Polymer Compositions Suitable for Electrostatic Discharge Applications

Abstract

A polyaryl ether composition (C) comprising at least one poly(aryl ether ketone) polymer ("PAEK polymer"), at least one poly(biphenyl ether sulfone) polymer ("PPSU polymer") and / or polyether sulfone ("PES polymer"), at least one conductive fibrous carbon-based filler ("component B1"), and at least one conductive particulate carbon-based filler ("component B2"). An article, particularly for electrostatic dissipation applications, such as a substrate carrier, comprising the polyaryl ether composition (C). The polymer composition is suitable for electrostatic discharge applications.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to reinforced polyarylether compositions and articles comprising or made therefrom that are particularly suitable for electrostatic discharge applications. [Background technology]

[0002] Conductive thermoplastic polymer compositions are known to be applicable for protection against electrostatic discharge (ESD). These specialized polymer compositions are generally tailored to span the surface resistivity spectrum and can often be formulated for injection molding or extrusion processes.

[0003] Several techniques are available to impart conductive properties to otherwise inherently insulating thermoplastics, providing the precise degree of conductivity required for ESD protection. Among other things, conductive fillers can be added to thermoplastic polymers.

[0004] Fine-sized conductive fillers, such as chopped or crushed carbon fibers, are known to be one of the most important filler materials.

[0005] For example, U.S. Pat. No. 5,820,788 discloses an antistatic polymer containing a mixture of a thermoplastic resin and about 8-20% by weight of electrically conductive, partially carbonized, chopped linear carbonaceous fibers having a carbon content of about 70-85%, which is 10 4 ~10 10 Static control materials and structures can further be provided with surfaces having controlled surface resistivities in the ohm / sq range.

[0006] Mold shrinkage is the shrinkage of a polymer as it cools after the molding process. It is typically used to properly machine injection molds to ensure the final part dimensions are as desired. Therefore, there remains a need to optimize conductive thermoplastic polymer compositions to improve the mold shrinkage of filled ESD polymer materials by using standard conductive carbon fillers with higher carbon content. Summary of the Invention

[0007] Therefore, the first object of the present invention is to at least one poly(aryl ether ketone) polymer (hereinafter "PAEK polymer"); at least one poly(biphenyl ether sulfone) polymer (hereinafter "PPSU polymer") and / or polyether sulfone (hereinafter "PES polymer"); At least one conductive fibrous carbon-based filler (hereinafter referred to as "component B1"), at least one conductive particulate carbonaceous filler (hereinafter referred to as "component B2"); The present invention relates to a polyaryl ether composition (C) comprising:

[0008] Another object of the present invention is to provide an article comprising or made from said polyaryl ether composition (C), said article having a molecular weight of 1.10 +5 Ω.cm ~ 5·10 max +12 The article has a volume resistivity measured according to ASTM D257 up to Ω.cm.

[0009] Applicant has found that the polyarylether composition (C) of the present invention, as detailed herein, is effective in improving the mold shrinkage of filled ESD polymer materials, by virtue of the blending of PAEK, PPSU polymer and / or PES polymer with Component B1 and Component B2, without sacrificing mechanical performance. DETAILED DESCRIPTION OF THE INVENTION

[0010] The polyaryl ether composition (C) according to the present invention comprises: - 40% to 90% by weight of PAEK polymers and PPSU polymers and / or PES polymers taken together, - 10% to 60% by weight of components B1 and B2 taken together may include The weight percentages are based on the total weight of the polyaryl ether composition (C).

[0011] The polyaryl ether composition (C) according to the present invention comprises: - 50% to 80% by weight of PAEK polymers and PPSU polymers and / or PES polymers taken together, - 20% to 50% by weight of components B1 and B2 taken together may include The weight percentages are based on the total weight of the polyaryl ether composition (C).

[0012] The polyaryl ether composition (C) according to the present invention comprises: - 60% to 80% by weight of PAEK polymers and PPSU polymers and / or PES polymers taken together, - 20% to 40% by weight of components B1 and B2 taken together may include The weight percentages are based on the total weight of the polyaryl ether composition (C).

[0013] The polyaryl ether composition (C) according to the present invention comprises: - at least 30% by weight and at most 50% by weight of a PAEK polymer, - at least 20% by weight and at most 40% by weight of PPSU polymers and / or PES polymers, - at least 5% by weight and at most 25% by weight of component B1, - at least 5% by weight and at most 25% by weight of component B2; may include The weight percentages are based on the total weight of the polyaryl ether composition (C).

[0014] The polyaryl ether composition (C) according to the present invention comprises: - at least 35% by weight and at most 45% by weight of a PAEK polymer, - at least 25% by weight and at most 35% by weight of PPSU polymers and / or PES polymers, - at least 10% by weight and at most 20% by weight of component B1, - at least 10% by weight and at most 20% by weight of component B2; may include The weight percentages are based on the total weight of the polyaryl ether composition (C).

[0015] The polyarylether composition (C) according to the present invention may further comprise optional additives, generally not exceeding 10% by weight, based on the total weight of composition (C). The combined weight of the at least one PAEK polymer, the PPSU polymer and / or the PES polymer, component B1, component B2, and the optional additives is not more than 100% by weight of composition (C).

[0016] Some polyarylether compositions (C) according to the present invention may exclude a PES polymer. In such cases, the polyarylether composition (C) comprises a PAEK polymer, a PPSU polymer, and components B1 and B2, but does not comprise a PES polymer. Thus, any disclosure referring to "PPSU polymer and / or PES polymer," such as their weight contents and ranges in composition (C) as provided herein, is equally applicable to polyarylether compositions (C) of the present invention in which a PPSU polymer is present and a PES polymer is absent.

[0017] Poly(aryl ether ketone) (PAEK) As previously mentioned, the polyaryl ether composition (C) comprises at least one PAEK polymer.

[0018] For purposes of the present invention, the term "poly(aryl ether ketone)" or "PAEK" refers to a polymer having more than 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt% repeat units of the following formulae (I)-(V): [ka] (In the formula: Ar is independently a divalent aromatic group selected from phenylene, biphenylene, or naphthylene; X is independently O, C(═O) or a direct bond; n is an integer from 0 to 3; b, c, d and e are 0 or 1; a is an integer from 1 to 4, - preferably, when b is 1, d is 0) is intended to mean any polymer in which one or more repeating units (R1) of

[0019] The repeating unit (R1) may be, inter alia: [ka] [ka] may be selected from:

[0020] Preferably, the repeating unit (R1) is [ka] is selected from.

[0021] More preferably, the repeating unit (R1) is [ka] is.

[0022] For the purposes of the present invention, polyetheretherketone (PEEK polymer) is intended to mean any polymer of which more than 50% by weight of repeating units are repeating units (R1) of formula (VII). Preferably, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% by weight of the repeating units of the PEEK polymer are repeating units (R1) of formula (VII). Even more preferably, the repeating units of the PEEK polymer are essentially all repeating units (R1) of formula (VII). Most preferably, all repeating units of the PEEK polymer are repeating units (R1) of formula (VII).

[0023] Preferably, the PAEK used for the present invention is not sulfonated.

[0024] Excellent results are obtained when the PAEK polymer is a polyetheretherketone homopolymer, i.e., a polymer in which essentially all, if not all, of its repeat units are of formula (VII). Non-limiting examples of suitable commercially available PEEK homopolymers are VICTREX® PEEK manufactured by Victrex Manufacturing Ltd., KETASPIRE® PEEK manufactured by Solvay Specialty Polymers, and Zypeek® manufactured by Jilin Joint Polymer Co., Ltd.

[0025] The PAEK polymer may have an intrinsic viscosity (IV) of at least 0.50 dl / g, preferably at least 0.60 dl / g, and more preferably at least 0.70 dl / g, as measured in 95-98% sulfuric acid (d=1.84 g / ml) at a PAEK concentration of 0.1 g / 100 ml.

[0026] PAEK polymers, e.g., PEEK polymers, have a melting point of 400°C and 1000s as measured using a capillary rheometer according to ASTM D3835. -1PAEK polymers, such as PEEK polymers, may have melt viscosities as high as 0.25 kPa-s, but preferably less than 0.20 kPa-s, and most preferably less than 0.18 kPa-s, at shear rates of 1000 rpm. PAEK polymers, for example PEEK polymers, may have melt viscosities as low as 0.05 kPa-s.

[0027] PAEK polymers, for example, PEEK polymers, have a modulus of elasticity (V) at 400°C and 1000 s as measured using a capillary rheometer according to ASTM D3835 in the range of about 0.05 kPa-s to about 0.25 kPa-s, preferably about 0.06 kPa-s to about 0.20 kPa-s, preferably about 0.07 kPa-s to about 0.18 kPa-s, preferably about 0.08 kPa-s to about 0.15 kPa-s. -1 The melt viscosity at a shear rate of

[0028] As the capillary rheometer, a Kayeness Galaxy V Rheometer (Model 8052 DM) can be used.

[0029] PAEK polymers, such as PEEK polymers, can be prepared by any method.

[0030] One method known in the art involves reacting a substantially equimolar mixture of at least one bisphenol with at least one dihalobenzoid compound or at least one halophenol compound, as described in Canadian Patent No. 847,963. Non-limiting examples of bisphenols useful in such a process include hydroquinone, 4,4'-dihydroxyphenyl, and 4,4'-dihydroxybenzophenone; non-limiting examples of dihalobenzoid compounds useful in such a process include 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 4-chloro-4'-fluorobenzophenone; non-limiting examples of halophenol compounds useful in such a process include 4-(4-chlorobenzoyl)phenol and (4-fluorobenzoyl)phenol. Thus, PEEK homopolymers can be produced by a nucleophilic process, as described, for example, in U.S. Patent No. 4,176,222, the entire contents of which are incorporated herein by reference.

[0031] Another method known in the art for producing PEEK homopolymer involves electrophilically polymerizing phenoxyphenoxybenzoic acid in the presence of a condensing agent using an alkane sulfonic acid as a solvent, such as the process described in U.S. Patent No. 6,566,484, the entire contents of which are incorporated herein by reference. Other poly(aryl ether ketones) can be produced by the same method starting from monomers other than phenoxyphenoxybenzoic acid, such as those described in U.S. Patent Application Publication No. 2003 / 0130476, the entire contents of which are also incorporated herein by reference.

[0032] The polyaryl ether composition (C) can comprise one and only one PAEK polymer. Alternatively, it can comprise two, three, or even four or more PAEK polymers. Particularly preferred mixtures of PAEK polymers include those in which (i) more than 50 wt. % of their repeating units, preferably essentially all of their repeating units, and even more preferably all of their repeating units, are of the formula [ka] and at least one poly(aryl ether ketone) (PAEK)-a, (ii) more than 50% by weight of its repeating units, preferably essentially all of the repeating units, and even more preferably all of the repeating units, are of the formula [ka] and optionally additionally (iii) at least one other poly(aryl ether ketone) (PAEK)-c different from poly(aryl ether ketone) (PAEK)-a and (PAEK)-b; in particular mixtures consisting of (i) at least one poly(aryl ether ketone) (PAEK)-a whose repeat units are essentially all, if not all, of formula (VII) and (ii) at least one poly(aryl ether ketone) (PAEK)-b whose repeat units are essentially all, if not all, of formula (IX); and even more in particular binary mixtures consisting of (i) one poly(aryl ether ketone) (PAEK)-a whose repeat units are all of formula (VII) and (ii) one poly(aryl ether ketone) (PAEK)-b whose repeat units are all of formula (IX).

[0033] The amount of PAEK polymer is at least 40% by weight, preferably at least 41% by weight, or at least 42% by weight, or at least 43% by weight, or at least 44% by weight, or at least 45% by weight, or at least 47% by weight, or at least 49% by weight, or at least 55% by weight, or at least 55% by weight and / or less than 89% by weight, preferably at most 88% by weight, or at most 87% by weight, or at most 86% by weight, or at most 85% by weight, or at most 80% by weight, or at most 79% by weight, or at most 78% by weight, or at most 75% by weight, based on the total weight of the polyaryl ether composition (C).

[0034] Poly(biphenyl ether sulfone) polymer (PPSU polymer) For purposes of the present invention, a poly(biphenyl ether sulfone) is one in which at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of its repeating units are [ka] It is intended to mean a polycondensation polymer in which the repeating units (R2) are selected from:

[0035] The mole percent is based on the total moles of repeat units in the poly(biphenyl ether sulfone) polymer.

[0036] The use of repeating units of formula (2) in repeating units (R2) generally provides the best overall cost-property balance and the highest level of toughness. For the purposes of the present invention, polyphenylsulfone is intended to mean any polycondensation polymer of which at least 50% by weight of repeating units are repeating units (R2) of formula (2).

[0037] The poly(biphenyl ether sulfone) (PPSU polymer) may be, inter alia, a homopolymer, a random, alternating or block copolymer.

[0038] When the poly(biphenyl ether sulfone) (PPSU polymer) is a copolymer, its repeating units may be, inter alia, (i) repeating units (R2) of at least two different formulae selected from formulae (2) to (6), or (ii) repeating units (R2) of one or more formulae (2) to (6) (in particular, repeating units of formula (2)) and repeating units (R2*) different from repeating units (R2), such as: [ka] It can consist of, etc.

[0039] Preferably, greater than 70 mole %, more preferably greater than 85 mole %, of the repeat units of the poly(biphenyl ether sulfone) (PPSU polymer) are repeat units (R2) of formula (2), where mole % is based on the total number of moles of repeat units in the poly(biphenyl ether sulfone) polymer. Even more preferably, essentially all of the repeat units of the poly(biphenyl ether sulfone) (PPSU polymer) are repeat units (R2) of formula (2). Most preferably, all of the repeat units of the poly(biphenyl ether sulfone) (PPSU polymer) are repeat units (R2) of formula (2).

[0040] Excellent results are generally obtained when the poly(biphenyl ether sulfone) (PPSU polymer) is a polyphenylsulfone homopolymer, i.e., a polymer whose repeating units are essentially all, if not all, of formula (2). RADEL® polyphenylsulfone, manufactured by Solvay Specialty Polymers USA, LLC, is an example of a polyphenylsulfone homopolymer.

[0041] Poly(biphenyl ether sulfone) (PPSU polymer) can be prepared by any method, including those well known in the art, such as those described in U.S. Patent Nos. 3,634,355; 4,008,203; 4,108,837; and 4,175,175, the entire contents of which are incorporated herein by reference.

[0042] The polyaryl ether composition (C) can comprise one and only one poly(biphenyl ether sulfone) (PPSU polymer), or it can comprise two, three, or even four or more poly(biphenyl ether sulfone)s (PPSU polymers).

[0043] Polyethersulfone (PES polymer) For purposes of the present invention, a polyethersulfone (PES polymer) is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of a polymer having formula (J): [ka] Repeating units (R PES ) is meant any polymer containing

[0044] The mole % is based on the total moles of repeat units in the PES polymer.

[0045] PES polymers can be prepared by known methods, such as the condensation of bisphenol S with dichlorodiphenol sulfone, and are available as VERADEL® PESU from Solvay Specialty Polymers USA, LLC, among others.

[0046] When poly(biphenyl ether sulfone) (PPSU polymer) or polyether sulfone (PES polymer) is present in the polyaryl ether composition (C), the weight of the PAEK polymer is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight and / or at most 90% by weight, preferably at most 80% by weight, based on the combined weight of the PAEK polymer and the PPSU polymer / PES polymer in the polyaryl ether composition (C).

[0047] Some polyarylether compositions (C) according to the present invention may be free of PES polymers.

[0048] Carbon-based fillers For purposes of the present invention, the term "carbonaceous filler" is intended to include graphitized, partially graphitized and non-graphitized carbon reinforcing fillers or any mixtures thereof.

[0049] The term "graphitized" is intended to mean a carbon filler obtained by high-temperature pyrolysis (above 2000° C.) of a carbon filler in which the carbon atoms are arranged similarly to the graphite structure.

[0050] Carbon-based fillers useful in the present invention can be advantageously obtained by heat treatment and pyrolysis of different polymer precursors, such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamides or phenolic resins; carbon fillers useful in the present invention can also be obtained from pitch materials.

[0051] Carbon-based fiber fillers useful in the present invention are preferably selected from the group consisting of PAN-based carbon fillers, pitch-based carbon fillers, graphitized pitch-based carbon fillers, and mixtures thereof.

[0052] The carbon-based fillers useful in the present invention may be metallized, however, the carbon-based fillers useful in the present invention are preferably non-metallized.

[0053] Fibrous fillers are considered herein to be three-dimensional materials having a length, width, and thickness, with the average length being significantly greater than both the width and thickness. Generally, such materials have an aspect ratio, defined as the ratio between the average length and the maximum of the average width and thickness, of at least 5, at least 10, at least 20, or at least 50.

[0054] Conductive fibrous carbon filler (component B1) Component B1 in polyaryl ether composition (C) is a fibrous filler having an elemental carbon purity of more than 85%, with the remainder consisting of possible residual impurities. Preferably, component B1 contains at least 90% elemental carbon, more preferably at least 95% elemental carbon. Good results are obtained when the elemental carbon purity is greater than 85% and less than 99%. In some embodiments, component B1 consists essentially of elemental carbon.

[0055] In some embodiments, component B1 is a fibrous filler having a purity of less than 70% elemental carbon, with the remainder consisting of optional residual impurities. Preferably, component B1 contains at most 65% elemental carbon, more preferably at most 60% elemental carbon.

[0056] Component B1 is a fibrous filler having an average length of 1 to 20 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm, even more preferably 3 to 6 mm.

[0057] Component B1 is generally a fibrous filler having an equivalent diameter of 1 to 20 μm, preferably 2 to 15 μm, more preferably 3 to 10 μm, and most preferably 6 to 8 μm.

[0058] Component B1 represents at least 1 wt. %, preferably at least 5 wt. %, more preferably at least 10 wt. % and / or at most 50 wt. %, preferably at most 40 wt. %, more preferably at most 30 wt. %, based on the total weight of the polyaryl ether composition (C).

[0059] Preferably, component B1 has an electrical resistivity of 1.0 to 30 μΩ.m, preferably 2.0 to 20 μΩ.m, more preferably 10 to 20 μΩ.m.

[0060] Advantageously, chopped carbon fibers are present in the polyaryl ether composition (C) as component B1. Chopped carbon fibers are commercially available, inter alia, from Teijin (e.g., PSC171100 Chopped carbon fibers, 3 μm, etc.) and Procotex (e.g., APPLY CARBON chopped Carbon Fibers CF.OS.U1-6MM, etc.).

[0061] Conductive fine carbonaceous filler (component B2) Advantageously, comminuted carbon fibers are present in the polyaryl ether composition (C) as component B2.

[0062] Excellent results are obtained when the ground carbon fiber is a pitch-based carbon fiber.

[0063] Preferably, the pulverized carbon fibers are pitch-based carbon fibers having an average length of 0.01 to 2 mm, preferably 0.1 to 1 mm, more preferably 0.2 to 0.8 mm.

[0064] Preferably, the pulverized carbon fibers are pitch-based carbon fibers having an average diameter of 5 to 50 μm, preferably 10 μm to 30 μm, more preferably 10 μm to 15 μm.

[0065] The pitch-based carbon fibers are commercially available, inter alia, from Osaka Gas Chemical (OGC). In some embodiments, the comminuted carbon fibers are PAN-based carbon fibers. PAN-based carbon fibers advantageously have a diameter of 3 to 20 μm, preferably 4 to 15 μm, more preferably 5 to 10 μm, and most preferably 6 to 8 μm. Good results have been obtained with PAN-based carbon fibers (PAN-CF) having a diameter of 7 μm.

[0066] Other suitable milled carbon fibers have an average monofilament diameter of 7 microns, a median length of 80 to 250 microns, and a thickness of 15.10 microns. -4 Ω.cm~Maximum 20·10 -4 It is available commercially as CF.LS-MLD80 to CF.LS-MLD250 from Procotex with volume resistivities up to Ω.cm.

[0067] The conductive particulate carbonaceous filler (component B2) is present in an amount of at least 1 wt. %, preferably at least 10 wt. %, more preferably at least 15 wt. % and / or at most 40 wt. %, preferably at most 30 wt. %, more preferably at most 20 wt. %, based on the total weight of the polyaryl ether composition (C).

[0068] Preferably, component B2 has a volume resistivity of about 5.0 to 100 μΩ.m, preferably 10.0 to 50 μΩ.m, more preferably 15 to 45 μΩ.m.

[0069] Preferably, the combined weight of components B1 and B2 is more than 10 wt.-%, or at least 20 wt.-%, or at least 25 wt.-% and / or at most 50 wt.-%, preferably at most 40 wt.-%, more preferably at most 35 wt.-%, based on the total weight of polyarylether composition (C).

[0070] Advantageously, the weight of the comminuted carbon fibre is greater than 50% by weight, based on the combined weight of the comminuted and chopped carbon fibre in the composition.

[0071] When component B1 and component B2 are present in the polyaryl ether composition (C), the PAEK is preferably not crosslinked to component B1 and / or component B2.

[0072] Optional Additives In some embodiments, the polyaryl ether composition (C) according to the present invention comprises an additive selected from the group consisting of ultraviolet (“UV”) stabilizers, heat stabilizers, pigments, dyes, flame retardants, impact modifiers, lubricants, nucleating agents, antioxidants, processing aids, and any combination of one or more thereof.

[0073] In some embodiments where the polyaryl ether composition (C) includes optional additives, the total concentration of the additives is 15 wt% or less, 10 wt% or less, 5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, or 0.1 wt% or less.

[0074] One or more pigments may be particularly desirable additives in composition (C) for producing white, black, or colored articles. The pigments may be black pigments such as carbon black, white pigments such as zinc oxide, zinc sulfide, lithopone, antimony white, and titanium dioxide (rutile or anatase, preferably rutile), and / or colored pigments. The pigments are generally present in an amount of 0 to 6% by weight, preferably 0.05 to 5% by weight, and particularly 0.1 to 3% by weight, based on the total weight of polyaryl ether composition (C).

[0075] Antioxidants can be particularly desirable additives in the polyaryl ether composition (C). Antioxidants can improve the thermal stability and light stability of the polyaryl ether composition (C). For example, antioxidants that are thermal stabilizers can improve the thermal stability of the composition during manufacturing (or in high-temperature application settings) by, for example, helping to prevent polymer degradation while making the polymer processable at high temperatures.

[0076] Method for producing polyaryl ether composition (C) The polyaryl ether composition (C) according to the present invention can be prepared using methods well known in the art.

[0077] For example, the polyaryl ether composition (C) is produced by melt blending at least one PAEK polymer, a PPSU polymer and / or a PES polymer, a conductive fibrous carbon-based filler (component B1), a conductive particulate carbon-based filler (component B2), and any optional components or additives. Any suitable melt blending method can be used to combine the components of the polyaryl ether composition (C). For example, all of the components can be fed into a melt mixer, such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a Banbury mixer. The components can be added to the melt mixer all at once or gradually in batches. When the components are added gradually in batches, a portion of the components is added first and then melt mixed with the remaining portion of the components, which are then added until a properly mixed composition is obtained.

[0078] Goods As mentioned above, another aspect of the present invention further relates to articles, preferably shaped articles, comprising or made from said polyaryl ether composition (C).

[0079] The polyaryl ether composition (C), as detailed above, can be processed by conventional melt processing techniques, such as extrusion, injection molding, and compression molding, among others, to provide shaped articles.

[0080] Such items are 1·10 +5 Ω.cm ~ 5·10 max +12 It has a volume resistivity, measured according to ASTM D257, of up to Ω.cm.

[0081] The item must be at least 10 6 and at most 10 9 It was found to have a surface resistivity of Ω / sq.

[0082] Volume resistivity is the resistance to leakage current through the body of an insulating material. Surface resistivity is the resistance to leakage current along the surface of an insulating material.

[0083] The articles have been found to have a flow molding shrinkage based on method ASTM D955 of at most 0.60%, at most 0.50%, preferably 0.10-0.60%, or more preferably 0.10-0.25%, and / or a transverse molding shrinkage based on method ASTM D955 of at most 0.8%, preferably 0.1-0.6%, more preferably 0.2-0.5%.

[0084] In a preferred embodiment, the ratio of flow molding shrinkage to lateral molding shrinkage is 1:1 to 1:2.5, preferably 1:1 to 1:2.

[0085] As used herein, the term "mold shrinkage" refers to the shrinkage of a polymer as it cools after the molding process. It is typically used to properly machine an injection mold so that the final part dimensions are as desired. Flow mold shrinkage refers to mold shrinkage in the flow direction. Transverse mold shrinkage (or cross-flow mold shrinkage) refers to mold shrinkage in the transverse (cross-flow) direction.

[0086] Shaped articles according to the present invention are preferably selected from the group consisting of: (i) extruded shapes, preferably selected from the group consisting of rods, slabs, tubing, pipes or profiles; and (ii) injection molded articles.

[0087] According to certain embodiments, the shaped article is in the form of a substantially two-dimensional article, such as a film, sheath, or sheet, such as a part in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length).

[0088] According to other embodiments, the shaped article is provided as a three-dimensional part, e.g., in the form of a complex-shaped part having concave or convex portions, possibly including undercuts, inserts, etc., e.g., substantially spanning three dimensions of space in a similar manner.

[0089] The polyaryl ether composition (C) can be used to manufacture electrostatic dissipative articles, such as, but not limited to, substrate carriers, including, but not limited to, wafer carriers, reticle pods, shippers, chip trays, test sockets, head trays (read and / or write); fluid tubing, chemical containers, and the like.

[0090] Shaped articles may include, but are not limited to, portions or all of reticle carriers such as those illustrated in U.S. Pat. Nos. 6,513,654 and 6,216,873; disc shippers such as those illustrated in U.S. Pat. Nos. 4,557,382 and 5,253,755; chip trays such as those illustrated in U.S. Pat. No. 6,857,524; and wafer carriers such as those illustrated in U.S. Pat. No. 6,848,578; each of these references is hereby incorporated by reference in its entirety into this application.

[0091] According to a particular embodiment, a shaped article made from the polyaryl ether composition (C), as detailed above, is provided as a component of an electrostatic discharge (ESD) protection device, which may be designed, for example, to be connected to a semiconductor wafer intended for chip manufacturing. [Example]

[0092] The present invention will now be described in connection with the following examples, the purposes of which are merely illustrative and not intended to limit the scope of the invention. As used in the examples, "E" refers to an example embodiment of the invention, and "CE" refers to a counterexample.

[0093] material PEEK: Ketaspire® KT-880P manufactured by Solvay Specialty Polymers PPSU: Radel® R-5900 from Solvay Specialty Polymers Component B1: Teijin PSC171100 3-mm chopped carbon fibers Component B2: DONACARBO S-2415, a pitch-based carbon fiber powder manufactured by OGC Optional additive: Zinc oxide "Zinkoxyd aktiv" from Lanxess

[0094] Test Method Tensile properties - ISO527 Tensile modulus, tensile strength, and elongation at break were measured on five injection molded ISO Type 1a tensile specimens (total length = 170 mm, gauge length = 50 mm, test section width = 10 mm, and thickness = 4 mm). Impact strength - ISO180 Notched and unnotched Izod impact strength properties were measured using ten injection-molded ISO Type 1A specimens (80±2 mm long, 10±0.2 mm wide, 4±0.2 mm thick) in kJ / m 2 Measured in units. Mold shrinkage - ISO294 (ASTM D955) The mold shrinkage (flow direction mold shrinkage (%) and transverse direction mold shrinkage (%)) was measured on five injection molded plaques of dimensions 60 mm width x 60 mm length x 2 mm thickness. Volume and Surface Resistivity - ASTM D257 Volume and surface resistivities were measured on five injection molded plaques measuring 4 inches x 4 inches x 1 / 8 inch (length x width x thickness) or 60 mm x 60 mm x 2 mm (length x width x thickness).

[0095] Example 1 Resin, filler, and additives were fed into a ZSK-26 mm co-rotating twin screw extruder using gravimetric feeders adjusted for each run to achieve the target blend ratios in Table 1.

[0096] Compounding conditions for all blends and controls are shown in Table 2. Extruder set points were the same for all runs.

[0097] The prepared compositions were then processed into shaped articles by injection molding according to ASTM D3641.

[0098] [Table 1]

[0099] [Table 2]

[0100] Comparative Example 2 The components for preparing sample CE2 are listed in Table 1.

[0101] The composition and shaped article of Comparative Example 2 were prepared in the same manner as in Example 1.

[0102] Comparative Example 3 The components for preparing sample CE3 are listed in Table 1.

[0103] The composition and shaped article of Comparative Example 3 were prepared in the same manner as in Example 1.

[0104] As shown by the results in Table 3, composition E1 according to the present invention was effective in optimizing mold shrinkage of the article, reducing the flow and lateral mold shrinkage to 0.24% and 0.47%, respectively, compared to the higher flow and lateral mold shrinkage of the CE2 sample without PPSU (0.28% and 0.81%, respectively). Due to composition E1, the difference between flow and lateral mold shrinkage is smaller compared to the CE2 sample.

[0105] Composition E1 was effective in optimizing mold shrinkage of the article, reducing the lateral mold shrinkage to 0.47% compared to the higher lateral mold shrinkage (0.83%) of the CE3 sample, which contained only component B2 and no PPSU. Due to composition E1, the difference between flow mold shrinkage and lateral mold shrinkage is smaller compared to the CE3 sample.

[0106] [Table 3]

[0107] The disclosures of all patent applications and publications cited herein, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein, are hereby incorporated by reference. In the event that the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the statement of this application to the extent that a term may be unclear, the statement shall control. Any incorporation by reference of a public document is limited so that no subject matter contrary to the express disclosure herein is incorporated.

[0108] While preferred embodiments of the present invention have been shown and described, modifications thereof can be made by those skilled in the art without departing from the teachings of the present invention. The embodiments described herein are illustrative only and not limiting. Many variations and modifications of the compositions, articles, and methods are possible and within the scope of the present invention. Accordingly, the scope of protection is not limited by the description set forth above, but only by the claims that follow, which scope encompasses all equivalents of the subject matter of the claims. Each and every claim is incorporated herein by reference as an embodiment of the present invention. Accordingly, the claims are further explanations and additions to the preferred embodiments of the present invention.

Claims

1. at least one poly(aryl ether ketone) polymer (“PAEK polymer”); at least one poly(biphenyl ether sulfone) polymer (“PPSU polymer”) and / or polyether sulfone (“PES polymer”); at least one conductive fibrous carbon-based filler (“Component B1”); at least one conductive particulate carbon-based filler (“Component B2”); The polyaryl ether composition (C) comprises:

2. The PAEK polymer may comprise more than 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, based on the total weight of repeat units in the PAEK polymer, of a repeat unit of the following formulae (I)-(V): 【Chemical 1】 (In the formula: Ar is independently a divalent aromatic radical selected from phenylene, biphenylene or naphthylene; X is independently O, C(═O) or a direct bond; n is an integer from 0 to 3, b, c, d and e are 0 or 1; a is an integer from 1 to 4, Preferably, when b is 1, d is 0. A repeating unit (R ＰＡＥＫ The polyaryl ether composition (C) of claim 1, comprising:

3. 3. The polyarylether composition (C) according to claim 1 or 2, wherein the polyarylether composition (C) comprises components B1 and B2 in a combined amount of more than 20 wt. %, or at least 25 wt. % and / or at most 50 wt. %, preferably at most 40 wt. %, more preferably at most 35 wt. %, based on the total weight of the polyarylether composition (C).

4. The polyaryl ether composition (C) according to any one of claims 1 to 3, wherein chopped carbon fibers are present in the polyaryl ether composition (C) as component B1, and pulverized carbon fibers are present in the polyaryl ether composition (C) as component B2.

5. The polyaryl ether composition (C) of claim 4, wherein the weight of the pulverized carbon fiber is more than 50 weight percent based on the combined weight of the pulverized carbon fiber and chopped carbon fiber in the polyaryl ether composition (C).

6. The polyarylether composition (C) according to any one of claims 1 to 5, wherein the polyarylether composition (C) comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, and / or at most 90 wt%, preferably at most 80 wt%, of PAEK polymer, based on the combined weight of the PAEK polymer and the PPSU polymer and / or PES polymer in the polyarylether composition (C).

7. The PPSU polymer may comprise at least 50 mol %, at least 60 mol %, at least 70 mol %, at least 80 mol %, at least 90 mol %, at least 95 mol %, or at least 99 mol %, based on the total number of moles of repeat units in the PPSU polymer, of the repeat units of the following formulas (2) to (6): 【Chemistry 2】 The polyaryl ether composition (C) according to any one of claims 1 to 6, comprising a repeating unit (R2) represented by any formula selected from the following, preferably represented by formula (2) and / or (4):

8. The polyaryl ether composition (C) of claim 7, wherein more than 70 mol %, preferably more than 85 mol %, of the repeating units of the poly(biphenyl ether sulfone (PPSU polymer) are repeating units (R2) of formula (2).

9. The polyethersulfone (PES polymer) may comprise at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%, based on the total number of moles of repeat units in the PES polymer, of formula (J): 【Chemistry 3】 Repeating units (R ＰＥＳ The polyaryl ether composition (C) according to any one of claims 1 to 8, comprising:

10. The polyaryl ether composition (C) according to any one of claims 1 to 9, wherein the PAEK polymer is not crosslinked to the component B1 and / or component B2.

11. 40% to 90% by weight collectively of the PAEK polymer and the PPSU polymer and / or PES polymer; 10% to 60% by weight of components B1 and B2 taken together; Composition (C) according to any one of claims 1 to 10, comprising: Composition (C), wherein said weight percentages are based on the total weight of said polyarylether composition (C).

12. at least 30 wt. % and at most 50 wt. % of said PAEK polymer; at least 20% by weight and at most 40% by weight of said PPSU polymer and / or PES polymer; at least 5% by weight and at most 25% by weight of component B1; at least 5% by weight and at most 25% by weight of component B2; Composition (C) according to any one of claims 1 to 11, comprising: The weight percentages are based on the total weight of the polyaryl ether composition (C).

13. 13. A method for producing the polyaryl ether composition (C) according to any one of claims 1 to 12, comprising melt-blending the PAEK polymer, the PPSU polymer and / or the PES polymer, component B1, component B2, and any optional additives.

14. An article comprising or made from the polyarylether composition (C) according to any one of claims 1 to 12, wherein the article has a viscosity of 1.10 ＋５ Ω.cm to a maximum of 5.10 ＋１２ The article has a volume resistivity, measured in accordance with ASTM D257, of Ω.cm.

15. 15. The article of claim 14, having a flow molding shrinkage based on method ASTM D955 of at most 0.60%, at most 0.50%, preferably 0.10 to 0.60%, or more preferably 0.10 to 0.25%, and / or a transverse molding shrinkage based on method ASTM D955 of at most 0.8%, preferably 0.1 to 0.6%, more preferably 0.2 to 0.5%.

16. At least 10 ６ and at most 10 ９ 16. The article of claim 14 or 15, having a surface resistivity of Ω / sq.

17. The article of any one of claims 14 to 16, which is a substrate carrier selected from the group consisting of a wafer carrier, a reticle pod, a shipper, a chip tray, a test socket, a head tray, fluid tubing, and a chemical container.

Images