Thermoplastic resin composition and method for producing same

Abstract

To provide a thermoplastic resin composition that can give a molding having excellent heat resistance while having high tensile strength and high weld strength, and a method for producing the same.SOLUTION: A thermoplastic resin composition is primarily composed of a thermoplastic resin (A) with a melting point of 270°C or higher and a fluorine-based resin (B) of 5-50 pts.mass relative to 100 pts.mass of the thermoplastic resin (A). In the fluorine-based resin (B), the Ni content CBNi is expressed as 0.003 ppm≤CBNi<1 ppm. There is also provided a method for producing the same.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition and a method for producing the same. [Background technology]

[0002] Thermoplastic resins are widely used in industrial parts due to their excellent heat resistance, mechanical properties, moldability, etc. For example, polyamide resins are widely used in automobile parts and the like due to their excellent properties in addition to the above (e.g., relatively low cost and easy availability, high chemical resistance and oil resistance). In these applications, the operating environment is harsher than that of general industrial parts, so strict standards are required for the performance of parts, such as weld strength and sliding properties, and improvements are being actively studied (see, for example, Patent Documents 1 to 3). In particular, polyamide resins composited with fluororesins have excellent mechanical strength and are used in applications such as automotive parts where friction is a problem (see Patent Documents 4 to 7). Welds occur, for example, at locations where molten resin flows injected into a mold cavity diverge and converge during injection molding. Although welds in molded products are formed by the fusion of molten resins, their mechanical properties are generally more likely to deteriorate than non-weld areas due to the lack of uniform mixing of the resins. Weld strength refers to the strength of the welds in such molded products. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-297338 [Patent Document 2] Japanese Patent Application Publication No. 2017-095542 [Patent Document 3] Patent Publication No. 2021-017493 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-070538 [Patent Document 5] Japanese Patent Application Laid-Open No. 2007-106917 [Patent Document 6] Japanese Patent Application Publication No. 2018-002906 [Patent Document 7] Japanese Patent Publication No. 2020-037656 Summary of the Invention [Problem to be solved by the invention]

[0004] However, during heat molding, the fluororesin contained in the polyamide resin forms foreign matter agglomerates, which can cause insufficient strength at these locations. While methods to address this lack of strength include kneading the resin at high temperatures for extended periods to strengthen the kneading process, this method also poses the problem of inducing degradation of the thermoplastic resin itself. Furthermore, in injection molding, the strength of the resin can be increased by adding reinforcing fibers such as glass fiber. However, even if the strength is increased by adding reinforcing fibers, the strength of the welds, where the resins meet, is weakened. Therefore, when the shape of the molded product becomes complex, the weld strength decreases significantly.

[0005] Therefore, an object of the present invention has been made in consideration of the above-mentioned conventional problems, and is to provide a thermoplastic resin composition that exhibits excellent heat resistance and from which molded articles having high tensile strength and weld strength can be obtained, and a method for producing the same. [Means for solving the problem]

[0006] The present inventors have found that the above-mentioned problems can be solved by adjusting the content of a predetermined metal within a predetermined range in a thermoplastic resin composition containing a thermoplastic resin having a predetermined melting point and a fluororesin, and have thus completed the present invention.

[0007] The present invention relates to the following [1] to

[11] . [1] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component, and containing 5 to 50 parts by mass of a fluorine-containing resin (B) per 100 parts by mass of the thermoplastic resin (A), Ni content in fluororesin (B)CB Ni However, 0.003 ppm or less CB Ni <1 ppm. [2] Mn content in fluororesin (B)CB Mn But 0 ppm <CB Mn The thermoplastic resin composition according to the above [1], wherein the content of HCl is less than 1 ppm. [3] Mn content in fluororesin (B)CB mn However, 0.003 ppm or less CB Mn The thermoplastic resin composition according to the above [1] or [2], wherein the content of the hydroxybenzoates is ≦1 ppm. [4] Al content in fluororesin (B) CB Al But 0 ppm <CB Al The thermoplastic resin composition according to any one of the above [1] to [3], wherein the content of HCl is less than 0.4 ppm. [5] The thermoplastic resin composition according to any one of the above [1] to [4], wherein the fluorine-based resin (B) is polytetrafluoroethylene. [6] The thermoplastic resin composition according to any one of the above [1] to [5], wherein the thermoplastic resin (A) is a polyamide resin. [7] The thermoplastic resin composition according to any one of the above [1] to [6], further comprising a filler. [8] A thermoplastic resin composition containing, as a main component, a thermoplastic resin (A) having a melting point of 270°C or higher, and containing 5 to 50 parts by mass of a fluorine-containing resin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the thermoplastic resin composition satisfies the following conditions (i) to (iii): (i) The thermoplastic resin composition contains Ni. (ii) The tensile strength of a molded article of the thermoplastic resin composition, measured in accordance with JIS K7161 (2014), is 150 MPa or more. (iii) The weld strength of a molded article of the thermoplastic resin composition is 56 MPa or more, as measured in accordance with JIS K7161 (2014). [9] The thermoplastic resin composition according to [8] above, further satisfying the following conditions (iv) and (v): (iv) The specific abrasion rate of a molded article of the thermoplastic resin composition is 50 or less. (v) The coefficient of dynamic friction of a molded article of the thermoplastic resin composition is 0.25 or less.

[10] A method for producing the thermoplastic resin composition according to any one of [1] to [9] above, A thermoplastic resin (A) and a fluorine-based resin (B) containing Ni are melt-kneaded to obtain the thermoplastic resin. resin A method for producing a thermoplastic resin composition, comprising:

[11] Ni content CB for 100 parts by mass of thermoplastic resin (A) having a melting point of 270°C or higher Ni 0.003 ppm or less CB Ni A method for producing a thermoplastic resin composition, comprising melt-kneading 5 to 50 parts by mass of a fluorine-based resin (B) having a fluorine content of less than 1 ppm. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a thermoplastic resin composition and a method for producing the same, which can give a molded article having excellent heat resistance, high tensile strength, and high weld strength. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described. The present invention also includes any selected or combined embodiment of the matters described in this specification. In this specification, preferred definitions can be selected arbitrarily, and combinations of preferred definitions can be considered more preferred. In this specification, the expression "XX to YY" means "XX or more and YY or less." In this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, the term "unit" (where "" indicates a monomer) means "a structural unit derived from", for example, a "dicarboxylic acid unit" means "a structural unit derived from a dicarboxylic acid", and a "diamine unit" means "a structural unit derived from a diamine". As used herein, "derived from" with respect to each structural unit means that said monomer has undergone the structural changes necessary for polymerization. In this specification, "ppm" means "ppm by mass."

[0010] [Thermoplastic resin composition] The thermoplastic resin composition according to the first embodiment of the present invention contains a thermoplastic resin (A) having a melting point of 270°C or higher as a main component, and contains 5 to 50 parts by mass of a fluororesin (B) relative to 100 parts by mass of the thermoplastic resin (A), and the Ni content CB Ni 0.003 ppm or less CB Ni <1 ppm.

[0011] The thermoplastic resin composition according to the above embodiment is expected to prevent the fluororesin (B) from agglomerating within the thermoplastic resin composition, facilitate dispersion of the fluororesin (B) throughout the thermoplastic resin composition, and facilitate the development of the properties and functions of the fluororesin (B). Furthermore, the favorable dispersion of the fluororesin (B) throughout the thermoplastic resin composition eliminates the need for extended high-temperature kneading to overcome strength deficiencies, in addition to the usual melt-kneading process, and thus helps prevent deterioration of the thermoplastic resin composition. As a result, it is expected that a thermoplastic resin composition can be provided that has excellent heat resistance, high tensile strength, and high weld strength. In this specification, "containing thermoplastic resin (A) as a main component" means that the thermoplastic resin composition contains 50 mass % or more of thermoplastic resin (A). Above Ni content CB Niis measured by inductively coupled plasma mass spectrometry (ICP-MS). In this measurement, an inductively coupled plasma (ICP) is used as an ion source, a liquid sample is atomized and introduced into the ICP, and the trace elements contained in the ionized sample are detected by a mass spectrometer (MS), allowing each element to be quantified. The contents of other metals described below are also measured by ICP-MS. The contents of each metal are measured in detail by the methods described in the Examples.

[0012] A thermoplastic resin composition according to a second embodiment of the present invention is a thermoplastic resin composition containing, as a main component, a thermoplastic resin (A) having a melting point of 270°C or higher, and containing 5 to 50 parts by mass of a fluorine-containing resin (B) per 100 parts by mass of the thermoplastic resin (A), and satisfies the following conditions (i) to (iii): (i) The thermoplastic resin composition contains Ni. (ii) The tensile strength of a molded article of the thermoplastic resin composition is 150 MPa or more, as measured in accordance with JIS K7161 (2014). (iii) The weld strength of a molded article of the thermoplastic resin composition is 56 MPa or more, as measured in accordance with JIS K7161 (2014).

[0013] The thermoplastic resin composition according to the second embodiment satisfies the above condition (i), thereby enhancing the dispersibility of the fluororesin (B) in the thermoplastic resin composition and making it easier to satisfy the above conditions (ii) and (iii). Furthermore, by satisfying the above conditions (ii) and (iii), the thermoplastic resin composition has high mechanical strength and injection moldability.

[0014] The thermoplastic resin composition according to the second embodiment preferably further satisfies the following conditions (iv) and (v). (iv) The specific abrasion rate of a molded article of the thermoplastic resin composition is 50 or less. (v) The coefficient of dynamic friction of a molded article of the thermoplastic resin composition is 0.25 or less. In the following, the first and second embodiments may be collectively referred to as "the above embodiments."

[0015] <Ni content in fluororesin (B)CB Ni > As described above, the Ni content CB in the fluorine-based resin (B) used in the thermoplastic resin composition according to the first embodiment Ni 0.003 ppm ≤ CB Ni <1 ppm. CB Ni When the content of Ni in the fluororesin (B) is within the above range, the fluororesin (B) is prevented from agglomerating into foreign matter in the thermoplastic resin composition, and a molded article having high tensile strength and high weld strength can be obtained. Ni is preferably in the above range. From the viewpoint of easily increasing the weld strength, it is preferable that 0.005 ppm≦CB Ni ≦0.7 ppm, more preferably 0.007 ppm≦CB Ni ≦0.6 ppm, more preferably 0.01 ppm≦CB Ni ≦0.5 ppm.

[0016] <Mn content in fluororesin (B)CB Mn > From the viewpoint of easily increasing the weld strength, the Mn content CB Mn is preferably 0 ppm <CB Mn <1 ppm, more preferably 0.003 ppm ≤ CB Mn ≦1 ppm, more preferably 0.005 ppm≦CB Mn ≦0.5 ppm, even more preferably 0.007 ppm≦CB Mn ≦0.25 ppm, even more preferably 0.008 ppm≦CB Mn ≦0.1 ppm, particularly preferably 0.009 ppm≦CBMn ≦0.05 ppm.

[0017] <Al content in fluororesin (B)CB Al > From the viewpoint of heat resistance and sliding property, the Al content CB Al is preferably 0 ppm <CB Al <0.4 ppm, 0.047 ppm ≤ CB Al It may be <0.4 ppm.

[0018] The metal content in the fluorine-based resin (B) is CB Ni , C.B. Mn , and C.B. Al As a method for making the content of the fluorine-containing resin within the above range, for example, a method of using a raw material or a catalyst having a low metal content may be mentioned.

[0019] <Other metals> The fluororesin (B) used in the thermoplastic resin composition according to the above embodiment may or may not contain metals other than Ni, Mn, and Al. For example, metals such as Na, Ca, Cu, and Fe tend to be contained in relatively large amounts in the fluororesin (B), but the inventors' studies have revealed that the presence of these metals does not significantly affect the tensile strength, weld strength, and sliding properties. Of the above metals, Na is preferably 70 ppm or less in the fluororesin (B), Ca is preferably 4 ppm or less in the fluororesin (B), Cu is preferably 6 ppm or less in the fluororesin (B), and Fe is preferably 6 ppm or less in the fluororesin (B). The components of the thermoplastic resin composition other than the fluororesin (B) may include Ni contained in the fluororesin (B), Mn and Al that may be contained in the fluororesin (B), or other metals. For example, the components of the thermoplastic resin composition other than the fluororesin (B) may include metals that are mixed in during the production of the thermoplastic resin composition or metals derived from fillers such as glass fibers. The inventors have found that, as long as the fluororesin (B) contains the above-mentioned predetermined amount of Ni, even if the components other than the fluororesin (B) in the thermoplastic resin composition contain metals such as Ni, Mn, Al, Na, Ca, Cu, and Fe, the presence of these metals does not significantly affect the tensile strength, weld strength, and sliding properties.

[0020] <Thermoplastic resin (A)> The thermoplastic resin (A) used in the thermoplastic resin composition according to the above embodiment has a melting point of 270°C or higher, preferably 290°C or higher, and more preferably 300°C or higher. There is no particular upper limit to the melting point of the thermoplastic resin (A), but from the viewpoint of moldability, it is preferably 330°C or lower. In other words, the melting point of the thermoplastic resin (A) is preferably 270 to 330°C. If the melting point of the thermoplastic resin (A) is lower than 270°C, the thermal stability of the molten state of a molded article produced using a thermoplastic resin composition containing the thermoplastic resin (A) may be insufficient. The melting point of the thermoplastic resin (A) can be determined as the peak temperature of the melting peak that appears when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) analyzer, and more specifically, can be determined by the method described in the examples below.

[0021] Examples of the thermoplastic resin (A) include polyamide resin, polyphenylene sulfide resin, polyamideimide resin, liquid crystal polymer, etc. These resins may be used alone as the thermoplastic resin (A), or a plurality of types may be used in combination. From the viewpoint of heat resistance, the thermoplastic resin (A) is preferably a polyamide resin, and the polyamide resin is preferably a semi-aromatic polyamide produced using an aliphatic diamine and an aromatic dicarboxylic acid such as terephthalic acid.

[0022] Examples of diamine units constituting the semi-aromatic polyamide include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17- Linear aliphatic diamines such as heptadecanediamine and 1,18-octadecanediamine; 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl- 1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-ethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl- branched aliphatic diamines such as 1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 5-methyl-1,9-nonanediamine;Examples of structural units include those derived from alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethyldiamine; and aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether. These structural units may be contained alone or in combination of two or more types.

[0023] Of the above diamine units, from the viewpoint of making the effects of the present invention more pronounced, structural units derived from at least one diamine selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines are preferred, and structural units derived from at least one diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and 2-methyl-1,8-octanediamine are more preferred. Furthermore, from the viewpoint of further enhancing the effects of the present invention, it is more preferable that 60 mol % or more and 100 mol % or less of the diamine units, and even more preferable that 70 mol % or more and 100 mol % or less of the diamine units are at least one of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine.

[0024] Examples of dicarboxylic acid units constituting the semi-aromatic polyamide include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid; terephthalic acid, isophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, and 1,3 Examples of structural units include those derived from aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; and those derived from alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclodecanedicarboxylic acid. Only one type of these structural units may be contained, or two or more types may be contained.

[0025] Of the above dicarboxylic acid units, from the viewpoint of making the effects of the present invention more pronounced, structural units derived from aromatic dicarboxylic acids are preferred, and structural units derived from at least one of terephthalic acid and naphthalenedicarboxylic acid are more preferred. Furthermore, from the viewpoint of further enhancing the effects of the present invention, it is more preferable that 60 mol % or more and 100 mol % or less of the dicarboxylic acid units, and even more preferable that 70 mol % or more and 100 mol % or less of the dicarboxylic acid units are at least one of terephthalic acid and naphthalenedicarboxylic acid.

[0026] The semi-aromatic polyamide preferably contains, as the diamine unit, at least one of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine, and, as the dicarboxylic acid unit, at least one of terephthalic acid and naphthalenedicarboxylic acid.

[0027] It is more preferable that 60 mol % or more and 100 mol % or less of the diamine units are at least one of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine, and that 60 mol % or more and 100 mol % or less of the dicarboxylic acid units are at least one of terephthalic acid and naphthalenedicarboxylic acid.

[0028] The molar ratio of diamine units to dicarboxylic acid units in the semi-aromatic polyamide [diamine units / dicarboxylic acid units] is preferably 45 / 55 to 55 / 45. When the molar ratio of diamine units to dicarboxylic acid units is within the above range, the polymerization reaction proceeds smoothly, and a semi-aromatic polyamide having the desired excellent physical properties is easily obtained. The molar ratio of the diamine unit to the dicarboxylic acid unit can be adjusted depending on the compounding ratio (molar ratio) of the raw material diamine to the raw material dicarboxylic acid.

[0029] The total proportion of dicarboxylic acid units and diamine units in the semi-aromatic polyamide (the proportion of the total number of moles of dicarboxylic acid units and diamine units to the total number of moles of all structural units constituting the polyamide) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and may be 95 mol% or more, or even 100 mol%. When the total proportion of dicarboxylic acid units and diamine units is within the above range, a semi-aromatic polyamide having more excellent desired physical properties is more easily obtained.

[0030] The semi-aromatic polyamide may further comprise aminocarboxylic acid units in addition to the dicarboxylic acid units and diamine units. Examples of the aminocarboxylic acid unit include structural units derived from lactams such as caprolactam and lauryllactam, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. The content of the aminocarboxylic acid unit in the semi-aromatic polyamide is preferably 40 mol % or less, and more preferably 20 mol % or less, relative to 100 mol % in total of the dicarboxylic acid units and diamine units constituting the semi-aromatic polyamide.

[0031] The semi-aromatic polyamide may also contain structural units derived from trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid, to the extent that melt molding is possible, as long as the effects of the present invention are not impaired.

[0032] The semi-aromatic polyamide may contain structural units derived from an end-capping agent (end-capping agent units). The content of the terminal blocking agent units is preferably 1.0 mol% or more, more preferably 1.5 mol% or more, and preferably 10 mol% or less, more preferably 5.0 mol% or less, relative to 100 mol% of the diamine units. When the content of the terminal blocking agent units is within the above range, a semi-aromatic polyamide having the desired excellent physical properties is easily obtained. The content of the terminal blocking agent units can be adjusted within the above desired range by appropriately adjusting the amount of terminal blocking agent when charging the polymerization raw materials. Taking into consideration the volatilization of the monomer components during polymerization, it is desirable to finely adjust the amount of terminal blocking agent charged so that the desired amount of terminal blocking agent units is incorporated into the resulting polyamide resin. Methods for determining the content of end-capping agent units in semi-aromatic polyamides include, for example, a method as disclosed in JP-A-7-228690, in which the solution viscosity is measured, the total amount of end groups is calculated from the relationship between the viscosity and the number average molecular weight, and the amount of amino groups and the amount of carboxyl groups determined by titration are subtracted from the total amount, or a method in which the amount of end-capping agent units is determined using H-NMR based on the integrated values ​​of the signals corresponding to the diamine units and the end-capping agent units, respectively, and the latter method is preferred.

[0033] As the terminal blocking agent, a monofunctional compound reactive with a terminal amino group or a terminal carboxyl group can be used. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoints of reactivity and the stability of the blocked terminals, monocarboxylic acids are preferred as terminal blocking agents for terminal amino groups, and monoamines are preferred as terminal blocking agents for terminal carboxyl groups. From the viewpoints of ease of handling, monocarboxylic acids are more preferred as terminal blocking agents.

[0034] The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it is reactive with an amino group, and examples thereof include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; and mixtures thereof. Among these, at least one selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid is preferred from the standpoints of reactivity, stability of the blocked end, cost, and the like.

[0035] The monoamine used as the terminal blocking agent is not particularly limited as long as it is reactive with a carboxyl group, and examples thereof include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and any mixtures thereof. Among these, at least one selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferred in terms of reactivity, high boiling point, stability of blocked terminals, and cost.

[0036] When producing a semi-aromatic polyamide, in addition to an end-capping agent, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, or a salt or ester thereof may be added as a catalyst. Examples of the salt or ester include salts of phosphoric acid, phosphorous acid, or hypophosphorous acid with metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony; ammonium salts of phosphoric acid, phosphorous acid, or hypophosphorous acid; and ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, decyl esters, stearyl esters, and phenyl esters of phosphoric acid, phosphorous acid, or hypophosphorous acid.

[0037] <Fluorine-based resin (B)> Examples of the fluorine-based resin (B) used in the thermoplastic resin composition according to the above embodiment include polytetrafluoroethylene and polyvinylidene fluoride. From the viewpoint of easily ensuring good sliding properties, the fluorine-based resin (B) is preferably polytetrafluoroethylene. The polytetrafluoroethylene may contain structural units other than the tetrafluoroethylene unit. Examples of such structural units include an ethylene unit, a hexafluoro-1,2-propylene unit, and [—CF(OC m F 2m+1 )-CF2-] (wherein m represents a positive integer), a 1-chloro-1,2,2-trifluoroethylene unit, and the like. As the fluorine-based resin (B), commercially available products can be used as they are.

[0038] <Thermoplastic resin (A) and fluororesin (B) content> From the viewpoint of heat resistance and weld strength, the content ratio of the thermoplastic resin (A) to the fluorine-based resin (B), (A) / (B), is preferably 95 / 5 to 51 / 49, more preferably 92 / 8 to 55 / 45, even more preferably 90 / 10 to 60 / 40, and still more preferably 88 / 12 to 65 / 35.

[0039] <Other ingredients> The thermoplastic resin composition may contain, as resin components other than the thermoplastic resin (A) and the fluororesin (B), unmodified polyolefins, modified polyolefins (such as those obtained by copolymerizing an olefinic compound with an α,β-unsaturated carboxylic acid or its ester, or a metal salt derivative, or those obtained by grafting a carboxylic acid or an acid anhydride onto a polyolefin), polystyrene polystyrene, butadiene-styrene copolymer, styrene-ethylene-butene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), (meth)acrylic resins, polyamide resins other than those specified as polyamide resin (I), fluororesins other than those specified as fluororesins (II), polyesters, polycarbonates, polysulfones, polyethersulfones, polyimides, polyetheretherketones, polyoxymethylene, polyphenylene sulfides, polyphenylene ethers, and polyarylates, provided that the effects of the present invention are not impaired. These may be used alone or in combination of two or more. Among these, modified polyolefins are preferred because of their particularly high impact resistance and toughness-improving properties. The content of the other polymer components is preferably in the range of 0.5 to 50 parts by mass, more preferably in the range of 2 to 30 parts by mass, per 100 parts by mass of the polyamide resin (I) contained in the thermoplastic resin composition.

[0040] Examples of components other than the resin component that may be contained in the thermoplastic resin composition include, but are not limited to, additives such as antioxidants, ultraviolet absorbers, light stabilizers, heat-shielding materials, antiblocking agents, pigments, dyes, softeners, crosslinking agents, crosslinking aids, crosslinking accelerators, fillers, reinforcing materials, lubricants, antistatic agents, flame retardants, foaming agents, water repellents, waterproofing agents, electrical conductivity imparting agents, thermal conductivity imparting agents, electromagnetic wave shielding agents, fluorescent agents, and antibacterial agents. These may be used alone or in combination of two or more.

[0041] From the viewpoint of easily improving the tensile properties, it is preferable that the thermoplastic resin composition further contains a filler. Examples of the filler include inorganic fillers such as talc, clay, mica, calcium silicate, glass, hollow glass spheres, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, carbon fiber, activated carbon, hollow carbon spheres, calcium titanate, lead zirconate titanate, silicon carbide, and mica; organic fillers such as wood flour and starch; conductive fillers such as carbon black, graphite, and carbon nanotubes; and metal fillers such as silver powder, copper powder, nickel powder, tin powder, copper fiber, stainless steel fiber, aluminum fiber, and iron fiber.

[0042] Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, amine-based antioxidants, and sulfur-based antioxidants. Examples of the ultraviolet absorber that can be used include benzotriazole-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers, as well as triazine-based compounds, benzophenone-based compounds, malonic acid ester compounds, and oxalic acid anilide compounds. Examples of the light stabilizer include hindered amine light stabilizers. Examples of heat-shielding materials include resins or glass containing heat-shielding particles or organic dye compounds. Examples of particles with heat-shielding properties include oxide particles such as tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide, as well as particles of inorganic materials with heat-shielding properties, such as LaB6 (lanthanum hexaboride) particles. Examples of organic dye compounds with heat-shielding properties include diimonium dyes, aminium dyes, phthalocyanine dyes, anthraquinone dyes, polymethine dyes, benzenedithiol ammonium compounds, thiourea derivatives, and thiol metal complexes. Antiblocking agents include inorganic and organic particles. Inorganic particles include oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and hydrated compounds thereof of Group IA, IIA, IVA, VIA, VIIA, VIIIA, IB, IIB, IIIB, and IVB elements, as well as composite compounds and natural mineral particles based on these. Organic particles include fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resin silicones, and crosslinked products thereof. Examples of pigments include organic pigments and inorganic pigments. Examples of organic pigments include azo pigments, quinacridone pigments, and phthalocyanine pigments. Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, carbon black, lead pigments, cadmium pigments, cobalt pigments, iron pigments, chromium pigments, ultramarine, and Prussian blue. Examples of dyes include azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, perylene-based, dioxazine-based, anthraquino-based, indolinone-based, isoindolino-based, quinoneimine-based, triphenylmethane-based, thiazole-based, nitro-based, and nitroso-based dyes. Examples of softeners that can be used include known softeners such as hydrocarbon oils such as paraffinic, naphthenic, and aromatic oils; vegetable oils such as peanut oil and rosin; phosphate esters; low-molecular-weight polyethylene glycol; liquid paraffin; and hydrocarbon synthetic oils such as low-molecular-weight polyethylene, ethylene-α-olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or its hydrogenated product, and liquid polybutadiene or its hydrogenated product. These may be used alone or in combination of two or more.

[0043] Examples of the crosslinking agent include a radical generator, sulfur, and sulfur compounds. Examples of the radical generator include organic peroxides such as dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide; diperoxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, bis(t-butyldioxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis(t-butylperoxy)valerate; diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; monoacyl alkyl peroxides such as t-butyl peroxybenzoate; percarbonates such as t-butylperoxyisopropyl carbonate; and diacyl peroxides such as diacetyl peroxide and lauroyl peroxide. These may be used alone or in combination of two or more. Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferred from the viewpoint of reactivity. Examples of sulfur compounds include sulfur monochloride and sulfur dichloride. Other crosslinking agents that can be used include phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p-quinonedioxime and lead dioxide, and p,p'-dibenzoylquinonedioxime and trimead tetroxide.

[0044] The crosslinking aid may be a known crosslinking aid, such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and other polyfunctional monomers; stannous chloride, ferric chloride, organic sulfonic acid, polychloroprene, chlorosulfonated polyethylene, and the like. The crosslinking aid may be used alone or in combination of two or more.

[0045] Examples of the crosslinking accelerator include thiazoles such as N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, and 2-(4-morpholinodithio)benzothiazole; guanidines such as diphenylguanidine and triphenylguanidine; aldehyde-amine-based reaction products or aldehyde-ammonia-based reaction products such as butyraldehyde-aniline reaction product and hexamethylenetetramine-acetaldehyde reaction product; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethylurea, dibutylthiourea, and trimethylthiourea. Examples of the crosslinking accelerator include thioureas such as diorthotolylthiourea, dibenzothiazyl disulfide, thiuram monosulfides or thiuram polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and pentamethylenethiuram tetrasulfide, thiocarbamates such as zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate, xanthogenates such as zinc dibutylxanthogenate, and zinc oxide. One type of crosslinking accelerator may be used alone, or two or more types may be used in combination.

[0046] The content of the additive contained in the thermoplastic resin composition is not particularly limited and can be appropriately adjusted depending on the type of the additive, etc. When the thermoplastic resin composition contains the additive, the content of the additive may be, for example, 50% by mass or less, 45% by mass or less, or 30% by mass or less, or 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, relative to the total mass of the thermoplastic resin composition.

[0047] The thermoplastic resin composition of the present invention may be any of the following embodiments [X1] to [X20]. [X1] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm. [X2] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0.003 ppm <CB Mn <1 ppm. [X3] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm. [X4] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn<1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm. [X5] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm.

[0048] [X6] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, and the fluorine-based resin (B) is polytetrafluoroethylene. [X7] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn<1 ppm, and the fluorine-based resin (B) is polytetrafluoroethylene. [X8] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, and the fluorine-based resin (B) is polytetrafluoroethylene. [X9] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, and the fluorine-based resin (B) is polytetrafluoroethylene. [X10] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al<0.4 ppm, and the fluorine-based resin (B) is polytetrafluoroethylene.

[0049] [X11] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, and the thermoplastic resin (A) is a polyamide resin. [X12] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, and the thermoplastic resin (A) is a polyamide resin. [X13] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al<0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, and the thermoplastic resin (A) is a polyamide resin. [X14] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, and the thermoplastic resin (A) is a polyamide resin. [X15] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, and the thermoplastic resin (A) is a polyamide resin.

[0050] [X16] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB NiHowever, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition further contains a filler. [X17] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition further contains a filler. [X18] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition further contains a filler. [X19] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni<1 ppm, and the Mn content in fluorine-based resin (B) CB Mn But 0 ppm <CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition further contains a filler. [X20] A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component and containing 5 to 50 parts by mass of a fluororesin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the Ni content CB Ni However, 0.003 ppm or less CB Ni <1 ppm, and the Mn content in fluorine-based resin (B) CB Mn However, 0.003 ppm or less CB Mn <1 ppm, and the Al content in fluorine-based resin (B) CB Al But 0 ppm <CB Al <0.4 ppm, the fluorine-based resin (B) is polytetrafluoroethylene, the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition further contains a filler.

[0051] [Physical properties of thermoplastic resin composition] The thermoplastic resin composition preferably satisfies the following physical properties.

[0052] (tensile strength) From the viewpoint of ensuring high mechanical strength, the tensile strength of a molded article of the thermoplastic resin composition according to the second embodiment is 150 MPa or more, preferably 170 MPa or more, more preferably 180 MPa or more, even more preferably 188 MPa or more, and still more preferably 190 MPa or more. The tensile strength is measured by molding the thermoplastic resin composition to prepare an ISO multipurpose test piece A1 type dumbbell, and performing a tensile test in accordance with JIS K7161 (2014) under conditions of a chuck distance of 115 mm, a tensile speed of 5 mm / min, and a temperature of 23°C. Although there is no particular upper limit to the tensile strength, from the viewpoint of ease of production, it is, for example, 250 MPa. In other words, the tensile strength of the thermoplastic resin composition is preferably 150 to 250 MPa. It is preferable that the tensile strength of a molded article of the thermoplastic resin composition according to the first embodiment also falls within the above range. More specifically, the tensile strength is measured according to the method described in the Examples.

[0053] (weld strength) From the viewpoints of mechanical strength and injection moldability, the weld strength of a molded article of the thermoplastic resin composition according to the second embodiment is 56 MPa or more, preferably 57 MPa or more, more preferably 58 MPa or more, even more preferably 59 MPa or more, and even more preferably 60 MPa or more. The weld strength is measured by molding the thermoplastic resin composition to include a weld portion to prepare an ISO multipurpose test piece A1 type dumbbell, and performing a tensile test in accordance with JIS K7161 (2014) under conditions of a chuck distance of 115 mm, a tensile speed of 5 mm / min, and a temperature of 23°C. Although there is no particular upper limit to the weld strength, from the viewpoint of ease of production, it is, for example, 80 MPa. In other words, the tensile strength of the thermoplastic resin composition is preferably 50 to 80 MPa. It is preferable that the tensile strength of a molded article of the thermoplastic resin composition according to the first embodiment also falls within the above range. More specifically, the weld strength is measured according to the method described in the Examples.

[0054] (specific wear rate and dynamic friction coefficient) Molded articles of the thermoplastic resin composition according to the above embodiment may have predetermined sliding characteristics depending on the application. The sliding characteristics can be evaluated, for example, by the specific wear rate and the dynamic friction coefficient. The specific wear rate is calculated by, with reference to JIS 7218 (1986), contacting a flat test piece with a ring-shaped steel material at a predetermined surface pressure and rotating the flat test piece a predetermined number of times at a predetermined peripheral speed to perform an abrasion test. The specific wear rate is calculated by dividing the abrasion rate, which is the difference in mass before and after the test, by the density of the flat test piece, the load applied to the flat test piece, and the sliding distance of the flat test piece. The dynamic friction coefficient is calculated based on the average load and the mass of the test piece over a certain period of time after the rotation of the flat test piece in the abrasion test. In this specification, the specific wear rate and the dynamic friction coefficient are measured in more detail according to the methods described in the Examples. When good sliding properties are required, the specific wear rate of an article molded from the thermoplastic resin composition is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less. There is no particular lower limit to the specific wear rate, but from the viewpoint of ease of production, it is, for example, 5 or more. In other words, the specific wear rate of an article molded from the thermoplastic resin composition is preferably 5 to 50. Furthermore, when good sliding properties are required, the dynamic friction coefficient of the molded article of the thermoplastic resin composition is preferably 0.25 or less, more preferably 0.22 or less, and even more preferably 0.21 or less. There is no particular lower limit for the dynamic friction coefficient, but from the viewpoint of ease of production, it is, for example, 0.1 or more. In other words, the dynamic friction coefficient of the molded article of the thermoplastic resin composition is preferably 0.1 to 0.25. As a method for setting the specific wear rate and dynamic friction coefficient within the above ranges, for example, the above CB Al is set to the above-mentioned range.

[0055] [Method of producing thermoplastic resin composition] The method for producing the thermoplastic resin composition is not particularly limited, and any known method can be used. For example, the thermoplastic resin composition can be produced by mixing the thermoplastic resin (A) and the Ni-containing fluorine-based resin (B) using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or by mixing the thermoplastic resin (A) and the Ni-containing fluorine-based resin (B) and then melt-kneading the mixture using a single-screw extruder, a twin-screw extruder, a kneader, or the like. Preferably, in the method for producing the thermoplastic resin composition, the Ni content CB Ni 0.003 ppm or less CB Ni For example, 5 to 50 parts by mass of a fluorine-based resin (B) having a fluorine content of less than 1 ppm is melt-kneaded. Even when the thermoplastic resin composition contains other metals or additives as described above in addition to the thermoplastic resin (A) and the fluororesin (B), the resin composition can be produced by mixing the other metals or additives in addition to the thermoplastic resin (A) and the fluororesin (B) in the mixer described above, or by melt-kneading the mixture in the apparatus described above after mixing.

[0056] [Molded body] A molded article according to an embodiment of the present invention is a molded article made from the thermoplastic resin composition. Molded articles obtained using the thermoplastic resin composition can be obtained, for example, by extrusion molding or injection molding. Extrusion molding is a method of processing a molten material placed in a pressure-resistant mold by applying pressure to extrude the material into any desired shape. Generally, the material tends to remain in the molten state, placing it in a state where it is susceptible to deterioration. The thermoplastic resin composition has excellent thermal stability in the molten state, and is therefore less likely to deteriorate during extrusion molding. Therefore, as described above, it is possible to obtain molded articles of excellent quality that have high heat resistance, high tensile strength, and weld strength, as well as reduced defects and color changes.

[0057] Examples of the molded article include molded articles in the form of a sheet, tube, monofilament, multifilament, pipe, round bar, wire coating, etc., and the molded article can be used for any part such as an automobile part, industrial material, industrial supplies, electric and electronic parts, machine parts, office equipment parts, household goods, etc.

[0058] The thermoplastic resin composition may be used to obtain a film-shaped molded product. In this case, a preferred molding method is, for example, a melt extrusion method. The melt extrusion method is not particularly limited and can be performed by any melt extrusion method known in the art, such as a T-die method or an inflation method. The film-like molded article produced by the above method may be further subjected to a stretching treatment, which is a combination of a preheating step, a stretching step, a heat setting step, and a relaxation step. By performing the stretching treatment, the mechanical properties and the like are further improved, and the advantages in industrial use are enhanced.

[0059] The film-like molded article may be subjected to activation treatment such as corona treatment, plasma treatment, glow discharge treatment, acid treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc., in order to improve the adhesiveness of the film surface. Also, a hard coat layer may be provided to improve the surface hardness (pencil hardness, scratch resistance).

[0060] The uses of the film-like molded body are not particularly limited, and it can be used alone or as a laminate with other layers such as a hard coat layer as an electrical insulating material for motors, transformers, cables, etc.; dielectric materials for capacitors, etc.; electronic component packaging materials for semiconductor packages, etc.; pharmaceutical packaging materials; food packaging materials such as retort foods; display cover windows, solar cell substrates, liquid crystal panels, conductive films, protective plates for display devices, etc.; LED mounting boards, flexible printed circuit boards, flexible flat cables, and other electronic substrate materials; FPC cover lay films, heat-resistant masking tapes, industrial process tapes, and other heat-resistant adhesive tapes; heat-resistant barcode labels; heat-resistant reflectors; various release films; heat-resistant adhesive base films; photographic films; molding materials; agricultural materials; medical materials; civil engineering and construction materials; filtration membranes; and films for household and industrial materials. [Example]

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0062] Measurement of the physical properties of the materials used in the examples and comparative examples, and measurement and evaluation of the physical properties of the compositions and molded articles in the examples and comparative examples were carried out according to the methods shown below.

[0063] <Melting point of thermoplastic resin (A)> The melting point of the polyamide resin as the thermoplastic resin (A) was measured using a differential scanning calorimeter "DSC7020" manufactured by Hitachi High-Tech Science Corporation. The melting point was measured in accordance with ISO 11357-3 (2011, 2nd edition). Specifically, in a nitrogen atmosphere, a sample was heated from 30°C to 340°C at a rate of 10°C / min, held at 340°C for 5 minutes to completely melt the sample, then cooled to 50°C at a rate of 10°C / min and held at 50°C for 5 minutes. The peak temperature of the melting peak that appeared when the sample was again heated to 340°C at a rate of 10°C / min was taken as the melting point (°C). If there were multiple melting peaks, the peak temperature of the highest melting peak was taken as the melting point (°C).

[0064] <ICP-MS Analysis> (Analysis Method) The metal content contained in each fluororesin was measured by inductively coupled plasma mass spectrometry (ICP-MS). In this measurement method, an inductively coupled plasma (ICP) is used as an ion source, a liquid sample is introduced into the ICP in a mist form, and trace elements contained in the ionized sample are detected by a mass spectrometer (MS), so that each metal can be quantified. However, since fluoropolymers do not dissolve in commonly used acid solvents, only the components extracted from the fluororesin were measured after performing special pretreatment according to the following procedure. (Pretreatment Extraction Method) · Apparatus name: Microwave digestion apparatus "ETHOS-1" (manufactured by Milestone General) · Weigh 0.1 g of the sample into a quartz insert dedicated to the apparatus, and add 6 ml of nitric acid (specific gravity: 1.42). Put the quartz insert into a digestion vessel containing 5 ml of water and 2 ml of hydrogen peroxide, seal it, and perform microwave (MW) digestion at a maximum output of 1,000 W. The sample temperature and holding time are shown below. After cooling, make up to 50 ml, and use the filtrate filtered through a 0.45 μm pore size filter for ICP-MS measurement. The MW digestion conditions are as follows. Treatment Time (min) Treatment Temperature (°C) · 3:00 70 · 2:00 50 ·20:00 230 ·15:00 230 (ICP-MS Measurement Conditions) · Apparatus name: Agirent7900 (manufactured by Agilent Technologies, Inc.) · RF output: 1500 W · Carrier gas flow rate: 0.7 L / min · Plasma mode: Cool plasma, Hot plasma · Elements measured in cool mode: Li, K · Elements measured in NoGas mode: B, Na, Mg, Al · Elements measured in H2 mode: Si, Ca, Mn, Se · He mode measurement elements: V, Fe, Ni, Co, Cu, Zn, Ga, Ge, Rb, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Cs, Ba, W, Pb, U · HEHe mode measurement elements: P, Ti, Cr, As · Standard solution: XSTC-622 (manufactured by SPEX) · Standard solution for calibration curve: 1.4 mol / L nitric acid solution with solution concentrations of 0, 0.5, 5.0, 10.0, 30.0, 50.0 ng / ml

[0065] In the analysis based on the above ICP-MS, the detection limits of Mn, Ni, and Al are as follows. · Detection limit of Mn: 0.003 ppm · Detection limit of Ni: 0.003 ppm · Detection limit of Al: 0.047 ppm The measurement of the metal content was carried out 3 times. When the value was below the detection limit, it was taken as 0 ppm, and their average value was calculated as the measured value. Since there are cases where the values in the three measurements include those above the detection limit and those below the detection limit, the values described in Table 1 may include values below the detection limit.

[0066] <Weight average molecular weight (Mw)> For the thermoplastic resin (A), it was determined as the molecular weight in terms of standard polymethyl methacrylate by gel permeation chromatography (GPC). An HFIP solution in which sodium trifluoroacetate was dissolved at a ratio of 0.85 g per 1 kg of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was used as the eluent. The sample was weighed 1.5 mg in terms of resin and dissolved in 3 mL of the above eluent. The solution was passed through a 0.2 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows. <<GPC measurement device and measurement conditions>> · Device: GPC device "HLC-8320" (manufactured by Tosoh Corporation) · Separation column: Two "TSK gel Super HM-H" columns manufactured by Tosoh Corporation were connected in series. · Eluent: 0.085% sodium trifluoroacetate / HFIP solution ·Eluent flow rate: 0.5mL / min Sample concentration: 1.5mg / 3mL Column temperature: 40℃ Detector: UV (254 nm) detector Standard polymethyl methacrylate: Showa Denko Co., Ltd., Shodex Standard M-75; Agilent Technologies Co., Ltd., Polymethylmethacrylate, molecular weight 1010, 535

[0067] <Tensile test> (Preparation of ISO multipurpose test specimen A1 type dumbbell) The pellets obtained in the examples and comparative examples were used to mold polyamide resin composition molded articles, namely, ISO multipurpose test specimen A1 type dumbbell (4 mm thick, total length 170 mm, parallel portion length 80 mm, parallel portion width 10 mm) and ISO multipurpose test specimen A1 type dumbbell with weld (4 mm thick, total length 170 mm, parallel portion length 80 mm, parallel portion width 10 mm) using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., mold clamping force: 100 tons, screw diameter: 32 mm) with a T-runner mold under conditions of a cylinder temperature of 320°C, a mold temperature of 140°C, and a cycle time of 40 seconds or less.

[0068] (Measurement of tensile strength and weld strength) Measurements were carried out in accordance with JIS K7161 using an Instron universal testing machine (5969). ISO multipurpose test specimens, type A1 dumbbell, were used to measure tensile strength and weld strength. The chuck distance was 115 mm, and the pulling speed was 5 mm / min. Measurements were carried out at 23°C.

[0069] <Evaluation of sliding characteristics> (Preparation of test specimens for sliding measurement) The pellets obtained in the examples and comparative examples were used to produce a polyamide resin composition molded product, a flat plate (dimensions: length x width x thickness = 80 mm x 80 mm x 3 mm) for evaluating sliding properties, by molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., mold clamping force: 100 tons, screw diameter: 32 mm) under conditions of a cylinder temperature of 320°C, a mold temperature of 140°C, and a cycle time of 40 seconds or less.

[0070] (Measurement of specific wear rate and dynamic friction coefficient) A friction and wear tester (manufactured by A&D Co., Ltd.) was used, and the surface pressure was 20 kgf / cm 2 The flat plate test piece prepared by the above method was brought into contact with a ring made of S45C steel (sandpaper finished) under the condition of a sliding peripheral speed of 50 cm / sec, and the specific wear rate was measured when the flat plate was rotated for 100 minutes. The specific wear rate was calculated by dividing the wear rate, which is the difference between the weight of the flat plate before the test and the mass of the flat plate after the test, by the density of the flat plate, the load applied to the flat plate, and the sliding distance of the flat plate. In addition, the average load F from the start of rotation of the flat plate test piece until 100 minutes later, measured by the above testing machine, was D The coefficient of dynamic friction was calculated by dividing by the normal force Fp generated by the mass of the test piece.

[0071] <Preparation of Fluorine-Based Resin (B)> The following fluorine-based resin (B) was used. PTFE-1: Kitamura Co., Ltd. "KTL620" PTFE-2: Kitamura Co., Ltd. "KT600M" PTFE-3: 3M (registered trademark) Dyneon TF 9207Z PTFE-4: INOLUB (registered trademark) T315F manufactured by Gujarat Fluorochemicals Limited PTFE-5: "Polyflon PTFE L-5" manufactured by Daikin Industries, Ltd. PTFE-6: 3M (registered trademark) Dyneon TF 9205

[0072] [Production Example 1] Production of Polyamide 9T (PA9T) 7,783 g of 1,9-nonanediamine, 1,946 g of 2-methyl-1,8-octanediamine (1,9-nonanediamine:2-methyl-1,8-octanediamine = 80:20 (molar ratio)), 10,083 g of terephthalic acid, 187.7 g of benzoic acid, 20 g of sodium hypophosphite monohydrate, and 5,000 g of water were placed in a reactor and purged with nitrogen. The internal temperature was raised to 220°C over 3 hours. At this time, the autoclave pressure was raised to 2 MPa. The reaction was continued for 4 hours while gradually releasing water vapor to maintain the pressure at 2 MPa. The pressure was then reduced to 1.2 MPa over 30 minutes, yielding a prepolymer. The prepolymer was pulverized and dried at 120°C under reduced pressure for 12 hours. This was polymerized under conditions of 200°C and 13.3 Pa for 2 hours, and then under conditions of 235°C and 13.3 Pa in a solid state to obtain polyamide 9T (PA9T) with a melting point of 300°C and a weight-average molecular weight of 23,000.

[0073] [Production Example 2] Production of Polyamide 10T (PA10T) A reactor was charged with 8,462 g of 1,10-decanediamine, 2,116 g of 2-methyl-1,9-nonanediamine (1,10-decanediamine:2-methyl-1,9-nonanediamine = 80:20 (molar ratio)), 10,083 g of terephthalic acid, 187.7 g of benzoic acid, 20 g of sodium hypophosphite monohydrate, and 5,000 g of water, and the atmosphere was purged with nitrogen. The internal temperature was raised to 220°C over 3 hours. At this time, the autoclave pressure was raised to 2 MPa. The reaction was continued for 4 hours while gradually releasing water vapor to maintain the pressure at 2 MPa. The pressure was then reduced to 1.2 MPa over 30 minutes, yielding a prepolymer. The prepolymer was pulverized and dried at 120°C under reduced pressure for 12 hours. This was subjected to solid-state polymerization at 200°C and 13.3 Pa for 2 hours, and then at 235°C and 13.3 Pa to obtain polyamide 10T (PA10T) with a melting point of 300°C and a weight-average molecular weight of 23,000.

[0074] [Example 1] 55 parts by mass of the polyamide PA9T obtained in Production Example 1 and 10 parts by mass of the fluororesin PTFE-1 were dry-blended, and then fed into the upstream hopper of a twin-screw extruder "TEM-26SS" (manufactured by Toshiba Machine Co., Ltd.), and 35 parts by mass of glass fiber was fed into the barrel on the downstream side of the extruder through a side feed port. The mixture was melt-kneaded and extruded at a cylinder temperature of 320°C, followed by cooling and cutting to produce pellets of a thermoplastic resin composition. Using pellets of the above thermoplastic resin composition, ISO multipurpose test specimens A1 type dumbbells (test specimens) for measuring physical properties were prepared by the above-mentioned method at a cylinder temperature of 300°C, and tensile strength and weld strength were evaluated. In addition, using pellets of the above thermoplastic resin composition, a flat plate for measuring physical properties (dimensions: length × width × thickness = 80 mm × 80 mm × 3 mm) was prepared at a cylinder temperature of 320°C by the above-mentioned method, and the sliding properties were evaluated using this measuring plate.

[0075] [Examples 2 to 4] Pellets of the thermoplastic resin composition were prepared in the same manner as in Example 1, except that the fluororesin was changed to one shown in Table 1. Test pieces and measurement plates were prepared using these pellets, and the tensile strength, weld strength, and sliding properties were evaluated.

[0076] [Example 5] Except for changing the polyamide resin from PA9T to PA10T, pellets of the thermoplastic resin composition were prepared in the same manner as in Example 1. Test pieces and measurement plates were prepared using these pellets, and the tensile strength, weld strength, and sliding properties were evaluated.

[0077] [Comparative Examples 1 to 3] Pellets of the thermoplastic resin composition were prepared in the same manner as in Example 1, except that the fluororesin was changed to one shown in Table 1. Test pieces and measurement plates were prepared using these pellets, and the tensile strength, weld strength, and sliding properties were evaluated.

[0078] Table 1 shows the compositions of the thermoplastic resin compositions of the examples and comparative examples, and the measurement results of the physical properties of the test pieces and measurement plates as molded articles made from these compositions.

[0079] [Table 1]

[0080] The molded articles of the thermoplastic resin compositions of Examples 1 to 5 have high heat resistance because they are made of a thermoplastic resin composition containing, as a main component, a thermoplastic resin (A) having a melting point of 270°C or higher. As is clear from Table 1, the Ni content CB Ni 0.003 ppm or less CB Ni It can be seen that the molded articles of the thermoplastic resin compositions of Examples 1 to 5, which satisfy the <1 ppm requirement, have greater weld strength and tensile strength than the molded articles of the thermoplastic resin compositions of Comparative Examples 1 and 2, which do not satisfy this requirement, and also exhibit values ​​equal to or greater than the tensile strength of the molded articles of the thermoplastic resin compositions of the Comparative Examples. As is clear from Table 1, the Mn content CB Mn 0.003 ppm or less CB Mn It can be seen that the molded articles of the thermoplastic resin compositions of Examples 1 to 5, which satisfy the <1 ppm requirement, have greater weld strength and tensile strength values ​​equal to or greater than the tensile strength of the molded article of the thermoplastic resin composition of Comparative Example 1, which does not satisfy this requirement. As is clear from Table 1, the Al content CB Al 0 ppm ≤ CB Al It can be seen that the molded articles of the thermoplastic resin compositions of Examples 1, 3, and 5, which satisfy the <0.4 ppm requirement, have a smaller specific wear rate than the molded article of the thermoplastic resin composition of Example 2, which does not satisfy this requirement, and also have a larger dynamic friction coefficient than the molded article of the thermoplastic resin composition of Example 3, which does not satisfy this requirement. [Industrial Applicability]

[0081] The thermoplastic resin composition of the present invention can give molded articles having high tensile strength and high weld strength while having excellent heat resistance, and therefore can be used for automobile casings, various automobile-mounted parts and their housings, etc. Furthermore, molded articles of the thermoplastic resin composition have heat resistance against heat such as frictional heat, and further, the thermoplastic resin composition can impart excellent sliding properties to molded articles under high surface pressure, etc., and therefore is suitable for gears, bearings, bearing retainers, chain tensioner guides, etc. In addition, the material can be used in various electrical products in the home appliance field, such as televisions, various recorders such as Blu-ray recorders and HDD recorders, projectors, game consoles, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, fax machines, copy machines, telephones, door phones, rice cookers, microwave ovens, oven ranges, refrigerators, dishwashers, dish dryers, induction cooking heaters, hot plates, vacuum cleaners, washing machines, chargers, sewing machines, irons, dryers, electric bicycles, air purifiers, water purifiers, electric toothbrushes, lighting equipment, air conditioners, outdoor units of air conditioners, dehumidifiers, and humidifiers.

Claims

1. A thermoplastic resin composition containing a thermoplastic resin (A) having a melting point of 270°C or higher as a main component, and containing a fluorine-containing resin (B) in an amount of 5 to 50 parts by mass per 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (A) is a polyamide resin, Ni content in fluororesin (B) CB Ｎｉ However, 0.003 ppm≦CB Ｎｉ < 1 ppm.

2. Mn content in fluororesin (B) CB Ｍｎ However, 0 ppm < CB Ｍｎ 2. The thermoplastic resin composition of claim 1, wherein the hydroxyl group is hydroxypropyltrimonials.

3. Mn content in fluororesin (B) CB Ｍｎ However, 0.003 ppm≦CB Ｍｎ 3. The thermoplastic resin composition according to claim 1, wherein the total amount of the hydroxybenzoates is ≦1 ppm.

4. Al content in fluororesin (B) CB Ａｌ However, 0 ppm < CB Ａｌ The thermoplastic resin composition according to any one of claims 1 to 3, wherein the SiO2 content is less than 0.4 ppm.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the fluorine-based resin (B) is polytetrafluoroethylene.

6. The thermoplastic resin composition according to any one of claims 1 to 5, further comprising a filler.

7. The thermoplastic resin composition according to claim 6, wherein the filler is talc, clay, mica, calcium silicate, glass, hollow glass spheres, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, carbon fiber, activated carbon, hollow carbon spheres, calcium titanate, lead zirconate titanate, silicon carbide, mica, graphite, carbon nanotubes, silver powder, copper powder, nickel powder, tin powder, copper fiber, stainless steel fiber, aluminum fiber, or iron fiber.

8. A thermoplastic resin composition containing, as a main component, a thermoplastic resin (A) having a melting point of 270°C or higher, and containing 5 to 50 parts by mass of a fluorine-containing resin (B) per 100 parts by mass of the thermoplastic resin (A), wherein the thermoplastic resin (A) is a polyamide resin, and the thermoplastic resin composition satisfies the following conditions (i) to (iii): (i) The thermoplastic resin composition contains Ni. (ii) The tensile strength of a molded article of the thermoplastic resin composition, measured in accordance with JIS K7161 (2014), is 150 MPa or more. (iii) The weld strength of a molded article of the thermoplastic resin composition, measured in accordance with JIS K7161 (2014), is 56 MPa or more.

9. The thermoplastic resin composition according to claim 8, further satisfying the following conditions (iv) and (v): (iv) The specific wear rate of a molded article of the thermoplastic resin composition is 50 or less. (v) The coefficient of dynamic friction of a molded article of the thermoplastic resin composition is 0.25 or less.

10. A method for producing the thermoplastic resin composition according to any one of claims 1 to 9, A method for producing a thermoplastic resin composition, comprising melt-kneading a thermoplastic resin (A) and a fluorine-containing resin (B) containing Ni to produce the thermoplastic resin composition.

11. The Ni content CB is calculated based on 100 parts by mass of the thermoplastic resin (A) which is a polyamide resin having a melting point of 270°C or higher. Ｎｉ is 0.003 ppm or less CB Ｎｉ A method for producing a thermoplastic resin composition, comprising melt-kneading 5 to 50 parts by mass of a fluorine-containing resin (B) having a fluorine content of <1 ppm.

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