otherwise specified.

[0082] When quantities, concentrations, dimensions, and other parameters are expressed in the form of a range, a preferred range, an upper limit, a lower limit, or preferred upper and lower limits, it should be understood that any range that can be obtained by combining any upper limit or preferred value with any lower limit or preferred value is also specifically disclosed, regardless of whether the range obtained is explicitly mentioned in the context.

[0083] The present invention will be described with reference to the following embodiments, but will not be limited thereto.

[0084] Examples

[0085] analysis technology

[0086] Acid number (AN): The acid value (AN) is the amount of potassium hydroxide (KOH) required in milligrams to neutralize the free acid in 1 g of compatibilizer, and was determined by titration using a Metrohm 876 Dosimat Plus equipped with a Metrohm 801 stirrer. Samples were prepared by weighing 0.5 g of polymer into a 250 mL Erlenmeyer flask, followed by the addition of 100 mL of a pre-neutralized DCM / methanol (4 / 1 vol%) mixture. After complete dissolution, 3 drops of 1 wt% phenolphthalein solution in ethanol were added, and the mixture was titrated with 0.1 M ethanolic KOH until a pink color was obtained that lasted for at least 15 seconds. The amount of KOH required in mL (a) was recorded, and the acid value was calculated according to the following formula.

number

[0087] Relative gel permeation chromatography (GPC): A gel permeation chromatograph (Agilent 1200 series) measures the relative number average molecular weight and weight average molecular weight (M) of the compatibilizer relative to a polystyrene standard. n and M w The GPC system was used to measure [the following]. The GPC system consists of a guard column, two PL gel mixed D columns, and an evaporative light scattering detector (ELSD). HPLC-grade chloroform (Biosolve) stabilized with ethanol was used as the mobile phase at a flow rate of 1 mL / min, and the measurements were performed at 35°C. A sample of 15 mg of compatibilizer was dissolved in 15 mL of chloroform and then filtered through a 0.45 μm filter before GPC analysis. The GPC system was calibrated using a narrow polystyrene standard.

[0088] Headspace GC-MS method for TEA quantification: 100 mg of the coated glass fiber was extracted with dimethyl sulfoxide (DMSO) containing deuterated triethylamine (d-TEA) as an internal standard. Imidazole was added to the DMSO to liberate the TEA from the compatibilizer. The sample was incubated at 100°C for 20 minutes and then analyzed using a headspace GC-MS instrument. The column used was TG-624 (30 m × 0.25 mm × 1.40 μm), and helium was used as the carrier gas.

[0089] A calibration curve for TEA was prepared using the same internal standard material as the sample. The results were normalized by the polymer content on the glass fiber measured by the ignition technique. Quantitative analysis by GC-MS was performed twice for each sample.

[0090] Particle size of nanodispersions: The particle size was measured using dynamic light scattering with a Malvern ZetaSizer nano. The test was performed on diluted aqueous samples in disposable plastic cuvettes according to the ASTM E3247 method. At least three measurements were taken for each sample, and the average value was reported. The D90 value was determined by this method.

[0091] Quantification of moisture content: The coulometric Karl-Fisher titration method was used to determine the water content of glass-sized samples. Key parameters were sample weight and vial temperature. The test was performed with a sample weight of 0.1 ± 0.01 grams and a temperature of 130°C.

[0092] Loss on ignition method: Loss on ignition (LOI) technique is a suitable technique for determining the sizing agent content of glass fiber samples. The sizing agent content of 1 ± 0.2 g of sample was determined using a LECO 701 macro thermogravimetric analyzer (TGA). The test began by recording the sample in the software, followed by determining the initial (empty) crucible weight (with lid). Once the initial weight was measured, the sample was added to the crucibles at their individual positions, and the instrument determined the weight of the sample. Subsequently, the instrument was heated to 110°C and maintained for 30 minutes. After 30 minutes, the instrument was heated to 565°C at a rate of 25°C / min and held at that temperature for 2 hours. While the instrument was operating, the weight was determined at regular time intervals, and the mass loss percentage for each step was calculated and reported. In the first step (110°C), the moisture content in the sample was measured without burning any sizing agent from the fibers. At a higher temperature (565°C), the dry sizing content was obtained by burning off the sizing agent on the glass fibers.

[0093] Single fiber pull-out test method for measuring interfacial shear strength (IFSS) Single fibers were separated from a bundle of glass fibers by immersion in acetone. A portion of the same fiber was used to measure its diameter. Another portion was embedded in a polymer using TextTechno FimaBond. The polymer granules were melted in an aluminum crucible at 270°C for 5 minutes. While the polymer was melting, a single fiber was inserted into a hollow needle positioned directly above the crucible containing the polymer. Once the polymer was completely melted, the fiber was lowered into the center of the molten polymer mass and made contact with the polymer. The fiber was then embedded in the molten polymer to an embedding depth of 220 microns. The polymer was then held at 150°C for a further minute to allow for entanglement, and then cooled to room temperature. The sample was removed from the FimaBond and placed upside down in a Favimat equipped with a FimaTest fiber pull-out fixture. The Favimat was equipped with a highly sensitive 210 cN load cell. The fiber was gripped using a rubber grip directly beside the polymer and pulled at 0.6 mm / min. The test was performed at ambient temperature. The test stopped when the force dropped to zero, and the apparent interfacial shear strength (IFSS) was automatically calculated by software based on the fiber diameter, embedding depth, and maximum force. At least 10 samples were tested for each fiber group, and the average value was reported.

[0094] Example 1: Synthesis of carboxylic acid-functionalized poly(lactide / ε-caprolactone) 75 / 25 (molar ratio) (compatibility agent)

[0095] A mixture of L-lactide (3.50 mol) and ε-caprolactone (1.17 mol) was bulk polymerized using tin 2-ethylhexanoate as a catalyst and 1,4-butanediol (0.2 mol) as an initiator. The resulting poly(lactide / ε-caprolactone)diol was subsequently acid-functionalized by reaction with succinic anhydride (0.44 mol). Residual monomers were removed by ultrafiltration. The final polymer was amorphous (Tg=18°C), with a weight-average molecular weight (Mw) of 5.6 kg / mol and a number-average molecular weight (Mn) of 3.6 g / mol (both determined by GPC against a polystyrene standard), and an acid value of 26.9 mg KOH / g polymer. The residual amount of Sn, determined via ICP, was 140 ppm.

[0096] Compatibilizers with different molecular weights and acid values ​​were manufactured using a similar method, and their properties are summarized in Table 1 below.

[0097] [Table 1]

[0098] Example 2: Preparation of a dispersion of compatibilizer in water

[0099] The aqueous dispersion of the compatibilizer can be prepared using either the solvent-assisted method or the melt dispersion method.

[0100] (a) Solvent-assisted method A 75 / 25 molar ratio of poly(lactide / ε-caprolactone), starting with 1,4-butanediol and end-capped with succinic anhydride, was dissolved in acetone (43 wt%). The copolymer was neutralized by adding triethylamine (0.6 mol TEA / mol COOH). The neutralized copolymer was added to Milli-Q water at approximately 20°C, and the acetone was gently removed under vacuum. A bluish dispersion (approximately 20 wt%) with a particle size of 100 nm (D90) was obtained (measured by dynamic light scattering using a ZetaSizer-nano according to ASTM E3247).

[0101] (b) Melt dispersion method Starting with 1,4-butanediol, poly(lactide / ε-caprolactone) 75 / 25 (molar ratio) end-capped with succinic anhydride (acid value: 26.9 mg KOH / g polymer) melted the poly(lactide / ε-caprolactone) at 90°C, and triethylamine (0.9 mol TEA / mol COOH) was added to the polymer to obtain a dispersion of the compatibilizer in water. After the mixture was stirred for 5 minutes, Milli-Q water preheated to 50°C was added, and stirring was continued until a bluish dispersion (approximately 20% by weight) with a particle size of 260 nm (D90) was obtained.

[0102] Example 3: Effect of neutralization degree

[0103] This experiment illustrates the effect of the degree of neutralization on the final properties of a nano-dispersion (aqueous). Nine grams of acid-functionalized random poly(lactide / ε-caprolactone) in a 75 / 25 molar ratio with an acid value of 31.1 mg KOH / g were dissolved in 200 mL of acetone. After complete dissolution, a predetermined amount of TEA was added. Subsequently, the solution was stirred in a sealed container at ambient temperature for 30 minutes for the purpose of neutralization. Next, the solution was gradually added to 200 mL of Milli-Q water under stirring. The resulting dispersion was stirred in an open beaker in a fume hood for approximately 24 hours until all the acetone had evaporated and approximately 5 wt% of the polymer remained in the water. Particle size was measured using a Malvern Zeta sizer nano. Table 2 below summarizes the particle size of the dispersions obtained at different degrees of neutralization (0.4, 0.5, 0.6, 0.7, and 1 mole of TEA per mole of acid).

[0104] [Table 2]

[0105] Example 3a: Preparation of dispersion in the absence of TEA

[0106] The procedure of Example 3 was repeated, except that TEA was not added to the polymer solution. Similar to Example 3, the polymer solution was gradually added to 200 mL of Milli-Q water under stirring. The resulting dispersion was stirred in an open beaker in a fume hood for approximately 24 hours until all the acetone had evaporated and approximately 5% by weight of polymer remained in the water. The polymer was not in the form of a nanodispersion. Rather, large particles formed, which aggregated and settled at the bottom of the container. The PSD(D90) was estimated to be on the order of tens to hundreds of microns, and it could not maintain a suspended state and therefore could not be measured via a DLS (dynamic light scattering) instrument such as a ZetaSizer-nano.

[0107] Example 4: Effect of molecular weight

[0108] Acid-functionalized random poly(lactide / ε-caprolactone) copolymers with a molar ratio of 75 / 25, varying molecular weights, and corresponding acid values ​​(compatibility agents 2, 3, 4, and 5 from Example 1) were dissolved in acetone at a 5% by weight concentration, followed by the addition of triethylamine at a 1:1 molar ratio to the acid. After stirring the solution for 30 minutes, the polymer solution was gradually added to purified Milli-Q water. The acetone was evaporated in a fume hood over 24 hours to obtain a 5% by weight aqueous polymer dispersion. Particle size (D90) was measured by DLS (ZetaSizer). Table 3 below provides molecular weight data, acid value data, and particle size data.

[0109] [Table 3]

[0110] Example 5: Synthesis and testing of sizing agent

[0111] An acid-functionalized poly(lactide / ε-caprolactone) copolymer having 75 / 25 mol%, Mn 5 kg / mol, and Mw 8 kg / mol (measured by relative GPC) was dissolved in acetone to prepare a 10% (weight / weight) solution. The acid value of the copolymer was 32.5 mg KOH / g. Upon complete dissolution, triethylamine (TEA) was added to the container in a carboxylic acid / TEA molar ratio of 1:0.6 to neutralize the acid. The neutralized polymer solution was gradually added to Milli-Q water (equal in volume of acetone) with stirring in a mixer. The acetone was removed by evaporation, either by applying a vacuum (Hg, -15 to -20) for at least 7 hours or until all acetone was removed. At this point, it was assumed that all acetone had been removed from the system and a solids content of more than 10% had been achieved. This yielded an aqueous dispersion with D90 < 350 nm and pH < 7.8. Next, the dispersion was mixed with hydrolyzed silane (3-glycidyloxypropyltriethoxysilane) to achieve a molar ratio of 0.5 to the acid in the final sizing solution, thereby achieving a solid content of 5% by weight in the sizing agent.

[0112] Next, the sizing agent was applied via a kiss roller to freshly drawn glass fibers having a target composition of SiO2 67.8 wt%, P2O 51.5 wt%, B2O 32.3 wt%, CaO 9 wt%, MgO 5.4 wt%, and Na2O 14 wt%, which were formed in the melt spinning process. The fibers were then wound onto a core for further processing.

[0113] A moist glass fiber cake was dried under an airflow for 24 hours, followed by drying under vacuum (p=0.66kPa) for another 24 hours. The moisture content was less than 1000 ppm, and the TEA content was 3448 ppm, which corresponds to a TEA / COOH molar ratio of 0.05 or 1:20. During the drying process, the reaction between the silanol groups and the glass was accelerated.

[0114] Next, to promote the reaction between the acid terminal groups of the compatibilizer and the epoxy groups, the fiber cake was cured at 90°C for 16 hours. After curing, to remove any remaining TEA, it was subjected to deep vacuum at 90°C for 2 hours. The sizing agent content, determined by the loss on ignition (TGA) method, was 1.2% by weight. The amount of TEA was quantified and found to be 2 ppm on the coated glass fibers.

[0115] Example 6: Grafting Efficiency

[0116] Depending on the manufacturing process of the composite, various amounts of sizing agent may be required. For sizing compatible with a thermoplastic matrix polymer, it may be preferable to have at least a monolayer of sizing agent. For a given glass diameter and a compatibilizer of a specific molecular weight, the amount of this monolayer can be calculated as a percentage of the glass by weight. For a glass fiber filament with a diameter of 12 microns and a compatibilizer having 3 kg / mol of Mn, the calculated amount of sizing agent to form a monolayer covalently bonded to the glass fiber with the help of epoxysilane is approximately 0.3 wt% of glass fiber. This calculation also assumes that the silanol bond reactable with epoxysilane is 4.6 OH / nm. 2 It is assumed that it has a density of OH / nm. This means that the average density of silanols in amorphous silica is typically about 4.8 OH / nm. 2 This is based on literature suggesting that the covalently bonded sizing agent is not washed away with acetone.

[0117] To confirm the grafting of the sizing agent onto the glass fibers, sized fibers obtained according to the procedure described in Example 5 were immersed in acetone for 10 minutes and then washed at least twice with cleaner acetone to remove any remaining unreacted compatibilizer. The samples were dried and the sizing agent content was analyzed via loss on ignition technique using LECO macro TGA 701. The sizing agent content on the glass fibers before washing was 0.94% by weight, while the sizing agent content after washing away the unreacted sizing agent from the glass fibers was approximately 0.39% by weight. This experiment confirmed the presence of a monolayer of covalently bonded sizing agent on the surface of the glass fibers. The excess and unreacted sizing agent helps to hold the fibers together in the glass fiber bundle and protects the fibers from abrasion during the winding and composite manufacturing processes.

[0118] Example 7: Effect of Compatibilizer

[0119] Adhesion strength was measured directly using the single-fiber pulping method. Glass fibers were first treated with silane and then cured. Subsequently, the treated glass fibers were coated with a compatibilizer used in Example 5, followed by a curing step in which the compatibilizer reacted with silane. Next, a single glass fiber filament was embedded in the matrix polymer (Purasorb PLDL 7030) and pulping using a Fimatest fixture in a Favimat machine. Glass fibers treated with silane alone were used as a negative control.

[0120] The apparent interfacial shear strength (IFSS) for silane-treated fibers was 36±17 MPa, which jumped to 42±15 MPa for fibers coated with a PLC compatibilizer with a calculated Mn value of 3 kg / mol. Further improvements were observed when glass fibers coated with a PLC compatibilizer prepared to have calculated Mn values ​​of 13 kg / mol and 17 kg / mol, with IFSS measured at 51±9 MPa and 53±8 MPa, respectively.

[0121] Example 8 - A sizing agent containing polycaprolactone as a compatibilizer is applied to glass fibers, and the coated fibers are incorporated into a polycaprolactone matrix to form a polycaprolactone glass fiber reinforced composite material, and then this is further processed to form a composite plaque.

[0122] 1. Preparation of silane-treated glass fibers A hydrolyzed silane solution was prepared by dissolving 117 g of 3-glycidyloxypropyltriethoxysilane in 10 kg of ASTM Type II purified water at 50°C for 90 minutes. The hydrolyzed silane solution was then applied in-line via a kiss roller onto freshly drawn glass fibers formed during the melt spinning process. The composition of the glass was the same as that applied in Example 5. The resulting fiber bundles were wound onto a core for further processing. The wet glass fibers were air-dried and then vacuum-dried at room temperature to reduce the moisture level to less than 1000 ppm. The dried glass fibers were heat-treated at 90°C for 4 hours to covalently bond the silane to the hydroxyl groups on the surface of the glass fibers.

[0123] 2. Preparation of aqueous PC(IV 0.15) nanodispersion Forty g of acid-functionalized polycaprolactone with an IV of 0.15 dL / g (measured according to ASTM 2857) and an acid value of 39.4 mg KOH / g was dissolved in 1600 g of acetone over 1 hour. After complete dissolution, triethylamine (TEA, from Sigma Aldrich) was added in a 1:1 molar ratio to the acid to neutralize the acid terminal groups. After stirring for 15 minutes, the polymer solution was gradually added to ASTM Type II purified water. After evaporating for 24 hours to remove the acetone, an aqueous nanodispersion with a solid content of approximately 3% by weight was obtained. The average particle size (z-mean), measured by DLS (Malvern ZetaSizer-nano), was found to be 37 nanometers, and the D90 was 39 nm.

[0124] 3. Preparation of uniformly sized glass fibers of PC(IV 0.15) The silane-treated glass fibers (having an average diameter of 16 microns) obtained in step 1 were further treated with the compatibilizing polymer (PC, IV 0.15 dL / g) prepared in step 2 by passing them in a continuous manner through a polymer nanodispersion bath in an offline reel-to-reel sizing applicator system. The line speed was 5 m / min. The sized fibers were collected on a separate perforated stainless steel (SS) core. Subsequently, the fibers were vacuum-dried at room temperature and then cured at 90°C for 16 hours to facilitate the reaction between the acid-terminated groups of the compatibilizer and the epoxy groups of the silane already covalently bonded to the glass surface. The TEA present at the reaction site acted as a catalyst and was ultimately removed by applying vacuum.

[0125] After curing, PC-sized glass fiber samples were tested for the presence of a sizing agent layer, which is a PC(IV 0.15) compatibilizer, via the TGA loss-on-ignition method. The results confirmed the presence of 1 ± 0.5% by weight of the sizing agent on the glass fibers.

[0126] 4. Manufacturing of a composite tape containing a polycaprolactone polymer and fibers sized together with a polycaprolactone compatibilizer. A 10 wt% solution of high molecular weight polycaprolactone (Purasorb PC17, IV 1.7 dL / g, commercially available from Corbion Purac) was prepared in acetone at 50°C. A bundle of uniformly sized PC fibers (576 filaments) obtained in step 3 was coated with polymer by passing it through a polymer solution bath using a continuous reel-to-reel applicator system. The polymer solution bath was equipped with rollers and pins to spread the fibers for better wettability. The solvent was removed by passing the coated fibers through an anti-solvent (ethyl alcohol) bath at a line speed of 2 m / min at room temperature, followed by air drying for 24 hours. After drying, the polymer-coated fibers appeared as thin and narrow tape. The coated and dried fibers were analyzed for fiber / polymer content by the LECO, TGA701 thermal loss method. The polymer content was 14.2% by weight.

[0127] 5. Composite plaques obtained by compression molding a composite containing polycaprolactone and coated glass fibers. The composite tape obtained in step 4 above was cut into 100 mm long strips, and a predetermined amount was stacked uniformly in the cavity of a preheated mold, then spread out to prepare a sample for mechanical testing. An additional polymer (Purasorb PC17, Tm60℃) film was added as a top layer on the coated fiber stack to bring the fiber content in the final molded product to 50% by weight. The mold cavity was 100 mm × 100 mm × 1 mm. Next, these coated fiber bundles and polymer film layers were heated above the softening temperature of the polymer, pressed, and subsequently cooled, and then removed from the mold. A composite plaque was obtained, which was used for analytical purposes.

[0128] 6. Mechanical testing of the composite The composite plaques from step 5 above were cut into rectangular coupons (50 × 13 × 1 mm; LxWxT), and bending properties tests (3-point bending tests) were performed according to ASTM D7264 / D7264M-15 using a Lloyd universal mechanical tester equipped with a 3-point bend fixture and a 2.5 kN load cell. A span-to-thickness ratio of 16:1 was used. The standard width was 13 mm, and the length of the test specimen was approximately 20% longer than the support span (10% on each side). The average strength for the 6 samples tested was 147 ± 7.6 MPa (a 600% improvement from the base polymer strength of 23 MPa), and the modulus of elasticity was 6.46 ± 0.68 GPa (a 58-fold improvement from the base polymer strength of 110 MPa). The tested samples were analyzed for fiber content via the TGA thermal loss method, and it was found that the average fiber content of the composite was 50.4% by weight.

[0129] Example 9 - A glass fiber having poly(DL-lactide) (PDL) as a compatibilizer is provided, and the coated fiber is incorporated into a poly(DL-lactide) matrix to form a poly(DL-lactide) glass fiber reinforced composite material, and further processed to form a composite plaque.

[0130] Epoxy-functionalized, silane-treated glass fibers were prepared as described in Example 8 above.

[0131] Thirty g of an acid-functionalized poly(DL lactide) (50 / 50) polymer with an IV of 0.4 dL / g and an acid value of 4.1 mg KOH / g was dissolved in 1500 g of acetone over 1 hour. After complete dissolution, TEA was added in a molar ratio of 1:1.3 to the acid to neutralize the acid terminal groups. After stirring the solution for 15 minutes, the polymer solution was gradually added to ASTM Type II purified water. After evaporating for 24 hours to remove the acetone, an aqueous dispersion of approximately 3 wt% was obtained. The average particle size (z-mean), measured by DLS (Malvern ZetaSizer-nano), was found to be 30 nanometers, and the D90 was 24 nm.

[0132] Silane-treated glass fibers were further treated with a compatibilizing polymer by passing the glass fiber bundles continuously through a bath of the polymer nanodispersion described above in an offline reel-to-reel sizing applicator system. The line speed was 5 m / min. The sized fibers were collected on a separate perforated SS core. The fibers were vacuum-dried at room temperature and then cured at 90°C for 16 hours to facilitate the reaction between the -COOH terminal groups of the compatibilizing polymer and the epoxy terminals of the silane already covalently bonded to the glass surface. TEA present at the reaction site acted as a catalyst and was ultimately removed by applying vacuum.

[0133] Once cured, the glass sample was tested for the presence of a sizing agent layer via the TGA ignition loss method. The results confirmed the presence of 1 ± 0.5% by weight of sizing agent on the glass fibers.

[0134] A 10 wt% solution (IV 2.0 dL / g) of high molecular weight poly(DL lactide) was prepared in acetone. A bundle (576 filaments) of the above-described size (average diameter 16 microns) was coated with high molecular weight poly(DL lactide) by passing it through a polymer solution bath using a continuous reel-to-reel applicator system. The polymer solution bath was equipped with rollers and pins to spread the fibers to obtain better wettability. The solvent was removed by passing the coated fibers through an anti-solvent (ethyl alcohol) bath at room temperature. The line speed was 1 m / min. The coated fibers were air-dried for 24 hours. After drying, the coated fibers appeared as thin and narrow tape. The coated and dried fibers were analyzed for fiber / polymer content by the LECO TGA701 thermal loss method. The polymer content was 15.4 wt%.

[0135] The resulting composite tape was cut into 100 mm long strips, and a predetermined amount was stacked uniformly in the cavity of a preheated mold, then spread out to prepare a sample for mechanical testing. An additional polymer (Purasorb PLDL7020) film was added as a top layer on the coated fiber stack to bring the fiber content in the final molded product to 50% by weight. The mold cavity was 100 mm × 100 mm × 1 mm. Next, these coated fiber bundles and polymer film layers were heated above the softening temperature of the polymer, pressed, and subsequently cooled, and then removed from the mold. A composite plaque was obtained, which was used for analytical purposes.

[0136] Next, the composite plaque was cut into rectangular coupons (50 × 13 × 1 mm; LxWxT) and subjected to bending property tests (3-point bending tests) using a Lloyd universal mechanical tester equipped with a 3-point bend fixture and a 2.5 kN load cell, according to ASTM D7264 / D7264M-15. A span-to-thickness ratio of 16:1 was used. The standard width was 13 mm, and the length of the test specimen was approximately 20% longer than the support span (10% on each side). The average strength for the 6 samples tested was 491.3 ± 38.6 MPa (a 446% improvement from the base polymer's strength of 110 MPa), and the modulus of elasticity was 12.72 ± 1.5 GPa (a 374% improvement from the base polymer's 3.4 GPa). The tested samples were analyzed for fiber content via the TGA thermal loss method, and it was found that the average fiber content of the composite was 52% by weight.

[0137] Example 10 - A sizing agent containing poly(DL-lactide / glycolide) (PDLG) as a compatibilizer is provided to glass fibers, the sized fibers are incorporated into the poly(DL-lactide / glycolide) matrix to form a poly(DL-lactide / glycolide) glass fiber reinforced composite material, and then the composite is further processed to form a composite plaque.

[0138] Epoxy-functionalized, silane-treated glass fibers were prepared as described in Example 8 above.

[0139] 30 g of 50 / 50 acid-functionalized poly(DL lactide / glycolide) from Corbion, with an IV of 0.4 and an acid value of 4.1 mg KOH / g, was dissolved in 1500 g of acetone over 1 hour. After complete dissolution, triethylamine was added in a 1:1.3 molar ratio to the acid to neutralize the acid terminal groups. After stirring the solution for 15 minutes, the polymer solution was gradually added to ASTM Type II purified water. After evaporating for 24 hours to remove the acetone, an aqueous dispersion of approximately 3 wt% was obtained. The average particle size (z-mean), measured by DLS (Malvern ZetaSizer-nano), was found to be 46 nanometers, and the D90 was 46 nm.

[0140] Silane-treated glass fibers were further treated with the aforementioned polymer nanodispersion by passing the glass fibers in a continuous manner through a bath of the aforementioned polymer nanodispersion in an offline reel-to-reel sizing applicator system. The line speed was 5 m / min. The sized fibers were collected on a separate perforated SS core. The fibers were vacuum-dried at room temperature and then cured at 90°C for 16 hours to facilitate the reaction between the -COOH terminal groups of the compatibilizer polymer and the epoxy terminals of the silane already covalently bonded to the glass surface. TEA present at the reaction site acted as a catalyst and was ultimately removed by applying vacuum.

[0141] Once cured, the glass sample was tested for the presence of a sizing agent layer via the TGA ignition loss method. The results confirmed the presence of a coating of 1 ± 0.5% by weight on the glass fibers.

[0142] A 10 wt% solution of high molecular weight poly(DL lactide / glycolide) 85 / 15 having an IV of 2.3 dL / g was prepared in acetone at 50°C. A bundle (576 filaments) of uniformly sized PDLG fibers (having an average diameter of 16 microns) was coated with PDLG85 / 15 by passing it through a polymer solution bath using a continuous reel-to-reel applicator system. The polymer solution bath was equipped with rollers and pins to spread the fibers for better wettability. The solvent was removed by passing the coated fibers through an anti-solvent (alcohol) bath at room temperature. The line speed was 2 m / min. The coated fibers were air-dried for 24 hours. After drying, the coated fibers appeared as a thin and narrow tape. The coated and dried fibers were analyzed for fiber / polymer content via the LECO TGA701 thermal loss method. The polymer content was 32.6% by weight.

[0143] The resulting composite tape was cut into 100 mm long strips, and a predetermined amount was stacked uniformly in the cavity of a preheated mold, then spread out to prepare a sample for mechanical testing. An additional polymer (Purasorb PLDG85 / 15) film was added as a top layer on the coated fiber stack to bring the fiber content in the final molded product to 50% by weight. The mold cavity was 100 mm × 100 mm × 1 mm. Next, these coated fiber bundles and polymer film layers were heated above the softening temperature of the polymer, pressed, and subsequently cooled, and then removed from the mold. A composite plaque was obtained, which was used for analytical purposes.

[0144] The composite plaque was cut into rectangular coupons (target 50 × 13 × 1 mm; LxWxT) and subjected to bending property tests (3-point bending tests) using a Lloyd universal mechanical tester equipped with a 3-point bend fixture and a 2.5 kN load cell, according to ASTM D7264 / D7264M-15. A span-to-thickness ratio of 16:1 was used. The standard width was 13 mm, and the length of the test specimen was approximately 20% longer than the support span (10% on each side). The average strength of the 6 samples tested was measured at 770.7 ± 131 MPa (a 770% improvement from the base polymer's strength of 100 MPa), and the modulus of elasticity was measured at 23.9 ± 5.4 GPa (a 570% improvement from the base polymer's 4.2 GPa). The tested samples were analyzed for fiber content via the TGA thermal loss method, and it was found that the average fiber content of the composite was 55.7% by weight. In one embodiment, the present invention may be configured as follows. [Section 1] A reabsorbable, biocompatible glass fiber coated with a sizing agent, wherein the sizing agent comprises a thermoplastic, reabsorbable, and biocompatible compatibilizer covalently bonded to the glass fiber through a coupling agent having at least one silane moiety, and the coated glass fiber has an apparent interfacial shear strength for a reference matrix polymer determined in a single-fiber pulp test, wherein the apparent interfacial shear strength is at least 10% higher than the apparent interfacial shear strength of a bare glass fiber for the same reference matrix polymer. [Section 2] The coated glass fiber according to claim 1, wherein the coated glass fiber contains an amount of volatile tertiary amine less than 10 ppm or between 0.1 ppm and 10 ppm. [Section 3] The coated glass fiber according to claim 1 or 2, wherein the sizing agent does not contain a surfactant, and preferably the coated glass fiber does not contain a surfactant. [Section 4] The coated glass fiber according to any one of claims 1 to 3, wherein the coated glass fiber has an apparent interfacial shear strength with respect to the reference matrix polymer determined in the single fiber pulping test, and the apparent interfacial shear strength is at least 20%, particularly at least 30%, higher than the apparent interfacial shear strength of a bare glass fiber with respect to the same reference matrix polymer. [Section 5] The coated glass fiber according to any one of claims 1 to 4, wherein the coated glass fiber has an apparent interfacial shear strength due to the reference matrix polymer determined in the single fiber pulping test, and the apparent interfacial shear strength is at least 10 MPa, particularly at least 15 MPa, more particularly at least 20 MPa, more particularly at least 30 MPa, preferably at least 40 MPa, and even more preferably at least 50 MPa. [Section 6] A method for producing a reabsorbable and biocompatible glass fiber coated with a sizing agent, particularly a coated reabsorbable and biocompatible glass fiber as described in any one of items 1 to 5, a) Glass fiber, A coupling agent having at least one epoxy moiety and at least one silanol group in a liquid medium, and In a liquid medium, a reaction product is obtained from the reaction of a compatibilizer with a volatile tertiary amine, wherein the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups. By bringing the glass fibers into contact with the sizing composition, b) subjecting the coated glass fibers to a drying process, c) The dried coated glass fibers are subjected to a curing process at an elevated temperature. d) The cured coated glass fibers are subjected to a step of evaporating the volatile tertiary amine. The method comprising the step of [Section 7] The method according to claim 6, wherein the tertiary amine acts as a catalyst for the reaction between the epoxy moiety and the neutralized compatibilizer. [Section 8] The method according to claim 6 or 7, wherein the coupling agent and the reaction product of the reaction between the compatibilizer and the volatile tertiary amine are present in the same liquid medium. [Section 9] The method according to claim 6 or 7, wherein the coupling agent and the reaction product of the reaction between the compatibilizer and the volatile tertiary amine are present in different liquid media, the glass fiber is first in contact with the coupling agent in the liquid media, and then in contact with the reaction product of the reaction between the compatibilizer and the volatile tertiary amine in the liquid media, and optionally subjected to a drying and / or curing step between contact with the coupling agent and contact with the reaction product of the reaction between the compatibilizer and the volatile tertiary amine. [Section 10] The method according to any one of claims 6 to 9, wherein the product of the reaction of a compatibilizer with a volatile tertiary amine is in an aqueous medium, preferably the product of the reaction of a compatibilizer with a volatile tertiary amine is dispersed in the aqueous medium in the form of a microdispersion, preferably in the form of a nanodispersion. [Section 11] The method according to any one of claims 6 to 10, wherein the volatile tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldimethylamine, methyldiethylamine, dimethylethanolamine, diethylethanolamine, N'-methylmorpholine, N'-ethylmorpholine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2,6-lutidine. [Section 12] The method according to any one of claims 6 to 11, wherein at least a portion of the tertiary amine is removed under reduced pressure. [Section 13] The compatibilizer is polylactide (PLA), poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), polyglycolide (PGA), poly(ε-caprolactone) (PCL), glycolide copolymer, glycolide / trimethylene carbonate copolymer (PGA / TMC), lactide / tetramethylglycolide copolymer, lactide / trimethylene carbonate copolymer, lactide / d-valerolactone copolymer Polymers, lactide / ε-caprolactone copolymer, L-lactide / DL-lactide copolymer (PLDLA), glycoside / L-lactide copolymer (PGA / PLLA), polylactide-co-glycolide, lactide / glycolide / trimethylene carbonate terpolymer, lactide / glycolide / ε-caprolactone terpolymer, PLA / polyethylene oxide copolymer, asymmetric 3,6-substituted poly-1,4-dioxy A method according to any one of claims 6 to 12, or a glass fiber according to any one of claims 1 to 5, comprising a polymer selected from the group consisting of san-2,5-dione, polyhydroxybutyrate (PHB), PHB / b-hydroxyvalerate copolymer (PHB / PHV), poly-β-hydroxypropionate (PHPA), poly-p-dioxanone (PDO), poly-d-valerolactone-poly-ε-caprolactone, poly(ε-caprolactone-DL-lactide) copolymer, oxalic acid polyester, poly-β-malic acid (PMLA), poly-β-alkanoic acid, polyorthoester, poly(ester anhydride), and mixtures thereof, particularly a polymer selected from the group consisting of polylactide, poly(lactide-co-glycolide), poly(lactide-co-ε-caprolactone), polyglycolide (PGA), and poly(ε-caprolactone) (PCL). [Section 14] A component kit suitable for coating glass fibers, which is reabsorbable, biocompatible, and preferably bioactive, Compatibilizer containing a certain amount of a thermoplastic, reabsorbable and biocompatible polymer, including a carboxylic acid moiety. Tertiary amines, and A coupling agent having at least one epoxy moiety and at least one silane moiety. The aforementioned parts kit includes the following: [Section 15] A composite comprising a plurality of glass fibers as described in any one of items 1 to 5, or a product of the method described in any one of items 6 to 13 embedded in a reabsorbable and biocompatible polymer matrix. [Section 16] The composite according to claim 15, wherein the composite is in the form of a unidirectional composite tape, or in the form of strands, (cannula-like) rods, tubes, pellets or granules, particularly in the form of a unidirectional tape. [Section 17] A medical device comprising a plurality of glass fibers as described in any one of items 1 to 5, or a product of the method described in any one of items 6 to 13, or a composite as described in item 15 or 16.

Claims

1. A reabsorbable and biocompatible glass fiber coated with a sizing agent, wherein the sizing agent comprises a thermoplastic, reabsorbable and biocompatible compatibilizer covalently bonded to the glass fiber through a coupling agent having at least one silane moiety, the glass fiber having an apparent interfacial shear strength for a reference matrix polymer determined in a single fiber pulp test, the apparent interfacial shear strength being at least 10% higher than the apparent interfacial shear strength of a bare glass fiber for the same reference matrix polymer, and the coated glass fiber being a reaction product of a reaction between a thermoplastic, reabsorbable and biocompatible polymer containing carboxylic acid terminal groups in a liquid medium and a volatile tertiary amine.

2. The coated glass fiber according to claim 1, wherein the coated glass fiber contains an amount of volatile tertiary amine less than 10 ppm.

3. The coated glass fiber according to claim 1, wherein the coated glass fiber contains an amount of 0.1 ppm to 10 ppm of a volatile tertiary amine.

4. The coated glass fiber according to claim 1, wherein the sizing agent does not contain a surfactant.

5. The coated glass fiber according to claim 1, wherein the coated glass fiber has an apparent interfacial shear strength due to the reference matrix polymer determined in the single fiber pulping test, and the apparent interfacial shear strength is at least 20% higher than the apparent interfacial shear strength of a bare glass fiber with the same reference matrix polymer.

6. The coated glass fiber according to claim 1, wherein the coated glass fiber has an apparent interfacial shear strength due to the reference matrix polymer determined in the single fiber pulping test, and the apparent interfacial shear strength is at least 10 MPa.

7. A method for producing reabsorbable and biocompatible glass fibers coated with a sizing agent, a) Glass fiber, A coupling agent having at least one epoxy moiety and at least one silanol group in a liquid medium, and In a liquid medium, a reaction product is obtained from the reaction of a compatibilizer with a volatile tertiary amine, wherein the compatibilizer is a thermoplastic, reabsorbable, and biocompatible polymer containing carboxylic acid terminal groups. By bringing the glass fibers into contact with the sizing composition, b) subjecting the coated glass fibers to a drying process, c) The dried coated glass fibers are subjected to a curing process at an elevated temperature. d) The cured coated glass fibers are subjected to a step of evaporating the volatile tertiary amine. The method comprising the step of

8. The method according to claim 7, wherein the tertiary amine acts as a catalyst for the reaction between the epoxy moiety and the neutralized compatibilizer.

9. The method according to claim 7, wherein the coupling agent and the reaction product of the reaction between the compatibilizer and the volatile tertiary amine are present in the same liquid medium.

10. The method according to claim 7, wherein the coupling agent and the reaction product of the reaction between the compatibilizer and the volatile tertiary amine are present in different liquid media, the glass fiber is first in contact with the coupling agent in the liquid media, and then in contact with the reaction product of the reaction between the compatibilizer and the volatile tertiary amine in the liquid media, and optionally subjected to a drying and / or curing step between contact with the coupling agent and contact with the reaction product of the reaction between the compatibilizer and the volatile tertiary amine.

11. The method according to claim 7, wherein the product of the reaction of the compatibilizer with a volatile tertiary amine is in an aqueous medium.

12. The method according to claim 11, wherein the product of the reaction between a compatibilizer and a volatile tertiary amine is dispersed in the aqueous medium in the form of a microdispersion.

13. The method according to claim 12, wherein the product of the reaction between a compatibilizer and a volatile tertiary amine is dispersed in the aqueous medium in the form of a nanodispersion.

14. The method according to claim 7, wherein the volatile tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldimethylamine, methyldiethylamine, dimethylethanolamine, diethylethanolamine, N'-methylmorpholine, N'-ethylmorpholine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2,6-lutidine.

15. The method according to claim 7, wherein at least a portion of the tertiary amine is removed under reduced pressure.

16. The compatibilizer is polylactide (PLA), poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), polyglycolide (PGA), poly(ε-caprolactone) (PCL), glycolide copolymer, glycolide / trimethylene carbonate copolymer (PGA / TMC), lactide / tetramethylglycolide copolymer, lactide / trimethylene carbonate copolymer, lactide / d-valerolactone copolymer, lactide / ε-caprolactone copolymer, L-lactide / DL-lactide copolymer (PLDLA), glycolide / L-lactide copolymer (PGA / PLLA), polylactide-co-glycolide, lactide / glycolide / trimethylene carbonate copolymer, lact The method according to claim 7, comprising a polymer selected from the group consisting of thio / glycolide / ε-caprolactone terpolymer, PLA / polyethylene oxide copolymer, asymmetric 3,6-substituted poly-1,4-dioxan-2,5-dione, polyhydroxybutyrate (PHB), PHB / β-hydroxyvalerate copolymer (PHB / PHV), poly-β-hydroxypropionate (PHPA), poly-p-dioxanone (PDO), poly-d-valerolactone-poly-ε-caprolactone, poly(ε-caprolactone-DL-lactide) copolymer, oxalic acid polyester, poly-β-malic acid (PMLA), poly-β-alkanoic acid, polyorthoester, poly(ester anhydride), and mixtures thereof.

17. A component kit suitable for coating reabsorbable, biocompatible glass fibers, Compatibilizer containing a certain amount of a thermoplastic, reabsorbable and biocompatible polymer, including a carboxylic acid moiety. Tertiary amines, and A coupling agent having at least one epoxy moiety and at least one silane moiety. The aforementioned parts kit includes the following:

18. A composite comprising a plurality of glass fibers according to any one of claims 1 to 6, embedded in a reabsorbable and biocompatible polymer matrix.

19. The composite according to claim 18, wherein the composite is in the form of a unidirectional composite tape, or in the form of strands, (cannula-like) rods, tubes, pellets, or granules.

20. A medical device comprising a plurality of glass fibers as described in any one of claims 1 to 6.

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