Resin composition, molded article, composite, and uses thereof

Abstract

Provided are: a molded body having high bend elasticity and also having exceptional heat resistance and impact resistance at low temperature; and a resin composition with which it is possible to obtain the molded body.　The present invention is: a resin composition containing a polyallyl ether ketone, a fluorine-containing elastomer, and an inorganic filler, the proportion of the fluorine-containing elastomer being 1-45 vol% relative to the total of the volume of the polyallyl ether ketone and the volume of the fluorine-containing elastomer, the proportion of the inorganic filler being 1-50 mass%, and the resin composition having a higher loaded deflection temperature under a load of 1.82 MPa in conformance with ASTM D648 than the comparative composition described below; and a molded body of the resin composition.　Comparative composition: a resin composition that contains a polyallyl ether ketone and a fluorine-containing elastomer but does not contain an inorganic filler, said resin composition having the same type of polyallyl ether ketone, the same type of fluorine-containing elastomer, and the same volume proportion of fluorine-containing elastomer relative to the total of the volume of the polyallyl ether ketone and the volume of the fluorine-containing elastomer as the resin composition described above, excluding the difference regarding the presence of the inorganic filler.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a molded article, a composite, and uses thereof. [Background technology]

[0002] Polyaryletherketone (polyaryletherketone, polyetherketone, polyetherketoneketone, etc.) has excellent heat resistance and a high flexural modulus, and is therefore widely used in a variety of fields as a material for molded articles. However, molded articles of polyaryl ether ketone have insufficient impact resistance at room temperature or low temperature.

[0003] The following has been proposed as a resin composition capable of producing a molded article of polyaryl ether ketone having improved impact resistance. A resin composition comprising polyaryletherketone and a fluorine-containing elastomer, in which the fluorine-containing elastomer is dispersed in the polyaryletherketone, the number average particle size of the fluorine-containing elastomer is 1 to 300 μm, the volume ratio of the polyaryletherketone to the fluorine-containing elastomer is 97:3 to 55:45, and the resin composition has a flexural modulus of 1000 to 3700 MPa (Patent Document 1). A resin composition comprising polyaryletherketone and a fluorine-containing elastomer, wherein the ratio of the melt flow rate of the polyaryletherketone to the fluorine-containing elastomer under specific conditions is 0.2 to 5.0, and the proportion of the volume of the polyaryletherketone in the total volume of the polyaryletherketone and the fluorine-containing elastomer is 60 to 97% by volume (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 188280 [Patent Document 2] International Publication No. 2019 / 198771 Summary of the Invention [Problem to be solved by the invention]

[0005] The resin compositions described in Patent Documents 1 and 2 contain a fluorine-containing elastomer, which may impair the high flexural modulus of polyaryl ether ketone. In addition, the heat resistance of a molded article is insufficient, and there is also room for improvement in impact resistance at low temperatures. The present invention provides a molded article having a high flexural modulus and excellent heat resistance and impact resistance at low temperatures, and a resin composition from which such a molded article can be obtained. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by a specific resin composition containing polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler. According to the common knowledge of a person skilled in the art, it is expected that when three components, i.e., polyaryl ether ketone, fluorine-containing elastomer, and inorganic filler, are used, the heat resistance and flexural modulus of a molded article will be lower than those of a composition containing two components, i.e., polyaryl ether ketone and inorganic filler. However, the present inventors unexpectedly found that a resin composition containing polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler provides a molded article with improved heat resistance, flexural modulus, and low-temperature impact resistance beyond the range normally expected by a person skilled in the art, compared with a composition containing two components, polyaryl ether ketone and an inorganic filler, and completed the present invention.

[0007] The present invention has the following aspects. [1] A resin composition comprising a polyaryletherketone, a fluorine-containing elastomer, and an inorganic filler, wherein the volume ratio of the fluorine-containing elastomer is 1 to 45% by volume relative to the total volume of the polyaryletherketone and the fluorine-containing elastomer, and the mass ratio of the inorganic filler is 1 to 50% by mass relative to the resin composition, and the resin composition has a deflection temperature under load measured under a load of 1.82 MPa in accordance with ASTM D648 that is higher than the deflection temperature under load of the following comparative composition: Comparative composition: A resin composition containing the polyaryletherketone and the fluorine-containing elastomer but not the inorganic filler, which is the same as the resin composition in the type of the polyaryletherketone, the type of the fluorine-containing elastomer, and the volume ratio of the fluorine-containing elastomer to the total volume of the polyaryletherketone and the fluorine-containing elastomer, except for the presence or absence of the inorganic filler.

[0008] [2] The resin composition of [1], wherein the fluorine-containing elastomer is a copolymer having units based on tetrafluoroethylene and units based on propylene, a copolymer having units based on hexafluoropropylene and units based on vinylidene fluoride, or a copolymer having units based on tetrafluoroethylene and units based on a compound represented by the following formula (1): CF2=CF(OR F ) ···(1) However, R F is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms. [3] The resin composition according to [1] or [2], wherein the polyaryletherketone is polyetherketone, polyetheretherketone, or polyetherketoneketone. [4] Lightness L in hue measurement according to JIS-Z8781-4 * The resin composition according to any one of [1] to [3], wherein the value of [R] is 60 or more.

[0009] [5] The resin composition according to any one of [1] to [4], wherein the inorganic filler is a fibrous inorganic filler, a tabular inorganic filler, or a granular inorganic filler. [6] The resin composition according to any one of [1] to [5], wherein the inorganic filler is at least one selected from the group consisting of carbon fiber, graphite, carbon nanotube, glass fiber, and silica. [7] The resin composition according to any one of [1] to [6], wherein at least a part of the inorganic filler is carbon fiber or glass fiber.

[0010] [8] The resin composition according to any one of [1] to [7], further comprising a polymer filler. [9] The resin composition according to [8], wherein the polymer filler is polytetrafluoroethylene.

[10] The resin composition according to any one of [1] to [9], further comprising at least one selected from the group consisting of a plasticizer, an ultraviolet absorber, and a light stabilizer.

[0011]

[11] A molded article which is a molded article of the resin composition according to any one of [1] to

[10] above.

[12] A composite in which the molded article according to

[11] above is combined or laminated with another material.

[13] A portable electronic device, a sliding member, a three-dimensional circuit component, an electric wire, or a member for excavating energy resources, comprising the molded article according to

[11] or the composite according to

[12] . [Effects of the Invention]

[0012] According to the resin composition of the present invention, a molded article having a high flexural modulus, excellent heat resistance, and excellent impact resistance at low temperatures can be obtained. The molded article of the present invention has a high flexural modulus, and is excellent in heat resistance and impact resistance at low temperatures. DETAILED DESCRIPTION OF THE INVENTION

[0013] The meanings and definitions of terms used in this specification are as follows: The "volume" of polyaryletherketone or fluorine-containing elastomer is calculated by multiplying the mass (g) of the polyaryletherketone or fluorine-containing elastomer by its specific gravity (g / cm 3 ) is the value calculated by dividing The "specific gravity" of the polyaryletherketone or fluorine-containing elastomer is a value at 23°C measured by the water displacement (suspension) method. The "number average particle size" of the fluorine-containing elastomer in the resin composition is determined by observing a molded product of the resin composition under a scanning electron microscope, measuring the maximum diameters of 100 randomly selected particles, and calculating the arithmetic mean. The "number average particle size" of the fluoroelastomer before melt-kneading is the arithmetic mean value of the maximum diameters of 100 randomly selected particles measured by observing the fluoroelastomer under an optical microscope. The "flexural modulus" of the molded article is a value measured in accordance with ASTM D790. The "melting point" of a polyaryletherketone is the temperature corresponding to the maximum value of the melting peak as measured by differential scanning calorimetry (DSC). The "fluorine content" of a fluorine-containing elastomer refers to the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluorine-containing elastomer. The fluorine content is a value calculated from the molar ratio of each unit in the fluorine-containing elastic copolymer determined by melt NMR measurement and total fluorine content measurement. Mooney viscosity (ML) of fluorine-containing elastomer 1+10 ,121℃) is a value measured in accordance with JIS K 6300-1:2000 (corresponding international standards ISO 289-1:2005, ISO 289-2:1994). The term "monomer-based unit" refers collectively to an atomic group formed directly by polymerizing one monomer molecule and an atomic group obtained by chemically converting a portion of the atomic group. In this specification, a monomer-based unit is also simply referred to as a monomer unit. For example, a TFE-based unit is also referred to as a TFE unit. "Monomer" means a compound having a polymerizable carbon-carbon double bond.

[0014] <Resin composition> The resin composition of the present invention contains polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler. The resin composition of the present invention may contain components other than the polyaryl ether ketone, the fluorine-containing elastomer, and the inorganic filler (hereinafter referred to as "other components"), as necessary, within the range that does not impair the effects of the present invention.

[0015] The deflection temperature under load T0 of the resin composition of the present invention is higher than the deflection temperature under load T1 of the comparative composition (1) below. The deflection temperature under load T0 is a value measured for the resin composition of the present invention in accordance with ASTM D648 under a load of 1.82 MPa. Comparative composition (1): A resin composition containing polyaryletherketone and a fluorine-containing elastomer but not containing an inorganic filler. Except for the presence or absence of an inorganic filler, the type of polyaryletherketone, the type of fluorine-containing elastomer, and the total volume V of the polyaryletherketone and the fluorine-containing elastomer are the same. A+B The volume ratio of the fluorine-containing elastomer to the resin composition is the same as that of the resin composition.

[0016] When the resin composition of the present invention does not contain other components, the comparative composition (1) is a composition consisting only of polyaryl ether ketone and a fluorine-containing elastomer. Therefore, the composition of the comparative composition (1) can be determined based on the volume of the polyaryl ether ketone and the volume of the fluorine-containing elastomer in the resin composition of the present invention. When the resin composition of the present invention contains other components, the comparative composition (1) is a composition consisting of polyaryl ether ketone, a fluorine-containing elastomer, and other components. In this case, the contents of the other components in the comparative composition (1) relative to the polyaryl ether ketone, the fluorine-containing elastomer, and the total amount thereof are all the same as the contents of the other components in the resin composition of the present invention. The polyaryletherketone, fluorine-containing elastomer, and other components in the comparative composition (1) are all the same as the polyaryletherketone, fluorine-containing elastomer, and other components in the resin composition of the present invention. Therefore, the deflection temperature under load T1 is a value measured under a load of 1.82 MPa in accordance with ASTM D648 for the comparative composition (1) whose composition is determined based on the composition of the resin composition of the present invention.

[0017] The lower limit of the difference between the deflection temperature under load T0 and the deflection temperature under load T1 (T0-T1) is above 0°C, preferably 40°C or higher, more preferably 60°C or higher, even more preferably 80°C or higher, and most preferably 100°C or higher. When T0-T1 is equal to or higher than the lower limit, the heat resistance of the molded article becomes even more excellent. The upper limit of T0-T1 is not particularly limited, and the higher the value, the better. T0-T1 may be, for example, 180°C or lower, or 160°C or lower.

[0018] The lower limit of the deflection temperature under load T0 of the resin composition of the present invention is not particularly limited as long as it is a value greater than the deflection temperature under load T1, but is preferably 160°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, and most preferably 240°C or higher. If the deflection temperature under load T0 is equal to or greater than the lower limit, the heat resistance of the molded article will be even better. The upper limit of the deflection temperature under load T0 is not particularly limited, and the higher the value, the better. The deflection temperature under load T0 may be, for example, 330°C or lower, or 320°C or lower.

[0019] The deflection temperature under load T0 of the resin composition of the present invention is preferably higher than the deflection temperature under load T2 of the comparative composition (2) described below. Comparative composition (2): A resin composition containing polyaryletherketone and an inorganic filler but not a fluorine-containing elastomer, in which the type of polyaryletherketone and the type of inorganic filler are the same as those in the composition of the present invention, and the volume of the polyaryletherketone is 1 / 3 the total volume V of the polyaryletherketone and the fluorine-containing elastomer in the resin composition of the present invention. A+Band the mass ratio of the inorganic filler is the same as the mass ratio of the inorganic filler in the resin composition of the present invention.

[0020] When the resin composition of the present invention does not contain other components, the comparative composition (2) is a composition consisting only of polyaryl ether ketone and an inorganic filler. Therefore, the composition of the comparative composition (2) can be determined based on the volume of the polyaryl ether ketone, the volume of the fluorine-containing elastomer, and the mass of the inorganic filler in the resin composition of the present invention. When the resin composition of the present invention contains other components, the composition of the comparative composition (2) can be determined based on the volume of the polyaryl ether ketone, the volume of the fluorine-containing elastomer, the amounts of the other components, and the mass of the inorganic filler in the resin composition of the present invention. The polyaryletherketone, inorganic filler, and other components in the comparative composition (2) are all the same as those in the resin composition of the present invention. Therefore, the deflection temperature under load T2 is a value measured under a load of 1.82 MPa in accordance with ASTM D648 for the comparative composition (2) whose composition is determined based on the composition of the resin composition of the present invention.

[0021] The lower limit of the difference between the deflection temperature under load T0 and the deflection temperature under load T2 (T0 - T2), is preferably above 0°C, more preferably 5°C or higher, even more preferably 10°C or higher, particularly preferably 15°C or higher, and most preferably 20°C or higher. When T0 - T2 is equal to or higher than the lower limit, the heat resistance of the molded article is even better. Typically, when three components (polyaryletherketone, fluorine-containing elastomer, and inorganic filler) are used, the heat resistance is expected to be lower than that of a composition containing only two components (polyaryletherketone and inorganic filler) due to the use of the fluorine-containing elastomer. Therefore, when the deflection temperature under load T0 is higher than the deflection temperature under load T2, the heat resistance of the molded article can be said to be significantly better, contrary to the expectations of those skilled in the art. The upper limit of T0 - T2 is not particularly limited, and the higher the value, the better. T0 - T2 may be, for example, 80°C or lower, or 70°C or lower.

[0022] The volume ratio of the fluorine-containing elastomer to the total volume of the polyaryl ether ketone and the fluorine-containing elastomer is 1 to 45% by volume, preferably 2 to 42% by volume, more preferably 3 to 40% by volume, and even more preferably 5 to 35% by volume. When the volume ratio of the fluorine-containing elastomer is at least the lower limit of the above range, a molded article having excellent impact resistance can be obtained. When the volume ratio of the fluorine-containing elastomer is at most the upper limit of the above range, a molded article having excellent heat resistance and mechanical properties can be obtained.

[0023] The ratio of the total volume of the polyaryletherketone and the fluorine-containing elastomer to the volume of the resin composition excluding the volume of the inorganic filler is preferably 50 to 100% by volume, more preferably 60 to 100% by volume, and even more preferably 70 to 100% by volume. When the ratio is less than 100% by volume, the resin composition contains other components. When the total volume of the polyaryl ether ketone and the fluorine-containing elastomer is at least the lower limit of the above range, the molded article can fully exhibit heat resistance, mechanical properties, and impact resistance. When the resin composition contains other components, when the ratio of the total volume of the polyaryl ether ketone and the fluorine-containing elastomer to the volume of the resin composition excluding the inorganic filler is 99% by volume or less, the molded article can be endowed with new properties derived from the other components.

[0024] The mass proportion of the inorganic filler is 1 to 50 mass%, preferably 5 to 45 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 40 mass%, relative to the resin composition of the present invention. When the mass proportion of the inorganic filler is equal to or greater than the lower limit, the molded article has excellent heat resistance and low-temperature impact resistance, and a high flexural modulus. In addition, the deflection temperature under load T0 is higher than the deflection temperature under load T1. When the mass proportion of the inorganic filler is equal to or less than the upper limit, the resin composition of the present invention has good fluidity during molding and is easy to mold.

[0025] In the resin composition of the present invention, it is preferred that the fluorine-containing elastomer is dispersed in the polyaryl ether ketone, in order to improve the moldability of the resin composition. The number average particle size of the dispersed fluorine-containing elastomer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm. When the number average particle size of the fluorine-containing elastomer is at least the lower limit of the above range, the impact resistance of the fluorine-containing elastomer in the resin composition can be sufficiently ensured. When the number average particle size of the fluorine-containing elastomer is at most the upper limit of the above range, the fluorine-containing elastomer is uniformly dispersed in the polyaryl ether ketone.

[0026] In the resin composition of the present invention, the flexural modulus of a 4.0 mm thick test piece is preferably 3 GPa or more, more preferably 3.5 GPa or more, even more preferably 4 GPa or more, and particularly preferably 4.5 GPa or more. If the flexural modulus is equal to or greater than the lower limit, the mechanical properties of the molded product will be even better. The upper limit of the flexural modulus is not particularly limited and may be, for example, 15 GPa or less, or 13 GPa or less.

[0027] In the resin composition of the present invention, the bending strength of a test piece having a thickness of 4.0 mm is preferably 110 MPa or more, more preferably 120 MPa or more, even more preferably 130 MPa or more, and particularly preferably 140 MPa or more. If the bending strength is equal to or greater than the lower limit, the mechanical properties of the molded article will be even better. The upper limit of the bending strength is not particularly limited, and may be, for example, 250 MPa or less, or 240 MPa or less.

[0028] In the resin composition of the present invention, the Izod impact strength at -40°C when a 4.0 mm thick test piece is formed is preferably 0.6 J / cm or more, more preferably 0.65 J / cm or more, even more preferably 0.7 J / cm or more, and particularly preferably 0.75 J / cm or more. If the Izod impact strength at -40°C is equal to or greater than the lower limit, the impact resistance of the molded article at low temperatures will be even better. The upper limit of the Izod impact strength at -40°C is not particularly limited, and may be, for example, 1.5 J / cm or less, or 1.2 J / cm or less.

[0029] In the resin composition of the present invention, the Izod impact strength at 23°C of a 4.0 mm thick test piece is preferably 0.6 J / cm or more, more preferably 0.65 J / cm or more, even more preferably 0.70 J / cm or more, and particularly preferably 0.75 J / cm or more. If the Izod impact strength at 23°C is equal to or greater than the lower limit, the molded article will have excellent impact resistance at room temperature. The upper limit of the Izod impact strength at 23°C is not particularly limited, and may be, for example, 1.6 J / cm or less, or 1.3 J / cm or less.

[0030] In the resin composition of the present invention, the lightness L * is preferably 60 or more, more preferably 65 or more, even more preferably 70 or more, even more preferably 75 or more, and particularly preferably 80 or more. * When L is equal to or greater than the lower limit, the molded article has excellent lightness. * The upper limit is 100.

[0031] (Polyaryletherketone) As the polyaryletherketone, from the viewpoints of mechanical properties and heat resistance, polyetherketone (hereinafter also referred to as "PEK"), polyetheretherketone (hereinafter also referred to as "PEEK"), or polyetherketoneketone (hereinafter also referred to as "PEKK") is preferred, with PEEK being particularly preferred. Examples of polyether ether ketone include VictrexPEEK (manufactured by Victrex), VestaKeep (manufactured by EVONIK), and Ketaspire (manufactured by Solvay Specialty Polymers), but the polyether ether ketone is not limited to these examples. An example of polyether ketone ketone is Kepstan (manufactured by Arkema), but the polyether ketone ketone is not limited to this example. Although two or more types of polyaryl ether ketones may be used in combination, it is preferable to use one type alone.

[0032] The melting point of the polyaryl ether ketone is preferably 200 to 430°C, more preferably 250 to 400°C, and even more preferably 280 to 380°C. When the melting point of the polyaryl ether ketone is at least the lower limit of the above range, the heat resistance of the molded article is further improved. When the melting point of the polyaryl ether ketone is at most the upper limit of the above range, deterioration of the physical properties due to thermal decomposition of the fluorine-containing elastomer during melt-kneading can be suppressed, and the properties of the fluorine-containing elastomer (impact resistance, chemical resistance, etc.) can be maintained.

[0033] The polyaryl ether ketone may be a commercially available product, or may be produced from various raw materials by a known method.

[0034] (Fluorine-containing elastomer) The fluorine-containing elastomer is preferably a fluorine-containing elastic copolymer having units based on at least one monomer (hereinafter also referred to as "monomer (m1)") selected from the group consisting of tetrafluoroethylene (hereinafter also referred to as "TFE"), hexafluoropropylene (hereinafter also referred to as "HFP"), vinylidene fluoride (hereinafter also referred to as "VdF") and chlorotrifluoroethylene (hereinafter also referred to as "CTFE"). Fluorine-containing elastomers are elastic copolymers that have no melting point and exhibit a storage modulus G' of 80 or more at 100°C and 50 cpm as measured in accordance with ASTM D6204, and are distinguished from fluororesins. Although two or more kinds of fluorine-containing elastomers may be used in combination, it is preferable to use one kind alone.

[0035] The fluorine-containing elastomer may be a fluorine-containing elastic copolymer consisting of only two or three types of units selected from the group consisting of TFE units, HFP units, VdF units and CTFE units, or may be a fluorine-containing elastic copolymer consisting of units based on monomer (m1) and one or more types of units based on the following monomer (m2) copolymerizable with monomer (m1):

[0036] The monomer (m2) is a monomer selected from the group consisting of ethylene (hereinafter also referred to as "E"), propylene (hereinafter also referred to as "P"), perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), vinyl fluoride (hereinafter also referred to as "VF"), 1,2-difluoroethylene (hereinafter also referred to as "DiFE"), 1,1,2-trifluoroethylene (hereinafter also referred to as "TrFE"), 3,3,3-trifluoro-1-propylene (hereinafter also referred to as "TFP"), 1,3,3,3-tetrafluoropropylene, and 2,3,3,3-tetrafluoropropylene.

[0037] PAVE is a compound represented by the following formula (1): CF2=CF(OR F ) (1) However, R F is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms. Examples of PAVE include perfluoro(methyl vinyl ether) (hereinafter also referred to as "PMVE"), perfluoro(ethyl vinyl ether) (hereinafter also referred to as "PEVE"), perfluoro(propyl vinyl ether) (hereinafter also referred to as "PPVE"), and perfluoro(butyl vinyl ether) (hereinafter also referred to as "PBVE").

[0038] The fluorine-containing elastomer may have one or more units based on a monomer other than the monomer (m1) and the monomer (m2) (hereinafter also referred to as "monomer (m3)") which is copolymerizable with the monomer (m1) and which results in an elastic copolymer when copolymerized with the monomer (m1). The proportion of units based on the monomer (m3) is preferably from 0 to 20 mol %, more preferably from 0 to 5 mol %, particularly preferably 0 mol %, based on all units constituting the fluorine-containing elastomer.

[0039] The fluorine-containing elastomer preferably comprises all units derived from two or three types of monomers (m1), or one or more types of units derived from monomers (m1) and one or more types of units derived from monomers (m2), although it may contain other units as impurities, etc., within the range that does not affect the properties of the resin composition of the present invention. An elastic fluorinated copolymer comprising two or three types of units based on monomer (m1), and an elastic fluorinated copolymer comprising one or more types of units based on monomer (m1) and one or more types of units based on monomer (m2) contribute to the impact resistance of molded articles.

[0040] Examples of the fluorine-containing elastomer include the following three types of copolymers. Here, the total proportion of the units specifically shown in the following three types of copolymers is preferably 50 mol % or more based on all units constituting the copolymer. a copolymer having TFE units and P units (hereinafter also referred to as a "TFE / P-containing copolymer"); Copolymers having HFP units and VdF units (excluding those having P units) (hereinafter also referred to as "HFP / VdF-containing copolymers"); A copolymer having a TFE unit and a PAVE unit (excluding those having a P unit or a VdF unit) (hereinafter also referred to as "TFE / PAVE-containing copolymer").

[0041] Examples of the TFE / P-containing copolymer include the following. Examples include TFE / P (meaning a copolymer composed of TFE units and P units, the same applies to others), TFE / P / VF, TFE / P / VdF, TFE / P / E, TFE / P / TFP, TFE / P / PAVE, TFE / P / 1,3,3,3-tetrafluoropropene, TFE / P / 2,3,3,3-tetrafluoropropene, TFE / P / TrFE, TFE / P / DiFE, TFE / P / VdF / TFP, and TFE / P / VdF / PAVE, and among these, TFE / P is preferred.

[0042] Examples of HFP / VdF-containing copolymers include HFP / VdF, TFE / VdF / HFP, TFE / VdF / HFP / TFP, TFE / VdF / HFP / PAVE, VdF / HFP / TFP, and VdF / HFP / PAVE, with HFP / VdF being preferred.

[0043] Examples of the TFE / PAVE-containing copolymer include TFE / PAVE, and particularly preferred are TFE / PMVE and TFE / PMVE / PPVE, in which the PAVE is PMVE or PPVE, with TFE / PMVE being particularly preferred.

[0044] Other examples of the fluorine-containing elastomer include TFE / VdF / 2,3,3,3-tetrafluoropropylene, VdF / PAVE, VdF / 2,3,3,3-tetrafluoropropylene, and E / HFP.

[0045] The fluorine-containing elastomer is preferably a TFE / P-containing copolymer, a HFP / VdF-containing copolymer, or a TFE / PAVE-containing copolymer, more preferably a TFE / P-containing copolymer, and particularly preferably TFE / P. TFE / P has good thermal stability during melt-kneading and stabilizes transportability during melt-kneading. In addition, discoloration and foaming of the molded article of the present invention are reduced.

[0046] The ratio of each unit constituting the fluorine-containing elastomer is preferably within the following range, since it contributes to the impact resistance of the molded article. The molar ratio of each unit in TFE / P (TFE:P; the same applies hereinafter) is preferably 30-80:70-20, more preferably 40-70:60-30, and even more preferably 60-50:40-50. In the TFE / P / VF, the TFE:P:VF ratio is preferably 30-60:60-20:0.05-40. In the TFE / P / VdF, the TFE:P:VdF ratio is preferably 30-60:60-20:0.05-40. In the TFE / P / E, the TFE:P:E ratio is preferably 20-60:70-30:0.05-40. In the TFE / P / TFP, the TFE:P:TFP ratio is preferably 30-60:60-30:0.05-20. In the TFE / P / PAVE, the TFE:P:PAVE ratio is preferably 40-70:60-29.95:0.05-20. In the TFE / P / 1,3,3,3-tetrafluoropropene, the ratio of TFE:P:1,3,3,3-tetrafluoropropene is preferably 30-60:60-20:0.05-40. In the TFE / P / 2,3,3,3-tetrafluoropropene, the ratio of TFE:P:2,3,3,3-tetrafluoropropene is preferably 30-60:60-20:0.05-40. In the TFE / P / TrFE, the TFE:P:TrFE ratio is preferably 30-60:60-20:0.05-40. In the TFE / P / DiFE, the ratio of TFE:P:DiFE is preferably 30-60:60-20:0.05-40. In the TFE / P / VdF / TFP ratio, the TFE:P:VdF:TFP ratio is preferably 30-60:60-20:0.05-40:0.05-20. In the TFE / P / VdF / PAVE, the ratio of TFE:P:VdF:PAVE is preferably 30-70:60-20:0.05-40:0.05-20.

[0047] In the HFP / VdF ratio, the HFP:VdF ratio is preferably 99-5:1-95. In the TFE / VdF / HFP mixture, the TFE:VdF:HFP ratio is preferably 20-60:1-40:20-60. In the TFE / VdF / HFP / TFP ratio, the ratio of TFE:VdF:HFP:TFP is preferably 30-60:0.05-40:60-20:0.05-20. In the TFE / VdF / HFP / PAVE ratio, the TFE:VdF:HFP:PAVE ratio is preferably 30-70:60-20:0.05-40:0.05-20. In the VdF / HFP / TFP ratio, the VdF:HFP:TFP ratio is preferably 1-90:95-5:0.05-20. In the VdF / HFP / PAVE ratio, the VdF:HFP:PAVE ratio is preferably 20-90:9.95-70:0.05-20.

[0048] In the TFE / PAVE, the TFE:PAVE ratio is preferably 40-70:60-30. When the PAVE is PMVE, the TFE:PMVE ratio is preferably 40-70:60-30. In the TFE / PMVE / PPVE ratio, the TFE:PMVE:PPVE ratio is preferably 40-70:3-57:3-57.

[0049] In the TFE / VdF / 2,3,3,3-tetrafluoropropylene, the ratio of TFE:VdF:2,3,3,3-tetrafluoropropylene is preferably 1-30:30-90:5-60. In the VdF / PAVE, the VdF:PAVE ratio is preferably 3-95:97-5. In the VdF / 2,3,3,3-tetrafluoropropylene ratio, the VdF:2,3,3,3-tetrafluoropropylene ratio is preferably 30-95:70-5. In E / HFP, the E:HFP ratio is preferably 40-60:60-40.

[0050] The fluorine content of the fluorine-containing elastomer is preferably 50 to 74% by mass, more preferably 55 to 70% by mass. The fluorine content is preferably 57 to 60% by mass for TFE / P, 66 to 71% by mass for HFP / VdF, and 66 to 70% by mass for TFE / PMVE. When the fluorine content is at least the lower limit of the aforementioned range, the heat resistance and chemical resistance of the molded article are further improved. When the fluorine content is at most the upper limit of the aforementioned range, the impact resistance of the molded article is improved.

[0051] The number-average molecular weight of the fluorine-containing elastomer is preferably from 10,000 to 1,500,000, more preferably from 20,000 to 1,000,000, even more preferably from 20,000 to 800,000, and particularly preferably from 50,000 to 600,000. When the number-average molecular weight of the fluorine-containing elastomer is at least the lower limit of the above range, the mechanical properties of the molded article will be even better. When the number-average molecular weight of the fluorine-containing elastomer is at most the upper limit of the above range, the fluidity will be high and dispersion in polyaryl ether ketone will be good, improving the impact resistance of the molded article.

[0052] Mooney viscosity (ML) of fluorine-containing elastomer 1+10 , 121°C) is preferably 20 to 200, more preferably 30 to 150, and even more preferably 40 to 120. Mooney viscosity is a measure of molecular weight, and a higher Mooney viscosity value indicates a higher molecular weight, while a lower Mooney viscosity value indicates a lower molecular weight. If the Mooney viscosity is within the above range, the resin composition has better moldability and the molded product has better mechanical properties.

[0053] The fluorine-containing elastomer can be produced by polymerizing one or more types of monomer (m1), and, if necessary, one or more types of monomer (m2) and / or monomer (m3). Examples of the polymerization method include emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, etc. The emulsion polymerization method in which monomers are polymerized in the presence of an aqueous medium and an emulsifier is preferred, as it allows easy adjustment of the number average molecular weight and copolymer composition of the fluorinated elastic copolymer and is excellent in productivity. In the emulsion polymerization method, a latex of an elastomer is obtained by polymerizing a monomer in the presence of an aqueous medium, an emulsifier, and a radical polymerization initiator. A pH adjuster may be added during the polymerization of the monomer.

[0054] (inorganic filler) The shape of the inorganic filler is not particularly limited, and may be fibrous, plate-like, or particulate (including spherical). From the viewpoint of mechanical properties and friction and wear characteristics, fibrous fillers are preferred. In applications requiring isotropy of the molded product, plate-like inorganic fillers and particulate inorganic fillers are preferred. The size of the inorganic filler is not particularly limited. Inorganic fillers of any size, such as nano-size, micrometer-size, or millimeter-size, can be used depending on the application of the molded product. Two or more inorganic fillers may be used in combination, and it is particularly preferable to use a fibrous inorganic filler in combination with a particulate or tabular inorganic filler.

[0055] The fiber length of the fibrous inorganic filler is not particularly limited, but is preferably 0.5 μm or more and 10 mm or less. Continuous fibers with a substantially infinite fiber length are also preferred. For example, the fiber length of the fibrous inorganic filler may be 0.5 to 10 μm, 10 to 1000 μm, or 1 to 10 mm. When the fiber length of the fibrous inorganic filler is equal to or greater than the lower limit, the heat resistance of the molded article is further improved. Furthermore, the mechanical properties and friction and wear characteristics of the molded article are also improved. When the fiber length of the fibrous inorganic filler is equal to or less than the upper limit, it is easy to ensure fluidity during molding.

[0056] The diameter of the fibrous inorganic filler is not particularly limited, but is preferably 0.001 μm or more and 30 μm or less. For example, the diameter of the fibrous inorganic filler may be 0.001 to 1 μm, 1 to 5 μm, or 5 to 30 μm. When the diameter of the fibrous inorganic filler is equal to or greater than the lower limit, the heat resistance of the molded body is further improved. Furthermore, the mechanical properties and friction and wear characteristics of the molded body are also improved. When the diameter of the fibrous inorganic filler is equal to or less than the upper limit, the dispersibility of the fibrous inorganic filler is improved.

[0057] The average particle size of the particulate inorganic filler is not particularly limited, but is preferably 0.5 μm or more and 10 mm or less. The average particle size of the particulate inorganic filler may be, for example, 0.5 μm to 10 μm, 10 μm to 1000 μm, or 1 mm to 10 mm. When the average particle size of the particulate inorganic filler is equal to or greater than the lower limit, the heat resistance of the molded body is further improved. In addition, the mechanical properties and friction and wear characteristics of the molded body are also improved. When the average particle size of the particulate inorganic filler is equal to or less than the upper limit, fluidity during molding is easily ensured.

[0058] The thickness of the plate-like inorganic filler is not particularly limited, but is preferably 1 nm or more and 100 μm or less. The thickness of the plate-like inorganic filler may be, for example, 1 nm to 10 nm, 10 nm to 1 μm, or 1 μm to 100 μm. When the thickness of the plate-like inorganic filler is equal to or more than the lower limit, the heat resistance of the molded body is further improved. In addition, the mechanical properties and friction and wear characteristics of the molded body are also improved. When the thickness of the plate-like inorganic filler is equal to or less than the upper limit, it is easy to ensure flowability during molding.

[0059] The major axis of the plate-like inorganic filler is not particularly limited, but is preferably 0.5 μm or more and 1000 μm or less. The major axis of the plate-like inorganic filler may be, for example, 0.5 μm to 10 μm, 10 μm to 100 μm, or 100 μm to 1000 μm. When the major axis of the plate-like inorganic filler is equal to or greater than the lower limit, the heat resistance of the molded body is further improved. In addition, the mechanical properties and friction and wear characteristics of the molded body are also improved. When the particle diameter of the plate-like inorganic filler is equal to or less than the upper limit, flowability during molding is easily ensured.

[0060] Examples of inorganic fillers include carbon fiber, graphite, graphene, carbon nanotubes, glass fiber, gypsum fiber, mica, talc, glass flakes, wollastonite, potassium titanate, aluminum borate, boron nitride, aluminum nitride, calcium carbonate, silicon oxide (silica), titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, clay, carbon black, inorganic pigments, molybdenum disulfide, metal powder, magnetic materials, and zeolite. Among these, carbon fiber, graphite, carbon nanotubes, and glass fiber are preferred because the molded article has even better heat resistance, glass fiber and carbon fiber are more preferred, and glass fiber is particularly preferred because the molded article has excellent brightness.

[0061] Examples of glass fibers include chopped fibers, milled fibers, and flat glass fibers with irregular cross sections. Also, glass fibers with low dielectric constants can be used in terms of electrical properties. Examples of carbon fibers include PAN-based carbon fibers, pitch-based isotropic carbon fibers, and pitch-based anisotropic carbon fibers. The shape of the carbon fibers can be selected from chopped fibers and milled fibers depending on the desired physical properties.

[0062] Fibrous inorganic fillers such as glass fibers and carbon fibers are also preferably used in combination with other inorganic fillers. Examples of such other inorganic fillers include particulate inorganic fillers and plate-like inorganic fillers. These other inorganic fillers may be even smaller than the preferred sizes (e.g., nano-sized particulate inorganic fillers). Examples of such other inorganic fillers include carbon black and silica. Specific examples of the use of fibrous inorganic fillers in combination with other inorganic fillers include the use of glass fibers and silica, or the use of carbon fibers and carbon black.

[0063] The carbon black may be any carbon black used as a filler for fluororubber. Examples include furnace black, acetylene black, thermal black, and channel black. Of these, furnace black is preferred. Examples of furnace black include HAF-LS carbon, HAF carbon, HAF-HS carbon, FEF carbon, GPF carbon, APF carbon, SRF-LM carbon, SRF-HM carbon, and MT carbon, with MT carbon being preferred.

[0064] When the resin composition contains carbon black and other inorganic fillers, the carbon black content is preferably 1 to 45% by mass, more preferably 3 to 20% by mass, based on the resin composition. When the carbon black content is equal to or greater than the lower limit of the above range, the strength of the molded body is improved, and the effects of adding carbon black are fully achieved. When the carbon black content is equal to or less than the upper limit of the above range, the molded body has excellent elongation. When the carbon black content is within the above range, the molded body has a good balance between strength and elongation.

[0065] (Other ingredients) Other components include additives such as polymer fillers, plasticizers, and flame retardants. Two or more of the other components may be used in combination.

[0066] Examples of polymer fillers include liquid crystal polymers, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyester elastomers, polyarylate, polycaprolactone, phenoxy resins, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 46, aromatic polyamides, polyamide elastomers, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene, acrylonitrile-butadiene-styrene copolymers (ABS resins), polymethyl methacrylate, polypropylene, polyethylene, polybutadiene, butadiene-styrene copolymers, ethylene-propylene-diene rubber (EPDM), styrene-butadiene block copolymers, butadiene-acrylonitrile copolymers, acrylic rubbers, styrene-maleic anhydride copolymers, styrene-phenylmaleimide copolymers, ethylene / acrylic acid / glycidyl methacrylate copolymers, silicone elastomers, and aramids. Among these, polytetrafluoroethylene is preferably used to further reduce the dielectric constant and dielectric loss tangent of the molded article. When the resin composition contains polytetrafluoroethylene, the content of polytetrafluoroethylene is preferably 3 to 30 mass %, more preferably 5 to 20 mass %, relative to 100 mass % of the resin composition of the present invention. When the polytetrafluoroethylene content is equal to or less than the upper limit, the strength of the molded article is further improved. When the polytetrafluoroethylene content is equal to or more than the lower limit, the effect of further improving the dielectric properties can be obtained.

[0067] Examples of the plasticizer include phthalates and adipates. Flame retardants include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, sodium antimonate, antimony pentoxide, phosphazene compounds, phosphate esters (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc.), ammonium polyphosphate, melamine, melam, melem polyphosphate, red phosphorus, molybdenum compounds, boric acid compounds, polytetrafluoroethylene, etc.

[0068] Other components include ultraviolet absorbers, light stabilizers, etc. Examples of ultraviolet absorbers include triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers. Benzotriazole-based ultraviolet absorbers are particularly preferred. Examples of light stabilizers include hindered amine-based light stabilizers. The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 10.0% by mass, and more preferably 0.1 to 5.0% by mass, based on 100% by mass of the resin composition of the present invention.

[0069] (Method of producing resin composition) The resin composition is produced by melt-kneading polyaryletherketone, a fluorine-containing elastomer, an inorganic filler, and, if necessary, other components. The inorganic filler may be added when the polyaryletherketone and the fluorine-containing elastomer are melt-kneaded, or may be added after the polyaryletherketone and the fluorine-containing elastomer are melt-kneaded. When other components are contained in the resin composition, the other components may be added when the polyaryl ether ketone and the fluorine-containing elastomer are melt-kneaded, or may be added after the polyaryl ether ketone and the fluorine-containing elastomer are melt-kneaded.

[0070] The fluorine-containing elastomer before melt-kneading is preferably in the form of crumbs from the viewpoint of ease of handling when preparing a compound. The number average particle size of the fluoroelastomer before melt-kneading is preferably 10 mm or less, more preferably 8 mm or less, and even more preferably 6 mm or less. When the number average particle size of the fluoroelastomer before melt-kneading is within the above range, the conveyability by a screw during melt-kneading is stable.

[0071] The volume ratio of the polyaryletherketone to the fluorine-containing elastomer in the melt-kneading is the same as the volume ratio of the polyaryletherketone to the fluorine-containing elastomer in the resin composition. When the volume ratio of the polyaryletherketone and the volume ratio of the fluorine-containing elastomer are within the above-mentioned ranges, the heat resistance, flexural modulus, and impact resistance of the molded article are improved.

[0072] The melt-kneading device may be a device having a known melt-kneading function. As the melt-kneading device, a single-screw extruder or a twin-screw extruder, which may be equipped with a screw having a high kneading effect, is preferred, a twin-screw extruder is more preferred, and a twin-screw extruder equipped with a screw having a high kneading effect is particularly preferred. As a screw having a high kneading effect, one that has a sufficient kneading effect on the material to be melt-kneaded and does not apply excessive shear force can be selected. As the melt-kneading device, a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd.) or a KZW series twin-screw kneading extruder (manufactured by Technovel Co., Ltd.) may be mentioned.

[0073] As a method for supplying the polyaryl ether ketone and the fluorine-containing elastomer to the melt kneader, the polyaryl ether ketone and the fluorine-containing elastomer may be mixed in advance and then supplied to the melt kneader, or the polyaryl ether ketone and the fluorine-containing elastomer may be supplied separately to the melt kneader. The inorganic filler is preferably supplied to the melt-kneading apparatus by melt-kneading the polyaryletherketone and the fluorine-containing elastomer and then adding the inorganic filler. The inorganic filler may be pre-mixed with the polyaryletherketone and the fluorine-containing elastomer and then supplied to the melt-kneading apparatus. When other components are contained in the resin composition, the other components may be mixed in advance with one of the polyaryletherketone and the fluorine-containing elastomer and then fed to the melt-kneading apparatus, or may be fed to the melt-kneading apparatus separately from the polyaryletherketone and the fluorine-containing elastomer. Alternatively, the other components may be added after the polyaryletherketone and the fluorine-containing elastomer are melt-kneaded.

[0074] The temperature at which the polyaryl ether ketone and the fluorine-containing elastomer are melt-kneaded (hereinafter also referred to as "melt-kneading temperature") is preferably set depending on the polyaryl ether ketone and the fluorine-containing elastomer. The melt-kneading temperature is preferably 220 to 480°C, more preferably 280 to 450°C, further preferably 290 to 420°C, and particularly preferably 300 to 400°C. The extrusion shear rate when melt-kneading the polyaryl ether ketone and the fluorine-containing elastomer is preferably set according to the melt viscosity of the melt-kneading target material consisting of the polyaryl ether ketone and the fluorine-containing elastomer at the melt-kneading temperature. -1 is preferable, and 10 to 2000 seconds -1 is more preferable, and 15 to 1500 seconds -1 is more preferable. The residence time of the material to be melt-kneaded in the melt-kneading device is preferably from 10 to 290 seconds, more preferably from 20 to 240 seconds, and even more preferably from 30 to 210 seconds.

[0075] The polyaryletherketone and the fluorine-containing elastomer are preferably melt-kneaded so that fluorine-containing elastomer particles having a number-average particle size of 0.5 to 10 μm are dispersed in the polyaryletherketone. By appropriately adjusting the melt-kneading temperature, extrusion shear rate, and residence time of the material to be melt-kneaded in the melt-kneading apparatus, fluorine-containing elastomer particles having a number-average particle size of 0.5 to 10 μm can be dispersed in the polyaryletherketone. By increasing the melt-kneading temperature, the fluorine-containing elastomer is easily dispersed in the polyaryl ether ketone, and coarse particles of the fluorine-containing elastomer are less likely to remain.By decreasing the melt-kneading temperature, thermal decomposition of the fluorine-containing elastomer is less likely to be promoted, the heat resistance of the resin composition is further improved, and the particle size of the fluorine-containing elastomer is not excessively reduced. By increasing the extrusion shear rate, the fluorine-containing elastomer is easily dispersed in the polyaryl ether ketone, and coarse particles of the fluorine-containing elastomer are less likely to remain. By decreasing the extrusion shear rate, the particle size of the fluorine-containing elastomer is not reduced too much. When the residence time of the material to be melt-kneaded in the melt-kneading apparatus is increased, the fluorine-containing elastomer is more easily dispersed in the polyaryl ether ketone, and coarse particles of the fluorine-containing elastomer are less likely to remain.When the residence time is decreased, thermal decomposition of the fluorine-containing elastomer is less likely to be promoted.

[0076] The melt-kneading is preferably carried out substantially in the absence of a crosslinking agent and a crosslinking aid. Melt-kneading substantially in the absence of a crosslinking agent and a crosslinking aid means melt-kneading without substantially crosslinking the fluorine-containing elastomer in the resin composition. Whether the fluorine-containing elastomer in the resin composition is substantially not crosslinked can be confirmed by the value of the flexural modulus of the resin composition.

[0077] A resin composition obtained by melt-kneading a melt-kneading object containing a polyaryl ether ketone and a fluorine-containing elastomer can be melt-molded and is useful as a material for molded articles. The resin composition of the present invention may be used as a coating material in the form of a powder. Applications of the coated article include those described in WO 2015 / 182702.

[0078] (Mechanism of action) The resin composition of the present invention described above has a deflection temperature under load T0 that is higher than the deflection temperature under load T1 of the comparative composition (1), and a molded article having excellent heat resistance can be obtained. Furthermore, the ratio of the volume of the fluorine-containing elastomer to the total volume of the polyaryl ether ketone and the fluorine-containing elastomer is 5% by volume or more, and the amount of the fluorine-containing elastomer is sufficient, thereby ensuring sufficient impact resistance of the molded article. In addition, the ratio of the volume of the fluorine-containing elastomer to the total volume of the polyaryletherketone and the fluorine-containing elastomer is 45% by volume or less, and the amount of polyaryletherketone is sufficient, thereby ensuring sufficient flexural modulus and heat resistance of the molded article. The resin composition of the present invention contains, in addition to polyaryl ether ketone and a fluorine-containing elastomer, 1 mass % or more of an inorganic filler based on the composition. Therefore, as shown in the examples described below, a synergistic effect is obtained by the actions of the three components: polyaryl ether ketone, fluorine-containing elastomer, and inorganic filler. As a result, the flexural modulus, heat resistance, and low-temperature impact resistance of the molded article are improved beyond the range normally expected by those skilled in the art. The reason for this synergistic effect is unclear, but it is thought to be due to the influence of crystallization of the polyaryl ether ketone. Therefore, the resin composition of the present invention can provide a molded article having a high flexural modulus, excellent heat resistance, and excellent impact resistance at low temperatures.

[0079] <Molded body> The molded article of the present invention is a molded product of the resin composition of the present invention. The shape of the molded article of the present invention is appropriately selected depending on the form, use, etc. of the molded article. The molded article of the present invention has a high flexural modulus, excellent heat resistance, and excellent impact resistance at low temperatures, and is therefore preferably used in applications where these properties are required.

[0080] When the resin composition of the present invention contains, for example, glass fiber and silica as inorganic fillers, the brightness of the molded product is high, making it suitable for use in applications where appearance is important. Polyaryletherketone is originally brownish-red. Therefore, polyaryletherketone is usually whitened using a white pigment or colored to a color other than brown before use. However, the use of such pigments for coloring may impair the excellent physical properties of polyaryletherketone. When the resin composition of the present invention contains, for example, glass fiber and silica as an inorganic filler, the L * The value of α is high and the brightness is high. Therefore, whitening or coloring treatment is not required, and the excellent physical properties of polyaryl ether ketone are unlikely to be impaired. Therefore, there is an advantage that it can be suitably used for portable electronic devices where appearance is important.

[0081] Examples of forms and applications of the molded article of the present invention include housings for portable electronic devices, connecting members for portable electronic devices, sliding members, three-dimensional circuit components, gears, actuators, pistons, bearings, aircraft interior materials, bushings, tubes (for fuel, etc.), hoses, tanks, seals, wires, insulating coating materials for electric wires (wires, cables, etc.), films, sheets, bottles, fibers, etc.

[0082] Since portable electronic devices are held in the hand, they are prone to adhesion of liquids such as oils contained in food and cosmetics, beverages, sweat, sebum, etc. The molded article of the present invention is resistant to discoloration and deterioration due to these adhesions, and is therefore suitable for use in portable electronic devices. Examples of portable electronic devices include mobile phones, personal digital assistants, laptop computers, tablet computers, radios, cameras, camera accessories, watches, calculators, music players, global positioning system receivers, portable games, hard drives, portable recording devices, portable playback devices, and portable radio receivers.

[0083] Examples of the housing of a portable electronic device include a back cover, a front cover, an antenna housing, a frame, and a backbone of the portable electronic device. The housing may be a member consisting of a single component of the molded article of the present invention, or a member consisting of multiple components. Here, the backbone is a member to which the components of the portable electronic device, such as electronics, a microprocessor, a screen, a keyboard, a keypad, an antenna, and a battery socket, are attached. When the housing is inside the portable electronic device, the housing may not be visible from the outside of the portable electronic device, or may be partially visible from the outside of the portable electronic device. The housing, such as a cover for protecting and supporting the internal structure, may be exposed to the outside of the portable electronic device.

[0084] Examples of the form of the coupling member for a portable electronic device include a snap connector between a circuit board, microphone, speaker, display, battery, cover, electrical connector, electronic connector, hinge, antenna, switch, switch pad, etc. The coupling member can be suitably applied to portable electronic devices such as mobile phones, personal digital assistants (PDAs), music storage devices, bugs, portable DVD players, electric multimeters, portable electronic game consoles, and portable personal computers (e.g., notebook computers).

[0085] Three-dimensional circuit components are components in which a circuit pattern is formed on the surface of a resin component molded into a three-dimensional shape, and are used as antenna components for mobile electronic devices and components for in-vehicle electronic devices. The circuit pattern is formed using the laser direct structuring (LDS) method, in which the circuit pattern is etched with a laser and then plated. The molded article of the present invention has excellent low dielectric properties and can be suitably used for three-dimensional circuit components.

[0086] Examples of uses for tubes, hoses, tanks, seals, and wires include those described in International Publication No. 2015 / 182702. Examples of uses for tubes and hoses include tubes for drilling for energy resources such as oil, natural gas, and shale oil. Among these, tubes for oil drilling are preferred. Examples of applications of insulating coating materials for electric wires include electric wires or rectangular copper wires for motor coils, particularly insulating coating materials for rectangular conductors in drive motors for hybrid electric vehicles (HEVs) and electric vehicles (EVs). The insulating coating material for rectangular conductors is preferably in the form of a film. Examples of applications of insulating coating materials for electric wires include insulating coating materials for downhole cables used in drilling for energy resources (oil, natural gas, shale oil, etc.). Of these, insulating coating materials for downhole cables used in oil mining are preferred. Applications for films and sheets include speaker diaphragms, plates for trauma and fractures, insulating paper for various electrical insulating adhesive tapes (such as insulating paper for motors), sealing tape for oil and natural gas pipes, and release films when molding thermosetting and thermoplastic composite materials.

[0087] When the molded article is a film, its applications include speaker diaphragms, wire covering films, flexible printed circuit boards, heat-resistant rolls for office automation equipment, and films for impregnating other fiber composites. The film thickness is preferably 1 to 100 μm, more preferably 2 to 80 μm, and even more preferably 5 to 50 μm. When the film thickness is equal to or greater than the lower limit of the above range, the strength of the film is improved. When the film thickness is equal to or less than the upper limit of the above range, the film is easy to handle in the next process. When the molded article is a tube, its use is preferably a medical catheter equipped with a tube, an electric wire coating, or a piping for an analytical instrument. When the extrusion molded product is a fiber, its use is preferably in protective clothing and various filters.

[0088] Examples of molding methods include injection molding, extrusion molding, co-extrusion molding, blow molding, compression molding, transfer molding, and calendar molding. When the molded product is a film, examples of the molding method include extrusion molding methods such as the T-die method and inflation method. In the T-die method, the flow rate of the molten resin and the thickness of the film can be precisely controlled by adjusting the choke bar and lip inside the T-die. In the inflation method, air is introduced into the extruded product through a circular die to expand it, resulting in a film of uniform thickness. When the molded article is a fiber, the molding method is preferably an extrusion molding method such as melt spinning.

[0089] <Complex> In the composite of the present invention, the molded article of the present invention is combined or laminated with other materials, such as metals, glass, plastics, and rubber. Specific examples of plastics include those described in International Publication No. 2015 / 182702, liquid crystal polymers, polyaryl ketones, polyethersulfones, polyphenylsulfones, polyacetals, polyurethanes, etc. Examples of polyamides include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6 / 66 copolymer, polyamide 6 / 66 / 610 copolymer, polyamide MXD6, polyamide 6T, polyamide 9T, polyamide 6 / 6T copolymer, etc. Among these, metals and glass are preferred as other materials, and preferred metals include iron, copper, stainless steel, steel, aluminum, magnesium, and titanium.

[0090] Since the composite of the present invention is a composite of a molded article having excellent chemical resistance and another material, the composite of the present invention is suitable for use in materials that are treated with strong chemicals during the manufacturing process. For example, just as composites of resin and metal, glass, etc. are widely used in portable electronic devices, the composite of the present invention and another material such as metal, glass, etc. can be suitably applied to portable electronic devices. Composites of metals (aluminum, stainless steel, etc.) and resins used in portable electronic devices and the like are generally anodized to improve surface hardness and appearance. Anodizing is a process that uses strong chemicals to form an oxide layer on the metal surface, thereby improving surface hardness. Therefore, composites of metals and resins that undergo anodizing are required to have excellent chemical resistance, particularly in the resin portion. The composite of the present invention is suitable for use in portable electronic devices, where appearance is important, because it is easily applicable to anodizing.

[0091] In the case of the composite of the molded article and a metal of the present invention, the metal portion does not transmit electromagnetic waves, so radio signals pass through the molded article portion of the present invention. Since the molded article of the present invention also has excellent low dielectric properties, the composite of the molded article and a metal of the present invention is suitable for use in portable electronic devices from the viewpoint of low dielectric properties.

[0092] The composite of the present invention can be produced, for example, by bonding a molded body and another material. The bonding method is not particularly limited, and various methods can be used. For example, there are mentioned a method of adhering the molded article of the present invention to another material such as a metal coated with an adhesive, and a method of injection molding in which a molten resin composition of the present invention is injection molded onto a metal member placed in a mold. When the molded article of the present invention is combined with a metal by injection molding, it can be combined with the metal member as is, but it is also possible to perform injection molding after subjecting the surface of the metal member to a chemical adhesion treatment or a physical or chemical treatment for forming irregularities on the surface of the metal member. For chemical adhesion treatment, a metal member coated with an adhesive can be used. For physical treatment, the unevenness can be formed by, for example, laser processing or mechanical processing. For chemical treatment, the unevenness can be formed by, for example, chemical etching. The composite of the molded body produced by injection molding and the metal can be machined and cut to a desired shape. [Example]

[0093] The present invention will be described in more detail below using examples, but is not limited to the following examples. Examples 1 to 4, 7 to 10, and 14 to 18 are working examples, and Examples 5, 6, and 11 to 13 are comparative examples.

[0094] (Preparation of injection molded articles for evaluation) The resin composition was injection molded using an injection molding machine (ROBOSHOT α-50, manufactured by Fanuc Corporation) under conditions of a cylinder temperature of 380°C and a mold temperature of 170°C, to obtain an injection molded article for evaluation having a thickness of 4.0 mm.

[0095] (flexural modulus, flexural strength) Test pieces measuring 80 mm in length and 10 mm in width were cut out from the injection-molded articles for evaluation. The flexural modulus and flexural strength of the test pieces were measured using a TENSILON (A&D Co., Ltd., RTF-1350) in accordance with JIS K7171, with a load cell rating of 10 kN, a support distance of 64 mm, and a speed of 2 mm / min.

[0096] (tensile strength, tensile elongation) The tensile strength and tensile elongation of the injection molded articles for evaluation were measured using a TENSILON (manufactured by A&D, model: RTF-1350) in accordance with JIS K7161, with a load cell rating of 10 kN, a chuck distance of 115 mm, and a speed of 50 mm / min.

[0097] (Izod impact strength) A test piece measuring 80 mm in length and 10 mm in width was cut out from the injection molded article for evaluation, and a notch was made in the test piece at a height of 40 mm. The Izod impact strength of the test specimens was measured using an Izod tester (manufactured by Toyo Seiki Seisakusho, Ltd.) under the following conditions: hammer capacity: 2.75 J, hammer load: 13.97 N, distance from the shaft center to the center of gravity: 10.54 cm, distance from the shaft center to the impact point: 33.5 cm. The measurements were carried out at 23°C and -40°C.

[0098] (heat deflection temperature) A test piece measuring 80 mm in length and 10 mm in width was cut out from the injection-molded article for evaluation. In accordance with ASTM D648, a Toyo Seiki HDT & VSPT TESTER was used to measure the temperature at which the deflection reached 0.254 mm under conditions of a load of 1.82 MPa and a heating rate of 2°C / min.

[0099] (Dielectric constant) The resin composition was press-molded using a melt heat press to obtain a pressed sheet with a thickness of 0.24 mm. The dielectric constant of the pressed sheet was measured using a PNA-L network analyzer (Agilent Technologies, N5230A) and a cavity resonator (Kanto Electronics Application Development, CP481) at a temperature of 23°C, a humidity of 50% RH, and a frequency of 10 GHz, in accordance with ASTM D2520.

[0100] (dynamic friction coefficient) The test was carried out using the Matsubara friction measurement method (cylindrical ring-on-ring) in accordance with JIS K-7218 using a friction and wear tester FRT IIEAA manufactured by TSE Corporation. At room temperature, a cylindrical test piece made by injection molding from a resin composition was attached to a mating ring (material: SUS316, contact area: 2 cm). 2 The dynamic friction coefficient of the test piece was measured by bringing the test piece into contact with the test piece under the conditions of a pressure of 0.4 MPa, a rotation speed of 0.5 m / sec, and a test time of 1 hour.

[0101] (hue measurement) The injection molded products for evaluation were subjected to color measurement in accordance with JIS-Z8781-4 using the SM Color Computer SM-T manufactured by Suga Test Instruments Co., Ltd., and the L * , a * , b * was measured.

[0102] (chemical resistance) After immersion in a 70% sulfuric acid solution at 23°C for 24 hours and 168 hours, a tensile test was carried out on each of the injection molded articles for evaluation, and the tensile strength and tensile elongation were measured.

[0103] (raw materials) Polyaryletherketone (A-1): PEEK (melting point: 340°C, melt flow rate: 22 g / 10 min, specific gravity: 1.32, manufactured by Daicel-Evonik Co., Ltd., VestaKeep 3300G). Fluorine-containing elastomer (B-1): Tetrafluoroethylene-propylene copolymer (melt flow rate: 11 g / 10 min, specific gravity: 1.55, Mooney viscosity (ML 1+10 , 121°C): 100, storage modulus G' (100°C, 50 cpm): 390, AGC, AFLAS (registered trademark) 150FC). Inorganic filler (C-1): Glass fiber (Nitto Boseki, NE Glass CN 3DE-451). Inorganic filler (C-2): Glass fiber (Nitto Boseki, NE Glass CN 3DE-941). Inorganic filler (C-3): Carbon fiber (ZOLTEK, PXCA0250-83). Polymer filler (D-1): Polytetrafluoroethylene (AGC L169J). Polymer filler (D-2): Polytetrafluoroethylene (AGC L170JE) UV absorber (E-1): Hydroxyphenyltriazine (HPT) UV absorber (BASF Tinuvin 479) Light stabilizer (E-2): Hindered amine light stabilizer (HALS) (BASF Tinuvin PA144)

[0104] (Examples 1-4, 7-10) Polyaryl ether ketone (A-1), fluorine-containing elastomer (B-1), inorganic filler (C-1), inorganic filler (C-2), or inorganic filler (C-3) and polymer filler (D-1) were mixed in the proportions shown in Tables 1 and 2, and the mixture was fed to the base end of the screw of a twin-screw kneading extruder (Technovel Co., Ltd., KZW15TW-45HG1100, screw diameter: 15 mm, L / D: 45) using a feeder at a rate of 2.0 kg / h. The screw rotation speed was 200 rpm, and the cylinder, die, and head temperatures were set as follows: C1 = 340 °C, C2 = 350 °C, C3 = 360 °C, C4 = 370 °C, C5 = 370 °C, C6 = 370 °C, D = 350 °C, and H = 350 °C. The strand extruded from the die tip was cooled in a water bath and cut using a pelletizer to obtain pellets of the resin composition. In the formulations shown in Tables 1 and 2, the "volume ratio (vol %)" refers to the ratio of the volume of the polyaryletherketone (A-1) to the total volume of the fluorine-containing elastomer (B-1). The "proportion (mass %) of inorganic filler" and the "proportion (mass %) of polymer filler" refer to the proportion of each inorganic filler and polymer filler relative to 100 mass % of the resin composition. This also applies to the other examples shown below.

[0105] (Examples 5 and 11) Pellets of a resin composition were obtained in the same manner as in Example 1, except that no inorganic filler was used and polyaryl ether ether ketone (A-1) and fluorine-containing elastomer (B-1) were mixed in the proportions shown in Tables 1 and 2. Here, the composition of Example 5 is a comparative composition (1) for the resin compositions of Examples 1 to 4 and 7. The composition of Example 11 is a comparative composition (1) for the resin compositions of Examples 8 to 10.

[0106] (Example 6) Pellets of a resin composition were obtained in the same manner as in Example 1, except that neither the fluorine-containing elastomer nor the inorganic filler was used, and only the polyaryl ether ketone (A-1) was used.

[0107] (Examples 12 and 13) Pellets of a resin composition were obtained in the same manner as in Example 1, except that no fluorine-containing elastomer was used and polyaryl ether ketone (A-1) and inorganic filler (C-1) or inorganic filler (C-2) were mixed in the formulation shown in Table 2. Here, the composition of Example 12 is a comparative composition (2) for the resin compositions of Examples 1 and 8. The composition of Example 13 is a comparative composition (2) for the resin compositions of Examples 2, 7, and 9.

[0108] (Examples 14-18) The same preparation as in Example 10 was carried out except that the formulation was as shown in the table.

[0109] The blending compositions of the resin compositions in Examples 1 to 18 and the physical properties of the resulting resin compositions are shown in Tables 1 to 3 below.

[0110] [Table 1]

[0111] [Table 2]

[0112] [Table 3]

[0113] The deflection temperature under load of the resin compositions of Examples 1 to 4 and 7 was higher than that of the composition of Example 5. The resin compositions of Examples 1 to 4 and 7 were superior to the composition of Example 5 in flexural modulus, heat resistance, and impact resistance at low temperatures. The deflection temperatures under load of the resin compositions of Examples 8 to 10 were higher than that of the composition of Example 11. The resin compositions of Examples 8 to 10 were superior to the composition of Example 11 in flexural modulus, heat resistance, and impact resistance at low temperatures.

[0114] Examples 1 and 8, in which inorganic filler (C-1) was used, were superior in heat resistance and impact resistance to Example 12, in which the same inorganic filler (C-1) was used. Examples 2 and 9, in which inorganic filler (C-2) was used, were superior in heat resistance and impact resistance to Example 13, in which the same inorganic filler (C-2) was used.

[0115] Regarding heat resistance, according to the ordinary knowledge of a person skilled in the art, the resin compositions of Examples 1, 2, 8 and 9 contain the fluorine-containing elastomer (B-1) in addition to the polyaryl ether ketone (A-1) and the inorganic filler (C-1) or (C-2), and therefore are predicted to have lower heat resistance than the compositions of Examples 12 and 13 which consist of two components, the polyaryl ether ketone (A-1) and the inorganic filler (C-1) or (C-2). However, the deflection temperatures under load of the resin compositions of Examples 1 and 8 were higher than that of the composition of Example 12, which consisted of two components, polyaryletherketone (A-1) and inorganic filler (C-1).Furthermore, the deflection temperatures under load of the resin compositions of Examples 2 and 9 were also higher than that of the composition of Example 13, which consisted of two components, polyaryletherketone (A-1) and inorganic filler (C-2). From these results, it is considered that a resin composition containing polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler produces a synergistic effect due to the actions of these three components, and the heat resistance of the molded product is improved beyond the range normally expected by a person skilled in the art.

[0116] Regarding the flexural modulus, according to the ordinary knowledge of a person skilled in the art, the resin compositions of Examples 1, 2 and 9 contain the fluorine-containing elastomer (B-1) in addition to the polyaryl ether ketone (A-1) and the inorganic filler (C-1) or (C-2), and therefore are predicted to have a lower flexural modulus than the compositions of Examples 12 and 13 which consist of two components, that is, the polyaryl ether ketone (A-1) and the inorganic filler (C-1) or (C-2). However, the flexural modulus of the resin composition of Example 1 was higher than that of the composition of Example 12, which consisted of two components, polyaryl ether ketone (A-1) and inorganic filler (C-1).The flexural moduli of the resin compositions of Examples 2 and 9 were also equal to or higher than that of the composition of Example 13, which consisted of two components, polyaryl ether ketone (A-1) and inorganic filler (C-2). From these results, it is considered that a resin composition containing polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler produces a synergistic effect due to the actions of these three components, and the flexural modulus of a molded product is improved beyond the range normally expected by a person skilled in the art.

[0117] Regarding brightness, in examples 1, 2, 3, 8 to 10, brightness L * In Example 16, the lightness L * is 75 or more, and in examples 14, 15, 17, and 18, the lightness L * All scores were above 80, and the evaluation results were good. Regarding chemical resistance, the tensile strength and tensile elongation values ​​for Examples 1, 2, 8, and 9 are shown in Tables 1 and 2, and the values ​​before immersion in the 70% sulfuric acid solution were maintained. These results demonstrate that the chemical resistance is good. With regard to the dielectric constant, Examples 1 to 3 and Examples 8 to 10 had lower dielectric constants than Examples 12 and 13, and Example 7 had an even lower dielectric constant. These results showed that the low dielectric properties were excellent. [Industrial Applicability]

[0118] The molded article of the resin composition of the present invention has a high flexural modulus, and is excellent in heat resistance and impact resistance at low temperatures, and is therefore suitable for applications requiring these properties. The entire contents of the specifications, claims and abstracts of Japanese Patent Application No. 2020-136980 filed on August 14, 2020, and Japanese Patent Application No. 2020-204468 filed on December 9, 2020, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A resin composition containing polyaryl ether ketone, a fluorine-containing elastomer, and an inorganic filler, the fluorine-containing elastomer is an elastic copolymer having no melting point and exhibiting a storage modulus G' of 80 or more at 100°C and 50 cpm as measured in accordance with ASTM D6204; the volume ratio of the fluorine-containing elastomer is 1 to 45% by volume based on the total volume of the polyaryl ether ketone and the fluorine-containing elastomer, The mass ratio of the inorganic filler to the resin composition is 1 to 50 mass %, A resin composition having a deflection temperature under load measured in accordance with ASTM D648 under a load of 1.82 MPa that is higher than the deflection temperature under load of a comparative composition listed below, and the difference (T 0 -T 1 ) between the deflection temperature under load T 0 of the resin composition and the deflection temperature under load T 1 of the comparative composition is 100°C or more. Comparative composition: A resin composition containing the polyaryletherketone and the fluorine-containing elastomer but not the inorganic filler, which is the same as the resin composition in the type of the polyaryletherketone, the type of the fluorine-containing elastomer, and the volume ratio of the fluorine-containing elastomer to the total volume of the polyaryletherketone and the fluorine-containing elastomer, except for the presence or absence of the inorganic filler.

2. 2. The resin composition according to claim 1, wherein the fluorine-containing elastomer is a copolymer having units based on tetrafluoroethylene and units based on propylene, a copolymer having units based on hexafluoropropylene and units based on vinylidene fluoride, or a copolymer having units based on tetrafluoroethylene and units based on a compound represented by the following formula (1): CF ２ =CF(OR Ｆ ) ・・・(1) However, R Ｆ is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms.

3. The resin composition according to claim 1 or 2, wherein the polyaryletherketone is polyetherketone, polyetheretherketone, or polyetherketoneketone.

4. Lightness L in hue measurement according to JIS-Z8781-4 ＊ The resin composition according to any one of claims 1 to 3, wherein the tensile strength is 60 or more.

5. The resin composition according to any one of claims 1 to 4, wherein the inorganic filler is a fibrous inorganic filler, a tabular inorganic filler, or a granular inorganic filler.

6. The resin composition according to any one of claims 1 to 5, wherein the inorganic filler comprises at least one selected from the group consisting of carbon fiber, graphite, carbon nanotube, glass fiber, and silica.

7. The resin composition according to any one of claims 1 to 6, wherein at least a part of the inorganic filler comprises carbon fiber or glass fiber.

8. The resin composition according to any one of claims 1 to 7, further comprising a polymer filler.

9. The resin composition according to claim 8, wherein the polymer filler is polytetrafluoroethylene.

10. The resin composition according to any one of claims 1 to 9, further comprising at least one selected from the group consisting of a plasticizer, an ultraviolet absorber, and a light stabilizer.

11. A molded article which is a molded article of the resin composition according to any one of claims 1 to 10.

12. A composite in which the molded article according to claim 11 and another material are combined or laminated.

13. A portable electronic device, a sliding member, a three-dimensional circuit component, an electric wire, or a member for excavating energy resources, comprising the molded article according to claim 11 or the composite according to claim 12.

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