Polymer compositions suitable for electrostatic discharge applications

Abstract

A composition [composition (C)], comprising at least one poly(aryl ether ketone) polymer ("PAEK polymer"), at least one conductive carbon nanofiller ("component A1"), and at least one non-fibrous filler ("component A2"). An article, particularly for antistatic 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, particularly suitable for electrostatic discharge applications, and articles comprising or made therefrom. [Background technology]

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

[0003] To impart conductive properties to inherently insulating thermoplastics, several techniques are available to provide the precise conductivity required for ESD protection. Among these, conductive fillers can be added to thermoplastic polymers.

[0004] Small carbon materials such as nanotubes are one of the most important filler materials. They can advantageously increase the strength of polymer materials and make them conductive. However, due to their small size and fibrous structure, they are difficult to disperse uniformly in polymers.

[0005] U.S. Patent Application Publication No. 2010 / 0311869 A1 teaches that better dispersion can be achieved by using hollow carbon nanospheres, which are not commercially available, but require the use of complex processes to prepare the carbon nanospheres in order to achieve the desired shape.

[0006] U.S. Patent No. 8,128,844 B2 discloses that the use of organic nanoclays in conductive thermoplastic resin compositions minimizes or prevents the tendency of carbon nanotubes to aggregate or orient unexpectedly, allowing the carbon nanotubes to be uniformly dispersed in the resin. The organic nanoclays are typically prepared by organically modifying nanoscale layered silicates.

[0007] Among thermoplastic polymers, poly(aryl ether ketone)s (PAEKs), particularly polyether ether ketone (PEEK) and polyether ketone ketone (PEKK), offer excellent thermal stability, very high stiffness and strength, and excellent chemical resistance, including resistance to environmental stress fracture. However, they have drawbacks such as poor toughness and impact resistance (with brittle fracture), and relatively low heat distortion temperatures, making them generally unsuitable for ESD applications. Therefore, much effort has been devoted to improving the performance of conductive PAEK polymers. For example, International Publication No. 2008 / 003659A1 discloses a polymer composition (C) comprising at least one poly(aryl ether ketone) (PAEK), at least one poly(biphenyl ether sulfone), and at least one fibrous carbon nanofiller, which, among other things, provides excellent protection against electrostatic discharge, has substantially the same level of toughness as pure poly(biphenyl ether sulfone) (i.e., no breakage in an unnotched Izod ASTM D4812 test), and has much higher chemical resistance than that of poly(biphenyl ether sulfone). However, the publication does not teach how to uniformly disperse the conductive filler. Summary of the Invention

[0008] Thus, the first object of the present invention is to at least one poly(aryl ether ketone) polymer (hereinafter "PAEK polymer"); At least one conductive carbon nanofiller (hereinafter "component A1"), at least one non-fibrous filler (hereinafter "component A2"), The present invention relates to a polyaryl ether composition (C) comprising:

[0009] Another object of the present invention is to provide an article comprising or made from said polyarylether composition (C), having a viscosity of 1.10 MPa as measured according to ASTM D257. +5 Ω.cm to 5·10 +12 The article has a volume resistivity of up to Ω.cm.

[0010] Applicant has found that the inventive polyarylether composition (C) detailed herein, by blending the PAEK polymer with components A1 and A2, is effective in improving the uniformity of conductivity, thus optimizing the volume and surface resistivity and making the polymer material more suitable for ESD applications. Furthermore, the inventive polyarylether composition (C) also optimizes the mold shrinkage of filled ESD polymer materials without sacrificing their mechanical performance. DETAILED DESCRIPTION OF THE INVENTION

[0011] The polyaryl ether composition (C) according to the present invention comprises: at least 40% by weight and less than 89% by weight of at least one PAEK polymer, at least 1% by weight and at most 10% by weight of component A1, at least 10% by weight and at most 50% by weight of component A2, wherein 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: at least 40% by weight and at most 78% by weight of at least one PAEK polymer, at least 2% by weight and at most 10% by weight of component A1, at least 20% by weight and at most 50% by weight of component A2, wherein 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 55% by weight and at most 79% by weight of at least one PAEK polymer, at least 1% by weight and at most 5% by weight of component A1, at least 20% and at most 40% by weight of component A2, wherein the weight percentages are based on the total weight of the polyaryl ether composition (C).

[0014] The polyarylether composition (C) according to the present invention may further comprise at least one other polymer different from the PAEK polymer. The other polymer may comprise a polymeric carrier in which component A1 is dispersed before being mixed with the other components of the polyarylether composition (C). Alternatively or in addition, the other polymer may comprise at least one poly(biphenyl ether sulfone) (hereinafter "component A3") and / or at least one polyethersulfone (hereinafter "component A4"). In such cases, the total weight of the at least one PAEK polymer, component A1, optional other polymers (e.g., polymeric carrier, component A3, component A4), and component A2 is 100% by weight or less of the polyarylether composition (C).

[0015] The polyarylether composition (C) according to the present invention may further comprise optional additives, typically in an amount not exceeding 10% by weight, based on the total weight of the polyarylether composition (C). The total weight of the at least one PAEK polymer, component A1, optional other polymers, component A2, and optional additives is not more than 100% by weight of the polyarylether composition (C).

[0016] Poly(aryl ether ketone) ("PAEK") polymers As previously mentioned, the polyaryl ether composition (C) comprises at least one PAEK polymer.

[0017] For purposes of the present invention, the term "poly(aryl ether ketone)" or "PAEK" is intended to refer to any polymer in which more than 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight of the repeat units are one or more repeat units (R1) of formulae (I)-(V): [ka] (In these formulas, 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).

[0018] The repeating unit (R1) is in particular [ka] [ka] and [ka] You can choose from:

[0019] Preferably, the repeating unit (R1) is [ka] is selected from.

[0020] More preferably, the repeating unit (R1) is [ka] is.

[0021] For the purposes of the present invention, polyetheretherketone (PEEK) polymer is intended to mean a polymer in which more than 50% by weight of the 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%, or at least 99% by weight of the repeating units of the PEEK polymer are repeating units (R1) of formula (VII). More preferably, essentially all of the repeating units of the PEEK polymer are repeating units (R1) of formula (VII). Most preferably, all of the repeating units of the PEEK polymer are repeating units (R1) of formula (VII).

[0022] Preferably, the PAEK polymers, such as the PEEK polymers used in the present invention, are not sulfonated.

[0023] 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 include Victrex® PEEKS from Victrex Manufacturing Ltd., KETASPIRE® PEEKS from Solvay Specialty Polymers, and Zypeek® from Jilin Joint Polymer Co., Ltd.

[0024] 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, when measured in 95-98% sulfuric acid (d=1.84 g / ml) at a PAEK concentration of 0.1 g / 100 ml.

[0025] PAEK polymers, such as PEEK, have a melting point of 400°C and 1000s when measured using a capillary rheometer according to ASTM D3835. -1 PAEK polymers, such as PEEK polymers, may have melt viscosities as low as 0.05 kPa-s.

[0026] PAEK polymers, such as PEEK polymers, have a viscosity of 400°C and 1000s when measured using a capillary rheometer according to ASTM D3835. -1 At a shear rate 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.

[0027] As a capillary rheometer, a Kayeness Galaxy V rheometer (model 8052DM) may be used.

[0028] PAEK polymers, such as PEEK polymers, can be prepared by any method.

[0029] One method well 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'-dihydroxybiphenyl, 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 particularly produced by a nucleophilic process, as described, for example, in U.S. Pat. No. 4,176,222, the entire contents of which are incorporated herein by reference.

[0030] Another method known in the art for producing PEEK homopolymer involves the electrophilic polymerization of phenoxyphenoxybenzoic acid in the presence of a condensing agent using an alkane sulfonic acid as a solvent, such as the method 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 No. 2003 / 0130476, the entire contents of which are also incorporated herein by reference.

[0031] The polyaryl ether composition (C) can comprise only one PAEK polymer. Alternatively, it can comprise two, three, or even more than three PAEK polymers. Particularly preferred mixtures of PAEK polymers include those in which (i) more than 50 wt. % of the repeating units, preferably essentially all of the repeating units, and more preferably all of the repeating units, are of the formula [ka] and (ii) at least one poly(aryl ether ketone) (PAEK)-a in which more than 50% by weight of the repeating units, preferably essentially all of the repeating units, and more preferably all of the repeating units, are of the formula [ka] and (iii) optionally 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 of (i) at least one poly(aryl ether ketone) (PAEK)-a having essentially all, if not all, of its repeat units according to formula (VII) and (ii) at least one poly(aryl ether ketone) (PAEK)-b having essentially all, if not all, of its repeat units according to formula (IX); more particularly a binary mixture of (i) one poly(aryl ether ketone) (PAEK)-a having all repeat units according to formula (VII) and (ii) one poly(aryl ether ketone) (PAEK)-b having all repeat units according to formula (IX).

[0032] The amount of 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.%, or 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).

[0033] Conductive carbon nanofiller (component A1) Component A1 is at least one conductive carbon nanofiller comprising elemental carbon. Typically, more than 90% by weight of the nanofiller consists of elemental carbon. Preferably, more than 95% by weight of the nanofiller consists of elemental carbon. Even more preferably, more than 99% by weight of the nanofiller consists of elemental carbon. Good results are obtained when the nanofiller consists essentially of elemental carbon.

[0034] The at least one conductive carbon nanofiller useful in the present invention may be metallized, however, the at least one conductive carbon nanofiller is preferably not metallized.

[0035] From a practical standpoint, all nanofillers are three-dimensional and can therefore be characterized in particular by three characteristic dimensions ("length," "width," and "height"). However, some nanofillers have two of their characteristic dimensions that are significantly smaller than the third. The term "significantly smaller" should generally be understood as "more than 10 times smaller," preferably "more than 100 times smaller." To be precise, for the purposes of the present invention, carbon nanofillers have the shape of fibers. This means that two of their characteristic dimensions ("width" and "height") are, on average (in number), significantly smaller than the third dimension ("length"). Since the width is often close to the height of fibrous nanofillers, and the base of fibrous nanofillers is often circular, those skilled in the art generally understand the width and height as unique parameters, i.e., the diameters of the fibrous nanofillers. Therefore, fibrous nanofillers are generally characterized by their number-average diameter and number-average length. Generally, such materials have an aspect ratio, defined as the ratio of number average length to number average diameter, of at least 5, at least 10, at least 20, at least 50, or at least 100.

[0036] Component A1 is at least one fibrous carbon nanofiller whose number-average diameter is generally less than 1000 nm, preferably less than 500 nm, more preferably at most 200 nm.

[0037] The at least one fibrous carbon nanofiller may have a number average diameter (for bundles or ropes) of 1 nanometer (nm) to 3.5 nm or 4 nm. The at least one fibrous carbon nanofiller may have a number average length of at least 1 μm. The at least one fibrous carbon nanofiller may have an average aspect ratio, defined as the number average length divided by the number average diameter, of 100 or greater. The fibrous carbon nanofiller may have an average aspect ratio of 1000 or greater.

[0038] The number average diameter and number average length of the fibrous carbon nanofillers can be determined by any technique known to those skilled in the art, and advantageously, direct measurements on micrographs obtained by scanning electron microscopy (SEM) in combination with software image analysis techniques can be used.

[0039] The at least one fibrous carbon nanofiller contains more than 65% carbon. Preferably, the at least one fibrous carbon nanofiller contains at least 90% carbon, more preferably at least 95% carbon.

[0040] Component A1 is preferably 2·10 -2 Less than Ω.cm or up to 1·10 -2 Ω.cm, or 5-10 max. -3 Ω.cm, or 3·10 max. -3 Ω.cm, or 2·10 max. -3 Ω.cm, or 1·10 max -3 Component A1 preferably has a volume resistivity of at least 1·10 -6 Ω.cm, or at least 5·10 -6Ω.cm , or at least 1·10 -5 Component A1 has a volume resistivity of 1·10 -4 Ω.cm to 20·10 -4It may have a volume resistivity of up to Ω.cm.

[0041] The at least one carbon nanofiller (component A1) is selected from the group consisting of carbon nanotubes, surface-modified carbon nanotubes, carbon nanostructures, and any combination thereof.

[0042] Carbon nanotubes (CNTs) are intended to mean any material whose structure comprises at least one graphene layer rolled up in the form of a hollow cylinder capped at at least one, preferably each, of its ends by a fullerene half molecule. The term "cylinder" has a broad geometric meaning and must be understood as a surface resulting from the rotation of a line parallel to a fixed linear axis, thereby generating a curve around said axis. Circles and ellipses can be mentioned in particular as examples of possible shapes of this curve.

[0043] When the structure of a carbon nanotube useful in the present invention comprises only one graphene monolayer, the carbon nanotube is generally referred to as a "single-walled carbon nanotube" (SWCNT).

[0044] If the structure of a carbon nanotube useful in the present invention can comprise a coaxial aggregate of two SWCNTs, meaning one SWCNT is nested within the other, then the carbon nanotube is generally referred to as a "double-walled carbon nanotube" (DWCNT).

[0045] When the structure of a carbon nanotube useful in the present invention comprises a coaxial assembly of multiple SWCNTs (nested SWCNTs), the carbon nanotube is generally referred to as a "multi-walled carbon nanotube" (MWCNT). MWCNTs typically contain more than 3, preferably more than 6, more preferably more than 10 coaxial SWCNTs, and / or fewer than 60, preferably fewer than 40, more preferably fewer than 20 coaxial SWCNTs.

[0046] In the context of this disclosure, the term "carbon nanotubes" also includes carbon nanoropes, which refer to bundles of carbon nanotubes (eg, ropes of SWCNTs or MWCNTs).

[0047] Such carbon nanotubes are preferably selected from the group consisting of SWCNTs, DWCNTs, MWCNTs, ropes thereof, and any combination thereof, and more preferably selected from MWCNTs.

[0048] The number-average diameter of carbon nanotubes useful in the present invention can vary widely, particularly depending on whether SWCNTs, DWCNTs, or MWCNTs are used. Thus, the number-average diameter of SWCNTs is typically greater than 0.3 nm, preferably greater than 0.6 nm, and the diameter of SWCNTs is typically less than 3.0 nm, preferably less than 2.0 nm. The number-average diameter of DWCNTs is typically at least 0.5 nm, preferably greater than 0.8 nm, and typically less than 6 nm, preferably less than 5 nm, and more preferably less than 4 nm. The number-average diameter of MWCNTs is typically at least 3 nm, preferably greater than 6 nm, and typically less than 60 nm, preferably less than 40 nm, and more preferably less than 20 nm. Particularly suitable MWCNTs have a number-average diameter of about 10 to about 15 nm.

[0049] Carbon nanotubes useful in the present invention typically have lengths significantly greater than their diameters (e.g., Kirk-Othmer Encyclopedia of Chemical Technology (© John Wiley & Sons 2005), volume 17, Nanotechnology, pages 2-4). Specifically, the number-average length diameter of carbon nanotubes useful in the present invention, measured along their longitudinal axis, can be hundreds or even thousands of times greater than the number-average diameter. This number-average length is typically greater than 100 nm, preferably greater than 1 micron, more preferably greater than 3 microns, and / or typically less than 100 microns, preferably less than 50 microns, more preferably less than 30 microns.

[0050] The number average diameter and number average length of carbon nanotubes can be determined by any technique known to those skilled in the art, and advantageously by direct measurements on micrographs obtained by scanning electron microscopy (SEM) in combination with software image analysis techniques.

[0051] Carbon nanotubes useful in the present invention can be produced by any known technique. Non-limiting examples of such methods include arc discharge, pulsed laser vaporization (PLV), chemical vapor deposition (CVD), and gas-phase processes. Arc discharge is a plasma-based process that uses solid carbon electrodes for MWCNTs and carbon composites for SWCNTs. Pulsed laser vaporization (PLV) methods are essentially used to produce SWCNTs using a high-power pulsed laser directed at graphite powder supported on a metal catalyst. Chemical vapor deposition (CVD) can be used to produce both SWCNTs and MWCNTs by flowing heated precursor gases over a metal catalyst. Gas-phase processes can also be used to produce both SWCNTs and MWCNTs.

[0052] Carbon nanotubes typically have a purity of greater than 65% elemental carbon, with the remainder possibly consisting of residual catalyst impurities. Preferably, the carbon nanotubes contain at least 90% elemental carbon, more preferably at least 95% elemental carbon.

[0053] Preferably, the carbon nanotubes are 10 -2 ~10 -6 Ω.cm, preferably 10 -3 ~10 -5 It has a volume resistivity of Ω.cm.

[0054] SWCNTs are commercially available from Sumitomo Corporation, among others. DWCNTs are commercially available from Nanograf. MWCNTs are commercially available from Hyperion Catalysis, Mitsui & Co., Ltd., Nikkisou, Nanocyl, Applied Sciences, Shenzhen Nanotech, CNI, Sun Nanotech, and Iljin Nanotech, among others. Suitable MWCNTs include Nanocyl® NC7000 MWCNT grades with purities as low as 90% C purity, or Nanocyl® NC3100 MWCNT grades with purities greater than 95% C purity, both manufactured by Nanocyl (Belgium). Nanocyl® NC7000 MWCNTs have an average diameter of 9.5 nanometers, an average length of 1.5 microns, and a thickness of 250-300 m. 2 / g BET surface area and 1·10 -4 It has a volume resistivity of Ω.cm. Another suitable source for carbon nanotubes is FRIBIL® MWCNT from Hyperion Catalysis International, which has an outer diameter of about 10 nanometers and a length of greater than 10 microns.

[0055] As mentioned above, component A1 useful in the present invention may be at least one surface-modified carbon nanotube. That is, the outer surface of the carbon nanotubes may be chemically modified with functional groups, for example, to enhance their compatibility with at least one PAEK polymer. The functionalization of the carbon nanotubes may be non-covalent or covalent and is described, inter alia, in the Kirk-Othmer Encyclopedia of Chemical Technology, supra, pages 8-9. Covalent functionalization is often preferred and can be achieved in conventional ways by treating the carbon nanotubes with reagents such as oxidizing agents, acids, and bases. The functional groups may be, inter alia, carboxyl, ester, ketone, sulfonate, sulfonyl, or amino groups.

[0056] In a preferred embodiment, the surface-modified carbon nanotubes are amino-grafted carbon nanotubes, in particular as disclosed in Z. Cao et al. / Applied Surface Science 353 (2015) pp. 873-881.

[0057] The number average diameter and number average length of the surface-modified carbon nanotubes useful in the present invention can vary widely, particularly depending on the SWCNT, DWCNT, or MWCNT prior to modification.

[0058] As mentioned above, component A1 useful in the present invention may be carbon nanostructures, which are typically chemically crosslinked carbon nanotubes.

[0059] Bridged carbon nanotubes are notably the commercially available product Athlos™ available from Cabot Corporation.

[0060] The number average diameter and number average length of the nanostructures useful in the present invention, particularly the chemically crosslinked carbon nanotubes, can vary widely depending on the particular SWCNT, DWCNT, or MWCNT before they are crosslinked.

[0061] Advantageously, component A1 does not contain carbon hollow nanospheres.

[0062] Component A1 has a particle size of 100 to 800 μm when measured according to the Brunauer-Emmett-Teller method described in the journal "The Journal of the American Chemical Society, 60, 309 (1938)" such as ASTM D6556. 2 / g, preferably 150 to 600 μm 2 / g, more preferably 200 to 350 μm 2 / g, most preferably 200 to 300 μm 2 / g specific surface area (BET).

[0063] The amount of component A1 is at least 1 wt. %, preferably at least 1.5 wt. %, or more preferably at least 2 wt. %, based on the total weight of the polyaryl ether composition (C), and at most 10 wt. %, preferably at most 5 wt. %, more preferably at most 4 wt. %.

[0064] Because component A1 can be difficult to handle due to its nanostructure, component A1 may first be dispersed in a polymeric carrier to form a nanofiller masterbatch ("MB"). The PAEK polymer, nanofiller MB, at least one non-fibrous filler (component A2), and optional components or additives are then fed into a mixer, preferably a melt mixer. The polymeric carrier is preferably the same as the PAEK polymer in polyarylether composition (C), but may be different from the PAEK polymer. Typically, the polymeric carrier is selected from polyaryletherketone polymers, such as those containing 50% by weight of repeating units (R1) of any of formulas (I) to (XXI) described herein, but may also contain or consist of poly(biphenyl ether sulfone) or polyether sulfone. The polymeric carrier is preferably the same as the PAEK polymer used in polyarylether composition (C), with both the polymeric carrier and the PAEK polymer containing more than 50% by weight of repeating units (R1) of formula (VII).

[0065] Non-fibrous filler (component A2) Non-fibrous fillers (ingredient A2) are considered herein to have a three-dimensional structure having a length, width, and thickness (or height).

[0066] The dimensions (length, width, thickness) of non-fibrous fillers can be determined by direct measurement on micrographs obtained by scanning electron microscopy (SEM).

[0067] The average dimensions (i.e., length, width, and thickness) of the non-fibrous filler can be the average length of component A2 before it is incorporated into the polyaryl ether composition (C), or can be the average dimensions of component A2 in the polyaryl ether composition (C).

[0068] The non-fibrous filler (component A2) may be a particulate filler. Particulate fillers have a low aspect ratio, defined as the ratio of their largest dimension to their smallest dimension, of less than 2. Particulate fillers are usually spherical or ovoid in shape. Examples of particulate fillers are zinc oxide, zinc sulfide, silica, dolomite, alumina, calcium sulfate, calcium carbonate, titanium oxide, clay, glass powder, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluororesin, barium sulfate, graphite, and carbon powder.

[0069] The non-fibrous filler (component A2) may be in flake or plate-like form. The flake or plate-like filler may have an aspect ratio, defined as the ratio of its largest dimension to its smallest dimension, of greater than 5, preferably at least 10. The flake or plate-like filler has a substantially two-dimensional shape. This means that, like a thin plate, one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length). Examples of flake or plate-like fillers are talc, kaolin, mica, and glass flakes.

[0070] The glass flakes used as component A2 are silica-based glass compounds containing several metal oxides that can be tailored to form different types of glass. The primary oxide is silica in the form of silica sand; other oxides, such as calcium, sodium, and aluminum, are incorporated to lower the melting temperature and prevent crystallization. Any glass type, such as A, C, D, E, M, S, R, or T glass, or a mixture thereof, preferably C or E glass, can be used as the glass filler. C glass contains alkali components and has high acid resistance. E glass contains almost no alkali, so it has high stability in resins and is not electrically conductive.

[0071] The glass flakes as component A2 preferably comprise or consist of glass flakes using C-glass or E-glass. Suitable glass flakes (C) using E-glass or C-glass are commercially available from NSG under the trademark GLASFLAKE®. E-glass flakes are particularly effective in preventing warpage and improving dimensional accuracy in precision parts made from thermoplastic polymers. FINEFLAKE® glass flakes, also available from NSG with an average thickness of 0.4 to 1 micron, are suitable for fine, thin molded parts. In some embodiments, the glass flakes may be granulated. For example, FLEKA® granulated glass flakes using E-glass are commercially available from NSG.

[0072] Good results have been obtained with mica in the form of a plate-like filler, such as Suzorite® from IMERYS. For example, Suzorite® 200-HK, a phlogopite mica product, is a plate-like mineral with an average particle size of 60 microns.

[0073] The non-fibrous fillers (ingredient A2) useful in the present invention are preferably not electrically conductive.

[0074] Preferably, the non-fibrous filler (component A2) has a diameter, d, in the range of 1 to 300 μm, preferably 10 to 200 μm, preferably 10 to 180 μm, as measured by electron microscopy or laser scattering in isopropanol. 50 The average particle size distribution is also called

[0075] Component A2 may preferably be selected from the group consisting of mica, metal-coated mica, glass flake, wollastonite, talc, and any combination thereof.

[0076] The non-fibrous filler (component A2) is preferably not functionalized with at least one of sulfonate, phosphonic acid, carboxyl (e.g., carboxylic acid), amino, hydroxyl, or thiol groups.

[0077] The non-fibrous filler (component A2) contains C 12 ~C 36 Alkyl group or C5-C 30 It does not include organically modified micas such as micas organically modified with organic phosphates or ammonium salts substituted with aromatic groups.

[0078] When a flaky filler is present in the polyaryl ether composition (C), the average thickness of the flakes may be 0.1 to 5 μm, preferably 0.2 to 2 μm, more preferably 0.5 to 1.5 μm, as measured by electron microscopy.

[0079] The non-fibrous filler (component A2) represents 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, even more preferably at least 30% by weight, and / or at most 50% by weight, preferably at most 40% by weight, more preferably at most 35% by weight, based on the total weight of the polyaryl ether composition (C).

[0080] Furthermore, no pre-treatment is required to combine component A1 with component A2 prior to blending, e.g., component A1 does not need to be coated onto component A2.

[0081] When component A1 and component A2 are present in polyaryl ether composition (C), the weight of the PAEK polymer is at least 30 wt.-%, or at least 40 wt.-%, or at least 50 wt.-% and / or at most 90 wt.-%, preferably at most 80 wt.-%, more preferably at most 70 wt.-%, based on the total weight of polyaryl ether composition (C).

[0082] When components A1 and A2 are present in polyaryl ether composition (C), the PAEK polymer is preferably not crosslinked to components A1 and / or A2, in particular, no bonds exist between the PAEK polymer and component A2.

[0083] Optional Other Polymers The polyaryl ether composition (C) may further comprise at least one poly(biphenyl ether sulfone) (hereinafter "component A3") and / or at least one polyether sulfone (hereinafter "component A4").

[0084] For purposes of the present invention, poly(biphenyl ether sulfone) is a poly(biphenyl ether sulfone) 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 repeat units are repeat units (R2) selected from: [ka] is intended to represent a polycondensation polymer in which

[0085] The use of repeat units of formula (2) in repeat units (R2) generally provides the best overall cost-property balance and the highest level of toughness. For purposes of the present invention, polyphenylsulfone (PPSU) polymer is intended to refer to a polycondensation polymer in which at least 50 mole % of the repeat units are repeat units (R2) of formula (2).

[0086] The poly(biphenyl ether sulfone) (component A3) may in particular be a homopolymer, a random, alternating or block copolymer.

[0087] If the poly(biphenyl ether sulfone) (component A3) is a copolymer, its repeating units may in particular be (i) repeating units (R2) of at least two different formulae selected from the 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), e.g. [ka] It may be composed of:

[0088] Preferably, more than 70 mol %, more preferably more than 85 mol %, of the repeating units of the poly(biphenyl ether sulfone) (component A3) are repeating units (R2) of formula (2). Even more preferably, essentially all of the repeating units of the poly(biphenyl ether sulfone) (component A3) are repeating units (R2) of formula (2). Most preferably, all of the repeating units of the poly(biphenyl ether sulfone) (component A3) are repeating units (R2) of formula (2).

[0089] Superior results are usually obtained when the poly(biphenyl ether sulfone) (ingredient A3) is a polyphenylsulfone homopolymer, i.e., a polymer in which essentially all, if not all, of the repeating units are of formula (2). RADEL® polyphenylsulfone from Solvay Specialty Polymers USA, LLC is an example of a polyphenylsulfone homopolymer (PPSU).

[0090] Poly(biphenyl ether sulfone) (component A3) can be prepared by any method known in the art, such as those described in U.S. Patent Application Publication Nos. 3,634,355; 4,008,203; 4,108,837; and 4,175,175, the entire contents of which are incorporated herein by reference.

[0091] The polyaryl ether composition (C) may contain only one poly(biphenyl ether sulfone) (component A3), or it may contain two, three, or even more than three poly(biphenyl ether sulfone)s (component A3).

[0092] For purposes of the present invention, polyethersulfone (component A4) is defined as having 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% repeat units of formula (J) (R PES ): [ka] represents a polymer comprising:

[0093] The mole percent is based on the total moles of repeat units in the polyethersulfone polymer.

[0094] Polyethersulfone polymers can be prepared by known methods such as the condensation of bisphenol S with dichlorodiphenol sulfone, and are available, inter alia, as VERADEL® PESU from Solvay Specialty Polymers USA, LLC.

[0095] If poly(biphenyl ether sulfone) (component A3) and / or polyether sulfone (component A4) are present in the polyaryl ether 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 total weight of the PAEK polymer and component A3 / component A4 in the polyaryl ether composition (C).

[0096] The polyarylether composition (C) may further comprise a polymeric carrier different from the PAEK polymer present in the polyarylether composition (C). Typically, the polymeric carrier can be selected from polyaryletherketone polymers, such as those containing more than 50 wt. % of repeating units (R1) of any of formulas (I) to (XXI) described herein, but may also comprise or consist of poly(biphenylethersulfone) or polyethersulfone. The polymeric carrier preferably contains more than 50 wt. % of repeating units (R1) of formula (VII). When such a polymeric carrier different from the PAEK 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 95 wt. %, preferably at most 90 wt. %, based on the total weight of the PAEK polymer and the polymeric carrier in the polyarylether composition (C).

[0097] 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.

[0098] 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.

[0099] To produce white, black, or colored articles, one or more pigments may be particularly desirable additives in the polyaryl ether composition (C). The pigments may be black pigments such as carbon black, white pigments such as zinc oxide, zinc sulfide, lithopone, antimony white, titanium dioxide (rutile or anatase, preferably rutile), and / or colored pigments. The pigments are typically present in an amount of 0 to 6 wt. %, preferably 0.05 to 5 wt. %, and particularly 0.1 to 3 wt. %, based on the total weight of the polyaryl ether composition (C).

[0100] Antioxidants may be particularly desirable additives in the polyaryl ether composition (C). Antioxidants can improve the thermal 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 situations) by, for example, helping to prevent polymer degradation while making the polymer processable at higher temperatures.

[0101] Method for producing polyaryl ether composition (C) The polyaryl ether composition (C) of the present invention can be prepared using methods well known in the art.

[0102] For example, the polyaryl ether composition (C) is produced by melt blending at least one PAEK polymer, at least one electrically conductive carbon nanofiller (component A1), at least one non-fibrous filler (component A2), and 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 all at once to the melt mixer, or they can be added gradually in a batchwise manner. When the components are added gradually in a batchwise manner, a portion of the component is added first, then melt mixed with the remaining portion of the component, and thereafter added until a properly mixed composition is obtained.

[0103] Because the carbon nanofiller (component A1) can be difficult to handle due to its nanostructure, component A1 may first be dispersed in a polymeric carrier to form a nanofiller masterbatch ("MB"). The PAEK polymer, nanofiller MB (including component A1), at least one non-fibrous filler (component A2), and optional additives are then fed into a melt mixer. The polymeric carrier in the MB is preferably the same as the PAEK polymer in polyarylether composition (C), but may be different from the PAEK polymer. Typically, the polymeric carrier is selected from polyaryletherketone polymers, such as those containing more than 50 wt. % of repeating units (R1) of any of formulas (I) to (XXI) described herein, but may also comprise or consist of poly(biphenyl ether sulfone) or polyether sulfone. The polymeric carrier is preferably the same as the PAEK polymer used in polyarylether composition (C), with both the polymeric carrier and the PAEK polymer containing more than 50 wt. % of repeating units (R1) of formula (VII).

[0104] Goods As mentioned above, the present invention further relates to articles, preferably molded articles, comprising or made from said polyaryl ether composition (C).

[0105] The polyaryl ether compositions (C) detailed above can be processed by conventional melt processing techniques, including, inter alia, extrusion, injection molding, and compression molding, to provide shaped articles.

[0106] Such articles have a viscosity of 1·10 s, measured in accordance with ASTM D257. +5 Ω.cm to 5·10 +12 It has a volume resistivity of up to Ω.cm.

[0107] The item must be at least 10 6 Ω / sq and up to 10 9 It was found to have a surface resistivity of Ω / sq.

[0108] 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.

[0109] The articles have also been found to have a flow direction mold shrinkage or transverse direction mold shrinkage according to method ASTM D955 of at most 1.0%, at most 0.9%, at most 0.8%, or at most 0.7%, preferably 0.1-0.6%, more preferably 0.2-0.5%.

[0110] As used herein, the term "mold shrinkage" refers to the shrinkage of a polymer as it cools after the molding process. This is typically used to properly machine injection molds to achieve the desired dimensions of the final part. Flow direction mold shrinkage refers to the mold shrinkage in the flow direction. Transverse direction mold shrinkage (or cross-flow mold shrinkage) refers to the mold shrinkage in the transverse (cross-flow) direction.

[0111] The molded articles of the present invention are preferably selected from the group consisting of: (i) extruded shapes, preferably selected from the group consisting of rods, slabs, tubes, pipes or profiles; and (ii) injection molded articles.

[0112] According to certain embodiments, the shaped article is in the form of a substantially two-dimensional article, such as, for example, films, sheaths, and sheets, parts in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length).

[0113] According to another embodiment, the molded article is provided as a three-dimensional part that extends substantially in three dimensions of space in a similar manner, for example in the form of a complex shaped part having concave or convex portions, possibly including undercuts, inserts, etc.

[0114] The polyaryl ether composition (C) can be used to manufacture antistatic 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.

[0115] Molded articles include, but are not limited to, part or all of a reticle carrier such as those shown in U.S. Pat. Nos. 6,513,654 and 6,216,873; a disc shipper such as those shown in U.S. Pat. Nos. 4,557,382 and 5,253,755; a chip tray such as those shown in U.S. Pat. No. 6,857,524; and a wafer carrier such as those shown in U.S. Pat. No. 6,848,578, each of which references is incorporated herein by reference in its entirety.

[0116] According to a particular embodiment, a molded article made from the polyarylether composition (C) detailed above is provided as part 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]

[0117] 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.

[0118] material PEEK: Solvay Specialty Polymer's Ketaspire® KT-890P Component A1: MWCNT: Multi-walled carbon nanotubes Nanocyl (registered trademark) NC7000 from Mitsubishi Gas Chemical Company, Inc., with an average diameter of 9.5 nanometers, an average length of 1.5 microns, and a BET surface area of ​​250-300 m 2 / g, volume resistivity 1·10 -4 Ω.cm CNT Masterbatch (CNT MB): 10 wt% Nanocyl® NC7000 mixed with 90 wt% Ketaspire® KT-890P PEEK ·Ingredient A2: Plate-like morphology of mica: Suzorite® 200-HK from IMERYS Glass flakes: Nippon Sheet Glass Co., Ltd.'s very thin E-glass flakes MEG160FY-M03, average length 160 microns (flat surface), thickness 0.7 microns

[0119] 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, thickness = 4 mm). Impact strength - ISO180 Notched and unnotched Izod impact strength properties were measured in kJ / m using ten injection molded ISO Type 1A bars (length 80±2 mm, width 10±0.2 mm, thickness 4±0.2 mm). 2 Measured in units. Mold shrinkage rate - ISO294 (ASTM D955) Mold shrinkage (machine direction % mold shrinkage and cross direction % mold shrinkage) was measured on five injection molded plaques measuring 60 mm wide x 60 mm long x 2 mm thick. 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).

[0120] Example 1 Resin and filler were fed into a ZSK-26mm co-rotating twin-screw extruder using gravimetric feeders adjusted for each run to achieve the target blend ratios in Table 1. Compounding conditions for all blends and controls are listed in Table 2. Extruder settings were the same for all runs.

[0121] The prepared compositions were then processed into molded articles by injection molding according to ASTM D3641.

[0122] [Table 1]

[0123] [Table 2]

[0124] Example 2 The three ingredients for preparing Sample E2 are listed in Table 1. The composition and molded article of Example 2 were prepared in the same manner as Example 1.

[0125] Comparative Example 3 The two components (PEEK, A1) for preparing sample CE3 are listed in Table 1.

[0126] The composition and molded article of Comparative Example 3 were prepared in the same manner as Example 1.

[0127] As shown by the results in Table 3, compositions according to the present invention (E1 and E2) are effective in improving the volume and surface resistivity of the articles, making them suitable for ESD applications. In comparison, the CE3 sample, which contained only MWCNTs, had low volume and surface resistivities that were outside the range suitable for ESD applications.

[0128] Furthermore, the compositions according to the invention (E1 and E2) optimized the mold shrinkage of the articles, reducing it to 0.5% or 0.6% compared to CE3, which has much higher flow and transverse mold shrinkage (1.5% and 1.6%, respectively).

[0129] [Table 3]

[0130] 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, this statement shall control. Any incorporation by reference of a document is limited so that no subject matter contrary to the express disclosure herein is incorporated.

[0131] 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 following claims, which scope includes all equivalents of the subject matter of the claims. Each and every claim is incorporated herein as an embodiment of the present invention. Accordingly, the claims are further description 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 conductive carbon nanofiller (component A1), at least one non-fibrous filler (component A2); A polyaryl ether composition (C) containing:

2. The PAEK polymer comprises more than 50 weight percent, at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, at least 99 weight percent, based on the total weight of repeat units in the PAEK polymer, of the following formulas (I)-(V): 【Chemical 1】 (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. A repeating unit (R ＰＡＥＫ The polyaryl ether composition (C) of claim 1, comprising:

3. the at least one conductive carbon nanofiller (component A1) is selected from the group consisting of carbon nanotubes, surface-modified carbon nanotubes, carbon nanostructures, and any combination thereof; the carbon nanotubes or surface-modified carbon nanotubes are selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, ropes thereof, and any combination thereof, preferably multi-walled carbon nanotubes; The carbon nanostructures are chemically crosslinked carbon nanotubes. The polyaryl ether composition (C) according to claim 1 or 2.

4. The polyaryl ether composition (C) according to claim 3, wherein the surface-modified carbon nanotubes are amino-grafted carbon nanotubes.

5. The polyaryl ether composition (C) according to any one of claims 1 to 4, wherein component A1 does not contain hollow carbon nanospheres.

6. The polyarylether composition (C) according to any one of claims 1 to 5, wherein the polyarylether composition (C) comprises at least 1 wt%, preferably at least 1.5 wt%, more preferably at least 2 wt%, and / or at most 10 wt%, preferably at most 5 wt%, more preferably at most 4 wt%, of component A1, based on the total weight of the polyarylether composition (C).

7. The polyaryl ether composition (C) according to any one of claims 1 to 6, wherein component A2 is selected from the group consisting of mica, metal-coated mica, glass flake, wollastonite, talc, and any combination thereof.

8. The polyaryl ether composition (C) according to any one of claims 1 to 7, wherein component A2 is in a plate-like or flake-like form.

9. The polyaryl ether composition (C) according to any one of claims 1 to 8, wherein component A2 is not electrically conductive.

10. The polyarylether composition (C) according to any one of claims 1 to 9, comprising more than 10 wt%, preferably at least 15 wt%, more preferably at least 20 wt%, even more preferably at least 30 wt%, and / or up to 50 wt%, preferably up to 40 wt%, more preferably up to 35 wt%, of component A2, based on the total weight of the polyarylether composition (C).

11. The polyaryl ether composition (C) according to any one of claims 1 to 10, wherein the PAEK polymer is not crosslinked to the component A1 and / or the component A2.

12. at least 40% to less than 89% by weight of said at least one PAEK polymer; at least 1% by weight and at most 10% by weight of said component A1; more than 10% by weight and up to 50% by weight of said component A2; Contains The polyaryl ether composition (C) according to any one of claims 1 to 11, wherein the weight percentages are based on the total weight of the 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 electrically conductive carbon nanofiller (component A1), the at least one non-fibrous filler (component A2), and any optional components or additives.

14. 14. The method for producing the polyaryl ether composition (C) of claim 13, wherein the component A1 is first dispersed in a polymeric carrier to form a nanofiller masterbatch ("MB"), and then the PAEK polymer, the nanofiller MB, the at least one non-fibrous filler (component A2), and optional components or additives are fed into a melt-mixer.

15. A molded article suitable for electrostatic discharge applications, comprising or produced from the polyarylether composition (C) according to any one of claims 1 to 12, having a viscosity of 1.10 as measured according to ASTM D257. ＋５ Ω.cm up to 5-10 ＋１２ The molded article has a volume resistivity of Ω.cm.

16. At least 10 ６ Ω / sq and up to 10 ９ 16. The shaped article of claim 15, having a surface resistivity of Ω / sq and a flow direction mold shrinkage or transverse direction mold shrinkage according to method ASTM D955 of at most 1.0%, at most 0.9%, at most 0.8%, or at most 0.7%, preferably 0.1 to 0.6%.

17. 17. The molded article of claim 15 or 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, a fluid tube, and a chemical container.

Images