Polymer Composition Having Mold Release Properties - Patent application

Abstract

A fiber-reinforced thermoplastic polymer composition is disclosed that contains at least one release agent. The release agent may include polar and / or non-polar materials. In one embodiment, both polar and non-polar waxes are used. The polymer composition may also contain one or more friction modifiers. The friction modifier may include ultra-high molecular weight silicone.

Description

[Technical field]

[0001] Related Applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 177,210, having a filing date of April 20, 2021; U.S. Provisional Patent Application No. 63 / 208,250, having a filing date of June 8, 2021; and U.S. Provisional Patent Application No. 63 / 319,531, having a filing date of March 14, 2022, all of which are incorporated by reference herein. [Background technology]

[0002]

[0002] Engineering thermoplastic and elastomeric materials are often used in a large number of different applications to produce molded parts and products. For example, thermoplastic polymers are used to produce all different types of molded products, such as injection molded products, blow molded products, and the like. Thermoplastic polymers can be compounded, for example, to provide chemical resistance and superior strength properties, and compositions containing elastomers can be compounded to be flexible. Among other advantages, many polymers can be melt processed due to their thermoplastic nature. In addition, many polymers can be recycled or reprocessed. Summary of the Invention [Problem to be solved by the invention]

[0003]

[0003] One objective in producing molded parts from thermoplastic polymers is to be able to mold parts quickly and increase productivity. Each polymer formulation presents a unique set of problems related to the melt processing characteristics of the composition that can result in, for example, longer cycle times, cause the formation of mold deposits, and / or negatively affect the ability to remove the part from the mold. As a result, ideally, thermoplastic compositions are formulated to form a stable melt at melt processing conditions. In many applications, faster crystallization rates and / or faster melt-solidification rates are desired to shorten cycle times. [Means for solving the problem]

[0004]

[0004] In view of the above, the present disclosure is particularly directed to polymer compositions having improved melt processing characteristics. Alternatively, the present disclosure is also directed to formulating the polymer compositions to reduce mold deposits and / or to reduce the force required to remove a part or article from a mold. In one embodiment, the present disclosure is directed to a formulated polymer composition having at least one of the above characteristics improved and which can be formulated to be sufficiently safe for food contact applications.

[0005]

[0005] The present disclosure is generally directed to thermoplastic polymer compositions containing a mold release package. The mold release package can reduce mold deposits and / or reduce the amount of force required to remove a part or article from a mold after a molding process, such as an injection molding process. It has also been surprisingly discovered that the mold release packages of the present disclosure can positively affect the melt processing properties and behavior of a variety of different polymer compositions. As a result, in one aspect, the mold release packages of the present disclosure can be used to reduce molding cycle times when compounded with a variety of polymers.

[0006] In one aspect, all of the components contained in the polymer composition are approved for use in medical and / or food contact applications. For example, each polymer component contained in the polymer composition can be approved for use in accordance with United States Food and Drug Administration standards codified in 21 CFR 177. For example, the components of the release packaging can be selected such that the components meet all government regulations for use in food handling and / or medical applications.

[0007] The polymer composition contains a thermoplastic matrix polymer. The thermoplastic polymer may include, for example, a polyamide polymer, a polyester polymer, a polyetheretherketone polymer, a polyphenylene sulfide polymer, or a polyacetal polymer. For example, the thermoplastic polymer may be a polybutylene terephthalate polymer or a polyoxymethylene polymer. The thermoplastic matrix polymer may be present in the polymer composition in an amount generally greater than about 40% by weight, such as greater than about 50% by weight, such as greater than about 60% by weight, such as greater than about 65% by weight. The thermoplastic matrix polymer is generally present in the polymer composition in an amount less than about 99% by weight, such as less than about 90% by weight, such as less than about 80% by weight.

[0008]

[0008] The polymer composition generally contains at least one of a nucleant, a friction modifier, or a reinforcing fiber. When reinforcing fibers are included, the reinforcing fibers may be, for example, glass fibers. The incorporation of reinforcing fibers into the polymer composition may cause problems during the molding process. Compositions reinforced with fibers may, for example, have a tendency to cause mold deposits and may also increase the ejection force required to remove the part from the mold. However, when the composition contains reinforcing fibers, one or more mold release agents may be present in the composition to counteract the above negative effects. When reinforcing fibers are included in the composition, they may generally be present in the composition in an amount greater than about 5% by weight, such as greater than about 10% by weight, such as greater than about 15% by weight. The reinforcing fibers are generally present in an amount less than about 50% by weight, such as less than about 45% by weight, such as less than about 35% by weight.

[0009] As mentioned above, the polymer composition further contains at least one release agent. In one embodiment, for example, the polymer composition may contain a single release agent comprising a polar polymer. Alternatively, the polymer composition may contain a first release agent and a second release agent. The first release agent may be a polar polymer, while the second release agent may be a non-polar polymer. The first release agent and the second release agent may be present in the polymer composition in a weight ratio of about 10:1 to about 1:10, such as about 5:1 to about 1:5, such as about 2:1 to about 1:2, such as about 1.8:1 to about 1:1.8.

[0010] In one embodiment, all of the release agents present in the polymer composition may be approved for food handling and / or medical applications. The polar polymer constituting the first release agent may be, for example, a polyolefin polymer, such as a polyethylene polymer. In one embodiment, for example, the polar polymer may be an oxidized polyethylene wax.

[0011] On the other hand, the non-polar polymer constituting the second release agent may also be a polyolefin polymer, for example, a polyethylene wax.

[0012] In one embodiment, the polymer composition can be formulated to contain only a single release agent, for example, only a polar release agent. The polar release agent can have, for example, an acid value generally greater than about 5 KOH / g, for example greater than about 10 KOH / g, for example greater than about 15 KOH / g, and generally less than about 90 KOH / g, for example less than about 70 KOH / g, for example less than about 60 KOH / g. The acid value of the polar release agent can be selected, for example, based on the specific application and the components contained in the polymer composition. In one embodiment, for example, the acid value of the polar release agent can be from about 13 KOH / g to about 23 KOH / g, for example from about 15 KOH / g to about 19 KOH / g. Alternatively, the polar release agent can have a higher acid value. For example, in an alternative embodiment, the polar release agent can have an acid value of from about 40 KOH / g to about 60 KOH / g, for example from about 45 KOH / g to about 55 KOH / g.

[0012]

[0013] The polar release agent may include an oxidized wax. For example, the polar release agent may be an oxidized polyethylene wax. Alternatively, the polar release agent may be an oxidized ester of a fatty acid. The oxidized ester of a fatty acid may be obtained from a biomass such as, for example, rice bran. In one embodiment, the oxidized ester of a fatty acid may be obtained from a blend of different fatty acids having different carbon chain lengths. In one embodiment, for example, the oxidized ester of a fatty acid may be obtained from more than 50% by weight of fatty acids having a carbon chain length of about 20 carbon atoms to about 40 carbon atoms. The oxidized ester of a fatty acid may also be obtained from a blend of fatty acids, in which 25% or more by weight of the fatty acids are derived from fatty acids having a carbon chain length of about 40 carbon atoms to about 64 carbon atoms.

[0013]

[0014] Each release agent contained in the polymer composition may generally be present in the composition in an amount less than about 2% by weight, such as less than about 1% by weight, such as less than about 0.8% by weight, such as less than about 0.5% by weight, such as less than about 0.4% by weight. Each release agent is generally present in the polymer composition in an amount greater than about 0.01% by weight, such as greater than about 0.08% by weight.

[0014]

[0015] The one or more release agents can help minimize mold deposits and can also reduce the force required to eject a molded part from a mold. For example, when tested according to the Part Ejection Test, the polymer compositions of the present disclosure can exhibit an ejection force of less than about 700 N.

[0015]

[0016] In one embodiment, the polymer composition may optionally contain one or more friction modifiers. In one embodiment, the friction modifier may include ultra-high molecular weight silicone. Ultra-high molecular weight silicone has a molecular weight of about 100,000 mm 2 / sec. For example, the ultra-high molecular weight silicone may be present in the polymer composition in an amount of about 0.1% to about 10% by weight, such as about 0.5% to about 3% by weight. In one embodiment, the ultra-high molecular weight silicone comprises polydimethylsiloxane.

[0016]

[0017] In an alternative embodiment, the friction modifier contained in the polymer composition may include a polytetrafluoroethylene polymer, which may be present alone or in combination with the ultra-high molecular weight silicone.

[0017]

[0018] The polymer composition can be formulated to have low friction properties.For example, the polymer composition can exhibit a dynamic friction coefficient of less than about 0.08 when tested against polycarbonate / ABS blend (Sabic CYCOLOY C1204H) according to VDA230-206 at a speed of 8 mm / s and a load of 30 N after 1,000 cycles.In one embodiment, the polymer composition can exhibit a dynamic friction coefficient of less than about 0.07, for example less than about 0.05, when tested against the above materials.

[0018]

[0019] When ultra-high molecular weight silicone is present in the composition, the silicone may be added with a carrier.In one embodiment, for example, ultra-high molecular weight silicone may be grafted to silica and added to the composition.Alternatively, ultra-high molecular weight silicone may be combined with a carrier polymer before blending with other components.The carrier polymer may include, for example, a polycarbonate polymer or a polyester polymer.The polyester polymer may include, for example, a polyethylene terephthalate, a copolyester, and / or a polyester elastomer.

[0019]

[0020] The polymeric composition of the present disclosure may also contain a nucleating agent. In one embodiment, the nucleating agent may be an inorganic nucleating agent. The inorganic nucleating agent may include talc and may be present in the polymeric composition in an amount of about 0.01% to about 1% by weight.

[0020]

[0021] In one embodiment, the polymeric compositions of the present disclosure are formulated to produce medical products. When producing medical products, the polymeric compositions can be formulated to be, for example, isocyanate-free.

[0021]

[0022] In one embodiment, the polymer composition can be used to produce medical inhalers, injection devices, surgical instruments, wearable devices, etc. The medical product can, for example, include a first slide member functionally associated with a second slide member. The first slide member and the second slide member can be arranged to move in contact with each other. At least one of the slide members can be made from the polymer composition of the present disclosure. In one embodiment, for example, both slide members are made from the polymer composition of the present disclosure.

[0022]

[0023] Other features and aspects of the present disclosure are discussed in greater detail below.

[0024] A detailed and enabling disclosure of the present invention is set forth in the remainder of the specification, including with reference to the accompanying drawings, in which: [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is a perspective view of a medical inhaler made in accordance with the present disclosure. [Diagram 2] FIG. 2 is a side view of a medical injector that can be made in accordance with the present disclosure. [Diagram 3] FIG. 3 is a perspective view of the dimensions of a molded article for use in performing part ejection testing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024]

[0025] Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous structures or elements of the present invention.

[0026] It will be understood by those skilled in the art that the discussion of the present invention is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0025]

[0027] In general, the present disclosure is directed to a thermoplastic polymer composition, and a polymer article made from such a composition, that has not only excellent strength properties but also improved demolding properties. The polymer composition formulated according to the present disclosure can, for example, exhibit reduced mold deposits and / or require a lower ejection force to remove a part from a mold. In one embodiment, the demolding package of the present disclosure can also be used to dramatically improve the melt processing behavior of the polymer composition. For example, it is believed that the demolding package can facilitate the formation of a stable melt under melt processing conditions, and can increase the crystallization rate and / or melt-solidification rate. In this manner, shorter cycle times can be observed, resulting in increased productivity.

[0026]

[0028] The release package of the present disclosure contains at least one release agent, optionally in combination with a nucleating agent, such as an inorganic nucleating agent. The at least one release agent may be a polar release agent, such as an oxidized wax.

[0027]

[0029] In one embodiment, the polymer composition contains a release package comprising a first release agent and a second release agent.In one embodiment, the first release agent is a polar polymer, while the second release agent is a non-polar polymer.The combination of the first release agent and the second release agent can exhibit synergistic effects in injection molding process, such as reducing mold deposits and / or lowering ejection force.Reducing mold deposits minimizes the need for cleaning tools, and lower ejection force allows easy part removal.

[0028]

[0030] In the past, lubricants have been added to polymer compositions to reduce mold deposits. For example, one particular type of lubricant that has been used in the past has been an ester of Montanic acid. However, Montanic acid esters are not approved for use in food handling and / or medical applications according to many government agencies. As a result, one aspect of the present disclosure is directed to incorporating into the polymer composition one or more mold release agents that are not only approved for food handling or medical applications, but also perform similar functions as lubricants that have been used in the past.

[0029]

[0031] In this regard, the polymer composition of the present disclosure can be formulated such that any component contained in the composition meets government regulations for food handling or medical use. For example, any component contained in the polymer composition can be approved for use according to the U.S. Food and Drug Administration's food contact standards and the approved list found in Title 21 of the Code of Federal Regulations (equivalent to those existing in March 2021). For example, each polymer contained in the polymer composition can be approved for food handling use as set forth in 21CFR177. Each component contained in the polymer composition can also be approved for food handling use by 21CFR174.

[0030]

[0032] Each component contained in the polymer composition may also meet or exceed all food contact standards, such as Regulation (EC) Nos. 1935 / 2004, 2023 / 2006, 10 / 2011, Resolution AP(89)1, German BfR IX, Spanish Real Decreto 847 / 2011, and Italian Decreto 21 / 3 / 73; and Chinese food contact standards, such as GB9685-2016.

[0031]

[0033] In addition to the thermoplastic polymer and one or more release agents, the polymer compositions of the present disclosure may also optionally contain one or more friction modifiers, reinforcing fibers, and / or nucleating agents.

[0032]

[0034] The compositions of the present disclosure can be formulated for medical applications that require low friction properties. For example, when used in medical applications, the polymeric compositions may not contain isocyanates, epoxy resins, carbodiimides or other similar compounds. In certain applications, medical devices require that the parts are not only made from high strength materials, but also provide very low friction and reduced wear for parts that are intended to slide against adjacent surfaces. As described in more detail below, the polymeric compositions made according to the present disclosure not only have excellent strength properties, but also exhibit very low friction properties.

[0033]

[0035] When two opposing surfaces slide against each other, the surfaces react in a manner known as the stick-slip phenomenon. The stick-slip phenomenon refers to the manner in which two opposing surfaces or objects slide against each other under frictional forces. Static friction is the friction between two or more objects that do not move relative to each other. On the other hand, kinetic friction occurs when two objects move relative to each other while remaining in contact. For one object to slide against another, a sufficient force must act on one object to overcome the force of static friction. When motion between two objects occurs, friction between the two surfaces can be reduced, causing a sudden increase in the speed of the motion. In other words, in some applications, when one object moves relative to another, less force is required to continue the motion. Friction between two surfaces can increase or decrease during the motion, depending on a number of factors, including the continuing speed of the motion. Stick-slip describes how surfaces alternate between sticking and sliding against each other when motion occurs between two surfaces or when motion conditions change.

[0034]

[0036] Polymeric articles with a relatively high coefficient of friction not only require a greater amount of force to slide one material over another, but may also be more susceptible to wear: over time, the materials may begin to degrade due to the forces of friction, for example.

[0035]

[0037] In one embodiment, the polymer composition of the present disclosure may optionally contain one or more friction modifiers to produce molded articles with low friction characteristics. The molded articles are particularly well suited for use in medical and / or food handling applications. For example, in one embodiment, the present disclosure is directed to a low friction assembly that includes a first slide member functionally associated with a second slide member. Both the first slide member and the second slide member may be made from a polymer composition formulated according to the present disclosure. When tested against each other or against a polycarbonate / ABS blend (CYCOLOY C1204H from SABIC), the compositions may be formulated to exhibit a dynamic coefficient of friction of less than about 0.08, such as less than about 0.07, such as less than about 0.06, such as less than about 0.05. The compositions or molded parts may be tested against each other according to the stick-slip test having test number VDA230-206.

[0036]

[0038] The specimens tested using the above method can also be analyzed to measure the width of the wear scar, which is the width that has been worn away. According to the present disclosure, the compositions and molded articles can show a wear scar width of less than 0.3 mm, for example less than about 0.25 mm, for example even less than about 0.2 mm, when tested after 1,000 cycles with a force of 30 N and a speed of 8 mm / s.

[0037]

[0039] The thermoplastic polymers used as matrix polymers to form molded articles in accordance with the present disclosure can vary depending on the particular application and the results desired. Thermoplastic polymers that can be used in accordance with the present disclosure include, for example, polyamide polymers, polyester polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, or polyacetal polymers, and combinations thereof.

[0038]

[0040] In certain embodiments, the thermoplastic polymer may be a polybutylene terephthalate polymer alone or in combination with a polyethylene terephthalate polymer. Alternatively, the thermoplastic polymer may be a polyoxymethylene copolymer.

[0039] Polyester Polymer

[0041] In one embodiment, the thermoplastic matrix polymer contained in the polymer composition comprises one or more polyester polymers. Polyester polymers generally comprise polyalkylene terephthalate polymers.

[0040]

[0042] Polyalkylene terephthalate polymers suitable for use herein are derived from an aliphatic or alicyclic diol, or mixtures thereof, containing from 2 to about 10 carbon atoms, and an aromatic dicarboxylic acid.

[0041]

[0043] Polyesters derived from cycloaliphatic diols and aromatic dicarboxylic acids are prepared, for example, by condensing either the cis or trans isomer of 1,4-cyclohexanedimethanol (or a mixture thereof) with an aromatic dicarboxylic acid.

[0042]

[0044] Examples of aromatic dicarboxylic acids include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, and the like, and mixtures thereof. All of these acids contain at least one aromatic nucleus. Fused 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 and isophthalic acids.

[0043]

[0045] In one embodiment, the polyalkylene terephthalate polymer present in the polymer composition comprises polybutylene terephthalate polymer.For example, the polymer composition may contain polybutylene terephthalate polymer in an amount greater than about 30% by weight, for example greater than about 40% by weight, for example greater than about 50% by weight, for example greater than about 60% by weight, for example greater than about 70% by weight.Polybutylene terephthalate polymer is generally present in an amount less than about 90% by weight, for example less than about 80% by weight.

[0044]

[0046] 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 polymers or polyethylene terephthalate copolymers. For example, polyethylene terephthalate copolymers or modified polyethylene terephthalate polymers can be produced using modifying acids or modifying diols.

[0045]

[0047] The terms "modifying acid" and "modifying diol" as used herein are meant to define compounds that can form part of the acid and diol repeat units of a polyester, respectively, and can modify the polyester so that its crystallinity is reduced or the polyester becomes amorphous. In one embodiment, however, the polyester present in the polymer composition of the present disclosure is unmodified and does not contain a modifying acid or a modifying diol.

[0046]

[0048] Examples of acid components having a modifying effect 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, 1,12-dodecanedioic acid, etc. In practice, it is often preferred to use their functional acid derivatives, such as the dimethyl, diethyl, or dipropyl esters of the dicarboxylic acids. Anhydrides or acid halides of these acids can also be employed, if practical. Isophthalic acid is preferred.

[0047]

[0049] Examples of diol components having a modifying effect include, but are not limited to, 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-[5.2.1.0]-decane (wherein Z is 3, 4, or 5); 1,4-bis(2-hydroxyethoxy)benzene. benzene, 4,4'-bis(2-hydroxyethoxy)diphenyl ether [bis-hydroxyethyl bisphenol A], 4,4'-bis(2-hydroxyethoxy)diphenyl sulfide [bis-hydroxyethyl bisphenol S] and diols containing one or more oxygen atoms in the chain, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc. These diols generally contain 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. The alicyclic diols may be employed in their cis or trans configuration, or as a mixture of both forms.

[0048]

[0050] The polyester polymer in combination with the polybutylene terephthalate, when present, may generally be added to the polymer composition in an amount greater than about 5% by weight, such as greater than about 10% by weight, such as greater than about 12% by weight. The polyester polymer is generally present in an amount less than about 40% by weight, such as less than about 30% by weight, such as less than about 20% by weight, such as less than about 15% by weight.

[0049] Polyoxymethylene Polymer

[0051] In one embodiment, the thermoplastic matrix polymer may be a polyoxymethylene polymer, such as a polyoxymethylene homopolymer or a polyoxymethylene copolymer. According to one embodiment, the polyoxymethylene is at least 50 mol.%, such as at least 75 mol.%, for example at least 90 mol.% -CH 2 O-repeat units, e.g., at least 97 mol.% of -CH 2 It is a homo- or copolymer containing O-repeat units.

[0050]

[0052] In one embodiment, a polyoxymethylene copolymer is used. The copolymer may contain about 0.01 mol.% to about 20 mol.%, particularly about 0.5 mol.% to about 10 mol.%, of repeating units, and the repeating units include saturated or ethylenically unsaturated alkylene or cycloalkylene groups having at least two carbon atoms with sulfur or oxygen atoms in the chain, and may include one or more substituents selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, halogen, or alkoxy. In one embodiment, a cyclic ether or acetal is used, which can be introduced into the copolymer via a ring-opening reaction.

[0051]

[0053] Preferred cyclic ethers or acetals are those represented by the formula:

[0052] [ka]

[0053] In the formula, x is 0 or 1; R 2 is C 2 ~C 4 -alkylene group, C 2 ~C 4 The alkylene group is optionally 1 ~C 4 -Alkyl group or C 1 ~C 4-alkoxy groups and / or one or more substituents which are halogen atoms, preferably chlorine atoms. Merely by way of example, cyclic ethers include ethylene oxide, propylene 1,2-oxide, butylene 1,2-oxide, butylene 1,3-oxide, 1,3-dioxane, 1,3-dioxolane, and 1,3-dioxepane, and comonomers include linear oligo- or polyformals, such as polydioxolane or polydioxepane. It is particularly advantageous to use copolymers consisting of 99.5-95 mol.% trioxane and 0.01-5 mol.%, for example 0.5-4 mol.% of one of the above-mentioned comonomers. In one embodiment, the polyoxymethylene polymer contains a relatively low amount of comonomer. For example, the comonomer may be present in an amount less than about 2 mol.%, such as less than about 1.5 mol.%, for example less than about 1 mol.%, such as less than about 0.8 mol.%, for example less than about 0.6 mol.%.

[0054]

[0054] The polymerization may be carried out as a precipitation polymerization or in the melt. By suitable selection of the polymerization parameters, such as the duration of the polymerization or the amount of molecular weight regulator, it is possible to adjust the molecular weight of the obtained polymer, and therefore the MVR value.

[0055] In one embodiment, the polyoxymethylene polymer used in the polymer composition may contain a relatively large amount of reactive or functional groups at the terminal positions. Reactive groups include, for example, -OH or -NH 2 It may contain a group.

[0056] In one embodiment, the polyoxymethylene polymer may have terminal hydroxyl groups, e.g., hydroxyethylene groups and / or hydroxyl side groups, at at least about 50% of all end sites of the polymer. For example, the polyoxymethylene polymer may have hydroxyl groups at at least about 70%, e.g., at least about 80%, e.g., at least about 85%, of its end groups, based on the total number of end groups present. It is to be understood that the total number of end groups present includes all side end groups.

[0057] In one embodiment, the polyoxymethylene polymer has a terminal hydroxyl group content of at least 15 mmol / kg, such as at least 18 mmol / kg, such as at least 20 mmol / kg. In one embodiment, the terminal hydroxyl group content is in the range of 18 to 50 mmol / kg. In an alternative embodiment, the polyoxymethylene polymer may contain terminal hydroxyl groups in an amount less than 20 mmol / kg, such as less than 18 mmol / kg, such as less than 15 mmol / kg. For example, the polyoxymethylene polymer may contain terminal hydroxyl groups in an amount of about 5 mmol / kg to about 20 mmol / kg, such as about 5 mmol / kg to about 15 mmol / kg. For example, polyoxymethylene polymers having lower terminal hydroxyl group content but higher melt volume flow rate may be used.

[0058] In addition to or instead of the terminal hydroxyl groups, the polyoxymethylene polymers may also have other terminal groups common to these polymers. Examples of these are alkoxy, formate, acetate or aldehyde groups. According to one embodiment, the polyoxymethylene contains at least 50 mol %, such as at least 75 mol %, for example at least 90 mol % -CH 2 O-repeat units, e.g., at least 95 mol % of -CH 2 It is a homo- or copolymer containing O-repeat units.

[0059] In one embodiment, polyoxymethylene polymers can be produced using a cationic polymerization process followed by solution hydrolysis to remove any unstable end groups. During cationic polymerization, glycols, such as ethylene glycol or methylal, may be used as chain terminators. Heteropolyacids, triflic acids or boron compounds may be used as catalysts.

[0060] The polyoxymethylene polymer may have any suitable molecular weight. The molecular weight of the polymer may be, for example, from about 4,000 grams / mol to about 20,000 grams / mol. However, in other embodiments, the molecular weight may be well above 20,000 grams / mol, for example, from about 20,000 grams / mol to about 100,000 grams / mol.

[0061] The polyoxymethylene polymer present in the composition generally has a viscosity of about 0.1 to about 80 cm when measured at 190° C. and 2.16 kg according to ISO 1133. 3 In one embodiment, the polyoxymethylene polymer may have a melt flow index (MFI) in the range of about 1 cm / 10 min. 3 / 10 minutes or more, for example, about 2 cm 3 / 10 minutes or more, for example, about 5 cm 3 / 10 minutes or more, for example, about 10 cm 3 / 10 minutes or more, for example, about 20 cm 3 / 10 minutes or more, for example, about 30 cm 3 The polymer may have a melt flow index of greater than about 55 cm / 10 min. 3 / Less than 10 minutes, for example, about 45 cm 3 / Less than 10 minutes, for example, about 35 cm 3 / Less than 10 minutes, for example, about 25 cm 3 / Less than 10 minutes, for example, about 15 cm 3 / Less than 10 minutes, for example, about 10 cm 3 / Less than 10 minutes, for example, about 5 cm 3The composition may have a melt flow index of less than 1 / 10 minutes.

[0062] The polyoxymethylene polymer may be present in the polymer composition in an amount of at least about 40% by weight, such as at least about 50% by weight, for example at least about 60% by weight. The polyoxymethylene polymer is generally present in the polymer composition in an amount of less than about 80% by weight, such as less than about 70% by weight, for example less than about 60% by weight.

[0063] Reinforcement Fiber

[0063] In addition to the thermoplastic polymer matrix, the polymer composition may optionally contain reinforcing fibers. Thermoplastic polymers, such as polyester and polyoxymethylene polymers, are combined with fibrous fillers to increase the modulus and / or tensile strength of parts and products made from the reinforced composition. However, to date, there have been problems in incorporating reinforcing fibers into a polymer matrix with a desired balance of properties. For example, a polymer composite containing reinforcing fibers may have sufficient strength properties, but may increase surface friction when moving across adjacent surfaces. The increased friction may cause abrasive wear, for example, after long-term use. These problems may be exacerbated when a first part made from a polymer matrix is ​​designed to slide or rub against an adjacent part made from the same reinforced polymer matrix.

[0064]

[0064] A variety of different friction modifying additives have been proposed for blending thermoplastic polymers with reinforcing fibers to reduce the coefficient of friction of fiber-reinforced polymers. Friction modifying additives can lower both friction and wear characteristics when the polymer composition is molded into a part and used in applications where the part contacts and slides against an adjacent surface. However, several components contained in the polymer composition can cause problems during the molding process, especially during the injection molding process. For example, many fiber-reinforced polymer compositions have a tendency to produce mold deposits that require regular tool cleaning. The mold cleaning process is not only time-consuming, but also causes delays in the production process.

[0065] In addition to causing mold deposits, fiber reinforced polymer compositions also require relatively high ejection forces to remove parts from the mold. The greater forces required to eject a part can result in part failure and can increase the accumulation of mold deposits.

[0066]

[0066] However, in accordance with the disclosure of the present invention, by incorporating one or more mold release agents into the composition, either alone or in combination with a nucleating agent, it is possible to incorporate reinforcing fibers into the polymer composition while minimizing mold deposits and reducing the force required to remove a part from a mold.

[0067]

[0067] Reinforcing fibres which may advantageously be used are mineral fibres, for example glass fibres, polymer fibres, in particular organic high-modulus fibres, for example aramid fibres, or metal fibres, for example steel fibres, or carbon fibres, or natural fibres, fibres from renewable resources.

[0068]

[0068] These fibres may be in modified or unmodified form and may be sized or chemically treated, for example to improve adhesion to plastics. Glass fibres are particularly preferred.

[0069]

[0069] Glass fibers are sized to protect them, to make them smooth, and also to improve adhesion between the fibers and the matrix material. Sizing usually contains silanes, film formers, lubricants, wetting agents, adhesives, optionally antistatic agents and plasticizers, emulsifiers, and optionally further additives.

[0070] 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, N-[3-(trimethoxysilyl)propyl]-1,2-ethane-diamine.

[0071]

[0071] Film-forming agents are, for example, polyvinyl acetates, polyesters and polyurethanes. Polyurethane-based sizings can be advantageously used.

[0072] The reinforcing fibers may be incorporated into the polymer matrix, for example in an extruder or kneader.

[0072]

[0073] According to one embodiment, the molding composition of the present disclosure includes at least one reinforcing fiber, which is a mineral fiber, preferably a glass fiber, more preferably a coated glass fiber or an impregnated glass fiber. Glass fibers suitable for the molding composition of the present disclosure are commercially available, such as Johns Manville, ThermoFlow® Chopped Strand 753, OCV Chopped Strand 408A, Nippon Electric Glass Co., Ltd. (NEG) Chopped Strand T-651.

[0073]

[0074] The diameter of the fibers may vary depending on the particular fiber used and whether the fibers are chopped or in continuous form. The fibers may have a diameter of, for example, about 5 μm to about 100 μm, such as about 5 μm to about 50 μm, such as about 5 μm to about 15 μm. The length of the fibers may vary depending on the particular application. For example, the fibers may have a length of more than about 100 micrometers, such as more than about 200 micrometers, such as more than about 300 micrometers, such as more than about 350 micrometers. The length of the fibers may generally be less than about 1,000 micrometers, such as less than about 800 micrometers, such as less than about 600 micrometers, such as less than about 500 micrometers. Once incorporated into the polymer composition and formed into an article, the length of the fibers may decrease. For example, the average fiber length in the final product may be about 100 micrometers to about 400 micrometers, such as about 100 micrometers to about 300 micrometers.

[0074]

[0075] Generally, the reinforcing fibers may be present in the polymer composition in an amount sufficient to increase the tensile strength of the composition. The reinforcing fibers may be present in the polymer composition in an amount of, for example, greater than about 5% by weight, for example, greater than about 10% by weight, for example, greater than about 15% by weight, for example, greater than about 20% by weight, for example, greater than about 25% by weight, for example, greater than about 30% by weight. The reinforcing fibers are generally present in an amount of 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, for example, less than about 30% by weight.

[0075] Release Agent

[0076] In accordance with the present disclosure, the polymer composition contains one or more mold release agents, which are added in an amount sufficient to reduce the force of ejection of a part from a mold, for example, from a mold during injection molding. Alternatively, the one or more mold release agents may be added in an amount sufficient to reduce mold deposits compared to an otherwise identical composition that does not contain the one or more mold release agents.

[0076]

[0077] In one aspect, one or more release agents, alone or in combination with a nucleating agent, can improve the melt processing behavior or properties of polymer compositions.The release packages of the present disclosure can, for example, increase the crystallization rate and melt-solidification rate.Polymer compositions incorporating release packages can also form more stable melts, which can significantly improve cycle times and increase production.

[0077]

[0078] In one embodiment, the polymer composition contains only a single release agent. The release agent may be, for example, a polar release agent and / or an oxidized release agent. The polar material, for example, blends well with other components. It has been found that the polar polymer for use in the present disclosure dramatically reduces mold deposits by interacting with other components during molding. The polar release agent may be, for example, an oxidized wax, for example, an oxidized polyolefin wax or an oxidized ester of a carboxylic acid. The oxidized polyolefin wax may be, for example, an oxidized polyethylene wax.

[0078]

[0079] The polarity of the release agent may vary depending on the particular application and the desired results. Polarity may be indicated, for example, by the acid number of the release agent. The acid number of a polar release agent may, for example, generally be greater than about 10 KOH / g, such as greater than about 15 KOH / g, such as greater than about 20 KOH / g, such as greater than about 25 KOH / g, such as greater than about 30 KOH / g, such as greater than about 35 KOH / g, such as greater than about 40 KOH / g, such as greater than about 45 KOH / g, such as greater than about 50 KOH / g. The acid number is generally less than about 95 KOH / g, such as less than about 90 KOH / g, such as less than about 85 KOH / g, such as less than about 80 KOH / g, such as less than about 75 KOH / g, such as less than about 70 KOH / g.

[0079]

[0080] In one embodiment, the acid number of the polar release agent can be from about 13 KOH / g to about 23 KOH / g, such as from about 15 KOH / g to about 19 KOH / g. In an alternative embodiment, the acid number of the polar release agent can be from about 40 KOH / g to about 65 KOH / g, such as from about 45 KOH / g to about 55 KOH / g.

[0080]

[0081] As mentioned above, in one embodiment, the polar release agent may be an oxidized ester of a carboxylic acid. In one form, the oxidized ester of a carboxylic acid may be obtained from a biomass material, such as rice bran.

[0081]

[0082] The different carboxylic acids used to produce the oxidized esters of fatty acids may vary depending on the fatty acid source and the desired results. In one embodiment, the oxidized esters of fatty acids may be obtained from at least 3 different fatty acids, such as at least 5 different fatty acids, such as at least about 8 different fatty acids, generally less than about 20 different fatty acids, such as less than about 15 different fatty acids. The fatty acids used to produce the oxidized esters may, for example, have a variety of different chain lengths. For example, of all the fatty acids present in the oxidized wax, more than about 20% by weight, such as more than about 30% by weight, such as more than about 40% by weight, such as more than about 50% by weight, such as more than about 60% by weight, may be obtained from fatty acids having a carbon chain length of about 20 carbon atoms to about 40 carbon atoms. The oxidized wax may also be obtained from fatty acids with longer chain lengths. For example, the oxidized wax may be derived from fatty acids having a carbon chain length of about 40 carbon atoms to about 64 carbon atoms, such as more than about 5% by weight, e.g., more than about 10% by weight, e.g., more than about 15% by weight, e.g., more than about 20% by weight, e.g., more than about 25% by weight, e.g., more than about 30% by weight, e.g., more than about 40% by weight, e.g., more than about 45% by weight, e.g., more than about 50% by weight. The carboxylic acid may be an aliphatic carboxylic acid. In one embodiment, the oxidized wax contains less than about 5% by weight of esters derived from fatty acids having a carbon chain length of less than about 14 carbon atoms, e.g., less than about 12 carbon atoms, e.g., less than about 10 carbon atoms, e.g., less than about 8 carbon atoms.

[0082]

[0083] In one particular embodiment, the polymer composition contains a first release agent and a second release agent, both of which are sufficiently safe for food handling and / or medical applications. The first release agent may be, for example, a polar polymer.

[0083]

[0084] A variety of different polar materials may be used as the first release agent, such as the polar polymer described above.The polar polymer may be, for example, a polyolefin polymer, and in particular a modified polyolefin polymer.The polar polyolefin polymer may be, for example, a polyethylene polymer or a polypropylene polymer, as well as their copolymers.In one particular embodiment, the first release agent may be an oxidized polyethylene wax.

[0084]

[0085] Other polar waxes may be polar modified polymers of ethylene and / or propylene, for example formed using metallocene catalysts. Examples may include homopolymers or copolymers of ethylene and / or propylene modified in the presence of hydrophilic groups, such as maleic anhydride, acrylic, methacrylic, or polyvinylpyrrolidone (PVP) groups. Examples include maleic anhydride modified polypropylene polymers (PPMA), or maleic anhydride polypropylene and ethylene copolymers. In one form, the polar wax may be obtained from rice bran, as described above.

[0085]

[0086] In addition to polar materials, effective mold release agents may also include non-polar materials, such as non-polar polymers. Non-polar polymers can migrate to the surface of polymeric articles made from the polymeric composition, for example, during molding. In this manner, non-polar polymeric materials according to the present disclosure can significantly reduce the amount of force required to release a part from a mold. Non-polar polymers that can be used according to the present disclosure include a variety of different non-polar polyolefin polymers, such as polyethylene polymers and polypropylene polymers. Polyolefin polymers can be homopolymers or copolymers. In one embodiment, the non-polar polymer can be polyethylene wax.

[0086]

[0087] In one particular embodiment, the polymer composition contains a first release agent comprising a polar polymer in combination with a second release agent comprising a non-polar polymer.

[0088] Each release agent may generally be present in the polymer composition in an amount less than about 2 wt%, such as less than about 1 wt%, such as less than about 0.8 wt%, such as less than about 0.6 wt%, such as less than about 0.4 wt%, such as less than about 0.2 wt%. One or more release agents are generally present in the polymer composition in an amount greater than about 0.01 wt%.

[0087]

[0089] When the polymer composition contains a first release agent in combination with a second release agent as described above, the weight ratio of the first release agent to the second release agent may be from about 10:1 to about 1:10, such as from about 5:1 to about 1:5, for example from about 2:1 to about 1:2.

[0088] Friction modifiers

[0090] In accordance with the present disclosure, the polymeric compositions and polymeric articles comprising the reinforced polymeric compositions may include at least one friction modifier.

[0089]

[0091] In one embodiment, ultra-high molecular weight silicone (UHMW-Si) can be used to modify thermoplastic polymer.Generally, UHMW-Si can have an average molecular weight of more than 100,000g / mol, for example more than about 200,000g / mol, for example more than about 300,000g / mol, for example more than about 500,000g / mol, and less than about 3,000,000g / mol, for example less than about 2,000,000g / mol, for example less than about 1,000,000g / mol, for example less than about 500,000g / mol, for example less than about 300,000g / mol.Generally, UHMW-Si can have an average molecular weight of more than 100,000mm 2 / sec, for example, about 200,000 mm 2 / sec, for example, about 1,000,000 mm 2 / sec, for example, about 5,000,000 mm2 / sec, for example, about 10,000,000 mm 2 / sec, for example, about 15,000,000 mm 2 / sec, greater than 50,000,000 mm 2 / sec, e.g., about 25,000,000 mm 2 / sec, e.g., about 10,000,000 mm 2 / sec, e.g., about 1,000,000 mm 2 / sec, e.g., about 500,000 mm 2 / sec, e.g., about 200,000 mm 2 The composition may have a kinematic viscosity, measured at 40° C. in accordance with DIN 51562, of less than 1 / s.

[0090]

[0092] The UHMW-silicone may comprise a siloxane, for example a polysiloxane or a polyorganosiloxane. In one embodiment, the UHMW-Si may comprise a dialkyl polysiloxane, such as dimethyl siloxane, an alkylaryl siloxane, such as phenylmethyl siloxane, a polysilsesquioxane, or a diaryl siloxane, such as diphenyl siloxane, or a homopolymer thereof (e.g. polydimethyl siloxane or polymethylphenyl siloxane), or a copolymer thereof, according to the molecular weight and / or dynamic viscosity requirements above. The polysiloxane or polyorganosiloxane may also be modified at the end of the molecule or in the backbone with a substituent such as an epoxy group, a hydroxyl group, a carboxy group, an amino group or a substituted amino group, an ether group, or a meth(acryloyl) group. The above UHMW-Si compounds may be used alone or in combination. Any of the above UHMW-Si compounds may be used according to the molecular weight and / or dynamic viscosity requirements above.

[0091]

[0093] The UHMW-silicone may be added to the polymer composition as a masterbatch, where the UHMW-Si is dispersed in a carrier polymer and the masterbatch is then added to the composition. The masterbatch may contain about 10 wt.% to about 60 wt.%, for example about 35 wt.% to about 55 wt.%, for example about 50 wt.%, UHMW-Si.

[0092]

[0094] The carrier polymer may vary depending on the particular application and the desired result. In one embodiment, for example, the carrier polymer may include a polyester polymer. The polyester carrier polymer may include, for example, polybutylene terephthalate, polyethylene terephthalate, copolyester, and / or polyester elastomer. The polyester elastomer may include a copolyester, such as a segmented thermoplastic copolyester. The polyester elastomer may include, for example, a multiblock copolymer.

[0093]

[0095] The UHMW-silicone may be present in the polymer composition in an amount of more than about 0.005 wt.%, such as more than about 0.1 wt.%, for example more than about 0.5 wt.%, for example more than about 0.75 wt.%, for example more than about 1 wt.%, for example more than about 2 wt.%, for example more than about 2.5 wt.%, typically less than about 10 wt.%, for example less than about 6 wt.%, for example less than about 5 wt.%, for example less than about 4 wt.%, for example less than about 3.5 wt.%, for example less than about 3 wt.%, wherein the weight is based on the total weight of the polymer composition.

[0094]

[0096] In an alternative embodiment, at least one friction modifying additive may include a fluoropolymer, such as a polytetrafluoroethylene powder. The fluoropolymer may be combined with ultra-high molecular weight silicone in one application. The polytetrafluoroethylene particles may have an average particle size of, for example, less than about 15 micrometers, such as less than about 12 micrometers, such as less than about 10 micrometers, such as less than about 8 micrometers. The average particle size of the polytetrafluoroethylene particles is generally greater than about 0.5 micrometers, such as greater than about 1 micrometer, such as greater than about 2 micrometers, such as greater than about 3 micrometers, such as greater than about 4 micrometers, such as greater than about 5 micrometers. The average particle size can be measured according to ISO test 13321.

[0095]

[0097] In one embodiment, the polytetrafluoroethylene particles may have a relatively low molecular weight. The polytetrafluoroethylene polymer may have a density of about 300 g / l to about 450 g / l, for example about 325 g / l to about 375 g / l, when tested according to ASTM test D4895. The polytetrafluoroethylene particles may have a density of about 5 mm when tested according to test DIN66132. 2 / g ~ approx. 15m 2 / g, for example, about 8m 2 / g ~ approx. 12m 2 The polytetrafluoroethylene polymer may have a specific surface area of ​​less than about 3 g / 10 min, such as less than about 2 g / 10 min, when tested according to ISO test 1133, performed at 372° C. with a load of 10 kg.

[0096]

[0098] The polytetrafluoroethylene particles may be present in the polymer composition in an amount greater than about 1% by weight, such as greater than about 2% by weight, such as greater than about 3% by weight, such as greater than about 4% by weight. The polytetrafluoroethylene polymer is generally present in the polymer composition in an amount less than about 20% by weight, such as less than about 15% by weight, such as less than about 10% by weight, such as less than about 8% by weight.

[0097] Other Additives

[0099] The polymer composition of the present disclosure may contain various other additives. For example, the composition may further include a nucleating agent present at a concentration of about 0.1-2% by weight, preferably about 0.001%-0.5%, based on the total weight of the composition. The nucleating agent may be selected from the group consisting of an alkali metal salt having an anion that is an oxide of an element from Group IV of the periodic table; barium sulfate; and talc.

[0098]

[0100] The polymer composition may also contain at least one stabilizer. The stabilizers may include antioxidants, light stabilizers, such as ultraviolet light stabilizers, heat stabilizers, and the like.

[0101] Sterically hindered phenolic antioxidants may be employed in the composition. 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; Hexamethylenebis(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-octyldiphenamine (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-4'hydroxybenzyl)benzene (Irganox® 1330); 2,4-bis(octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (Irganox® 1330) )® 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® TM4039); 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-diphenylphenol (Irganox® 1020); Irganox® 1063); 2,2'-ethylidenebis[4,6-di-tert-butylphenol] (Irganox® 129); N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (Irganox® 1098); diethyl(3,5-di-tert-butyl-4-hydroxyphenyl)phosphonate (Irganox® 1222); 4,4'-di-tert t-Octyldiphenylamine (Irganox® 5057); N-phenyl-1-napthalenamine (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]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (Sumilizer® AG80); pentaerythrityl tetrakis[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); 3,5-di-tert-butyl-4-hydroxytoluene (Lowinox BHT, Chemtura);

[0099]

[0102] Some examples of suitable sterically hindered phenolic antioxidants for use in the compositions of the present invention are the triazine antioxidants having the general formula:

[0100] [ka]

[0101] In the formula, each R is independently a phenol group, and the phenol group is 1 ~C 5 It may be attached to the triazine ring via an alkyl or ester substituent. Preferably, each R is one of the following formulae (I) to (III):

[0102] [ka]

[0103]

[0103] Commercially available examples of such triazine-based antioxidants are available from American Cyanamid under the designation Cyanox® 1790 (wherein each R group is represented by Formula III) and from Ciba Specialty Chemicals under the designations Irganox® 3114 (wherein each R group is represented by Formula I) and Irganox® 3125 (wherein each R group is represented by Formula II).

[0104] The sterically hindered phenolic antioxidant may comprise from about 0.01 wt.% to about 3 wt.%, in some embodiments from about 0.05 wt.% to about 1 wt.%, and in some embodiments from about 0.05 wt.% to about 0.1 wt.% of the total stabilized polymer composition. In one embodiment, for example, the antioxidant comprises pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0105]

[0105] Hindered amine light stabilizers ("HALS") may be employed in the polymer composition to inhibit degradation and extend its durability. Suitable HALS compounds can be derived from substituted piperidines, such as alkyl-substituted piperidyl, piperidinyl, piperazinone, alkoxypiperidinyl compounds, and the like. For example, hindered amines can be derived from 2,2,6,6-tetraalkylpiperidinyl. Regardless of the compound from which they are derived, hindered amines are typically oligomeric or polymeric compounds having a number average molecular weight of about 1,000 or greater, in some embodiments from about 1000 to about 20,000, in some embodiments from about 1500 to about 15,000, and in some embodiments from about 2000 to about 5000. Such compounds typically contain at least one 2,2,6,6-tetraalkylpiperidinyl group (e.g., 1 to 4) per polymer repeat unit.

[0106]

[0106] Without intending to be limited by theory, it is believed that high molecular weight hindered amines are relatively thermally stable and therefore capable of inhibiting photodegradation even after exposure to extrusion conditions. One particularly suitable high molecular weight hindered amine has the following general structure:

[0107] [ka]

[0108] wherein p is 4 to 30, in some embodiments 4 to 20, and in some embodiments 4 to 10. This oligomeric compound is commercially available from Clariant under the name Hostavin® N30 and has a number average molecular weight of 1200.

[0109] Another suitable high molecular weight hindered amine has the following structure:

[0110] [ka]

[0111] In the formula, n is 1 to 4; R 30 are independently hydrogen or CH 3 Such an oligomeric compound is available from Adeka Palmarole SAS (a joint venture between Adeka Corp. and the Palmarole Group) under the name ADK STAB® LA-63 (R 30 is CH 3 ) and ADK STAB® LA-68 (R 30 is hydrogen).

[0112] Other examples of suitable high molecular weight hindered amines include, for example, oligomers of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622 from Ciba Specialty Chemicals, MW=4000); oligomers of cyanuric acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; poly((6-morpholinyl)-2,2,6,6-tetramethyl-4-piperidinol; hexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb® UV3346 from Cytec, MW=1600); polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinylsiloxane (Great Lakes Chemical) Uvasil® 299, MW=1100-2500 from Lakes Chemical; copolymers of α-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleimide; 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanoltetramethyl polymer with 1,2,3,4-butanetetracarboxylic acid; and the like. Still other suitable high molecular weight hindered amines are described in U.S. Patent Nos. 5,679,733 to Malik et al. and 6,414,155 to Sassi et al., which are incorporated herein by reference in their entireties for all purposes.

[0113] In addition to the high molecular weight hindered amines, low molecular weight hindered amines may also be employed in the composition. Such hindered amines are generally monomeric in nature and have a molecular weight of about 1000 or less, in some embodiments from about 155 to about 800, and in some embodiments from about 300 to about 800.

[0114]

[0110] Specific examples of such low molecular weight hindered amines include, for example, bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Tinuvin® 770 from Ciba Specialty Chemicals, MW=481); bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-(3,5-ditert-butyl-4-hydroxybenzyl)butyl-propanedioate; bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-(3,5-ditert-butyl-4-hydroxybenzyl)butyl-propanedioate; methyl-4-piperidinyl)sebacate;8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-(4,5)-decane-2,4-dione, butanedioic acid-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-diazadispiro(5.1.11.2)heneicosane-20 -Propanoic acid, 2,2,4,4-tetramethyl-21-oxo, dodecyl 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) 3-Dodecyl-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); 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; 1-[2-(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy)ethyl]-4-(3,5-di-tert-butyl-4-hydroxylphenylpropionyloxy)-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-oxo-piperazinyl)ethane; 4-oleoyloxy-2,2,6,6-tetramethylpiperidine; and combinations thereof. Other suitable low molecular weight hindered amines are described in U.S. Pat. No. 5,679,733 to Malik et al.

[0115]

[0111] The hindered amines can be employed alone or in combination in any amount capable of achieving the desired properties, but typically comprise from about 0.01 wt. % to about 4 wt. % of the polymer composition.

[0116]

[0112] UV absorbers, such as benzotriazoles or benzophenones, may be employed in the compositions to absorb ultraviolet light energy.Suitable benzotriazoles include, for example, 2-(2-hydroxyphenyl)benzotriazoles, such as 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);2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole polyethylene glycol esters;2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]-benzotriazole;2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole;2-[2-Hydroxy-3-(2-hydroxyethyl)-5-tert-butylphenyl]benzotriazole;2-[2-Hydroxy-3-(2-hydroxyethyl)-5-tert-butylphenyl]benzotriazole 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole;2-[2-hydroxy-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-amyl ... 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.

[0117]

[0113] Exemplary benzophenone light stabilizers include, in turn, 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); hexadecyl-3,5-bis-tert-butyl-4-hydroxybenzophenone (Cyasorb® UV314 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.

[0118]

[0114] When employed, UV absorbers may comprise from about 0.01 wt.% to about 4 wt.% of the total polymer composition. In one embodiment, the polymer composition may contain a blend of stabilizers that provide UV resistance and color stability. The combination of stabilizers may allow for the production of products with bright, fluorescent colors. In addition, brightly colored products may be produced without significant fading over time. In one embodiment, for example, the polymer composition may contain a combination of a benzotriazole light stabilizer and a hindered amine light stabilizer, such as an oligomeric hindered amine.

[0119] In one embodiment, an amide wax may be present in the polymer composition. For example, an amide wax formed by the reaction of a fatty acid with a monoamine or diamine having 2 to 18, particularly 2 to 8, carbon atoms (e.g., ethylenediamine) may be employed. For example, an ethylenebisamide wax formed by the amidization reaction of ethylenediamine with a fatty acid may be employed. The fatty acid may be a C 12 ~C 30 For example, stearic acid (C 18 From N-(2-hydroxyethyl) 12-hydroxystearamide, and N,N'-(ethylenebis) 12-hydroxystearamide, ethylenebisstearamide wax is formed. Ethylenebisstearamide wax is commercially available from Lonza, Inc. under the name Acrawax® C, which has an individual melting temperature of 142°C. Other ethylenebisamides include bisamides formed from lauric acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, myristic acid, and undecalic acid. Still other suitable amide waxes are N-(2-hydroxyethyl) 12-hydroxystearamide, and N,N'-(ethylenebis) 12-hydroxystearamide.

[0120] In addition to the above components, the polymer composition may contain various other components. Colorants that can be used include any desired inorganic pigments, such as titanium dioxide, ultramarine blue, cobalt blue, and other organic pigments and dyes, such as phthalocyanines, anthraquinones, and the like. Other colorants include carbon black or various other polymer-soluble dyes. Colorants may generally be present in the composition in an amount up to about 2 percent by weight.

[0121] Polymer Articles The compositions of the present disclosure may be compounded and formed into polymeric articles using any technique known in the art. For example, the respective compositions may be thoroughly mixed to form a substantially homogeneous blend. The blend may be melt kneaded at elevated temperatures, e.g., above the melting points but below the decomposition temperatures of the polymers utilized in the polymeric composition. Alternatively, the respective compositions may be melted and mixed together in a conventional single or twin screw extruder. The melt mixing is preferably carried out at a temperature in the range of 150-300°C, e.g., 200-280°C, e.g., 220-270°C or 240-260°C. However, such processing should be carried out at the desired temperature for each respective composition to minimize any polymer degradation.

[0122]

[0119] After extrusion, the composition can be formed into pellets. The pellets can be molded into polymeric articles by techniques known in the art, such as injection molding, thermoforming, blow molding, rotational molding, etc. According to the present disclosure, the polymeric articles can demonstrate excellent behavior and mechanical properties. As a result, the polymeric articles can be used in a number of applications where low wear and excellent gliding properties are desirable.

[0123]

[0120] Polymer articles include any moving article or molding that comes into contact with another surface and may require high tribological requirements.For example, polymer articles include articles for the automotive industry, especially housings, latches such as rotary latches, window cleaning systems, wiper systems, pulleys, sunroof systems, seat adjustments, levers, bushes, gears, gearboxes, claws, pivot housings, wiper arms, brackets or seat rail bearings, zippers, switches, cams, rollers or rolling guides, sliding elements or glides such as slide plates, conveyor belt parts such as chain elements and links, casters, fasteners, levers, wear strips and guard rails of conveyor systems, medical devices such as medical inhalers, injection devices, surgical equipment, wearable devices, etc.A nearly limitless variety of polymer articles can be formed from the polymer compositions of the present disclosure.

[0124] In one embodiment, the composition of the present disclosure is used to produce a first slide member and a second slide member. Both the first and second slide members may be made from a composition according to the present disclosure. In particular, the first and second slide members may be made from a composition comprising a toughened thermoplastic polymer in combination with one or more release agents and ultra-high molecular weight silicone. The relative amounts of the components may be the same or different in each composition.

[0125]

[0122] The first and second slide members may be contained in an apparatus or may be operatively associated with one another such that the slide members move relative to one another. For example, in one embodiment, the first slide member may be stationary while the second slide member moves through the first slide member. Alternatively, both slide members may move while in contact with one another.

[0126]

[0123] In one embodiment, the slide members of the present disclosure can be used to produce a medical device. For example, referring to FIG. 1, an inhaler 20 is shown. The inhaler 20 includes a housing 22 attached to a mouthpiece 24. The housing 22 is operatively associated with a plunger 26 for receiving a canister containing a composition to be inhaled. The composition may include a spray or a powder. The inhaler 20 may include a first slide member operatively associated with a second slide member. For example, in certain embodiments, the housing 22 may include the first slide member and the plunger 26 may include the second slide member. Alternatively, the first slide member may include the housing 22 and the second slide member may include the mouthpiece 24. In yet another embodiment, the housing 22 may include an internal slide member that slides relative to the housing.

[0127]

[0124] In use, the inhaler 20 delivers a metered dose of a medication, for example an asthma medication, to a patient. The asthma medication may be suspended or dissolved in a propellant, or may be contained in powder form. When a patient activates the inhaler to inhale the medication, a valve opens, allowing the medication to exit the mouthpiece.

[0128]

[0125] In another embodiment of the present disclosure, the first slide member and the second slide member are contained in a medical injector 30, as shown in FIG. 2. The medical injector 30 includes a housing 32 operatively associated with a plunger 34. The housing 32 or the first slide member can slide relative to the plunger 34 or the second slide member. The medical injector 30 may be spring loaded. The medical injector 30 is for injecting a drug into a patient, typically in the thigh or buttocks. The medical injector may be needleless or may contain a needle. If it contains a needle, the tip of the needle is typically protected within the housing prior to injection. On the other hand, a needleless injector may contain a cylinder of pressurized gas that pushes the drug therapeutic agent through the skin without the use of a needle.

[0129] The polymeric compositions of the present disclosure are particularly well suited for constructing injectors, such as those shown in FIG. 2, including syringes and autoinjectors for dispensing highly viscous pharmaceuticals, such as biologics, including protein-based pharmaceuticals. As highly viscous pharmaceuticals become more prevalent in the pharmaceutical pipeline, delivery devices face a variety of serious problems that highly viscous drugs pose to traditional autoinjectors. Injectors are built with higher injection forces, for example, to avoid the need for larger diameter needles, which can result in increased pain for the patient. These forces can be stored in the device prior to actuation, usually as compressed springs.

[0130]

[0127] The polymer compositions are not only well suited for producing high pressure delivery devices, but can also contribute to sustainability by being reusable without loss of mechanical properties or precision, and by being capable of being exposed to sterilizing radiation. In particular, molded articles made according to the present disclosure are wear and creep resistant, even after multiple uses.

[0131]

[0128] Creep or cold flow refers to the tendency of a material to deform slowly when held under high stress for a long period of time. Thus, creep can be an important consideration when designing injectors for biologics. In order to deliver these viscous formulations without increasing the size of the needle, these injectors are required to have a greater force to push the drug through the needle than is typically required. Thus, there is a need for a greater force to be stored in the device before operation, usually in the form of a compressed spring. This means that the components of the device are placed under greater stress and therefore more susceptible to creep and also to loss of some of the stored force, which can reduce the reliability of the device. Molded articles made according to the present disclosure have enhanced creep properties and other properties that make the articles well suited for the above applications.

[0132] For example, in addition to excellent creep resistance, the polymer compositions of the present disclosure exhibit elongation retention suitable for snap-fit ​​assemblies, high strength and stiffness, excellent suitability for gamma sterilization, high abrasion resistance, low breakaway force, quiet sliding for improved patient comfort during delivery and elimination of stick-slip, excellent chemical resistance, and a smooth, attractive surface finish.

[0133] In one embodiment, the polymer composition of the present disclosure is used to produce an injector, particularly an autoinjector, designed to dispense a highly viscous fluid, such as a biologic. The biologic may, for example, have a relatively high molecular weight. The biologic may, for example, have an average molecular weight greater than about 50 kDa, such as greater than about 75 kDa, such as greater than about 100 kDa, such as greater than about 125 kDa. The biologic may be contained in a fluid having a viscosity greater than about 7 cP, such as greater than about 10 cP, such as greater than about 12 cP, such as greater than about 15 cP, such as greater than about 20 cP, such as greater than about 25 cP, such as greater than about 50 cP, such as greater than about 75 cP, such as greater than about 100 cP, such as greater than about 200 cP, such as greater than about 300 cP. The viscosity is generally less than about 1500 cP.

[0134] The injector may be designed to deliver a volume of fluid of more than about 0.25 mL, such as more than about 0.5 mL, for example more than about 0.75 mL, typically less than about 5 mL, such as less than about 4 mL, for example less than about 3 mL. The injector may include a needle having a bore size that is typically greater than about 0.08 mm, such as greater than about 0.1 mm, for example greater than about 0.12 mm, for example greater than about 0.14 mm, for example greater than about 0.16 mm, typically less than about 0.3 mm, such as less than about 0.25 mm, for example less than about 0.22 mm, for example less than about 0.2 mm.

[0135]

[0132] The injector can be designed to subcutaneously inject a fluid, e.g., a biologic, with a maximum force that is typically greater than about 2N. The maximum force is the greatest force before all contents are expelled from the injector. The maximum force may be greater than about 3N, such as greater than about 4N, such as greater than about 5N, such as greater than about 6N, such as greater than about 7N, such as greater than about 8N, such as greater than about 10N, such as greater than about 12N. The maximum force is typically less than about 20N. The pressure at which the fluid is released from the injector may generally be greater than about 100 mPa, such as greater than about 150 mPa, such as greater than about 175 mPa, such as greater than about 200 mPa, such as greater than about 225 mPa, such as greater than about 250 mPa, for example particularly about 275 mPa, such as greater than about 300 mPa, such as greater than about 325 mPa, and generally less than about 1,000 mPa.

[0136] characteristics

[0133] The polymer composition of the present disclosure can exhibit excellent mechanical properties. For example, the tensile modulus of the composition or polymer article measured according to ISO test number 527 can be greater than about 7000 MPa, such as greater than about 7200 MPa, such as greater than about 7500 MPa, and generally less than about 15,000 MPa, such as less than about 10,000 MPa.

[0137] The stress at break of the composition may generally be greater than about 100 MPa, such as greater than about 110 MPa, such as greater than about 115 MPa, such as greater than about 120 MPa, and generally less than about 180 MPa. The strain at break may generally be greater than about 2.0%, such as greater than about 2.3%, and generally less than about 4%. The composition has a strain at break of about 6 kJ / m when tested at 23° C. 2 Larger, e.g., about 8 kJ / m 2Larger, e.g., about 9 kJ / m 2 Much larger, typically around 20 kJ / m 2 Less than about 15 kJ / m 2 It can exhibit a Charpy notched impact strength of less than 1000 mm.

[0138]

[0135] The polymer compositions of the present disclosure may exhibit low part ejection force when measured according to the "part ejection test" due to the presence of one or more mold release agents. During the part ejection test, a part molded with a particular dimension is removed from the mold, for example after injection molding. A force transducer is then used to measure the amount of force required to eject the part from the mold. Any suitable force transducer known in the injection molding art may be used. The force transducer may operate with a resolution of at least 0.21 ms / 4800 Hz. The polymer compositions of the present disclosure may exhibit an ejection force of less than about 700 N. The ejection force is generally higher than about 200 N. Figure 3 illustrates the dimensions of a part molded according to the test. The part is molded using a shot weight of 39 grams.

[0139]

[0136] The present disclosure can be better understood with reference to the following examples. EXAMPLES

[0140] The following examples are presented by way of illustration and not by way of limitation. In order to demonstrate some of the benefits and advantages of the present invention, the following experiments were carried out.

[0141] Example 1 Various polymer compositions containing glass fibers and friction modifiers were formulated and tested for friction characteristics and physical properties. Each of the compositions contained polybutylene terephthalate polymer, polyethylene terephthalate polymer, and glass fibers in an amount of 22% by weight. Ultra-high molecular weight silicone was then added to the composition along with the polyester elastomer. Each composition contained talc nucleating agent.

[0142] Four different compositions were formulated. The first composition contained no release agent. The second composition contained a non-polar release agent, the third composition contained a polar release agent, and the fourth composition contained a combination of a non-polar and a polar release agent.

[0143] The following compositions were formulated and tested:

[0144] [Table 1]

[0145] The components of each respective composition were mixed together and mixed using a ZSK 25MC (Werner & Pfleiderer, Germany) twin screw extruder. The configuration of the screws with kneading elements was selected so that effective and thorough mixing of the components occurred. The compositions were extruded and pelletized. The pellets were dried at 120° C. for 4 hours and then injection molded.

[0146]

[0142] The compositions / molds were tested for various tribological and physical properties.

[0143] Stick-slip tests were performed to determine the dynamic coefficient of friction. Stick-slip tests were performed according to VDA230-206. A ball-on-plate configuration was utilized with a load of 30 N, a sliding speed of 8 mm / sec, and a test duration of 1000 cycles.

[0147]

[0144] Compositions formulated according to the present disclosure were formed into plates for dynamic coefficient of friction testing. In the first set of experiments, the compositions were tested against a ball made from polycarbonate and an acrylonitrile butadiene styrene polymer blend (CYCOLOY C1204H from SABIC). The following results were obtained:

[0148] [Table 2]

[0149] The compositions were also tested for physical properties. Tensile properties were tested according to ISO test 527:2012. Notched Charpy impact strength was tested according to ISO test 179-1:2010. Tests were performed using a type A notch (base circle radius of 0.25 mm) and type 1 sample size (length 80 mm, width 10 mm, and thickness 4 mm). Tests were performed at a temperature of 23° C. and the following results were obtained:

[0150] [Table 3]

[0151] The different polymer compositions were also tested for part ejection force according to the part ejection test described above. Sample No. 1 showed a part ejection force of 714 N. Sample No. 2 showed a part ejection force of 852 N. Sample No. 3 showed a part ejection force of 1,087 N. Sample No. 4 showed a part ejection force of 679 N. The different formulations were also subjected to a mold deposit study. The mold deposits were observed after 5,000 molding shots. A disk was molded during each shot. The amount of mold deposits was observed and ranked according to a ranking system of 1, 2, or 3, where 3 represents the most mold deposits and a ranking of 1 indicates that there was no or only little scratchable material inside the mold. Sample No. 1 showed a ranking of 3, sample No. 2 showed a ranking of 2, while sample Nos. 3 and 4 showed only a ranking of 1.

[0152]

[0147] Sample No. 4 above was further tested for creep performance and stability after gamma radiation exposure. Creep was measured at 20 MPa, 40 MPa, and 60 MPa for 1000 hours at 23° C. The following results were obtained:

[0153] [Table 4]

[0154] As shown, the composition exhibits a creep modulus of greater than about 5000 MPa, such as greater than about 5200 MPa, such as greater than about 5400 MPa, such as greater than about 5600 MPa, such as greater than about 5800 MPa, and less than about 7000 MPa when tested at 20 MPa. As shown, the composition exhibits a creep modulus of greater than about 4300 MPa, such as greater than about 4400 MPa, such as greater than about 4500 MPa, such as greater than about 4600 MPa, such as greater than about 4700 MPa, and less than about 6500 MPa when tested at 40 MPa. The composition exhibits a creep modulus of greater than about 3500 MPa, such as greater than about 3700 MPa, such as greater than about 3900 MPa, such as greater than about 4000 MPa, such as greater than about 4100 MPa, and less than about 6000 MPa when tested at 60 MPa.

[0155]

[0150] Test specimens made from sample number 4 were exposed to different levels of gamma radiation and then tested for tensile properties. The following results were obtained:

[0156] [Table 5]

[0157] As shown, the compositions were extremely stable even after exposure to high levels of energy, as shown above, the tensile modulus decreased by less than about 5%, such as less than about 3%, such as less than about 2%, and even less than about 1% after a gamma radiation dose of 150 kGy.

[0158] Example 2 A variety of different polymer compositions were formulated and tested for physical properties. The following compositions were formulated and tested:

[0159] [Table 6]

[0160] [Table 7]

[0161]

[0153] Samples Nos. 9 and 11 above exhibit superior physical properties compared to other samples. In addition, these samples are formulated to produce polymer compositions with improved melt processing properties for the purpose of reducing mold cycle times.

[0162]

[0154] These and other modifications and variations to the present invention may be implemented by those skilled in the art without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it is to be understood that aspects of the various embodiments may be interchanged in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention as further set forth in the appended claims. [Explanation of symbols]

[0163] 20 Inhaler 22 Housing 24 Mouthpiece 26 Plunger 30 Medical Injector 32 Housing 34 Plunger

Claims

1. Thermoplastic polymers; at least one of a friction modifier or a nucleating agent; Optionally, reinforcing fibers present in the polymer composition in an amount of about 5% to about 55% by weight; and At least one release agent A polymer composition comprising: The polymer composition above, wherein the at least one release agent comprises a polar release agent comprising an oxidized wax.

2. 10. The polymer composition of claim 1, wherein the polymer composition contains a plurality of release agents including a second release agent, the second release agent comprising a non-polar polymer, each release agent being present in the polymer composition in an amount of less than about 4 weight percent, and the weight ratio of the polar release agent to the second release agent is from about 10:1 to about 1:

10.

3. The polymer composition of claim 1 , wherein the thermoplastic polymer comprises a polyester polymer.

4. The polymer composition of claim 1 , wherein the thermoplastic polymer comprises a polybutylene terephthalate polymer.

5. The polymer composition of claim 1 , wherein the thermoplastic polymer comprises a polyoxymethylene polymer.

6. The polymer composition of any one of claims 1 to 5, wherein the polar release agent comprises a modified polyolefin.

7. The polymer composition of claim 6 , wherein the polyolefin comprises polyethylene.

8. The polymer composition of any one of claims 1 to 5, wherein the polar release agent comprises an oxidized polyethylene wax or a polyolefin polymer modified with maleic anhydride groups.

9. The polymer composition of claim 2 , wherein the non-polar polymer comprises a polyolefin polymer.

10. 10. The polymer composition of claim 9, wherein the non-polar polymer comprises a polyethylene wax.

11. The polymer composition of any one of claims 1 to 5, 9 and 10, wherein the polar release agent has an acid number of from about 10 KOH / g to about 25 KOH / g.

12. The polymer composition of any one of claims 1 to 5, 9 and 10, wherein the polar release agent has an acid number of about 30 KOH / g to about 75 KOH / g, such as an acid number of about 40 KOH / g to about 60 KOH / g.

13. The polymer composition of any one of claims 1 to 5, wherein the polar release agent comprises an oxidized ester of a fatty acid.

14. 14. The polymer composition of claim 13, wherein the oxidized esters of fatty acids are formed from at least 50% by weight of fatty acids having carbon chain lengths of from about 20 carbon atoms to about 40 carbon atoms.

15. 14. The polymer composition of claim 13, wherein the oxidized esters of fatty acids are formed from at least 25% by weight of fatty acids having carbon chain lengths of from about 40 carbon atoms to about 64 carbon atoms.

16. 3. The polymer composition of claim 2, wherein the polar polymer and the non-polar polymer are each present in the polymer composition in an amount less than about 2 wt%, such as less than about 1 wt%, such as less than about 0.8 wt%, such as less than about 0.5 wt%, such as less than about 0.4 wt%, and generally greater than 0.01 wt%.

17. 4. The polymer composition of claim 3, wherein the polymer composition contains the friction modifier, the friction modifier comprising ultra high molecular weight silicone and present in the polymer composition in an amount of about 0.1 wt % to about 10 wt %, for example about 0.5 wt % to about 3 wt %.

18. 18. The polymer composition of claim 17, wherein the ultra-high molecular weight silicone is polydimethylsiloxane.

19. 18. The polymer composition of claim 17, wherein the polyester polymer is present in the composition in an amount of about 50% to about 90% by weight, the polymer composition contains reinforcing fibers, the reinforcing fibers comprising glass fibers and are present in the polymer composition in an amount of about 5% to about 30% by weight, and the ultra high molecular weight silicone is present in the composition in an amount of about 0.5% to about 5% by weight.

20. The polymer composition according to any one of claims 1 to 5, 9, 10, and 16 to 19, wherein all polymer components contained in the polymer composition comply with the standards of the US Food and Drug Administration as listed in 21 CFR177.

21. The polymer composition of any one of claims 1 to 5, 9, 10, and 16 to 19, wherein the polymer composition further comprises an inorganic nucleating agent.

22. 22. The polymer composition of claim 21, wherein the inorganic nucleating agent comprises talc, and the talc is present in the polymer composition in an amount of about 0.01% to about 1% by weight.

23. 20. The polymer composition of any one of claims 1 to 5, 9, 10, and 16 to 19, exhibiting an adhesion force of less than about 700 N when tested according to the Part Emission Test.

24. 3. The polymer composition of claim 1 or 2, exhibiting a dynamic coefficient of friction of less than about 0.08 when tested according to VDA 230-206 against polycarbonate and acrylonitrile butadiene styrene blends at a speed of 8 mm / sec and a load of 30 N after 1,000 cycles.

25. 20. The polymer composition of claim 17 or 19, wherein the composition further comprises a carrier polymer for the ultra-high molecular weight silicone, the carrier polymer comprising a polycarbonate polymer, a polyester elastomer, a polyethylene terephthalate polymer, and / or a copolyester.

26. 10. The polymer composition of claim 1, wherein the polymer composition contains reinforcing fibers, the reinforcing fibers comprising glass fibers, the glass fibers being present in the polymer composition in an amount of about 5% to about 50% by weight.

27. A molded article made from the polymer composition of claim 1.

28. 28. The molded article of claim 27, wherein the molded article comprises a syringe for dispensing a liquid medicament, the syringe comprising a needle having a bore size of about 0.08 mm to about 0.25 mm, and the syringe comprising a spring member that dispenses a predetermined dose of medicament with a maximum force of greater than about 3 N.

29. 19. An apparatus comprising a first slide member operatively associated with a second slide member, the first slide member and the second slide member configured to remain in contact and move relative to one another, and at least one of the slide members comprising a molded polymeric article made from the polymer composition of any one of claims 1-5, 9, 10, 16-19, and 26.

30. 30. The apparatus of claim 29, wherein the first slide member and the second slide member are both made from the polymer composition of any one of claims 1-5, 9, 10, 16-19, and 26.

31. 30. The apparatus of claim 29 comprising a medical device.

32. 32. The apparatus of claim 31 , wherein the medical device comprises an inhaler, an infusion device, a surgical instrument, or a wearable device.

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