Resin composition, molded body, composite, and use thereof

Abstract

The present invention provides a molded article having high flexural modulus, excellent heat resistance and low-temperature impact resistance, and a resin composition from which the molded article can be obtained. The resin composition comprises a polyarylene ether ketone and a fluorine-containing elastomer and an inorganic filler, the proportion of the fluorine-containing elastomer to the total of the volume of the polyarylene ether ketone and the volume of the fluorine-containing elastomer is 1 to 45% by volume, the proportion of the inorganic filler is 1 to 50% by mass, and the load deflection temperature under a load of 1.82 MPa based on ASTM D648 is higher than that of a comparative composition, and a molded article of the resin composition. The comparative composition is a resin composition comprising a polyarylene ether ketone and a fluorine-containing elastomer but not containing an inorganic filler, the type of the polyarylene ether ketone, the type of the fluorine-containing elastomer and the volume proportion of the fluorine-containing elastomer to the total of the volume of the polyarylene ether ketone and the volume of the fluorine-containing elastomer are all the same as those of the resin composition except for the presence or absence of the inorganic filler.

Description

Technical Field

[0001] This invention relates to resin compositions, molded articles, composites, and their uses. Background Technology

[0002] Polyaryletherketones (PEKs, PEKs, PEK-ketones, etc.) exhibit excellent heat resistance and high flexural modulus. Therefore, PREs are widely used as materials for molded parts in various fields.

[0003] However, the molded polyaryletherketones have insufficient impact resistance at room temperature or low temperature.

[0004] The following resin composition is proposed as a resin composition that can produce a molded body with improved impact resistance of polyaryletherketone.

[0005] • A resin composition comprising polyaryletherketone and a fluorinated elastomer, wherein the fluorinated elastomer is dispersed in the polyaryletherketone, the number average particle size of the fluorinated elastomer is 1 to 300 μm, the volume ratio of polyaryletherketone to fluorinated elastomer is 97:3 to 55:45, and having a flexural modulus of 1000 to 3700 MPa (Patent Document 1).

[0006] • A resin composition comprising polyaryletherketone and a fluorinated elastomer, wherein the ratio of the melt flow rate of the polyaryletherketone to the fluorinated elastomer under specific conditions is 0.2 to 5.0, and the volume percentage of the polyaryletherketone in the total volume of the polyaryletherketone and the fluorinated elastomer is 60 to 97% by volume (Patent Document 2).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2017 / 188280

[0010] Patent Document 2: International Publication No. 2019 / 198771 Summary of the Invention

[0011] The technical problem that the invention aims to solve

[0012] The resin compositions described in Patent Documents 1 and 2 may impair the high flexural modulus of polyaryletherketones because they contain fluorinated elastomers. Furthermore, their heat resistance when formed into molded bodies is insufficient, and there is room for improvement in their impact resistance at low temperatures.

[0013] The present invention provides a molded article with high flexural elasticity, excellent heat resistance and low-temperature impact resistance, and a resin composition for obtaining the molded article.

[0014] Technical solutions adopted to solve technical problems

[0015] The inventor of the present invention has found through careful exploration that the above technical problems can be solved by using a specific composition containing a polyaryletherketone, a fluorine-containing elastomer, and an inorganic filler.

[0016] Here, based on the common knowledge of those skilled in the art, it can be predicted that if the three components of polyaryletherketone, fluorine-containing elastomer, and inorganic filler are used, the heat resistance and flexural modulus of elasticity of the molded body should be lower than those of a composition containing only the two components of polyaryletherketone and inorganic filler.

[0017] However, unexpectedly, the inventor has found that, compared with a composition containing the two components of polyaryletherketone and inorganic filler, the heat resistance, flexural modulus of elasticity, and low-temperature impact resistance of the molded body of the resin composition containing polyaryletherketone, fluorine-containing elastomer, and inorganic filler have increased beyond the normal expectation range of those skilled in the art, thus completing the present invention.

[0018] The present invention has the following embodiments.

[0019] [1] A resin composition, which is a resin composition containing a polyaryletherketone, a fluorine-containing elastomer, and an inorganic filler, wherein, relative to the total volume of the polyaryletherketone and the fluorine-containing elastomer, the volume ratio of the fluorine-containing elastomer is 1 to 45% by volume, and relative to the resin composition, the mass ratio of the inorganic filler is 1 to 50% by mass, and the load deflection temperature (Japanese: load deflection temperature) measured based on ASTM D648 under the condition of a load of 1.82 MPa is higher than that of the following comparative composition.

[0020] Comparative composition: A resin composition containing the polyaryletherketone and the fluorine-containing elastomer but not containing the inorganic filler, wherein, except for the difference in the presence or absence of the inorganic filler, the type of the polyaryletherketone, the type of the fluorine-containing elastomer, and the volume ratio of the fluorine-containing elastomer relative to the total volume of the polyaryletherketone and the fluorine-containing elastomer are the same as those of the resin composition.

[0021] [2] The resin composition according to [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).

[0022] CF2=CF(OR F ) (1)

[0023] wherein R F is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms.

[0024] [3] A resin composition such as [1] or [2], wherein the polyaryletherketone is selected from polyetherketone, polyetheretherketone or polyetherketoneketone.

[0025] [4] A resin composition of any one of [1] to [3], wherein the luminance L* in the hue measurement based on JIS-Z8781-4 is above 60.

[0026] [5] A resin composition of any one of [1] to [4], wherein the inorganic filler is a fibrous inorganic filler, a flat inorganic filler or a granular inorganic filler.

[0027] [6] A resin composition of any one of [1] to [5], wherein the inorganic filler comprises one or more selected from carbon fiber, graphite, carbon nanotubes, glass fiber and silicon dioxide.

[0028] [7] A resin composition of any one of [1] to [6], wherein, as at least a part of the inorganic filler, it comprises carbon fiber or glass fiber.

[0029] [8] A resin composition of any one of [1] to [7], wherein the resin composition further comprises a polymer filler.

[0030] [9] The resin composition of [8] wherein the polymer filler is polytetrafluoroethylene.

[0031]

[10] A resin composition of any one of [1] to [9], wherein the resin composition further comprises one or more selected from plasticizers, ultraviolet absorbers and light stabilizers.

[0032]

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

[10] .

[0033]

[12] A composite, which is a composite obtained by combining or laminating the shaped body of

[11] and other materials.

[0034]

[13] Portable electronic devices, sliding components, three-dimensional circuit components, wires or energy resource drilling components, having the shaped body of

[11] or the composite of

[12] .

[0035] Invention Effects

[0036] According to the resin composition of the present invention, molded articles with high flexural modulus, excellent heat resistance and low-temperature impact resistance can be obtained.

[0037] The molded articles of the present invention have high flexural modulus, excellent heat resistance and low-temperature impact resistance. Detailed Implementation

[0038] The meanings and definitions of the terms used in this specification are as follows.

[0039] The "volume" of polyaryletherketone or fluorinated elastomers is the mass (g) of the polyaryletherketone or fluorinated elastomer divided by its specific gravity (g / cm³). 3 The value calculated from this.

[0040] The "specific gravity" of polyaryletherketones or fluorinated elastomers is the value at 23°C determined by displacement (suspension) in water.

[0041] The "number-average particle size" of the fluorinated elastomer in the resin composition is obtained by observing the molded body of the resin composition with a scanning electron microscope, measuring the maximum diameter of 100 randomly selected particles, and then averaging the values.

[0042] The "number-average particle size" of the fluorinated elastomer before melt mixing is obtained by observing the fluorinated elastomer with an optical microscope, measuring the maximum diameter of 100 randomly selected particles, and then averaging the results.

[0043] The flexural modulus of the molded body is a value determined according to ASTM D790.

[0044] The "melting point" of polyaryletherketones is the temperature corresponding to the maximum value of the melting peak as determined by differential scanning calorimetry (DSC).

[0045] The "fluorine content" in fluorinated elastomers represents the proportion of fluorine atoms by mass relative to the total mass of all atoms constituting the fluorinated elastomer. The fluorine content is calculated based on the molar ratio of the units in the fluorinated elastic copolymer, determined by melt NMR and perfluorine content measurements.

[0046] Mooney viscosity (ML) of fluorinated elastomers 1+10 "121℃" is a value measured according to JIS K 6300-1:2000 (corresponding to international standards ISO 289-1:2005 and ISO 289-2:1994).

[0047] "Monomer-based unit" refers to a group of atoms directly formed by the polymerization of one monomer molecule, as well as a group of atoms obtained by chemically transforming a portion of that group. In this specification, monomer-based units will also be abbreviated as monomer units. For example, TFE-based units will also be abbreviated as TFE units.

[0048] "Monomer" refers to a compound that has polymerizable carbon-carbon double bonds.

[0049] <Resin Composition>

[0050] The resin composition of the present invention comprises polyaryletherketone, a fluorinated elastomer, and an inorganic filler.

[0051] The resin composition of the present invention may, as needed, contain components other than polyarylether ketones, fluorinated elastomers, and inorganic fillers (hereinafter referred to as "other components") without impairing the effects of the present invention.

[0052] The load deformation temperature T0 of the resin composition of the present invention is higher than the load deformation temperature T1 of the comparative composition (1) described below. The load deformation temperature T0 is a value obtained by measuring the resin composition of the present invention under a load of 1.82 MPa based on ASTM D648.

[0053] Comparative composition (1): A resin composition comprising polyaryletherketone and a fluorinated elastomer but without inorganic filler, wherein, except for the presence or absence of inorganic filler, the types of polyaryletherketone, the types of fluorinated elastomer, and the total V relative to the volume of polyaryletherketone and the volume of the fluorinated elastomer are the same. A+B The volume proportions of the fluorinated elastomers are the same as those of the resin composition.

[0054] When the resin composition of the present invention does not contain other components, the comparative composition (1) is a composition consisting only of polyarylether ketone and fluorinated elastomer. Therefore, the composition of the comparative composition (1) can be determined based on the volume of polyarylether ketone and the volume of fluorinated elastomer in the resin composition of the present invention.

[0055] When the resin composition of the present invention further comprises other components, the comparative composition (1) is a composition consisting of polyaryletherketone, a fluorinated elastomer, and other components. The contents of the other components in the comparative composition (1), relative to the contents of the polyaryletherketone, relative to the contents of the fluorinated elastomer, and relative to their total amount, are the same as those contents of the other components in the resin composition of the present invention.

[0056] Here, the polyaryletherketone, fluorinated elastomer, and other components in comparative composition (1) are the same as those in the resin composition of the present invention. Therefore, the load deformation temperature T1, which is determined by the composition of comparative composition (1) based on the resin composition of the present invention, is a value obtained by measuring under a load of 1.82 MPa based on ASTM D648.

[0057] The difference between the load deformation temperature T0 and the load deformation temperature T1 (T0-T1) has a lower limit exceeding 0°C, preferably above 40°C, more preferably above 60°C, further preferably above 80°C, and most preferably above 100°C. If T0-T1 is above the lower limit, the heat resistance of the molded article is better. The higher the upper limit of T0-T1, the better, but there is no particular limitation. T0-T1 can, for example, be below 180°C or below 160°C.

[0058] The lower limit of the load deformation temperature T0 of the resin composition of the present invention is not particularly limited as long as it is greater than the load deformation temperature T1, preferably 160°C or higher, more preferably 180°C or higher, further preferably 200°C or higher, and most preferably 240°C or higher. If the load deformation temperature T0 is above the lower limit, the heat resistance of the molded article is better. The higher the upper limit of the load deformation temperature T0, the better, and there is no particular limitation. For example, the load deformation temperature T0 can be below 330°C or below 320°C.

[0059] The load deformation temperature T0 of the resin composition of the present invention is preferably higher than the load deformation temperature T2 of the comparative composition (2) described below.

[0060] Comparative composition (2): A resin composition comprising polyaryletherketone and inorganic filler but without fluorinated elastomer, wherein 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 polyaryletherketone is V equal to the total volume of polyaryletherketone and fluorinated elastomer in the resin composition of the present invention. A+B The inorganic filler is the same, and the mass ratio of the inorganic filler is the same as that of the inorganic filler in the resin composition of the present invention.

[0061] When the resin composition of the present invention does not contain other components, the comparative composition (2) is a composition consisting only of polyarylether ketone and inorganic filler. Therefore, the composition of the comparative composition (2) can be determined based on the volume of polyarylether ketone, the volume of fluorinated elastomer, and the mass of inorganic filler in the resin composition of the present invention.

[0062] When the resin composition of the present invention also contains other components, the composition of the comparative composition (2) can be determined based on the volume of polyarylether ketone, the volume of fluorinated elastomer, the amount of other components, and the mass of inorganic filler in the resin composition of the present invention.

[0063] Here, the polyaryletherketone, inorganic filler, and other components in comparative composition (2) are the same as those in the resin composition of the present invention. Therefore, the load deformation temperature T2 for comparative composition (2), which is based on the composition of the resin composition of the present invention, is a value obtained by measuring under a load of 1.82 MPa based on ASTM D648.

[0064] The difference between the load deformation temperature T0 and the load deformation temperature T2 (T0-T2) has a lower limit of more than 0°C, preferably more than 5°C, more preferably more than 10°C, particularly preferably more than 15°C, and most preferably more than 20°C. If T0-T2 is above the lower limit, the heat resistance of the molded article is better. Generally, when using polyaryletherketone, fluorinated elastomer, and inorganic filler, it is predicted that the heat resistance will be lower than that of a composition containing only polyaryletherketone and inorganic filler due to the use of fluorinated elastomer. Therefore, if the load deformation temperature T0 is higher than the load deformation temperature T2, it can be said that the heat resistance of the molded article is significantly better than predicted by those skilled in the art. A higher upper limit for T0-T2 is better, but there is no particular limitation. T0-T2 can be, for example, below 80°C or below 70°C.

[0065] The volume ratio of the fluorinated elastomer to the total volume of the polyarylether ketone and the fluorinated elastomer is 1–45% by volume, preferably 2–42% by volume, more preferably 3–40% by volume, and even more preferably 5–35% by volume. If the volume ratio of the fluorinated elastomer is above the lower limit of the above range, a molded article with excellent impact resistance can be obtained. If the volume ratio of the fluorinated elastomer is below the upper limit of the above range, a molded article with excellent heat resistance and mechanical properties can be obtained.

[0066] The total volume ratio of the polyarylether ketone and the fluorinated elastomer relative to the volume of the resin composition after removing the inorganic filler is preferably 50-100% by volume, more preferably 60-100% by volume, and even more preferably 70-100% by volume. When the above ratio is less than 100% by volume, the resin composition also contains other components.

[0067] If the total volume of polyaryletherketone and the fluorinated elastomer is above the lower limit of the above range, the molded article can fully exert its heat resistance, mechanical properties, and impact resistance. When the resin composition also contains other components, if the total volume ratio of the polyaryletherketone and the fluorinated elastomer relative to the volume of the resin composition after removing the inorganic filler is less than 99% by volume, the molded article can impart new properties from the other components.

[0068] The proportion of inorganic filler relative to the mass of the composition of the present invention is 1 to 50% by mass, preferably 5 to 45% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 40% by mass. If the mass proportion of inorganic filler is above the lower limit above, the molded article exhibits excellent heat resistance and low-temperature impact resistance, and a higher flexural modulus. Furthermore, the load deformation temperature T0 is higher than the load deformation temperature T1. If the mass proportion of inorganic filler is below the upper limit above, the flowability during molding is better, and the resin composition of the present invention is easier to mold.

[0069] From the perspective of improving the molding and processability of the resin composition, in the resin composition of the present invention, it is preferable that the fluorinated elastomer is dispersed in polyaryletherketone.

[0070] The number-average particle size of the dispersed fluorinated elastomer is preferably 0.5–10 μm, more preferably 1–5 μm. If the number-average particle size of the fluorinated elastomer is above the lower limit of the above range, the impact resistance of the fluorinated elastomer in the resin composition can be sufficiently ensured. If the number-average particle size of the fluorinated elastomer is below the upper limit of the above range, the fluorinated elastomer can be uniformly dispersed in polyaryletherketone.

[0071] The resin composition of the present invention preferably has a flexural modulus of 3 GPa or higher when forming a test piece with a thickness of 4.0 mm, more preferably 3.5 GPa or higher, even more preferably 4 GPa or higher, and particularly preferably 4.5 GPa or higher. If the flexural modulus is above the aforementioned lower limit, the mechanical properties of the molded article are even better. There is no particular limitation on the upper limit of the flexural modulus; for example, it can be below 15 GPa or below 13 GPa.

[0072] The resin composition of the present invention preferably has a flexural strength of 110 MPa or more, more preferably 120 MPa or more, further preferably 130 MPa or more, and particularly preferably 140 MPa or more when forming a test piece with a thickness of 4.0 mm. If the flexural strength is above the aforementioned lower limit, the mechanical properties of the molded article are even better. There is no particular limitation on the upper limit of the flexural strength; for example, it can be below 250 MPa or below 240 MPa.

[0073] The cantilever beam impact strength of the resin composition of the present invention at -40°C when forming a test piece with a thickness of 4.0 mm 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 cantilever beam impact strength at -40°C is above the above-mentioned lower limit, the low-temperature impact resistance of the molded article is excellent. There is no particular limitation on the upper limit of the cantilever beam impact strength at -40°C; for example, it can be below 1.5 J / cm or below 1.2 J / cm.

[0074] The cantilever beam impact strength of the resin composition of the present invention at 23°C when forming a test piece with a thickness of 4.0 mm 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 cantilever beam impact strength at 23°C is above the above-mentioned lower limit, the room temperature impact resistance of the molded article is excellent. There is no particular limitation on the upper limit of the cantilever beam impact strength at 23°C; for example, it can be below 1.6 J / cm or below 1.3 J / cm.

[0075] In the resin composition of the present invention, the luminance L* when measuring the hue of an injection-molded plate with a thickness of 4 mm according to JIS-Z8781-4 is preferably 60 or higher, more preferably 65 or higher, even more preferably 70 or higher, even more preferably 75 or higher, and particularly preferably 80 or higher. If L* is above the lower limit value mentioned above, the luminance of the molded article is excellent. The upper limit value of L* is 100.

[0076] (Polyaryl ether ketone)

[0077] From the perspective of mechanical properties and heat resistance, polyether ketone (hereinafter also referred to as "PEK"), polyether ether ketone (hereinafter also referred to as "PEEK"), or polyether ketone ketone (hereinafter also referred to as "PEKK") are preferred as polyether ketones, with PEEK being particularly preferred.

[0078] Examples of polyetheretherketones (PEEKs) include VictrexPEEK, VestaKeep, and Ketaspire. However, polyaryletherketones are not limited to these examples.

[0079] Examples of polyetherketone ketones include Kepstan (manufactured by Arkema). However, polyetherketone ketones are not limited to this example.

[0080] Polyaryletherketones can be used in combination with two or more types, or they can be used alone.

[0081] The melting point of polyaryletherketone is preferably 200–430°C, more preferably 250–400°C, and even more preferably 280–380°C. If the melting point of polyaryletherketone is above the lower limit of the above range, the heat resistance of the molded article is more excellent. If the melting point of polyaryletherketone is below the upper limit of the above range, the deterioration of physical properties caused by the thermal decomposition of fluorinated elastomers during melt mixing can be suppressed, and the properties of fluorinated elastomers (impact resistance, chemical resistance, etc.) can be maintained.

[0082] Polyaryletherketones can be commercially available polyaryletherketones or can be manufactured from various raw materials using known methods.

[0083] (Fluoropolymer)

[0084] The fluorinated elastomer is preferably a fluorinated elastic copolymer having units based on at least one monomer (hereinafter referred to as "monomer (m1)") selected from tetrafluoroethylene (hereinafter also referred to as "TFE"), hexafluoropropylene (hereinafter also referred to as "HFP"), vinylidene fluoride (hereinafter also referred to as "VdF") and trifluorochloroethylene (hereinafter also referred to as "CTFE").

[0085] Fluorinated elastomers are elastic copolymers that, according to ASTM D6204, exhibit a storage modulus G' of 80 or higher at 100°C and 50 cpm and do not have a melting point, distinguishing them from fluoropolymers.

[0086] Fluorinated elastomers can be used in combination with two or more types, or they can be used alone.

[0087] Fluorinated elastomers can be fluorinated elastic copolymers composed of only two or three units selected from TFE units, HFP units, VdF units and CTFE units, or they can be fluorinated elastic copolymers composed of units based on monomers (m1) and one or more units based on monomers (m2) that can copolymerize with monomers (m1).

[0088] The monomer (m2) is selected from ethylene (hereinafter also referred to as "E"), propylene (hereinafter also referred to as "P"), perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), fluoroethylene (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.

[0089] PAVE is a compound represented by the following formula (1).

[0090] CF2 = CF(OR) F (1)

[0091] Among them, R F It is a straight-chain or branched perfluoroalkyl group with 1 to 8 carbon atoms.

[0092] Examples of PAVEs 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").

[0093] Fluorinated elastomers may also have one or more units of monomers other than monomers (m1 and m2) (hereinafter also referred to as "monomers (m3)") that are based on monomers (m1) and monomers (m2) that can copolymerize with monomers (m1) and whose copolymers with monomers (m1) are elastic copolymers.

[0094] The proportion of monomer (m3) units relative to all units constituting the fluorinated elastomer is preferably 0 to 20 mol%, more preferably 0 to 5 mol%, and particularly preferably 0 mol%.

[0095] In fluorinated elastomers, all units constituting the fluorinated elastomer are preferably composed of two or three monomer-based units (m1), or of one or more monomer-based units (m1) and one or more monomer-based units (m2). However, as long as it does not affect the properties of the resin composition of the present invention, units other than these units, such as impurities, may also be included.

[0096] Fluorinated elastic copolymers composed of two or three monomer-based units (m1), as well as fluorinated elastic copolymers composed of one or more monomer-based units (m1) and one or more monomer-based units (m2), contribute to the impact resistance of the molded articles.

[0097] As fluorinated elastomers, the following three copolymers can be cited as examples. Here, the total proportion of each unit shown in the following three copolymers is preferably 50 mol% or more relative to the total number of units constituting the copolymer.

[0098] Copolymers containing TFE units and P units (hereinafter also referred to as "TFE / P-containing copolymers")

[0099] Copolymers containing HFP units and VdF units (excluding polymers containing P units) (hereinafter also referred to as "HFP / VdF-containing copolymers")

[0100] Copolymers having TFE units and PAVE units (excluding polymers having P units or VdF units) (hereinafter also referred to as "TFE / PAVE copolymers").

[0101] Examples of TFE / P-containing copolymers include the following copolymers.

[0102] Examples include TFE / P (representing a copolymer composed of TFE and P units, and 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-tetrafluoropropylene, TFE / P / 2,3,3,3-tetrafluoropropylene, TFE / P / TrFE, TFE / P / DiFE, TFE / P / VdF / TFP, and TFE / P / VdF / PAVE, with TFE / P being the preferred choice.

[0103] 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 the preferred choice.

[0104] Examples of TFE / PAVE copolymers include TFE / PAVE, with TFE / PAVE being particularly preferred as PMVE or PPVE, and TFE / PMVE / PPVE being the most preferred.

[0105] Other examples of fluorinated elastomers include TFE / VdF / 2,3,3,3-tetrafluoropropylene, VdF / PAVE, VdF / 2,3,3,3-tetrafluoropropylene, and E / HFP.

[0106] As fluorinated elastomers, TFE / P copolymers, HFP / VdF copolymers, and TFE / PAVE copolymers are preferred, with TFE / P copolymers being more preferred, and TFE / P being particularly preferred. TFE / P exhibits good thermal stability during melt mixing and stable transportability during melt mixing. Furthermore, the moldings of the present invention exhibit reduced coloring and foaming.

[0107] From the perspective of easily contributing to the impact resistance of the molded article, the proportions of the units constituting the fluorinated elastomer are preferably within the following range.

[0108] The molar ratio of each unit in TFE / P (TFE:P, hereinafter the same) is preferably 30-80:70-20, more preferably 40-70:60-30, and even more preferably 60-50:40-50.

[0109] In TFE / P / VF, the preferred ratio of TFE:P:VF is 30-60:60-20:0.05-40.

[0110] In TFE / P / VdF, the preferred ratio of TFE:P:VdF is 30–60:60–20:0.05–40.

[0111] In TFE / P / E, the preferred ratio of TFE:P:E is 20–60:70–30:0.05–40.

[0112] In TFE / P / TFP, the preferred ratio of TFE:P:TFP is 30-60:60-30:0.05-20.

[0113] In TFE / P / PAVE, the preferred ratio is 40-70:60-29.95:0.05-20.

[0114] In TFE / P / 1,3,3,3-tetrafluoropropylene, the preferred ratio of TFE:P:1,3,3,3-tetrafluoropropylene is 30-60:60-20:0.05-40.

[0115] In TFE / P / 2,3,3,3-tetrafluoropropylene, the preferred ratio of TFE:P:2,3,3,3-tetrafluoropropylene is 30-60:60-20:0.05-40.

[0116] In TFE / P / TrFE, the preferred ratio of TFE:P:TrFE is 30–60:60–20:0.05–40.

[0117] In TFE / P / DiFE, the preferred ratio of TFE:P:DiFE is 30-60:60-20:0.05-40.

[0118] In TFE / P / VdF / TFP, the preferred ratio of TFE:P:VdF:TFP is 30~60:60~20:0.05~40:0.05~20.

[0119] In TFE / P / VdF / PAVE, the preferred ratio is 30~70:60~20:0.05~40:0.05~20.

[0120] In HFP / VdF, the preferred ratio of HFP:VdF is 99–5:1–95.

[0121] In TFE / VdF / HFP, the preferred ratio of TFE:VdF:HFP is 20-60:1-40:20-60.

[0122] In TFE / VdF / HFP / TFP, the preferred ratio of TFE:VdF:HFP:TFP is 30~60:0.05~40:60~20:0.05~20.

[0123] In TFE / VdF / HFP / PAVE, the preferred ratio is 30~70:60~20:0.05~40:0.05~20.

[0124] In VdF / HFP / TFP, the preferred ratio of VdF:HFP:TFP is 1~90:95~5:0.05~20.

[0125] In VdF / HFP / PAVE, the preferred ratio of VdF:HFP:PAVE is 20–90:9.95–70:0.05–20.

[0126] In TFE / PAVE, the preferred ratio of TFE:PAVE is 40–70:60–30.

[0127] Furthermore, when PAVE is PMVE, the TFE:PMVE ratio is preferably 40–70:60–30.

[0128] In TFE / PMVE / PPVE, the preferred ratio of TFE:PMVE:PPVE is 40-70:3-57:3-57.

[0129] In TFE / VdF / 2,3,3,3-tetrafluoropropylene, the preferred ratio of TFE:VdF:2,3,3,3-tetrafluoropropylene is 1~30:30~90:5~60.

[0130] In VdF / PAVE, the preferred ratio of VdF:PAVE is 3-95:97-5.

[0131] In VdF / 2,3,3,3-tetrafluoropropylene, the preferred ratio of VdF:2,3,3,3-tetrafluoropropylene is 30–95:70–5.

[0132] In E / HFP, the preferred ratio of E:HFP is 40–60:60–40.

[0133] The fluorine content in the fluorinated elastomer is preferably 50–74% by mass, more preferably 55–70% by mass. The fluorine content in TFE / P is preferably 57–60% by mass, in HFP / VdF it is preferably 66–71% by mass, and in TFE / PMVE it is preferably 66–70% by mass. If the fluorine content is above the lower limit of the above range, the molded article exhibits superior heat resistance and chemical resistance. If the fluorine content is below the upper limit of the above range, the molded article exhibits superior impact resistance.

[0134] The number-average molecular weight of the fluorinated elastomer is preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000, even more preferably 20,000 to 800,000, and particularly preferably 50,000 to 600,000. If the number-average molecular weight of the fluorinated elastomer is above the lower limit of the above range, the mechanical properties of the molded article are superior. If the number-average molecular weight of the fluorinated elastomer is below the upper limit of the above range, the article exhibits high flowability, good dispersion in polyaryletherketone, and superior impact resistance.

[0135] Mooney viscosity (ML) of fluorinated elastomers 1+10 The viscosity (121°C) is preferably 20–200, more preferably 30–150, and even more preferably 40–120. Mooney viscosity is an indicator of molecular weight; a higher Mooney viscosity value indicates a larger molecular weight, and a lower Mooney viscosity value indicates a smaller molecular weight. If the Mooney viscosity is within the above range, the resin composition has better processability and the molded article has better mechanical properties.

[0136] Fluorinated elastomers can be manufactured by polymerizing one or more of a monomer (m1), a monomer (m2) to be used as needed, and a monomer (m3) or both of them.

[0137] Examples of polymerization methods include emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. Considering the ease of adjusting the number-average molecular weight and copolymer composition of fluorinated elastic copolymers, as well as their excellent productivity, emulsion polymerization, which polymerizes monomers in the presence of an aqueous medium and an emulsifier, is preferred.

[0138] In emulsion polymerization, monomers are polymerized in the presence of an aqueous medium, an emulsifier, and a free radical polymerization initiator to obtain the latex of the elastomer. A pH adjuster can be added during monomer polymerization.

[0139] (Inorganic packing)

[0140] There are no particular limitations on the shape of the inorganic filler; it can be fibrous, plate-like, or granular (including spherical). From the viewpoint of mechanical properties and tribological properties, fibrous fillers are preferred. In applications requiring isotropic molding, plate-like or granular inorganic fillers are preferred. There are no particular limitations on the size of the inorganic filler. Depending on the application of the molded body, inorganic fillers of any size, including nanometer, micrometer, and millimeter sizes, can be used.

[0141] Two or more types of inorganic fillers can be used in combination. It is particularly preferred to use fibrous inorganic fillers and granular or flake inorganic fillers in combination.

[0142] The fiber length of the fibrous inorganic filler is not particularly limited, but is preferably 0.5 μm to 10 mm. Continuous fibers with essentially unlimited length are preferred. For example, the fiber length of the fibrous inorganic filler can be 0.5–10 μm, 10–1000 μm, or 1–10 mm. If the fiber length of the fibrous inorganic filler is above the aforementioned lower limit, the heat resistance of the molded article is further improved. Furthermore, the mechanical properties and tribological properties of the molded article are also enhanced. If the fiber length of the fibrous inorganic filler is below the aforementioned upper limit, flowability during molding is easily ensured.

[0143] There is no particular limitation on the diameter of the fibrous inorganic filler, but it is preferably 0.001 μm to 30 μm. For example, the fibrous inorganic filler may have a diameter of 0.001 to 1 μm, 1 to 5 μm, or 5 to 30 μm.

[0144] If the diameter of the fibrous inorganic filler is above the lower limit mentioned above, the heat resistance of the molded article is superior. Furthermore, the mechanical properties and tribological properties of the molded article are also improved. If the diameter of the fibrous inorganic filler is below the upper limit mentioned above, the dispersibility of the fibrous inorganic filler is improved.

[0145] There is no particular limitation on the average particle size of the granular inorganic filler, but it is preferably 0.5 μm to 10 mm. The average particle size of the granular inorganic filler can be, for example, 0.5 μm to 10 μm, 10 μm to 1000 μm, or 1 mm to 10 mm. If the average particle size of the granular inorganic filler is above the lower limit mentioned above, the heat resistance of the molded article is also superior. Furthermore, the mechanical properties and tribological properties of the molded article are also improved. If the average particle size of the granular inorganic filler is below the upper limit mentioned above, it is easier to ensure flowability during molding.

[0146] There is no particular limitation on the thickness of the plate-shaped inorganic filler, but it is preferably 1 nm to 100 μm. The thickness of the plate-shaped inorganic filler can be, for example, 1 nm to 10 nm, 10 nm to 1 μm, or 1 μm to 100 μm. If the thickness of the plate-shaped inorganic filler is above the above lower limit, the heat resistance of the molded article is better. In addition, the mechanical properties and tribological properties of the molded article are also improved. If the thickness of the plate-shaped inorganic filler is below the above upper limit, it is easier to ensure the flowability during molding.

[0147] There is no particular limitation on the length of the plate-shaped inorganic filler, but it is preferably 0.5 μm or more and 1000 μm or less. The major diameter of the plate-shaped inorganic filler can be, for example, 0.5 μm to 10 μm, 10 μm to 100 μm, or 100 μm to 1000 μm. If the major diameter of the plate-shaped inorganic filler is above the above-mentioned lower limit, the heat resistance of the molded article is better. In addition, the mechanical properties and tribological properties of the molded article are also improved. If the particle size of the plate-shaped inorganic filler is below the above-mentioned upper limit, the flowability during molding is easily ensured.

[0148] Examples of inorganic fillers include carbon fiber, graphite, graphene, carbon nanotubes, glass fiber, gypsum fiber, mica, talc, glass sheets, wollastonite, potassium titanate, aluminum borate, boron nitride, aluminum nitride, calcium carbonate, silicon dioxide, titanium dioxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, clay, carbon black, inorganic pigments, molybdenum disulfide, metal powders, magnetic materials, and zeolites.

[0149] From the viewpoint of superior heat resistance of the molded body, carbon fiber, graphite, carbon nanotubes, and glass fiber are preferred, with glass fiber and carbon fiber being more preferred. From the viewpoint of superior brightness of the molded body, glass fiber is particularly preferred.

[0150] Examples of glass fibers include chopped fibers, ground fibers, and flat glass fibers with irregular cross-sections. Furthermore, from an electrical property point of view, glass fibers with low dielectric constants can be used.

[0151] Examples of carbon fibers include PAN-based carbon fibers, pitch-based isotropic carbon fibers, and pitch-based anisotropic carbon fibers. Regarding the shape of carbon fibers, short-cut fibers or ground fibers can be selected based on the desired physical properties.

[0152] It is also preferable to use fibrous inorganic fillers such as glass fiber and carbon fiber in combination with other inorganic fillers. Examples of other inorganic fillers include granular inorganic fillers and plate-shaped inorganic fillers. The size of these other inorganic fillers can be smaller than the preferred sizes described above (e.g., nano-sized granular inorganic fillers). Examples of other inorganic fillers include carbon black and silica. Specific examples of using fibrous inorganic fillers in combination with other inorganic fillers include the combination of glass fiber and silica, and the combination of carbon fiber and carbon black.

[0153] As carbon black, carbon black used as a filler in fluororubber can be used. Examples include furnace black, acetylene black, pyrolysis carbon black, and channel black. Among 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.

[0154] When the resin composition contains carbon black and other inorganic fillers, the carbon black content relative to the resin composition is preferably 1 to 45% by mass, more preferably 3 to 20% by mass. If the carbon black content is above the lower limit of the above range, the strength of the molded article is improved, and the effect obtained by incorporating carbon black can be fully obtained. When the carbon black content is below the upper limit of the above range, the elongation of the molded article is excellent. When the carbon black content is within the above range, the strength and elongation of the molded article are well balanced.

[0155] (Other ingredients)

[0156] Other components include polymer fillers, plasticizers, flame retardants, and other additives.

[0157] Other ingredients can be used in combination of two or more.

[0158] Examples of polymer fillers include liquid crystal polymers, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyester elastomers, polyarylates, polycaprolactone, phenoxy resins, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 46, aromatic polyamides, polyamide elastomers, polyphenylene ether, polyphenylene sulfide, polytetrafluoroethylene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethyl methacrylate, polypropylene, polyethylene, polybutadiene, butadiene-styrene copolymer, ethylene-propylene-diene rubber (EPDM), styrene-butadiene block copolymer, butadiene-acrylonitrile copolymer, acrylic rubber, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, ethylene / acrylic acid / glycidyl methacrylate copolymer, silicone elastomers, and aramid fibers.

[0159] In order to further reduce the dielectric constant and dielectric loss tangent of the molded article, polytetrafluoroethylene (PTFE) is preferably used. When the resin composition contains PTFE, the PTFE content is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, relative to 100% by mass of the resin composition of the present invention. If the PTFE content is below the above-mentioned upper limit, the strength of the molded article is more excellent. If the PTFE content is above the above-mentioned lower limit, the effect of further improving the dielectric properties can be obtained.

[0160] Examples of plasticizers include phthalates and adipates.

[0161] Examples of flame retardants include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, sodium antimonate, antimony pentoxide, phosphazene compounds, phosphate esters (triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene phenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc.), ammonium polyphosphate, melamine polyphosphate, red phosphorus, molybdenum compounds, boric acid compounds, and polytetrafluoroethylene.

[0162] Other components may include ultraviolet absorbers and light stabilizers. Ultraviolet absorbers include triazine-based, hydroxyphenyltriazine-based, benzophenone-based, and benzotriazole-based ultraviolet absorbers. Benzotriazole-based ultraviolet absorbers are particularly preferred. Hindered amine-based light stabilizers are suitable as light stabilizers.

[0163] Relative to 100% by mass of the resin composition of the present invention, the contents of the ultraviolet absorber and the light stabilizer are preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, respectively.

[0164] (Method for manufacturing the resin composition)

[0165] The resin composition can be manufactured by melt-blending polyaryletherketone (PAEK) and fluorinated elastomers, inorganic fillers, and other components as needed. The inorganic fillers can be added during or after the melt-blending of PAEK and fluorinated elastomers.

[0166] If the resin composition contains other components, these components may be added during the melt blending of polyaryletherketone and fluorinated elastomer, or after the melt blending of polyaryletherketone and fluorinated elastomer.

[0167] From the perspective of ease of operation when making the compound, the fluorinated elastomer before melt mixing is preferably in the form of granules.

[0168] The number average particle size of the fluorinated elastomer before melt mixing is preferably less than 10 mm, more preferably less than 8 mm, and even more preferably less than 6 mm. If the number average particle size of the fluorinated elastomer before melt mixing is within the above range, the transportability by the screw during melt mixing is stable.

[0169] The volume ratio of polyaryletherketone (PAE) to fluorinated elastomer in the melt blending process is the same as that in the resin composition. If the volume ratio of PAE to fluorinated elastomer is within the above range, the heat resistance, flexural modulus, and impact resistance of the molded body are improved.

[0170] Examples of melt mixing apparatus include known devices with melt mixing functions. Among melt mixing apparatuses, single-screw extruders or twin-screw extruders with screws that provide high mixing efficiency are preferred, twin-screw extruders are more preferred, and twin-screw extruders with screws that provide high mixing efficiency are particularly preferred. For screws that provide high mixing efficiency, a screw that provides sufficient mixing effect to the melt-mixing target material without applying excessive shear force can be selected. Examples of melt mixing apparatuses include the LABOPLASTOMILL mixing machine (manufactured by Toyo Seiki Co., Ltd.) and the KZW series twin-screw mixing extruder (manufactured by Technovel Co., Ltd.).

[0171] As a method for supplying polyaryletherketone and fluorinated elastomer to a melt-blending unit, the polyaryletherketone and fluorinated elastomer can be pre-mixed and then supplied to the melt-blending unit, or the polyaryletherketone and fluorinated elastomer can be supplied to the melt-blending unit separately.

[0172] As a method for supplying inorganic fillers to the melt-blending unit, it is preferable to add the inorganic fillers after the polyarylether ketone and the fluorinated elastomer have been melt-blended. Alternatively, the inorganic fillers may be pre-mixed with the polyarylether ketone and the fluorinated elastomer separately before being supplied to the melt-blending unit.

[0173] When other components are included in the resin composition, they can be supplied to the melt-blending apparatus after pre-mixing with one of the polyaryletherketone and the fluorinated elastomer, or they can be supplied to the melt-blending apparatus separately from the polyaryletherketone and the fluorinated elastomer. Alternatively, other components can be added after the polyaryletherketone and the fluorinated elastomer have been melt-blended.

[0174] The temperature at which polyaryletherketone and fluorinated elastomer are melt-blended (hereinafter also referred to as "melt blending temperature") is preferably set according to the polyaryletherketone and the fluorinated elastomer. The melt blending temperature is preferably 220–480°C, more preferably 280–450°C, even more preferably 290–420°C, and particularly preferably 300–400°C.

[0175] The extrusion shear rate during melt blending of polyaryletherketone (PAE) and fluorinated elastomer is preferably set based on the melt viscosity of the melt-blended material composed of PAE and fluorinated elastomer at the melt blending temperature. The preferred extrusion shear rate during melt blending is 3–2500 seconds. -1 More preferably 10 to 2000 seconds -1 Further optimized to 15–1500 seconds -1 .

[0176] The residence time of the material to be melted and mixed in the melt-mixing apparatus is preferably 10 to 290 seconds, more preferably 20 to 240 seconds, and even more preferably 30 to 210 seconds.

[0177] The melt blending of polyaryletherketone (PAGE) and fluorinated elastomers is preferably carried out by dispersing fluorinated elastomer particles with a number average particle size of 0.5–10 μm in PAGE. By appropriately adjusting the melt blending temperature, extrusion shear rate, and residence time of the melt-blending material in the melt blending apparatus, fluorinated elastomer particles with a number average particle size of 0.5–10 μm can be dispersed in PAGE.

[0178] By increasing the melt mixing temperature, fluorinated elastomers are easily dispersed in polyaryletherketones, and large particles of fluorinated elastomers are less likely to remain. By decreasing the melt mixing temperature, the thermal decomposition of fluorinated elastomers is less likely to be promoted, resulting in better heat resistance of the resin composition and preventing the particle size of the fluorinated elastomers from becoming too small.

[0179] By increasing the extrusion shear rate, fluorinated elastomers are easily dispersed in polyaryletherketones, and large particles of fluorinated elastomers are less likely to remain. By decreasing the extrusion shear rate, the particle size of the fluorinated elastomers will not become too small.

[0180] If the residence time of the material to be melt-mixed is extended in the melt-mixing device, the fluorinated elastomer is more easily dispersed in the polyarylether ketone, and large particles of the fluorinated elastomer are less likely to remain. If the residence time is shortened, the thermal decomposition of the fluorinated elastomer is less likely to be promoted.

[0181] Melt blending is preferably carried out under conditions where crosslinking agents and crosslinking aids are substantially absent. Melt blending under conditions where crosslinking agents and crosslinking aids are substantially absent means melting the resin composition without substantially crosslinking the fluorinated elastomer. Whether the fluorinated elastomer in the resin composition is substantially crosslinked can be confirmed by the value of the flexural modulus of the resin composition.

[0182] Resin compositions obtained by melt-blending an object containing polyaryletherketone and fluorinated elastomers can be melt-molded and used as materials for molded articles.

[0183] The resin composition of the present invention can be formulated into a powder for use as a coating material. Examples of its use in coated articles include those described in International Publication No. 2015 / 182702.

[0184] (Mechanism of action)

[0185] The resin composition of the present invention described above has a load deformation temperature T0 that is higher than the load deformation temperature T1 of the comparative composition (1), and a molded article with excellent heat resistance can be obtained.

[0186] Furthermore, the volume ratio of the fluorinated elastomer to the total volume of the polyaryletherketone and the fluorinated elastomer is more than 5% by volume, indicating a sufficient amount of fluorinated elastomer. Therefore, the impact resistance of the molded part can be adequately ensured.

[0187] Furthermore, the volume ratio of the fluorinated elastomer to the total volume of the polyaryletherketone (PREE) and the fluorinated elastomer is less than 45% by volume, indicating that the amount of PREE is sufficient. Therefore, the flexural modulus and heat resistance of the molded article can be adequately ensured.

[0188] Furthermore, in addition to polyaryletherketone and fluorinated elastomer, the resin composition of the present invention also contains inorganic filler at 1% by mass relative to the composition. Therefore, as shown in the examples described later, a synergistic effect based on the three components—polyaryletherketone, fluorinated elastomer, and inorganic filler—can be obtained. As a result, the flexural modulus, heat resistance, and low-temperature impact resistance of the molded article are improved beyond what those skilled in the art would normally expect. The reason for obtaining the synergistic effect is not necessarily clear, but it is considered to be based on the effect of the crystallization of polyaryletherketone.

[0189] Therefore, the resin composition of the present invention can produce molded articles with high flexural modulus, excellent heat resistance and low-temperature impact resistance.

[0190] <Molded body>

[0191] 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 can be appropriately selected according to the shape, purpose, etc. of the molded article.

[0192] The molded articles of the present invention have high flexural modulus, excellent heat resistance and low-temperature impact resistance, and therefore can be used in applications requiring these properties.

[0193] When the resin composition of the present invention contains, for example, glass fiber and silica as inorganic fillers, the molded article has high gloss, and is therefore suitable for applications where appearance is important. Polyaryletherketones are originally brown. Therefore, polyaryletherketones are usually whitened with white pigments or the like, or colored to a color other than brown before use. However, using such coloring pigments may impair the excellent physical properties of polyaryletherketones.

[0194] When the resin composition of the present invention contains, for example, glass fiber and silica as inorganic fillers, the molded article exhibits a high L* value and high brightness in hue measurements based on JIS-Z8781-4. Therefore, whitening and coloring treatments are unnecessary, and the excellent physical properties of polyaryletherketone are not easily compromised. Consequently, it also has the advantage of being suitable for portable electronic devices where appearance is important.

[0195] Examples of the forms and uses of the molded bodies of the present invention include the housing (shell) of portable electronic devices, connecting components of portable electronic devices, sliding components, three-dimensional circuit components, gears, actuators, pistons, bearings, aircraft interior materials, bushings, pipes (for fuel, etc.), hoses, cans, seals, wires, insulating covering materials for wires (electrical wires, cables, etc.), films, sheets, bottles, fibers, etc.

[0196] Since portable electronic devices are used handheld, liquids such as oils, beverages, sweat, and sebum contained in food and cosmetics are likely to adhere to them. Because the molded articles of the present invention are not easily discolored or deteriorated by these deposits, they are suitable for use in portable electronic devices.

[0197] Examples of portable electronic devices include mobile phones, mobile terminals, laptop computers, tablet computers, radios, cameras, camera accessories, watches, calculators, music players, GPS receivers, mobile game consoles, hard disk drives, mobile recording devices, portable playback devices, and portable radio receivers.

[0198] Examples of housing forms for portable electronic devices include the back cover, front cover, antenna housing, frame, and skeleton. The housing can be a single component formed from the molded body of this invention, or it can be a component composed of multiple parts. Here, the skeleton is a component that mounts parts of the portable electronic device such as the electronic device, microprocessor, screen, keyboard, keypad, antenna, and battery socket.

[0199] When the enclosure is located inside the portable electronic device, it may be invisible from the outside of the portable electronic device, or it may be visible from the outside of the portable electronic device. Enclosures such as covers used to protect and support the internal structure may be exposed to the outside of the portable electronic device.

[0200] Examples of connecting components for portable electronic devices include circuit boards, microphones, speakers, displays, batteries, housings, electrical connectors, electronic connectors, hinges, antennas, switches, and snap-fit ​​connectors between switch pads. These connecting components are applicable to portable electronic devices such as mobile phones, mobile terminals (PDAs), music storage devices, listening devices, portable DVD players, galvanometers, portable video game consoles, and portable personal computers (e.g., laptops).

[0201] Three-dimensional circuit components are components in which circuit patterns are formed on the surface of resin components molded into three-dimensional shapes, and are used as antenna components for mobile electronic devices and components for automotive electronic devices. As a method for forming the circuit patterns, laser direct forming (LDS) is employed, which involves laser etching the circuit patterns followed by electroplating. The molded articles of this invention exhibit excellent low dielectric properties, making them suitable for three-dimensional circuit components.

[0202] For applications such as pipes, hoses, channels, seals, and wires, examples include those described in International Publication No. 2015 / 182702. Furthermore, for applications such as pipes and hoses, examples include pipes used in drilling for energy resources such as oil, natural gas, and shale oil. Among these, pipes used in oil drilling are preferred.

[0203] Applications of electrical wire insulation materials include wires or flat-angle copper wires for motor coils, and particularly the insulation materials for flat-angle conductors in drive motors of hybrid electric vehicles (HEVs) and electric vehicles (EVs). A film is preferred as the form of the insulation material for flat-angle conductors. Furthermore, applications of electrical wire insulation materials include the insulation materials for downhole cables used in energy resource (oil, natural gas, shale oil, etc.) drilling. Among these, the insulation materials for downhole cables used in oil drilling are preferred.

[0204] Examples of applications for membranes and sheets include loudspeaker diaphragms, flat plates for trauma and fractures, insulating paper for various electrical insulating adhesive tapes (such as insulating paper for motors), sealing tapes for oil and gas pipelines, and release films for thermosetting and thermoplastic composite molding.

[0205] When the molded body is a film, its preferred applications include speaker diaphragms, wire covering films, flexible printed circuit boards, heat-resistant rollers for OA equipment, and films for impregnation of other fiber composite materials. The film thickness is preferably 1–100 μm, more preferably 2–80 μm, and even more preferably 5–50 μm. If the film thickness is above the lower limit of this range, the film strength is improved. If the film thickness is below the upper limit of the above range, the film exhibits excellent processability in the next step.

[0206] When the molded body is a tube, its preferred applications are medical catheters with tubes, wire coverings, and piping for analytical instruments.

[0207] When the extruded material is fiber, its preferred applications are protective clothing and various filters.

[0208] Examples of forming methods include injection molding, extrusion molding, co-extrusion molding, blow molding, compression molding, transfer molding, and calendering.

[0209] When the molded product is a film, extrusion molding methods such as T-die molding and blow molding can be cited as examples. In T-die molding, the flow rate of molten resin and the thickness of the film can be precisely controlled by adjusting the throttling rod or die lip inside the T-die. In blow molding, air is introduced into the interior of the extruded product through a circular die to cause it to expand and form a film, thereby making the film thickness uniform.

[0210] When the shaped body is a fiber, the preferred forming method is an extrusion forming method such as melt spinning.

[0211] <Complex>

[0212] In the composite of the present invention, the molded body of the present invention is composited or laminated with other materials. Examples of other materials include metals, glass, plastics, and rubber.

[0213] Specific examples of plastics include those described in International Publication No. 2015 / 182702, such as liquid crystal polymers, polyaryl ketones, polyethersulfones, polyphenylsulfones, polyacetals, and polyurethanes. Examples of polyamides include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6 / 66 copolymers, polyamide 6 / 66 / 610 copolymers, polyamide MXD6, polyamide 6T, polyamide 9T, and polyamide 6 / 6T copolymers.

[0214] As for other materials, metals and glass are preferred. Among metals, iron, copper, stainless steel, steel, aluminum, magnesium, and titanium are preferred.

[0215] Since the composite of the present invention is a composite of a molded body with excellent chemical resistance and other materials, the composite of the present invention is suitable for use in materials treated with strong chemicals during the manufacturing process. Just as composites of resins with metals, glass, etc., are widely used in portable electronic devices, the composite of the molded body of the present invention with other materials such as metals and glass is suitable for use in portable electronic devices.

[0216] Composites of metals (aluminum, stainless steel, etc.) and resins used in portable electronic devices are typically anodized to improve surface hardness and appearance. Anodizing is a process that uses strong chemicals to form an oxide layer on a metal surface to increase surface hardness. Therefore, metal-resin composites requiring anodizing, especially the resin portion, exhibit excellent chemical resistance. Because the composites of the present invention are easily anodized, they are suitable for portable electronic devices where appearance is important.

[0217] The metal portion of the composite of the molded body and the metal of the present invention is not transparent to electromagnetic waves; therefore, electromagnetic signals can pass through the portion of the molded body of the present invention. Since the molded body of the present invention also exhibits excellent low dielectric properties, the composite of the molded body and the metal of the present invention is suitable for use in portable electronic devices from the viewpoint of low dielectric properties.

[0218] The composite of the present invention can be manufactured, for example, by bonding the molded body with other materials. There are no particular limitations on the bonding method; various methods can be used.

[0219] For example, a method for joining the molded body of the present invention with other materials such as metal coated with an adhesive; a method for injection molding the molten resin composition of the present invention into a metal part placed in a mold during injection molding.

[0220] When injection molding is combined with metal, the molded body of the present invention can be directly combined with a metal part, or injection molding can be performed after chemical bonding treatment of the surface of the metal part or physical or chemical treatment of the surface of the metal part to form an uneven surface.

[0221] As a chemical bonding process, metal parts coated with an adhesive can be used. Examples of methods for creating unevenness through physical processing include laser processing and machining. Examples of methods for creating unevenness through chemical treatment include chemical etching.

[0222] Composites of molded parts and metals manufactured by injection molding can be machined and cut to the desired shape.

[0223] Example

[0224] The present invention will now be described in more detail with reference to the embodiments, but the present invention is not limited to the following embodiments. Examples 1-4, 7-10, and 14-18 are embodiments, and Examples 5, 6, and 11-13 are comparative examples.

[0225] (Evaluation of injection molding)

[0226] Using an injection molding machine (ROBOSHOTα-50 manufactured by FANUC Corporation), the resin composition was injection molded at a barrel temperature of 380°C and a mold temperature of 170°C to obtain an evaluation injection molded body with a thickness of 4.0 mm.

[0227] (Flexural modulus of elasticity, flexural strength)

[0228] Test pieces with a length of 80 mm and a width of 10 mm were cut from the injection-molded body used for evaluation. For the test pieces, the flexural modulus and flexural strength were measured using TENSILON (manufactured by A&D Corporation, RTF-1350) according to JIS K7171, with a load cell rating of 10 kN, a distance between fulcrums of 64 mm, and a speed of 2 mm / min.

[0229] (Impact strength of cantilever beam)

[0230] A test piece with a length of 80 mm and a width of 10 mm was cut from the injection molded part for evaluation, and a cut was made at a height of 40 mm on the test piece.

[0231] For the test specimens, the cantilever beam impact strength was determined using a cantilever beam impact testing apparatus (manufactured by Toyo Seiki Co., Ltd.), with the following conditions: hammer capacity: 2.75J, hammer load: 13.97N, distance from the axis to the center of gravity: 10.54cm, and distance from the axis to the point of impact: 33.5cm. Tests were conducted at 23°C and -40°C.

[0232] (Load-induced deformation temperature)

[0233] Test pieces with a length of 80 mm and a width of 10 mm were cut from the injection-molded body for evaluation. According to ASTM D648, the temperature at which the deformation of 0.254 mm was achieved was determined using an HDT & VSPT TESTER manufactured by Toyo Seiki Co., Ltd. under a load of 1.82 MPa and a heating rate of 2 °C / min.

[0234] (Dielectric constant)

[0235] The resin composition was pressurized using a hot melt press to obtain a pressed sheet with a thickness of 0.24 mm. Referring to ASTM D2520, the dielectric constant of the pressed sheet was determined using a PNA-L network analyzer (Agilent Technologies N5230A) and a cavity resonator (Kanto Electronics Application Development Co., Ltd. CP481) at a temperature of 23°C, humidity of 50% RH, and frequency of 10 GHz.

[0236] (Coefficient of kinetic friction)

[0237] The friction and wear testing machine FRT IIEAA manufactured by TSE Corporation was used to conduct the test using the Matsubara friction measurement method (cylindrical ring to ring) based on JIS K-7218.

[0238] At room temperature, the ring (material: SUS316, contact area: 2 cm²) used as the opposing material was subjected to a pressure of 0.4 MPa, a rotation speed of 0.5 m / s, and a test time of 1 hour. 2 The sample is brought into contact with a cylindrical test piece made of a resin composition by injection molding. The coefficient of kinetic friction of the test piece is determined.

[0239] (Hue Measurement)

[0240] For the evaluation of injection molded parts, according to JIS-Z8781-4, the hue was measured using the SM-T color calibration computer manufactured by Suga Testing Machine Co., Ltd., and L*, a*, and b* were measured.

[0241] (Chemical resistance)

[0242] After immersing each evaluation injection molded part in a 70% sulfuric acid solution at 23°C for 24 hours and 168 hours respectively, tensile tests were performed on each evaluation injection molded part to determine tensile strength and tensile elongation.

[0243] (raw material)

[0244] Polyaryletherketone (A-1): PEEK (melting point: 340℃, melt flow rate: 22g / 10min, specific gravity: 1.32, manufactured by Daicel Evonik Co., Ltd., VESTAKEEP 3300G).

[0245] Fluorinated elastomer B-1: Tetrafluoroethylene-propylene copolymer (melt flow rate: 11 g / 10 min, specific gravity: 1.55, Mooney viscosity (mL) 1+10 ,121℃):100, Energy storage modulus G' (100℃, 50cpm):390, Manufactured by AGC Corporation, AFLAS (registered trademark) 150FC).

[0246] Inorganic filler (C-1): Glass fiber (manufactured by Nitto Boshoku Co., Ltd., NE Glass CN3DE-451)

[0247] Inorganic filler (C-2): Glass fiber (manufactured by Nitto Boshoku Co., Ltd., NE Glass CN3DE-941)

[0248] Inorganic filler (C-3): Carbon fiber (manufactured by Zoltek, PXCA0250-83)

[0249] Polymer filler (D-1): Polytetrafluoroethylene (manufactured by AGC Corporation L169J)

[0250] Polymer filler (D-2): Polytetrafluoroethylene (manufactured by AGC Corporation L170JE)

[0251] Ultraviolet absorber (E-1): Hydroxyphenyl triazine (HPT) is a type of ultraviolet absorber (BASF Tinuvin 479).

[0252] Light stabilizer (E-2): Hindered amine light stabilizer (HALS) (Tinuvin PA144 manufactured by BASF)

[0253] (Examples 1 to 4, 7 to 10)

[0254] Polyaryletherketone (A-1) and fluorinated elastomer (B-1) and inorganic filler (C-1), inorganic filler (C-2), or inorganic filler (C-3) and polymer filler (D-1) are mixed in the proportions shown in Tables 1 and 2, and fed into the base end of the screw of a twin-screw compounding extruder (TECHNOVEL, KZW15TW-45HG1100, screw diameter: 15mmΦ, L / D: 45) at a rate of 2.0 kg / hour using a feeder. Under the conditions of screw speed of 200 rpm and set temperatures of cylinder, die and die head of C1=340℃, C2=350℃, C3=360℃, C4=370℃, C5=370℃, C6=370℃, D=350℃, H=350℃, the extruded strands are extruded from the front end of the die, cooled in a water tank, and cut by a granulator to obtain granules of the resin composition.

[0255] In the proportions shown in Tables 1 and 2, "volume ratio (volume%)" refers to the ratio of the individual volumes relative to the total volume of polyaryletherketone (A-1) and the fluorinated elastomer (B-1). Furthermore, "inorganic filler ratio (mass%)" and "polymer filler ratio (mass%)" refer to the ratios of each inorganic filler and polymer filler relative to 100% by mass of the resin composition. These same provisions apply to the other examples shown below.

[0256] (Examples 5, 11)

[0257] Except that inorganic fillers were not used, and polyaryletherketone (A-1) and fluorinated elastomer (B-1) were mixed according to the proportions shown in Tables 1 and 2, the granules of the resin composition were prepared in the same manner as in Example 1. Here, the composition of Example 5 is a comparative composition (1) of the resin compositions of Examples 1 to 4 and 7. And the composition of Example 11 is a comparative composition (1) of the resin compositions of Examples 8 to 10.

[0258] (Example 6)

[0259] Except that no fluorinated elastomers and inorganic fillers were used, and only polyarylether ketone (A-1) was used, the resin composition particles were prepared in the same manner as in Example 1.

[0260] (Examples 12, 13)

[0261] Except that the fluorinated elastomer, polyarylether ketone (A-1), and inorganic filler (C-1) or inorganic filler (C-2) were not mixed according to the proportions shown in Table 2, the granules of the resin composition were prepared in the same manner as in Example 1. Here, the composition of Example 12 is a comparative composition (2) of the resin compositions of Examples 1 and 8. And the composition of Example 13 is a comparative composition (2) of the resin compositions of Examples 2, 7, and 9.

[0262] (Examples 14~18)

[0263] Except for following the proportions recorded in the table, the same procedure as in Example 10 shall be followed to manufacture the product.

[0264] The formulation composition 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.

[0265] [Table 1]

[0266]

[0267] [Table 2]

[0268]

[0269] [Table 3]

[0270]

[0271] The load deformation temperature of the resin compositions in Examples 1-4 and 7 is higher than that of the composition in Example 5. The flexural modulus, heat resistance, and low-temperature impact resistance of Examples 1-4 and 7 are superior to those of the composition in Example 5.

[0272] Furthermore, the load deformation temperature of the resin compositions of Examples 8-10 is higher than that of the composition of Example 11. The flexural modulus, heat resistance, and low-temperature impact resistance of Examples 8-10 are superior to those of the composition of Example 11.

[0273] Examples 1 and 8, which used inorganic filler (C-1), exhibited better heat resistance and impact resistance than Example 12, which also used inorganic filler (C-1).

[0274] Examples 2 and 9, which used inorganic filler (C-2), exhibited better heat resistance and impact resistance than Example 13, which also used inorganic filler (C-2).

[0275] Regarding heat resistance, based on the common knowledge of those skilled in the art, the resin compositions of Examples 1, 2, 8, and 9 contain a fluorinated elastomer (B-1) in addition to polyarylether ketone (A-1) and inorganic filler (C-1) or (C-2). Therefore, their heat resistance should be lower than that of the compositions of Examples 12 and 13, which are composed of two components: polyarylether ketone (A-1) and inorganic filler (C-1) or (C-2).

[0276] However, the load deformation temperature of the resin compositions of Examples 1 and 8 is higher than that of the composition of Example 12, which is composed of two components: polyaryletherketone (A-1) and inorganic filler (C-1). Moreover, the load deformation temperature of the resin compositions of Examples 2 and 9 is also higher than that of the composition of Example 13, which is composed of two components: polyaryletherketone (A-1) and inorganic filler (C-2).

[0277] The results show that by using a resin composition containing polyarylether ketone, fluorinated elastomer, and inorganic filler, the synergistic effect of these three components can be obtained, and the heat resistance of the molded article is improved beyond what is usually expected by those skilled in the art.

[0278] Regarding the flexural modulus, based on the common knowledge of those skilled in the art, the resin compositions of Examples 1, 2, and 9 contain a fluorinated elastomer (B-1) in addition to polyarylether ketone (A-1) and inorganic filler (C-1) or (C-2). Therefore, their flexural modulus should be lower than that of the compositions of Examples 12 and 13, which are composed of two components: polyarylether ketone (A-1) and inorganic filler (C-1) or (C-2).

[0279] However, the flexural modulus of the resin composition of Example 1 is higher than that of the composition of Example 12, which consists of two components: polyaryletherketone (A-1) and inorganic filler (C-1). Moreover, the flexural modulus of the resin compositions of Examples 2 and 9 is also equal to or higher than that of the composition of Example 13, which consists of two components: polyaryletherketone (A-1) and inorganic filler (C-2).

[0280] The results show that by using a resin composition containing polyaryletherketone, fluorinated elastomer, and inorganic filler, the synergistic effect of these three components can be obtained, and the flexural modulus of the molded article is increased beyond what is usually expected by those skilled in the art.

[0281] Regarding brightness, the brightness L* of Examples 1, 2, 3, and 8-10 are all above 80, indicating a good evaluation result. Furthermore, the brightness L* of Example 16 is above 75, and the brightness L* of Examples 14, 15, 17, and 18 are all above 80, indicating a good evaluation result.

[0282] Regarding chemical resistance, the tensile strength and elongation values ​​of Examples 1, 2, 8, and 9 are shown in Tables 1 and 2, respectively. These values ​​are maintained from the values ​​before immersion in 70% sulfuric acid solution, and based on these results, their chemical resistance can be considered good.

[0283] Regarding the dielectric constant, the dielectric constants of Examples 1-3 and Examples 8-10 are lower than those of Examples 12 and 13, and the dielectric constant of Example 7 is even lower. Based on these results, the low dielectric constant characteristic can be considered good.

[0284] Industrial applications

[0285] The molded articles of the resin composition of the present invention have high flexural modulus, excellent heat resistance and low-temperature impact resistance, and can therefore be used in applications requiring these properties.

[0286] The entire contents of the description, claims, and abstract 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 incorporated herein by reference as disclosure of the present invention.

Claims

1. A resin composition comprising polyaryletherketone, a fluorinated elastomer, and an inorganic filler. in, The fluorinated elastomer is a copolymer having tetrafluoroethylene-based units and propylene-based units, a copolymer having hexafluoropropylene-based units and vinylidene fluoride-based units, or a copolymer having tetrafluoroethylene-based units and units based on a compound represented by formula (1). CF2=CF(OR F ) (1) In the formula, R F It is a straight-chain or branched perfluoroalkyl group having 1 to 8 carbon atoms. As at least a part of the inorganic filler, it comprises carbon fiber or glass fiber. The volume ratio of the fluorinated elastomer to the total volume of the polyarylether ketone and the fluorinated elastomer is 1 to 45% by volume. The inorganic filler accounts for 20-30% by mass relative to the resin composition. The load deflection temperature, measured based on ASTM D648 under a load of 1.82 MPa, is higher than the load deflection temperature of the comparative compositions described below. Comparative composition: A resin composition comprising the polyarylether ketone and the fluorinated elastomer but excluding the inorganic filler, wherein, except for the presence or absence of the inorganic filler, the type of the polyarylether ketone, the type of the fluorinated elastomer, and the volume ratio of the fluorinated elastomer relative to the total volume of the polyarylether ketone and the fluorinated elastomer are the same as those in the resin composition.

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

3. The resin composition according to claim 1 or 2, wherein, Luminance L in Hue Measurement Based on JIS-Z8781-4 Above 60.

4. The resin composition according to claim 1 or 2, wherein, The inorganic packing material is a fibrous inorganic packing material, a plate-shaped inorganic packing material, or a granular inorganic packing material.

5. The resin composition according to claim 1 or 2, wherein, The inorganic filler comprises one or more selected from carbon fiber, graphite, carbon nanotubes, glass fiber, and silicon dioxide.

6. The resin composition according to claim 1 or 2, wherein, It also contains polymer fillers.

7. The resin composition of claim 6, wherein, The polymer filler is polytetrafluoroethylene.

8. The resin composition according to claim 1 or 2, wherein, It also contains one or more selected from plasticizers, ultraviolet absorbers and light stabilizers.

9. A molded article, which is a molded product of the resin composition according to any one of claims 1 to 8.

10. A composite obtained by combining or laminating the molded body of claim 9 with other materials.

11. Portable electronic devices, sliding components, three-dimensional circuit components, wires, or energy resource drilling components, comprising the shaped body of claim 9 or the composite of claim 10.

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