Polymer composition suitable for electrostatic discharge applications

Abstract

Disclosed is a polyarylether 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 polyethersulfone ("PES polymer"), at least one electrically conductive fibrous carbon-based filler ("component B1"), and at least one electrically conductive particulate carbon-based filler ("component B2"). An article, particularly for electrostatic dissipation applications such as a substrate carrier, comprising a polyarylether composition (C) suitable for electrostatic discharge applications is disclosed.

Description

Technical Field

[0001] The present invention relates to an enhanced polyarylether composition, which is notably suitable for use in electrostatic discharge applications, and to an article comprising or made from the same. Background Art

[0002] It is known that conductive thermoplastic polymer compositions can be used to prevent electrostatic discharge (ESD). These specialty polymer compositions are typically tailored to span the surface resistivity spectrum and can often be formulated for injection molding or extrusion processes.

[0003] A variety of techniques can be used to impart conductive properties to an otherwise insulating thermoplastic resin, thereby providing the precise degree of conductivity required for ESD protection. Among them, conductive fillers can be added to the thermoplastic polymer.

[0004] It is known that micro-sized conductive fillers, such as chopped carbon fibers or milled carbon fibers, are among the most important filler materials.

[0005] For example, US 5,820,788 discloses an antistatic polymer containing a mixture of a thermoplastic resin and about 8%-20% by weight of conductive partially carbonized chopped linear carbon-containing fibers (having a carbon content of about 70%-85%), which can further provide an electrostatic control material and structure having a surface with a controlled surface resistivity in the range of 10 4 to 10 10 Ω / sq.

[0006] Molding shrinkage is the shrinkage of a polymer when it cools after its molding process. It is typically used to properly process injection molding so that the final part dimensions are as desired. Therefore, there is still a need to optimize conductive thermoplastic polymer compositions to improve the molding shrinkage rate of filled ESD polymer materials by using standard conductive carbon fillers with a higher carbon content. Summary of the Invention

[0007] Thus, a first object of the present invention relates to a polyarylether composition (C) comprising:

[0008] at least one poly(aryl ether ketone) polymer (hereinafter referred to as "PAEK polymer"),

[0009] at least one poly(biphenyl ether sulfone) polymer (hereinafter referred to as "PPSU polymer") and / or polyethersulfone (hereinafter referred to as "PES polymer"),

[0010] at least one conductive fibrous carbon-based filler (hereinafter referred to as "component B1"), and

[0011] at least one conductive particulate carbon-based filler (hereinafter referred to as "component B2").

[0012] Another object of the present invention relates to an article comprising or made of said polyarylether composition (C), said article having a volume resistivity measured according to ASTM D257 from 1·10 +5 Ω.cm to 5·10 +12 Ω.cm.

[0013] The Applicant has found that due to the blending of PAEK, PPSU polymers and / or PES polymers with component B1 and component B2, the polyarylether composition (C) of the present invention as detailed herein is effective in improving the moulding shrinkage of filled ESD polymeric materials without sacrificing mechanical properties. DETAILED DESCRIPTION

[0014] The polyarylether composition (C) according to the present invention may comprise:

[0015] - In total from 40 wt.% to 90 wt.% of PAEK polymer and PPSU polymer and / or PES polymer, and

[0016] - In total from 10 wt.% to 60 wt.% of components B1 and B2,

[0017] Said wt.% is based on the total weight of the polyarylether composition (C).

[0018] The polyarylether composition (C) according to the present invention may comprise:

[0019] - In total from 50 wt.% to 80 wt.% of PAEK polymer and PPSU polymer and / or PES polymer, and

[0020] - In total from 20 wt.% to 50 wt.% of components B1 and B2,

[0021] Said wt.% is based on the total weight of the polyarylether composition (C).

[0022] The polyarylether composition (C) according to the present invention may comprise:

[0023] - In total from 60 wt.% to 80 wt.% of PAEK polymer and PPSU polymer and / or PES polymer, and

[0024] - In total from 20 wt.% to 40 wt.% of components B1 and B2,

[0025] Said wt.% is based on the total weight of the polyarylether composition (C).

[0026] The polyarylether composition (C) according to the present invention may comprise:

[0027] - At least 30 wt.% and at most 50 wt.% of a PAEK polymer,

[0028] - At least 20 wt.% and at most 40 wt.% of a PPSU polymer and / or a PES polymer,

[0029] - At least 5 wt.% and at most 25 wt.% of component B1, and

[0030] - At least 5 wt.% and at most 25 wt.% of component B2,

[0031] Said wt.% is based on the total weight of the polyarylether composition (C).

[0032] The polyarylether composition (C) according to the present invention may comprise:

[0033] - At least 35 wt.% and at most 45 wt.% of a PAEK polymer,

[0034] - At least 25 wt.% and at most 35 wt.% of a PPSU polymer and / or a PES polymer,

[0035] - At least 10 wt.% and at most 20 wt.% of component B1, and

[0036] - At least 10 wt.% and at most 20 wt.% of component B2,

[0037] Said wt% is based on the total weight of the polyarylether composition (C).

[0038] The polyarylether composition (C) according to the present invention may further comprise optional additives, typically not exceeding 10 wt.% based on the total weight of the composition (C). The combined weight of at least one PAEK polymer, PPSU polymer and / or PES polymer, component B1, component B2 and one or more optional additives is equal to or less than 100 wt.% of the composition (C).

[0039] Some polyarylether compositions (C) according to the present invention may not contain a PES polymer. In such cases, the polyarylether composition (C) comprises a PAEK polymer, a PPSU polymer, components B1 and B2, but does not contain a PES polymer. Accordingly, any disclosure regarding "PPSU polymer and / or PES polymer", such as its weight content and range in the composition (C) provided herein, equally applies to the polyarylether composition (C) of the present invention in which a PPSU polymer is present and a PES polymer is absent.

[0040] Poly(aryl ether ketone) (PAEK)

[0041] As previously mentioned, the polyarylether composition (C) comprises at least one PAEK polymer.

[0042] For the purposes of the present invention, the term "poly(aryl ether ketone)" or "PAEK" is intended to mean any polymer in which greater 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.% of the repeating units are repeating units (R1) having one or more of the following formulas (I) to (V):

[0043]

[0044] Wherein:

[0045] - Ar is independently a divalent aromatic group selected from phenylene, biphenylene or naphthylene,

[0046] - X is independently O, C(=O) or a direct bond,

[0047] - n is an integer from 0 to 3,

[0048] - b, c, d and e are 0 or 1,

[0049] - a is an integer from 1 to 4, and

[0050] - Preferably, when b is 1, d is 0.

[0051] The repeating unit (R1) may notably be selected from:

[0052]

[0053]

[0054]

[0055] And

[0056]

[0057] Preferably, the repeat (R1) is selected from:

[0058]

[0059] And

[0060]

[0061] More preferably, the repeating unit (R1) is:

[0062]

[0063] For the purposes of the present invention, polyaryletherketone (PAEK polymer) is intended to mean any polymer in which greater than 50 wt.% of the repeating units are repeating units (R1) having formula (VII). Preferably, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.% of the repeating units of the PAEK polymer are repeating units (R1) having formula (VII). Even more preferably, substantially all of the repeating units of the PAEK polymer are repeating units (R1) having formula (VII). Most preferably, all of the repeating units of the PAEK polymer are repeating units (R1) having formula (VII).

[0064] Preferably, the PAEK used in the present invention is not sulfonated.

[0065] Excellent results are obtained when the PAEK polymer is a polyetheretherketone homopolymer, i.e., a polymer in which substantially all (if not all) of the repeating units have formula (VII). Non-limiting examples of suitable commercially available PEEK homopolymers are those from Victrex Manufacturing Ltd., PEEK, those from Solvay Specialty Polymers PEEK and those from Jilin Joinature Polymer Co., Ltd

[0066] The PAEK polymer may have an intrinsic viscosity (IV) of at least 0.50 dl / g, preferably at least 0.60 dl / g, 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.

[0067] The PAEK polymer, such as the PEEK polymer, may have a melt viscosity of up to 0.25 kPa-s, but preferably less than 0.20 kPa-s and most preferably less than 0.18 kPa-s at a shear rate of 400 °C and 1000 s -1 as measured using a capillary rheometer according to ASTM D3835. The PAEK polymer, such as the PEEK polymer, may have a melt viscosity as low as 0.05 kPa-s.

[0068] The PAEK polymer, such as the PEEK polymer, may have a melt viscosity of up to 0.25 kPa-s, but preferably less than 0.20 kPa-s and most preferably less than 0.18 kPa-s at a shear rate of 400 °C and 1000 s -1The melt viscosity ranges from 0.05 kPa-s to 0.25 kPa-s, preferably from 0.06 kPa-s to 0.20 kPa-s, preferably from 0.07 kPa-s to 0.18 kPa-s, preferably from 0.08 kPa-s to 0.15 kPa-s at the shear rate of

[0069] For a capillary rheometer, the Kayeness Galaxy V rheometer (model 8052DM) can be used.

[0070] PAEK polymers, such as PEEK polymers, can be prepared by any method.

[0071] A well-known method in the art involves reacting a substantially equimolar mixture of at least one bisphenol and at least one dihalobenzene-type compound or at least one halophenol compound, as described in Canadian Patent No. 847,963. Non-limiting examples of bisphenols that can be used in this method are hydroquinone, 4,4'-dihydroxybiphenyl, and 4,4'-dihydroxybenzophenone; non-limiting examples of dihalobenzene-type compounds that can be used in this method are 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 4-chloro-4'-fluorobenzophenone; non-limiting examples of halophenol compounds that can be used in this method are 4-(4-chlorobenzoyl)phenol and (4-fluorobenzoyl)phenol. Thus, PEEK homopolymers can notably be produced by a nucleophilic method as described, for example, in U.S. Patent No. 4,176,222, the entire content of which is incorporated herein by reference.

[0072] Another well-known method for producing PEEK homopolymers in the art involves using an alkanesulfonic acid as a solvent and subjecting phenoxyphenoxybenzoic acid to electrophilic polymerization in the presence of a condensing agent, as described in U.S. Patent 6,566,484, the entire content of which is incorporated herein by reference. Other poly(aryl ether ketones) can be produced by the same method, starting from other monomers than phenoxyphenoxybenzoic acid, such as those described in U.S. Patent Application 2003 / 0130476, the entire content of which is also incorporated herein by reference.

[0073] The polyarylether composition (C) can comprise one and only one PAEK polymer. Alternatively, it can comprise two, three, or even more than three PAEK polymers. Some preferred mixtures of PAEK polymers are mixtures consisting of: (i) at least one poly(aryl ether ketone) (PAEK)-a in which more than 50 wt.%, preferably substantially all, and still more preferably all of the repeating units have the following formula:

[0074]

[0075] (ii) at least one poly(aryl ether ketone) (PAEK)-b in which greater than 50 wt.%, preferably substantially all, and even more preferably all of the repeating units have at least one of the following formulas:

[0076]

[0077] And, optionally in addition, (iii) at least one other poly(aryl ether ketone) (PAEK)-c different from poly(aryl ether ketone) (PAEK)-a and (PAEK)-b; in particular, a mixture consisting of: (i) at least one poly(aryl ether ketone) (PAEK)-a in which substantially all (if not all) of the repeating units have formula (VII), (ii) at least one poly(aryl ether ketone) (PAEK)-b in which substantially all (if not all) of the repeating units have formula (IX); even more particularly, a binary mixture consisting of: (i) one poly(aryl ether ketone) (PAEK)-a in which all of the repeating units have formula (VII), (ii) one poly(aryl ether ketone) (PAEK)-b in which all of the repeating units have formula (IX).

[0078] The amount of the PAEK polymer is at least 40 wt.%, preferably at least 41 wt.%, or at least 42 wt.%, or at least 43 wt.%, or at least 44 wt.%, or at least 45 wt.%, or at least 47 wt.%, or at least 49 wt.%, or at least 55 wt.%, or at least 55 wt.% and / or less than 89 wt.%, preferably at most 88 wt.%, or at most 87 wt.%, at most 86 wt.%, or at most 85 wt.%, or at most 80 wt.%, or at most 79 wt.%, or at most 78 wt.%, or at most 75 wt.%, based on the total weight of the polyaryl ether composition (C).

[0079] Poly(biphenyl ether sulfone) polymer (PPSU polymer)

[0080] For the purposes of the present invention, poly(biphenyl ether sulfone) is intended to mean a condensation polymer 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 the repeating units are repeating units (R2) selected from the following:

[0081]

[0082] And

[0083]

[0084] The mol% is based on the total number of moles of repeating units in the poly(biphenyl ether sulfone) polymer.

[0085] Using repeating units of formula (2) in the repeating unit (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 condensation polymer in which at least 50 mol% of the repeating units are repeating units (R2) of formula (2).

[0086] Poly(biphenyl ether sulfone) (PPSU polymer) notably can be a homopolymer, a random, alternating or block copolymer.

[0087] When poly(biphenyl ether sulfone) (PPSU polymer) is a copolymer, its repeating units notably can consist of (i) at least two different types of repeating units (R2) selected from formulae (2) to (6), or (ii) one or more repeating units (R2) of formulae (2) to (6) (especially repeating units of formula (2)) and repeating units (R2*) (different from repeating units (R2)), such as:

[0088]

[0089] and

[0090]

[0091] Preferably more than 70 mol%, more preferably more than 85 mol% of the repeating units of poly(biphenyl ether sulfone) (PPSU polymer) are repeating units (R2) of formula (2), the mol% being based on the total number of moles of repeating units in the poly(biphenyl ether sulfone) polymer. Even more preferably, substantially all of the repeating units of poly(biphenyl ether sulfone) (PPSU polymer) are repeating units (R2) of formula (2). Most preferably, all of the repeating units of poly(biphenyl ether sulfone) (PPSU polymer) are repeating units (R2) of formula (2).

[0092] When poly(biphenyl ether sulfone) (PPSU polymer) is a polyphenylsulfone homopolymer, i.e. a polymer in which substantially all (if not all) of the repeating units have formula (2), excellent results are generally obtained. Polyphenylsulfone from Solvay Specialty Polymers USA, L.L.C. is an example of a polyphenylsulfone homopolymer.

[0093] Poly(phenyl ether sulfone) (PPSU polymer) can be prepared by any method. Methods well-known in the art are 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.

[0094] The polyarylether composition (C) can comprise one and only one poly(phenyl ether sulfone) (PPSU polymer). Alternatively, it can comprise two, three, or even more than three poly(phenyl ether sulfone) (PPSU polymers).

[0095] Polyethersulfone (PES polymer)

[0096] For the purposes of the present invention, polyethersulfone (PES polymer) means any polymer comprising 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 repeating units (R PES ) having the formula (J):

[0097]

[0098] mol.% is based on the total number of moles of repeating units in the PES polymer.

[0099] PES polymers can be prepared by known methods, such as the condensation of bisphenol S and dichlorodiphenyl sulfone, and are notably available from Solvay Specialty Polymers USA, Inc. as PESU.

[0100] When poly(phenyl ether sulfone) (PPSU polymer) or polyethersulfone (PES polymer) is present in the polyarylether composition (C), the weight of the PAEK polymer is 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.%, based on the combined weight of the PAEK polymer and the PPSU polymer / PES polymer in the polyarylether composition (C).

[0101] Some polyarylether compositions (C) according to the present invention can be free of PES polymer.

[0102] Carbon-based filler

[0103] For the purposes of the present invention, the term "carbon-based filler" is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcing fillers or any mixture thereof.

[0104] The term "graphitized" is intended to denote a carbon filler obtained by high-temperature pyrolysis (above 2000 °C) of a carbon filler, in which the carbon atoms are arranged in a manner similar to the graphite structure.

[0105] The carbon-based fillers useful in the present invention can advantageously be obtained by heat treatment and pyrolysis of different polymer precursors such as, for example, man-made fibers, polyacrylonitrile (PAN), aromatic polyamides or phenolic resins; the carbon fillers useful in the present invention can also be obtained from pitch materials.

[0106] The carbon-based 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.

[0107] The carbon-based fillers useful in the present invention can be metallized. However, the carbon-based fillers useful in the present invention are preferably not metallized.

[0108] Fibrous fillers are considered herein to be three-dimensional materials having a length, a width, and a thickness, wherein the average length is significantly greater than both the width and the thickness. Generally, such materials have an aspect ratio defined as the ratio between the average length and the largest of the average width and the average thickness of at least 5, at least 10, at least 20, or at least 50.

[0109] Conductive fibrous carbon-based filler (Component B1)

[0110] Component B1 in the polyarylether composition (C) is a fibrous filler having an elemental carbon purity of greater than 85%, the remainder possibly consisting of residual impurities. Preferably, component B1 contains at least 90% elemental carbon, and 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.

[0111] In some embodiments, component B1 is a fibrous filler having an elemental carbon purity of less than 70%, the remainder possibly consisting of residual impurities. Preferably, component B1 contains at most 65% elemental carbon, and more preferably at most 60% elemental carbon.

[0112] Component B1 is a fibrous filler having an average length ranging from 1 to 20 mm, preferably from 2 to 15 mm, more preferably from 3 to 10 mm, and even more preferably from 3 to 6 mm.

[0113] Component B1 is a fibrous filler having an equivalent diameter generally ranging from 1 to 20 μm, preferably from 2 to 15 μm, more preferably from 3 to 10 μm, and most preferably from 6 to 8 μm.

[0114] Component B1 is 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 polyarylether composition (C).

[0115] Preferably, component B1 has a resistivity ranging from 1.0 to 30 μΩ·m, preferably from 2.0 to 20 μΩ·m, and more preferably from 10 to 20 μΩ·m.

[0116] Advantageously, chopped carbon fibers are present as component B1 in the polyarylether composition (C). Chopped carbon fibers are notably commercially available from Teijin (such as PSC171100 chopped carbon fibers, 3 mm) and Procotex (such as APPLY CARBON carbon chopped carbon fibers CF.OS.U1-6MM).

[0117] Conductive particulate carbon-based filler (Component B2)

[0118] Advantageously, milled carbon fibers are present as component B2 in the polyarylether composition (C).

[0119] Excellent results are obtained when the milled carbon fibers are pitch-based carbon fibers.

[0120] Preferably, the milled carbon fibers are pitch-based carbon fibers having an average length ranging from 0.01 to 2 mm, preferably from 0.1 to 1 mm, and more preferably from 0.2 to 0.8 mm.

[0121] Preferably, the milled carbon fibers are pitch-based carbon fibers having an average diameter ranging from 5 to 50 μm, preferably from 10 to 30 μm, and more preferably from 10 to 15 μm.

[0122] The pitch-based carbon fibers are notably commercially available from Osaka Gas Chemicals (OGC). In some embodiments, the milled carbon fibers are PAN-based carbon fibers. The PAN-based carbon fibers advantageously have a diameter in the range of 3 to 20 μm, preferably from 4 to 15 μm, more preferably from 5 to 10 μm, and most preferably from 6 to 8 μm. Good results are obtained when using PAN-based carbon fibers (PAN-CF) with a diameter of 7 μm.

[0123] Other suitable milled carbon fibers are commercially available from Procotex as CF.LS-MLD80 to CF.LS-MLD250, having an average monofilament diameter of 7 microns, a medium length of 80 - 250 microns, and a volume resistivity of 15·10 -4 Ω·cm to 20·10 -4 Ω·cm.

[0124] The electrically conductive particulate carbon-based filler (Component B2) is 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 polyarylether composition (C).

[0125] Preferably, Component B2 has a volume resistivity of about from 5.0 to 100 μΩ·m, preferably from 10.0 to 50 μΩ·m and more preferably from 15 to 45 μΩ·m.

[0126] Preferably, the combined weight of Components B1 and B2 is greater 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 the polyarylether composition (C).

[0127] Advantageously, the weight of the milled carbon fibers is greater than 50 wt.% based on the combined weight of the milled carbon fibers and the chopped carbon fibers in the composition.

[0128] When Components B1 and B2 are present in the polyarylether composition (C), PAEK is preferably not crosslinked with Component B1 and / or Component B2.

[0129] Optional additive

[0130] In some embodiments, the polyarylether composition (C) according to the present invention comprises additives 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.

[0131] In some embodiments in which the polyarylether composition (C) comprises optional additives, the total concentration of the additives is not more than 15 wt.%, not more than 10 wt.%, not more than 5 wt.%, not more than 1 wt.%, not more than 0.5 wt.%, not more than 0.4 wt.%, not more than 0.3 wt.%, not more than 0.2 wt.%, or not more than 0.1 wt.%.

[0132] One or more pigments may be particularly desired additives in the composition (C) to produce 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 type, preferably rutile type), and / or colored pigments. The pigments are generally present in an amount of from 0 to 6 wt.%, preferably from 0.05 to 5 wt.% and particularly from 0.1 to 3 wt.% based on the total weight of the polyarylether composition (C).

[0133] Antioxidants can be particularly desirable additives in the polyarylether composition (C). Antioxidants can improve the thermal stability and light stability of the polyarylether composition (C). For example, an antioxidant that is a heat stabilizer can improve the thermal stability of the composition during manufacture (or in a high-temperature application environment) by, for example, making the polymer processable at high temperatures while helping to prevent polymer degradation.

[0134] Method for preparing polyarylether composition (C)

[0135] The polyarylether composition (C) according to the present invention can be prepared using methods well known in the art.

[0136] For example, the polyarylether composition (C) is prepared by melt-blending at least one PAEK polymer, PPSU polymer, and / or 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 polyarylether composition (C). For example, all the components can be fed into a melt mixer such as a single-screw extruder or a twin-screw extruder, a blender, a single-screw or twin-screw kneader, or a Banbury mixer. The components can be added all at once to the melt mixer or added stepwise in batches. When adding the components stepwise in batches, a portion of the components is added first and then melt-blended with the remaining portion of the subsequently added components until a well-mixed composition is obtained.

[0137] Article

[0138] As previously mentioned, another aspect of the present invention further relates to an article, preferably a molded article, that comprises or is made of the polyarylether composition (C).

[0139] The polyarylether composition (C) as detailed above can be processed by conventional melt-processing techniques to provide molded articles, and these melt-processing techniques notably include extrusion molding, injection molding, and compression molding.

[0140] Such articles have a volume resistivity measured according to ASTM D257 from 1·10 +5 Ω.cm to 5·10 +12 Ω.cm.

[0141] It has been found that the articles have a surface resistivity of at least 10 6 and at most 10 9 Ω / sq.

[0142] Volume resistivity is the resistance to leakage current through the bulk of an insulating material. Surface resistivity is the resistance to leakage current along the surface of an insulating material.

[0143] It has been found that the article has a flow molding shrinkage rate of at most 0.60%, at most 0.50%, preferably from 0.10% to 0.60%, or more preferably from 0.10% to 0.25% based on method ASTM D955 and / or has a transverse molding shrinkage rate of at most 0.8%, preferably from 0.1% to 0.6%, more preferably from 0.2% to 0.5% based on method ASTM D955.

[0144] In a preferred embodiment, the ratio of the flow molding shrinkage rate to the transverse molding shrinkage rate is from 1:1 to 1:2.5 and preferably from 1:1 to 1:2.

[0145] As used herein, the term "molding shrinkage" refers to the shrinkage of a polymer upon cooling after its molding process. It is typically used to properly process injection molding such that the final part dimensions are as desired. Flow molding shrinkage refers to the molding shrinkage in the flow direction. Transverse molding shrinkage (or cross-flow molding shrinkage) refers to the molding shrinkage in the transverse (cross-flow) direction.

[0146] The molded article according to the present invention is preferably selected from the group consisting of: (i) extruded profiles, preferably selected from the group consisting of rods, plates, pipe fittings, pipes or profiles; and (ii) injection molded articles.

[0147] According to certain embodiments, the molded article is in the form of a substantially two-dimensional article, such as a part in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length), such as films, sheaths and sheets.

[0148] According to other embodiments, the molded article is provided as a three-dimensional part, for example, substantially extending in three dimensions of space in a similar manner, including in the form of a part having a complex geometry, such as having concave or convex portions, and may include undercuts, inserts, etc.

[0149] The polyarylether composition (C) can be used to manufacture electrostatic dissipation articles, such as but not limited to substrate carriers. Substrate carriers can include but are not limited to wafer carriers, reticle pods, shippers, chip trays, test sockets, head trays (for reading and / or writing); fluid pipes, chemical containers, etc.

[0150] The molded article may include, but is not limited to, some or all of the mask carriers as shown in U.S. Patent Nos. 6,513,654 and 6,216,873; the disk transporters as shown in U.S. Patent Nos. 4,557,382 and 5,253,755; the chip trays as shown in U.S. Patent No. 6,857,524; the wafer carriers as shown in U.S. Patent No. 6,848,578; each of these references being incorporated herein by reference in its entirety.

[0151] According to certain embodiments, a molded article made of the polyarylether composition (C) detailed above is provided as one or more parts of an electrostatic discharge (ESD) protection device, which may be designed, for example, to be connected to a semiconductor wafer intended for chip manufacturing.

[0152] Examples

[0153] The present invention will now be described with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the invention. As used in the examples, "E" represents an example embodiment of the present invention, and "CE" represents a comparative example.

[0154] Materials

[0155] ● PEEK: KT-880P from Solvay Specialty Polymers KT-880P

[0156] ● PPSU: R-5900 from Solvay Specialty Polymers R-5900

[0157] ● Component B1: PSC171100 3-mm chopped carbon fiber from Teijin Limited, Japan

[0158] ● Component B2: Pitch-based CF powder DONACARBO S-2415 from OGC

[0159] ● Optional additive: Zinc oxide "Zinkoxyd aktiv" from Lanxess

[0160] Test methods

[0161] ● Tensile properties - ISO 527

[0162] Tensile modulus, tensile strength, and elongation at break were measured on 5 injection-molded ISO 1a type tensile specimens (total length = 170 mm, gauge length = 50 mm, test section width = 10 mm, and thickness = 4 mm).

[0163] ● Impact strength - ISO 180

[0164] The notched and unnotched Izod impact strength properties were measured using 10 injection molded ISO 1A type bars (80 ± 2 mm in length, 10 ± 0.2 mm in width, 4 ± 0.2 mm in thickness) in kJ / m 2 2).

[0165] ● Molding shrinkage - ISO 294 (ASTM D955)

[0166] The molding shrinkage (molding shrinkage (%) in the flow direction and molding shrinkage (%) in the transverse direction) was measured on 5 injection molded substrates having dimensions of 60 mm width by 60 mm length by 2 mm thickness.

[0167] ● Volume and surface resistivity - ASTM D257

[0168] The volume and surface resistivity were measured on 5 injection molded substrates having dimensions of 4” × 4” × 1 / 8” (length × width × thickness) or 60 mm × 60 mm × 2 mm (length × width × thickness)

[0169] Example 1

[0170] The resin, filler, and additive were fed into a ZSK-26 mm co-rotating twin screw extruder using a gravity feeder, and the gravity feeder was adjusted for each run to achieve the target blend ratio in Table 1.

[0171] All blending and controlled compounding conditions are shown in Table 2. The set points on the extruder were the same for all runs.

[0172] The composition prepared by injection molding according to ASTM D3641 was then used to provide molded articles.

[0173] Table 1

[0174]

[0175] Table 2

[0176]

[0177]

[0178] Comparative Example 2

[0179] The components for preparing Sample CE2 are listed in Table 1.

[0180] The composition and molded articles of Comparative Example 2 were prepared in the same manner as Example 1.

[0181] Comparative Example 3

[0182] The components for preparing Sample CE3 are listed in Table 1.

[0183] The composition and molded article of Comparative Example 3 were prepared in the same manner as in Example 1.

[0184] As shown by the results in Table 3, compared with the higher flow molding shrinkage rate and transverse molding shrinkage rate (0.28% and 0.81% respectively) of Sample CE2 which does not contain PPSU, Composition E1 according to the present invention is effective in optimizing the molding shrinkage rate of the article, reducing the flow molding shrinkage rate and transverse molding shrinkage rate to 0.24% and 0.47% respectively. Compared with Sample CE2, Composition E1 has a smaller difference between the flow molding shrinkage rate and the transverse molding shrinkage rate.

[0185] Compared with the higher transverse molding shrinkage rate (0.83%) of Sample CE3 which does not contain PPSU and only contains Component B2, Composition E1 is effective in optimizing the molding shrinkage rate of the article, reducing the transverse molding shrinkage rate to 0.47%. Compared with Sample CE3, Composition E1 has a smaller difference between the flow molding shrinkage rate and the transverse molding shrinkage rate.

[0186] Table 3

[0187]

[0188]

[0189] *x-flow represents the transverse shrinkage rate.

[0190] The disclosures of all patent applications and publications cited herein are incorporated herein by reference to the extent that they provide exemplary, procedural, or other detailed supplementation for those presented herein. If the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that it may result in unclear terms, then this specification should prevail. Any incorporation of documents by reference is limited such that no subject matter contrary to the explicit disclosure herein is incorporated.

[0191] Although the preferred embodiments of the present invention have been shown and described, those skilled in the art can modify them without departing from the teachings of the present invention. The embodiments described herein are merely exemplary and non-limiting. Various variations and modifications of the composition, article, and method are possible and are within the scope of the present invention. Therefore, the scope of protection is not limited by the description presented above, but is only limited by the following claims, which include all equivalents of the subject matter of the claims. Each claim is incorporated into this specification as an embodiment of the present invention. Therefore, the claims are further descriptions and additions to the preferred embodiments of the present invention.

[0192] Claims

Claims

1. - A polyarylether 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 polyethersulfone ("PES polymer"), at least one conductive fibrous carbon-based filler ("Component B1"), and at least one conductive particulate carbon-based filler ("Component B2").

2. - The polyarylether composition (C) according to claim 1, wherein, The PAEK polymer comprises repeating units represented by any one of the following formulas (I) to (V) in an amount greater 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 the repeating units in the PAEK polymer (R PAEK ): Wherein: - 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, and - Preferably, when b is 1, d is 0.

3. - The polyarylether composition (C) according to claim 1 or 2, wherein, The polyarylether composition (C) comprises a combined weight of the Component B1 and B2 greater 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 polyarylether composition (C) according to any one of claims 1 to 3, wherein, Short carbon fibers are present as Component B1 in the polyarylether composition (C), and milled carbon fibers are present as Component B2 in the polyarylether composition (C).

5. - The polyarylether composition (C) according to claim 4, wherein, The weight of the milled carbon fibers is greater than 50 wt.% based on the combined weight of the milled carbon fibers and short carbon fibers in the polyarylether 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 the 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 polyarylether composition (C) according to any one of claims 1 to 6, wherein The PPSU polymer comprises 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 repeating units (R2) represented by any of the following formulas (2) to (6) based on the total molar number of the repeating units in the PPSU polymer: And Preferably represented by formula (2) and / or (4).

8. - The polyarylether composition (C) according to claim 7, wherein, Greater than 70 mol.%, preferably greater than 85 mol.% of the repeating units of the poly(biphenyl ether sulfone) (PPSU polymer) are repeating units (R2) having formula (2).

9. - The polyarylether composition (C) according to any one of claims 1 to 8, wherein, The polyethersulfone (PES polymer) comprises 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 repeating units of formula (J) based on the total molar amount of repeating units in the PES polymer (R PES ):

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

11. - The polyarylether composition (C) according to any one of claims 1 to 10, comprising: · In total from 40 wt.% to 90 wt.% of the PAEK polymer and the PPSU polymer and / or PES polymer, and · In total from 10 wt.% to 60 wt.% of the Component B1 and B2, wherein the wt% is based on the total weight of the polyarylether composition (C).

12. - The polyarylether composition (C) according to any one of claims 1 to 11, comprising: · At least 30 wt.% and at most 50 wt.% of the PAEK polymer, · at least 20 wt.% and at most 40 wt.% of the PPSU polymer and / or PES polymer, · at least 5 wt.% and at most 25 wt.% of component B1, and · at least 5 wt.% and at most 25 wt.% of component B2, wherein the wt.% is based on the total weight of the polyarylether composition (C).

13. - A method for preparing the polyarylether composition (C) according to any one of claims 1 to 12, the method 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, said article having a volume resistivity measured according to ASTM D257 from 1·10 +5 Ω·cm to 5·10 +12 Ω·cm.

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

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

17. - An article according to any one of claims 14 to 16, which is a substrate carrier selected from the group consisting of a wafer carrier, a photomask cassette, a transporter, a chip tray, a test socket, a head tray, a fluid conduit and a chemical container.

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