Food and medical polymer compositions and articles manufactured therefrom

Abstract

A fiber-reinforced polyester polymer composition specifically formulated for food contact applications and / or medical applications is disclosed. The polyester polymer composition contains glass fibers that are either bisphenol A-free or contain only trace / residual amounts of free bisphenol A. The composition can be formulated without the use of conventional stabilizers, antioxidants and / or lubricants. The polymer composition exhibits excellent mechanical properties.

Description

[Technical Field]

[0001] Related applications This application is based on and claims priority to U.S. Provisional Patent Application No. 63 / 495,672, filed April 12, 2023, which is incorporated herein by reference. [Background technology]

[0002] Engineering thermoplastics are often used in a wide variety of applications to manufacture molded parts and products. For example, thermoplastic polymers are used to manufacture all different types of molded products, such as injection-molded products and blow-molded products. Thermoplastic polymers may be formulated to be, for example, chemical resistant, have excellent strength properties, and be flexible when incorporated into compositions containing elastomers. Particularly advantageous, many polymers can be melt-processed due to their thermoplasticity. In addition, many polymers can be recycled and reprocessed.

[0003] One objective in manufacturing molded parts from thermoplastic polymers is to produce parts with desired mechanical properties. These mechanical properties may include a combination of tensile strength and impact resistance. For example, when manufacturing a polyester polymer composition, various additives can be blended with the polyester polymer to improve one or more properties. For instance, glass fibers are typically added to improve strength. In addition, various stabilizers are combined with the polymer to prevent the strength properties from degrading over time.

[0004] Another objective in manufacturing molded parts from thermoplastic polymers is the ability to quickly mold parts and increase productivity. For example, each polymer formulation may present a set of inherent problems related to the melt-working properties of the composition, which can result in longer cycle times, mold deposit formation, and / or negatively impact the ability to remove parts from the mold. To reduce cycle times and improve the stability of the polymer composition during molding, polyester polymer compositions are typically combined with various other additives such as lubricants, waxes, and various other stabilizers. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, many additives added to polymer compositions, particularly polyester polymer compositions, are not approved for a variety of different food handling and medical applications. For example, glass fibers are typically coated with sizing agents that may contain one or more chemicals not approved by many governments for food contact and / or medical applications. Thus, problems arise when formulating polyester polymer compositions that are still suitable for manufacturing components used in food contact and / or medical applications, while possessing the necessary mechanical properties. As a result, there is now a need for polyester polymer formulations that are approved for food handling and / or medical applications while still possessing the desired blend of mechanical and / or polymer processing properties. [Means for solving the problem]

[0006] Generally, this disclosure relates to polyester polymer compositions, particularly compositions containing polybutylene terephthalate polymers that are particularly well suited for food contact applications. This disclosure also relates to polyester polymer compositions that may also be used to manufacture a variety of medical products. The polymer compositions of this disclosure are formulated to have a blend of mechanical properties without containing many conventional additives that were previously considered necessary to achieve the strength and impact resistance properties required for specific applications.

[0007] In one embodiment, the disclosure relates to polymer compositions for food and medical use. The polymer composition comprises a polyester polymer containing a polybutylene terephthalate polymer. The polyester polymer is present in the composition in an amount greater than about 40% by weight, for example, greater than about 50% by weight, for example, greater than about 55% by weight, for example, greater than about 60% by weight. The polymer composition further contains an inorganic nucleating agent. The inorganic nucleating agent may be present in the composition in an amount less than about 0.8% by weight, for example, less than about 0.6% by weight, for example, less than about 0.4% by weight, and generally greater than about 0.01% by weight. The polymer composition further contains reinforcing fibers containing glass fibers. The reinforcing fibers are present in the polymer composition in an amount greater than about 3% by weight to about 50% by weight, for example, greater than about 15% by weight to about 45% by weight, for example, greater than about 25% by weight to about 35% by weight. According to one embodiment of the present disclosure, the reinforcing fibers contain free (chemically unbound) bisphenol A in amounts less than about 200 ppb, for example less than about 100 ppb, for example less than about 60 ppb, for example less than about 45 ppb, for example less than about 30 ppb, for example less than about 20 ppb, for example less than about 10 ppb, for example less than about 5 ppb. In one embodiment, the glass fibers incorporated into the polymer composition do not contain bisphenol A.

[0008] The polymer compositions of this disclosure can be formulated to be free from various conventional additives while still possessing excellent mechanical properties. For example, the polymer compositions can be formulated to be completely free of antioxidants, particularly hindered phenol antioxidants. The compositions can also be formulated to be completely free of thermal stabilizers, such as diphosphite stabilizers. In addition, the polymer compositions can be formulated to be free of lubricants and waxes. Thus, in one embodiment, the polybutylene terephthalate polymer, glass fibers, and inorganic nucleating agents can constitute more than about 95% by weight of the composition, for example more than about 97% by weight of the composition, for example more than about 99% by weight of the composition.

[0009] In one embodiment, glass fibers having a relatively small diameter can be used. For example, the glass fibers may have an average diameter of less than about 12 microns, for example less than about 11 microns, and generally greater than about 3 microns, for example greater than about 5 microns.

[0010] In one embodiment, the inorganic nucleating agent may be talc. The inorganic nucleating agent or talc may not be coated and may have a median particle size of less than about 4 microns, for example less than about 3 microns, for example less than about 2.5 microns. In one embodiment, microcrystalline talc particles that are at least about 90% by weight pure, for example at least about 95% by weight pure, are used.

[0011] The polymer compositions of this disclosure may exhibit excellent mechanical properties. For example, the polymer compositions may exhibit a breaking tensile strength of over approximately 135 MPa, for example, over approximately 140 MPa, for example, over approximately 145 MPa, for example, over approximately 150 MPa. The polymer compositions may exhibit a tensile modulus of over approximately 9,500 MPa, for example, over approximately 9,750 MPa, for example, over approximately 9,900 MPa. In addition, the polymer compositions may exhibit a tensile modulus of approximately 9 kJ / m 2 For example, about 9.2 kJ / m³ 2 A notched Charpy impact wrench can demonstrate exceptional impact strength.

[0012] Various different molded articles can be manufactured according to this disclosure for use in many applications. In one embodiment, a polymer article may be formed from a polymer composition using injection molding. In one embodiment, the polymer composition may be used to form at least one component of a baby bottle. In an alternative embodiment, the polymer composition may be used to form at least one component of a medical product. The medical product may be, for example, a syringe or an inhaler.

[0013] Other features and aspects of this disclosure are discussed in more detail below.

[0014] The complete and effective disclosure of this disclosure, including references to the accompanying drawings, is described in more detail in the remainder of this specification. [Brief explanation of the drawing]

[0015] [Figure 1] A perspective view of a baby bottle that may include components manufactured in accordance with the present disclosure. [Figure 2] A perspective view of a handle for a consumer appliance and / or a food handling device that may include components manufactured in accordance with the present disclosure. [Figure 3] A perspective view of a medical inhaler manufactured in accordance with the present disclosure [Figure 4] A side view of a medical syringe that may be manufactured in accordance with the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The repeated use of reference numerals in this specification and the drawings is intended to represent the same or similar features or elements of the present invention.

[0017] Definitions The following is a procedure for determining "free" bisphenol A in a sample, e.g., a sample of a formulated polymer composition, in accordance with the present disclosure. Bisphenol A in a sample can be present in free form and in bound form (e.g., chemically bound). The bound form can be present, for example, in an epoxy resin or a polycarbonate. When analyzing for free bisphenol A in a sample, if bound bisphenol A becomes free bisphenol A during sample preparation, e.g., by dissolving the sample in a solvent, false positives can occur. The following is a procedure for measuring only free bisphenol A in accordance with the present disclosure.

[0018] Extraction can be carried out with glass fiber or cryogenic ground glass fiber reinforced polymer (e.g., polybutylene terephthalate). Extract 10 grams of the sample via Soxhlet extraction in 50 mL of methanol at 55 °C for 48 hours. Filter the resulting slurry using Whatman filter paper and take an aliquot for analysis. Dry the sample at 60 °C. Resuspend the extract in 5 mL of methanol and perform high resolution mass spectrometry (UHPLC-HRMS). UHPLC-HRMS experimental conditions: System: Thermo Vanquish UPLC (LC-MS 2) coupled with Q-Exactive Plus Column: Phenomenex Kinetex 2.1x100mm, 2.6μm Column temperature: 35℃ Injection volume: 20μL Flow rate: 0.300mL / min Detector wavelength: 210nm, full scan 190nm~300nm Detector bandwidth: 10nm Free BPA results, mg / kg sample. *Detection limit: approximately 0.1 ppm.

[0019] Those skilled in the art will understand that this discussion is merely a description of exemplary embodiments and is not intended to limit any broader aspects of the disclosure.

[0020] Generally, this disclosure relates to thermoplastic polymer compositions and polymer articles produced from such compositions that not only possess excellent strength properties but are also specially formulated for food contact and / or medical applications. Typically, the polymer compositions of this disclosure contain glass-reinforced polyester polymers, particularly polybutylene terephthalate polymers. Certain glass fibers are selected that are coated with sizing agents specially formulated to meet various government regulations regarding use in food contact applications. For example, in the past, conventionally used sizing agents for glass fibers contained bisphenol A. However, the glass fibers selected for use in this disclosure are either bisphenol A-free or contain very small amounts of free bisphenol A, e.g., less than 100 ppb, e.g., less than about 65 ppb. In one embodiment, the glass fibers are also selected not to contain components produced from bisphenol A, e.g., polycarbonate or epoxy resins that may release bisphenol A during decomposition or chemical reactions during processing.

[0021] In addition to using specific types of reinforcing fibers, the formulations of this disclosure do not necessarily have to contain processing aids such as conventional stabilizers and lubricants. To improve molding cycle time or other properties, the polymer composition contains an inorganic nucleating agent, which is also approved for food contact applications. By using specific components in specific amounts, polymer compositions with excellent mechanical properties, particularly a combination of strength and impact resistance, can be produced.

[0022] For example, polymer compositions formulated in accordance with this disclosure may exhibit a tensile modulus greater than about 9,500 MPa, for example, greater than about 9,750 MPa, for example greater than about 9,900 MPa, and generally less than about 20,000 MPa when tested according to ISO Test 527.

[0023] The tensile strength at break of polymer compositions can also be relatively high. For example, the tensile strength at break may be greater than approximately 135 MPa, for example, greater than approximately 140 MPa, for example, greater than approximately 145 MPa, for example, greater than approximately 150 MPa, and generally less than approximately 300 MPa.

[0024] In addition to excellent tensile strength properties, polymer compositions can also exhibit excellent impact resistance. For example, a polymer composition can withstand approximately 9 kJ / m² when tested at 23°C. 2 For example, about 9.2 kJ / m³ 2 For example, approximately 9.3 kJ / m³ 2 In extreme cases, and generally around 20 kJ / m³ 2 It may exhibit a Charpy notch impact strength of less than 1.

[0025] Even considering the physical and mechanical properties described above, polymer compositions manufactured in accordance with this disclosure can still be formulated to be fully safe for food contact and medical applications without containing many conventional components that were previously considered necessary. In this regard, the polymer compositions of this disclosure can be formulated so that all components contained in the composition meet government regulations for food handling or medical applications. For example, all components contained in the polymer composition can be approved for use in accordance with the U.S. Food and Drug Administration's Food Contact Standards and the list of approved materials found in Title 21 of the Federal Regulatory Code (as existing in March 2021). For example, each polymer contained in the polymer composition can be approved for food handling applications as shown in 21 CFR 177. Each component contained in the polymer composition can be approved for food handling applications in accordance with 21 CFR 174.

[0026] Each component contained in the polymer composition may meet or exceed all food contact standards, e.g., Regulations (EC) 1935 / 2004, 2023 / 2006, 10 / 2011, Resolution AP(89)1, German BFR IX, Spanish Real Decreto 847 / 2011, and Italian Decreto 21 / 3 / 73, as well as Chinese food contact standards, e.g., GB 9685-2016.

[0027] In one embodiment, the polymer composition of the present disclosure contains one or more polyester polymers in combination with glass fibers coated with a specially selected sizing composition and a particularly selected inorganic nucleating agent. In one embodiment, the polyester polymer selected for use in the present disclosure is a polybutylene terephthalate polymer. The polybutylene terephthalate polymer may be bio-based. In one embodiment, the polybutylene terephthalate polymer, glass fibers, and inorganic nucleating agent may constitute more than 95% by weight of the polymer composition, for example, more than about 97% by weight of the polymer composition, for example, more than 99% by weight of the polymer composition. As described above, the polymer composition may be formulated without containing many conventional additives such as antioxidants, stabilizers, processing aids, waxes, and lubricants. In addition, the polymer composition may be formulated without containing any isocyanates, epoxy resins, carbodiimides, etc.

[0028] The thermoplastic polymer used as the matrix polymer to form the molded articles according to this disclosure may vary depending on the specific application and desired results. Examples of thermoplastic polymers that may be used in accordance with this disclosure include one or more polyester polymers. The matrix polymer may be, for example, a polybutylene terephthalate polymer alone or in combination with a polyethylene terephthalate polymer. In other embodiments, the thermoplastic polymer may include a polyamide polymer, a polyoxymethylene polymer, or a mixture thereof.

[0029] As described above, in one embodiment, the thermoplastic matrix polymer contained in the polymer composition comprises one or more polyester polymers. Polyester polymers generally include polyalkylene terephthalate polymers.

[0030] Polyalkylene terephthalate polymers suitable for use herein are derived from aliphatic or alicyclic diols or mixtures thereof containing 2 to about 10 carbon atoms and aromatic dicarboxylic acids.

[0031] Polyesters derived from alicyclic diols and aromatic dicarboxylic acids are prepared, for example, by condensing either the cis or trans isomer (or mixtures thereof) of 1,4 - cyclohexanedimethanol with an aromatic dicarboxylic acid.

[0032] Examples of aromatic dicarboxylic acids include isophthalic acid or terephthalic acid, 1,2 - di(p - carboxyphenyl)ethane, 4,4’ - dicarboxydiphenyl ether, etc., and mixtures thereof. All of these acids contain at least one aromatic nucleus. Condensed rings may also be present, for example, in 1,4 - or 1,5 - or 2,6 - naphthalene - dicarboxylic acid. In one embodiment, the dicarboxylic acid is terephthalic acid or a mixture of terephthalic acid and isophthalic acid.

[0033] In one embodiment, the polyalkylene terephthalate polymer present in the polymer composition includes a polybutylene terephthalate polymer. For example, the polymer composition may contain a polybutylene terephthalate polymer in an amount greater than about 40% by weight, for example, greater than about 45% by weight, for example, greater than about 50% by weight, for example, greater than about 55% by weight, for example, greater than about 60% by weight. The polybutylene terephthalate polymer is generally present in an amount less than about 90% by weight, for example, less than about 80% by weight.

[0034] The melt flow rate of a polyester polymer such as polybutylene terephthalate polymer can vary depending on the particular application and other components contained in the composition. Generally, the melt flow rate can be from about 20 cm 3 / 10 min to about 120 cm 3 / 10 min. In one particular application, the melt flow rate of the polyester polymer or polybutylene terephthalate polymer is from about 50 cm 3 / 10 min to about 80 cm 3 / 10 min. In an alternative embodiment, the melt flow rate of the polyester polymer is from about 25 cm 3 / 10 min to about 50 cm 3It may be / 10 minutes. When used herein, the melt flow rate of the polyester polymer is determined according to ISO Test 1133 at a temperature of 250°C and a load of 2.16 kg.

[0035] The polymer composition may contain polybutylene terephthalate polymer alone or in combination with other thermoplastic polymers. For example, polybutylene terephthalate polymer may be combined with other polyester polymers and / or polycarbonate polymers. Other polyester polymers that may be present in the composition include polyethylene terephthalate polymer or polyethylene terephthalate copolymer. For example, polyethylene terephthalate copolymer or modified polyethylene terephthalate polymer may be produced using a modified acid or a modified diol.

[0036] As used herein, the terms “modified acid” and “modified diol” mean compounds that can form part of the acid and diol repeating units of a polyester, and that can modify the polyester to reduce its crystallinity or make it amorphous. However, in one embodiment, the polyester present in the polymer composition of the Disclosure is unmodified and does not contain a modified acid or a modified diol.

[0037] Examples of modifying acid components include, but are not limited to, isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and 1,12-dodecanediic acid. In practice, it is often preferable to use functional acid derivatives of dicarboxylic acids, such as dimethyl, diethyl, or dipropyl esters. Anhydrides or acid halides of these acids may also be used in practical cases. Isophthalic acid is preferred.

[0038] Examples of modified diol components include neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, Z,8-bis(hydroxymethyltricyclo-[ Examples of diols include, but are not limited to, [5.2.1.0]-decane (wherein Z represents 3, 4, or 5), 1,4-bis(2-hydroxyethoxy)benzene, and diols containing one or more oxygen atoms in the chain, such as diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. Typically, these diols contain 2 to 18, preferably 2 to 8, carbon atoms. Alicyclic diols can be used in their cis or trans configuration, or as mixtures of both.

[0039] If present, the polyester polymer combined with polybutylene terephthalate can generally be added to the polymer composition in an amount greater than about 3% by weight, for example, greater than about 5% by weight, for example, greater than about 8% by weight. The polyester polymer is generally present in an amount less than about 25% by weight, for example, less than about 20% by weight, for example, less than about 15% by weight, for example, less than about 12% by weight.

[0040] In one embodiment, the polybutylene terephthalate polymer contained in the polymer composition includes a bio-based polyester polymer. For example, the polybutylene terephthalate polymer may be formed from butanediol produced from a renewable biosource. For example, butanediol may be produced from biomass or biogas. In one embodiment, for example, biomass can be used to produce ethanol or methanol, which is then converted to butanediol for the production of a polyester polymer.

[0041] Polymer compositions include reinforcing fibers in addition to a thermoplastic polymer matrix. Thermoplastic polymers, such as polyester polymers, are combined with fibrous fillers to increase the modulus of elasticity and / or tensile strength of parts and products manufactured from the reinforcing composition. However, until now, reinforcing fibers, particularly glass fibers, have been coated with sizing agents containing various components under government review when used in food handling and / or medical applications.

[0042] Sizing treatments have been applied to glass fibers to manufacture or process the fibers and / or to improve the adhesion of the fibers to a thermoplastic polymer matrix. Sizing compositions used in the past may contain, for example, silanes, film-forming agents, lubricants, wetting agents, adhesives, optionally antistatic agents and plasticizers, emulsifiers, and optionally further additives. Specific examples of silanes are aminosilanes, such as 3-trimethoxysilylpropylamine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-trimethoxysilanylpropyl)ethane-1,2-diamine, 3-(2-aminoethyl-amino)propyltrimethoxysilane, and N-[3-(trimethoxysilyl)propyl]-1,2-ethane-diamine.

[0043] However, the glass fibers incorporated into the polymer compositions of this disclosure may include specially formulated sizing compositions that do not contain many of the conventional components used in the past. In particular, past formulations contained free bisphenol A and / or components derived from bisphenol A, such as epoxy resins or polycarbonates, which were considered necessary or essential parts of the sizing composition.

[0044] However, in one embodiment, the glass fibers used in accordance with the Disclosure and the resulting compounded polymer composition contain free (chemically unbound) bisphenol A in amounts less than about 2 ppm, for example less than about 1.6 ppm, for example less than about 200 ppb, for example less than about 100 ppb, for example less than about 65 ppb, for example less than about 55 ppb, for example less than about 45 ppb, for example less than about 35 ppb, for example less than about 25 ppb, for example less than about 15 ppb, for example less than about 10 ppb, for example less than about 5 ppb, for example less than about 2 ppb. In one embodiment, the glass fibers incorporated into the polymer composition of the Disclosure do not contain bisphenol A.

[0045] The polymer composition may contain some chemically bound bisphenol A. For example, the polymer composition may contain a total amount of bisphenol A (free + bound) of less than about 5 ppm, for example less than about 3 ppm, for example less than about 2 ppm, for example less than about 500 ppb, for example less than about 250 ppb, for example less than about 165 ppb, for example less than about 130 ppb, for example less than about 100 ppb, for example less than about 80 ppb, for example less than about 60 ppb, for example less than about 40 ppb, for example less than about 20 ppb, for example less than about 10 ppb.

[0046] In various embodiments, the sizing composition applied to the glass fibers does not have to contain silane and can be made from a variety of other components. For example, in one embodiment, the glass fibers are coated with a food-grade polymer. In a particular embodiment, the food-grade polymer may be a polyurethane polymer.

[0047] Reinforcing fibers can be compounded into the polymer matrix, for example, in an extruder or kneader. Suitable glass fibers for the molding compositions of this disclosure can be obtained from Johns Manville, OCV, and Nippon Electric Glass Co.

[0048] The fiber diameter may vary depending on the specific fiber used and whether the fiber is in shredded or continuous form. In one embodiment, it has been found that using fibers with a relatively small average diameter can improve the mechanical properties of the polymer composition when coated with a sizing composition containing a small amount of bisphenol A. For example, the average diameter of glass fibers may be less than about 17 microns, e.g., less than about 14 microns, e.g., less than about 13 microns, e.g., less than 12 microns, and generally greater than about 3 microns, e.g., greater than about 6 microns, e.g., greater than 8 microns.

[0049] Typically, reinforcing fibers may be present in the polymer composition in an amount sufficient to increase the tensile strength of the composition. Reinforcing fibers may be present in the polymer composition in amounts, for example, more than about 5% by weight, for example more than about 10% by weight, for example more than about 15% by weight, for example more than about 20% by weight, for example more than about 25% by weight, for example more than about 30% by weight. Generally, reinforcing fibers are present in amounts less than about 55% by weight, for example less than about 50% by weight, for example less than about 45% by weight, for example less than about 40% by weight, for example less than about 35% by weight.

[0050] The polymer compositions of this disclosure may also contain inorganic nucleating agents. The nucleating agents may be selected from the group consisting of alkali metal salts having anions which are oxides of elements from Group IV of the periodic table, barium sulfate, and talc.

[0051] In one embodiment, the inorganic nucleating agent is talc. Talc (CAS number 14807-96-6) has the chemical composition Mg3[Si4O 10 It is a layered silicate containing [(OH)2], and depending on its polymorphism, it crystallizes as talc-1A in the triclinic system or as talc-2M in the monoclinic system. In one embodiment, the talc present in the polymer composition is microcrystalline talc with a relatively small particle size. Unlike when talc is used as a filler, the talc particles do not need to be coated.

[0052] In one embodiment, microcrystalline talc is used in which the median particle size d50 determined using SediGraph is in the range of 0.5 to 10 μm, for example, in the range of 1.0 to 7.5 μm, for example, in the range of 1.5 to 5.0 μm, for example, in the range of 1.8 to 4.5 μm.

[0053] The particle size of talc is determined by sedimentation in an aqueous medium in a completely dispersed state, using the "Sedigraph 5100" supplied by Micrometrics Instruments Corporation, Norcross, Ga., USA. The Sedigraph 5100 provides measurements and plots of cumulative percentage by weight of particles with a size called "equivalent sphere diameter" (ESD) after subtracting a given ESD value.

[0054] The median particle size d50 is a value determined from the particles esd, where 50% by weight of the particles have an equivalent spherical diameter smaller than this d50 value. The underlying standard is ISO 13317-3.

[0055] In one embodiment, microcrystalline talc is defined by its BET surface area. Microcrystalline talc for use in accordance with this disclosure can be determined in accordance with DIN ISO 9277, ranging from 5 to 25 m 2 ·g -1 A range, for example, 10-18m 2 ·g -1 A range, for example, 12-15m 2 ·g -1 It may have a BET surface area within the range of [this range].

[0056] The talc particles incorporated into the polymer composition may contain, for example, talc having a purity of more than 96% by weight in an amount greater than 97% by weight, for example greater than 98% by weight, for example greater than 99% by weight. The talc particles may contain less than about 2% by weight of chlorite, for example less than about 1% by weight, for example less than about 0.1% by weight, the talc particles may contain less than about 2% by weight of dolomite, for example less than about 1% by weight, for example less than about 0.1% by weight, the talc particles may contain less than about 2% by weight of magnesite, for example less than about 1% by weight, for example less than about 0.5% by weight, for example less than about 0.1% by weight. In one embodiment, the talc particles may not contain chlorite, may not contain dolomite, may not contain magnesite, or may not contain all of the above or at least two of the above.

[0057] Nucleating agents or talc particles may be present in polymer compositions in very relative amounts, yet still offer significant advantages and benefits. For example, nucleating agents may be present in polymer compositions in amounts less than about 1.5% by weight, e.g., less than about 0.8% by weight, e.g., less than about 0.6% by weight, e.g., less than about 0.4% by weight. Talc particles are generally present in polymer compositions in amounts greater than about 0.01% by weight, e.g., greater than about 0.05% by weight, e.g., greater than about 0.1% by weight.

[0058] As described above, the polymer compositions of this disclosure can be formulated to be free of many conventionally used additives and components while still maintaining an excellent balance between strength properties and impact resistance. In one embodiment, the polyester polymer compositions of this disclosure can be formulated to be free of many conventionally used lubricants and release agents. For example, the polymer compositions can be formulated to be free of certain fatty acid esters, particularly fatty acid esters having relatively long carbon chains. In one particular embodiment, for example, the compositions of this disclosure do not contain any fatty acid esters derived from montanic acid, such as montanic acid esters in combination with polyols. The compositions may not contain, for example, a mixture of montanic acid ester and calcium montanate.

[0059] Other lubricants that may be excluded from the polymer composition or included in very small amounts include waxes such as polyolefin waxes and amide waxes. Such waxes include ethylenebis-stearamide wax, other bisamides, N-(2-hydroxyethyl)12-hydroxystearamide and / or N,N'-(ethylenebis)12-hydroxystearamide.

[0060] The polymer composition may optionally be free from certain antioxidants that have been commonly used in the past. For example, in one embodiment, the polyester polymer composition of the Disclosure may be free from hindered phenol antioxidants or contain such antioxidants in very limited amounts. For example, the polymer composition may be formulated to contain a hindered phenol antioxidant in an amount of less than about 0.1% by weight, for example less than about 0.05% by weight, for example less than about 0.03% by weight, for example 0% by weight.

[0061] Examples of such phenolic antioxidants include, for example, calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (Irganox® 1425), terephthalic acid, 1,4-dithio-,S,S-bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ester (Cyanox® 1729), triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate), and hexamethylene bis(3,5-di-tert-butyl-4 -Hydroxyhydrocinnamate (Irganox® 259), 1,2-bis(3,5,di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide (Irganox® 1024), 4,4'-di-tert-octyldifenamine (Naugalube® 438R), phosphonic acid, (3,5-di-tert-butyl-4-hydroxybenzyl)-,dioctadecyl ester (Irganox® 1093), 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl Irganox® 1330, 2,4-bis(octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (Irganox® 565), isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1076), 3,7- Bis(1,1,3,3-tetramethylbutyl)-10H-phenothiazine (Irganox® LO3), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) monoacrylate (Irganox® 3052), 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl acrylate (Sumilizer® TM4039), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer® GS), 1,3-dihydro-2H-benzimidazole (Sumilizer® MB), 2-methyl-4,6-bis[(octylthio)methyl]phenol (Irganox® 1520), N,N'-trimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (Irganox® 1019), 4-n-octadecyloxy-2,6-diphenylpheno Irganox® 1063, 2,2'-ethylidenebis[4,6-di-tert-butylphenol](Irganox® 129), NN'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide)(Irganox® 1098), diethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate(Irganox® 1222), 4,4'-di-tert-octyldiphenylamine(Irganox® (Trademark) 5057), N-phenyl-1-naphthaleneamine (Irganox® L05), tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-6-methylphenylthio)-5-methylphenyl]phosphite (Hostanox® OSP1), zinc dinonyldithiocarbamate (Hostanox® VP-ZNCS1), 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]eth Examples include [L]-2,4,8,10-tetraoxaspiro[5.5]undecane (Sumilizer® AG80), pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010), ethylene-bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate (Irganox® 245), and 3,5-di-tert-butyl-4-hydroxytoluene (Lowinox BHT, Chemtura).

[0062] Reducing or eliminating the use of hindered phenol antioxidants may actually increase the bond strength between molded articles made from polyester compositions and elastomer materials, particularly elastomer materials formed from copolyester elastomers. Although unclear, it is thought that hindered phenol antioxidants may prevent transesterification in the boundary layer between the molded article and the elastomer material.

[0063] In addition to being free of phenolic antioxidants, the polymer compositions of this disclosure can also be formulated to be free of diphosphite stabilizers.

[0064] Another stabilizer that can be excluded from polyester compositions is a hindered amine light stabilizer ("HALS"). HALS compounds can be derived from substituted piperidines, such as alkyl-substituted piperidyls, piperidinyls, piperazinones, and alkoxypiperidinyl compounds. For example, a hindered amine can be derived from 2,2,6,6-tetraalkylpiperidinyl.

[0065] Specific examples of hindered amines include, for example, bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770, MW=481 from Ciba Specialty Chemicals), bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-(3,5-ditert.butyl-4-hydroxybenzyl)butyl-propanediate, bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspirol (4,5)-Decane-2,4-Dione, Butanediate-Bis-(2,2,6,6-Tetramethyl-4-Piperidinyl) ester, Tetrakis-(2,2,6,6-Tetramethyl-4-Piperidyl)-1,2,3,4-Butanetetracarboxylate, 7-Oxa-3,20-Diazadespiro(5.1.11.2)Heneikosan-20-Propanoate, 2,2,4,4-Tetramethyl-21-Oxododecyl ester, N -(2,2,6,6-tetramethyl-4-piperidinyl)-N'-amino-oxamide, ot-amyl-o-(1,2,2,6,6-pentamethyl-4-piperidinyl)-monoperoxycarbonate, β-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl), dodecyl ester, ethanediamide, N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N'-dodecyl, 3-dodecyl Cyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)-pyrrolidine-2,5-dione, 3-dodecyl-1-(1-acetyl,2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidine-2,5-dione (Sanduvar® 3058 from Clariant, MW=448).7) Examples include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy)ethyl]-4-(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy)-2,2,6,6-tetramethyl-piperidine, 2-methyl-2-(2",2",6",6”-tetramethyl-4”-piperidinylamino)-N-(2',2',6',6'-tetra-methyl-4'-piperidinyl)propionylamide, 1,2-bis-(3,3,5,5-tetramethyl-2-oxopiperazinyl)ethane, 4-oleoyloxy-2,2,6,6-tetramethylpiperidine, and combinations thereof.

[0066] UV absorbers such as benzotriazole or benzophenone may also be excluded from the polymer compositions of this disclosure.Such benzotriazoles include, for example, 2-(2-hydroxyphenyl)benzotriazole, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole (Cyasorb® UV5411 from Cytec), 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2 -Hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzo-triazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-Hyd [Loxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyl Examples include oxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole, and combinations thereof.

[0067] Benzophenone light stabilizers include 2-hydroxy-4-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (Cyasorb® UV209 from Cytec), 2-hydroxy-4-n-octyloxy)benzophenone (Cyasorb® 531 from Cytec), 2,2'-dihydroxy-4-(octyloxy)benzophenone (Cyasorb® UV314 from Cytec), and hexadecyl-3,5-bis-tert-butyl-4-hydroxy Examples include cibenzoate (Cyasorb® UV2908 from Cytec), 2,2'-thiobis(4-tert-octylphenolate)-n-butylamine nickel(II) (Cyasorb® UV1084 from Cytec), 3,5-di-tert-butyl-4-hydroxybenzoic acid, (2,4-di-tert-butylphenyl) ester (Cyasorb® 712 from Cytec), 4,4'-dimethoxy-2,2'-dihydroxybenzophenone (Cyasorb® UV12 from Cytec), and combinations thereof.

[0068] The polymer compositions of this disclosure may contain a variety of other additives and components, in particular additives and components that are safe for food contact and / or medical applications. For example, in one embodiment, one or more colorants may be incorporated into the polymer composition. One or more colorants may be present in the composition in an amount of less than about 2% by weight and generally greater than about 0.1% by weight. Possible colorants include any desired inorganic pigment, such as titanium dioxide, ultramarine blue, cobalt blue, and other organic pigments and dyes. Other colorants include carbon black or a variety of other polymer-soluble dyes.

[0069] The compositions of this disclosure can be formulated using any technique known in the art and formed into polymer articles. For example, each composition can be thoroughly mixed to form a substantially homogeneous blend. The blend can be melt-kneaded at a high temperature, for example, higher than the melting point of the polymer used in the polymer composition but lower than the decomposition temperature. Alternatively, each composition can be melted and mixed together in a conventional uniscrew or twin-screw extruder. Preferably, the melt-mixing is carried out at a temperature in the range of 150°C to 300°C, for example, 200°C to 280°C, for example, 220°C to 270°C or 240°C to 260°C. However, such processing should be carried out at a desired temperature for each composition to minimize polymer decomposition.

[0070] After extrusion, the composition can be formed into pellets. The pellets can be molded into polymer articles by techniques known in the art, such as injection molding, thermoforming, and blow molding.

[0071] In one embodiment, the polymer compositions of the present disclosure can be used to manufacture at least one component of a food contact article. For example, referring to Figure 1, a baby bottle 10 is shown. The baby bottle 10 includes a container 11 attached to a nipple 13 by a collar 12. In one embodiment, the polymer compositions of the present disclosure can be used to manufacture the collar 12 or components of the collar 12.

[0072] In alternative embodiments, the polymer compositions of the present disclosure can be used to manufacture one or more components of a consumer appliance or cooking device. For example, a cooking device 15 is shown in Figure 2. The cooking device 15 includes a cooking pot 18 that fits with a lid 19. The cooking device 15 further includes a handle 16. In one embodiment, the polymer compositions of the present disclosure may be used to manufacture at least one component of the handle 16. For example, the handle 16 may be formed from the polymer composition of the present disclosure, which is then overmolded with an elastomer material also formulated for food contact applications. The elastomer material may be, for example, a thermoplastic polyurethane elastomer, a silicone elastomer, or a copolyester elastomer.

[0073] In one embodiment, the elastomer component is formed from a copolyester elastomer. For example, in one embodiment, the elastomer material may contain a segmented thermoplastic copolyester. The thermoplastic polyester elastomer may include, for example, a multiblock copolymer. Useful segmented thermoplastic copolyester elastomers contain numerous repeating long-chain and short-chain ester units linked head-to-tail via ester bonds. The long-chain units are formed by the formula [ka] The short-chain unit can be represented by the formula [ka] It can be represented by the formula, where G is a divalent radical remaining after the removal of a terminal hydroxyl group from a long-chain polymer glycol having a number average molecular weight in the range of about 600 to 6,000 and a melting point less than about 55°C; R is a hydrocarbon radical remaining after the removal of a carboxyl group from a dicarboxylic acid having a molecular weight less than about 300; and D is a divalent radical remaining after the removal of a hydroxyl group from a low molecular weight diol having a molecular weight less than about 250.

[0074] Short-chain ester units in copolyether esters account for approximately 15–95% of the weight of the copolyether ester, and approximately 50–100% of the short-chain ester units in the copolyether ester are identical.

[0075] In one particular embodiment, the polyester thermoplastic elastomer is given by the following formula: -[4GT] x [BT] y (In the formula, 4G is a butylene glycol such as 1,4-butanediol, B is poly(tetramethylene ether glycol), T is terephthalate, x is approximately 0.60 to approximately 0.99, and y is approximately 0.01 to approximately 0.40).

[0076] In one embodiment, the thermoplastic polyester elastomer may be a block copolymer of polybutylene terephthalate and a polyether segment and / or a dimergol segment, with the following structure: [ka] (In the formula, a and b are integers and can vary between 2 and 50,000, for example, between approximately 2 and approximately 10,000.) It may have the following properties. The ratio between hard segments and soft segments in the block copolymer described above can be changed to alter the properties of the elastomer.

[0077] In one embodiment, the elastomer material may contain a copolyester elastomer comprising a block copolymer containing polybutylene terephthalate segments and polytetramethylene ether glycol terephthalate segments.

[0078] In one embodiment, the density of the polyester elastomer shown above is approximately 1.05 g / cm³. 3 ~Approx. 1.15g / cm 3 For example, approximately 1.08 g / cm³ 3 ~Approx. 1.2g / cm 3 It is possible.

[0079] In one embodiment, the copolyester elastomer may have a Shore D hardness of less than about 100, for example less than about 90, for example less than about 80, for example less than about 70, for example less than about 60, for example less than about 50, for example less than about 40. The Shore D hardness of the elastomer may generally be greater than about 10, for example greater than about 15, for example greater than about 20, for example greater than about 25.

[0080] Elastomer materials can be applied to polymer components manufactured from polyester compositions using any suitable method or technique. In one embodiment, for example, the elastomer material is overmolded onto the surface of the polymer component to form the elastomer component. For example, the polymer component can be first injection molded and then overmolded with the elastomer material using the same injection molding process before cooling.

[0081] As shown in Figure 2, the cooking device 15 may be used with a spatula 17. The spatula 17 may also be manufactured from the polymer composition of this disclosure.

[0082] In other embodiments, the polymer compositions of the present disclosure may be used to manufacture at least one component of a medical device. For example, referring to Figure 3, an inhaler 20 is shown. The inhaler 20 includes a housing 22 attached to a mouthpiece 24. Operately associated with the housing 22 is a plunger 26 for receiving a canister containing the composition to be inhaled. The composition may include a spray or a powder. The inhaler 20 may include a first sliding member operably associated with a second sliding member. For example, in a particular embodiment, the housing 22 may include the first sliding member, while the plunger 26 may include the second sliding member. Alternatively, the first sliding member may include the housing 22, and the second sliding member may include the mouthpiece 24. In yet another embodiment, an internal sliding member that slides against the housing may be included within the housing 22.

[0083] During use, the inhaler 20 administers a measured amount of medication, such as an asthma medication, to the patient. The asthma medication may be suspended or dissolved in the propellant, or contained in powder form. When the patient operates the inhaler to inhale the medication, a valve opens, allowing the medication to be dispensed from the mouthpiece.

[0084] In another embodiment, the polymer compositions of the present disclosure may be used to manufacture one or more components of a syringe, particularly an autoinjector. For example, a medical syringe 30 is shown in Figure 4. The medical syringe 30 includes a housing 32 operably associated with a plunger 34. The housing 32 or a first sliding member may slide against the plunger 34 or a second sliding member. The medical syringe 30 may be subjected to a spring load. The medical syringe 30 is intended for injecting a drug into a patient, typically in the thigh or buttocks. The medical syringe may be needleless or may include a needle. If it includes a needle, the needle tip is typically shielded within the housing before injection. Needleless syringes, on the other hand, may include a cylinder of pressurized gas that propels the drug through the skin without the use of a needle.

[0085] This disclosure may be better understood by referring to the following examples. [Examples]

[0086] The following examples are provided for illustrative purposes only, and not for limiting purposes. The following experiments were conducted to demonstrate some of the benefits and advantages of the present invention.

[0087] Example 1 Various polymer compositions containing glass fibers were formulated and tested for their physical properties. Each composition contained polybutylene terephthalate polymer, a talc nucleating agent, and 30% by weight of glass fibers.

[0088] Four different compositions were formulated. The first two compositions were formulated and tested for comparison. Samples 1 and 2 both contained glass fibers, and the sizing composition applied to the fibers contained a conventional amount of bisphenol A. Sample 3, prepared according to this disclosure, contained glass fibers, and the sizing composition for the fibers contained a small amount of bisphenol A. The glass fibers contained in sample 4 did not contain bisphenol A.

[0089] The following compositions were formulated and tested.

[0090] [Table 1]

[0091] The components of each composition were mixed and formulated together using a ZSK 25MC (Werner & Pfleiderer, Germany) twin-screw extruder. The screw configuration with a kneading element was selected to ensure effective and thorough mixing of the components. The compositions were extruded and pelletized. The pellets were dried at 120°C for 4 hours and then injection molded.

[0092] The composition was tested for its physical properties. Tensile properties were tested according to ISO Test 527:2012. Charpy impact strength with and without notches was tested according to ISO Test 179-1:2010. The tests were performed using Type A notches (base radius 0.25 mm) and Type 1 specimen sizes (length 80 mm, width 10 mm, and thickness 4 mm). The tests were conducted at a temperature of 23°C. The following results were obtained.

[0093] [Table 2]

[0094] As shown above, samples 3 and 4 manufactured in accordance with this disclosure exhibited dramatically improved strength and impact resistance compared to samples 1 and 2.

[0095] Using the extraction method described above, samples 3 and 4 were tested for free bisphenol A. Sample 3 was found to contain 1.54 ppm of free bisphenol A. The amount of free bisphenol A in sample 4 was below the detection limit, i.e., less than 0.1 ppm.

[0096] These and other modifications and variations of the present invention can be practiced by those skilled in the art without departing from the spirit and scope of the invention as described in more detail in the appended claims. In addition, it should be understood that the various embodiments may be interchangeable in whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is merely an example and is not intended to limit the invention as described in such way to such appended claims.

Claims

1. Food and medical polymer compositions, A polyester polymer containing a polybutylene terephthalate polymer, wherein the polyester polymer is present in the composition in an amount of more than about 40% by weight, An inorganic nucleating agent present in the composition in an amount of less than approximately 0.8% by weight, Reinforcing fibers containing glass fibers, present in the polymer composition in an amount of about 3% to about 50% by weight, and containing less than 2 ppm of free bisphenol A. Food and medical polymer compositions containing [the specified substance].

2. A food-grade and medical polymer composition according to claim 1, which does not contain a hindered phenol antioxidant.

3. A food-grade and medical polymer composition according to claim 1 or 2, which does not contain a diphosphite stabilizer.

4. A food-grade and medical polymer composition according to claim 1, which does not contain wax.

5. The food and medical polymer composition according to claim 1, wherein the polybutylene terephthalate polymer, the glass fiber, and the inorganic nucleating agent constitute at least about 95% by weight.

6. The food and medical polymer composition according to claim 1, wherein the glass fibers have an average diameter of less than about 17 microns and more than about 3 microns.

7. The food and medical polymer composition according to claim 1, wherein the inorganic nucleating agent comprises talc particles, and the talc particles are present in the polymer composition in an amount of about 0.01% to about 0.4% by weight.

8. The food and medical polymer composition according to claim 1, wherein all components contained in the polymer composition comply with the standards of the U.S. Food and Drug Administration as set forth in 21 CFR 177.

9. The food and medical polymer composition according to claim 1, wherein the glass fiber and / or the polymer composition contains less than about 100 ppb of free bisphenol A.

10. The food-grade and medical polymer composition according to claim 1, wherein the polybutylene terephthalate polymer has a melt flow rate of about 50 g / 10 min to about 80 g / 10 min.

11. The food-grade and medical polymer composition according to claim 1, wherein the polybutylene terephthalate polymer has a melt flow rate of about 25 g / 10 min to about 70 g / 10 min.

12. It exhibits a breaking tensile strength exceeding approximately 135 MPa, a tensile modulus exceeding approximately 9,500 MPa, and a tensile modulus of approximately 9 kJ / m². ２ A food-grade and medical polymer composition according to claim 1, exhibiting ultra-high impact strength with a Charpy notch.

13. Food and medical polymer compositions, A polyester polymer containing a polybutylene terephthalate polymer, wherein the polyester polymer is present in the composition in an amount of more than about 40% by weight, An inorganic nucleating agent present in the composition in an amount of less than approximately 0.8% by weight, A reinforcing fiber containing glass fibers, present in the polymer composition in an amount of about 3% to about 50% by weight, having an average diameter of less than about 11 microns and greater than about 5 microns, wherein the glass fibers are present in the polymer composition in an amount of about 15% to about 40% by weight, and Food and medical polymer compositions containing [the specified substance].

14. The food and medical polymer composition according to claim 13, wherein the glass fibers do not contain free bisphenol A.

15. The food and medical polymer composition according to claim 13, which does not contain a hindered phenol antioxidant, a diphosphite stabilizer, or a wax, and the polybutylene terephthalate polymer, the glass fiber, and the inorganic nucleating agent constitute at least about 95% by weight, for example at least about 97% by weight, for example at least about 99% by weight, of the polymer composition.

16. It exhibits a breaking tensile strength of approximately 135 MPa or more, for example, approximately 140 MPa or more, for example, approximately 145 MPa or more, for example, approximately 150 MPa, and a tensile modulus of approximately 9,500 MPa or more, for example, approximately 9,750 MPa or more, for example, approximately 9,900 MPa, and is approximately 9 kJ / m ２ For example, approximately 9.2 kJ / m³ ２ A food-grade and medical polymer composition according to claim 13, exhibiting ultra-high impact strength with a Charpy notch.

17. A molded article manufactured from the polymer composition described in claim 1.

18. A baby bottle, wherein at least one component of the bottle includes the molded article described in claim 17.

19. A medical device wherein at least one component of the medical device includes the molded article described in claim 17, and the medical device includes an inhaler or a syringe.

20. A method for determining the amount of free bisphenol A in a sample, Combining the sample with methanol, The sample and methanol combination is extracted via Soxhlet extraction at a temperature of approximately 50°C to approximately 60°C for 48 hours to form a slurry. The slurry is filtered and dried to form a residue. The aforementioned residue is suspended in methanol to form a suspension, The amount of free bisphenol A is determined by performing high-resolution mass spectrometry on the suspension. A method that includes this.

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