Fiber-reinforced polyamide resin composition and molded body

Abstract

This invention relates to fiber-reinforced polyamide resin compositions and molded articles. The invention provides a fiber-reinforced polyamide resin composition that imparts sufficient mechanical properties and reduces property variations. A fiber-reinforced polyamide resin composition comprising crystalline polyamide (A) and glass fiber (B), characterized in that the formic acid relative viscosity of the soluble component of the fiber-reinforced polyamide resin composition is 90 or higher, and the boron concentration of the glass fiber (B) is 1000 ppm or lower.

Description

Technical Field

[0001] The present invention relates to fiber-reinforced polyamide resin compositions with excellent sliding and mechanical properties, and molded articles comprising said fiber-reinforced polyamide resin compositions. More specifically, the present invention relates to fiber-reinforced polyamide resin compositions characterized by comprising polyamide having a specific viscosity and glass fibers having a specific composition, and molded articles comprising said fiber-reinforced polyamide resin compositions. Background Technology

[0002] Polyamide resins have long been widely used as materials for various components in industrial, automotive, electrical and electronic, and other applications due to their excellent sliding properties, processability, mechanical properties, and chemical resistance. In particular, considering their superior sliding and mechanical properties, polyamide resins are frequently used in sliding components such as gears and worm gears in automobiles. To improve these properties, compositions with higher molecular weights than conventional polyamides or those combined with inorganic fillers such as glass fibers, flake glass, alumina fibers, and layered inorganic compounds are being researched. Among these, glass fiber reinforced polyamide resin compositions containing high molecular weight polyamides and using glass fibers as inorganic fillers are of particular interest due to their high effectiveness in improving sliding and mechanical properties.

[0003] On the other hand, the need for lightweight automobiles from an environmental protection perspective also necessitates the miniaturization of sliding components such as gears and worm gears. This, in turn, requires improved material durability for these sliding components and reduced property variations in smaller components.

[0004] Regarding glass fiber reinforced polyamide resin compositions containing high molecular weight polyamide compositions, for example, Patent Documents 1 and 2 disclose compositions that can improve lubricity, mechanical properties, and productivity by incorporating specific glass fibers and coupling agents.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-197316

[0008] Patent Document 2: Japanese Patent Application Publication No. 2016-117817 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, in the aforementioned prior art, sufficient mechanical properties were not imparted and property variations were not reduced for polyamides in the high molecular weight region, and further improvements are desired.

[0011] The present invention was made in view of the above-mentioned problems, and its object is to provide fiber-reinforced polyamide resin compositions and molded articles that impart sufficient mechanical properties and reduce property variations.

[0012] means for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted repeated and in-depth research and found that if the fiber-reinforced polyamide resin composition and the molded body are under specified conditions, the above-mentioned problems can be solved, thus completing the present invention.

[0014] That is, the fiber-reinforced polyamide resin composition and molded articles of the present invention are as follows.

[0015] (1) A fiber-reinforced polyamide resin composition comprising crystalline polyamide (A) and glass fiber (B), characterized in that the formic acid relative viscosity of the soluble component of the fiber-reinforced polyamide resin composition is 90 or more, and the boron concentration of the glass fiber (B) is 1000 ppm or less.

[0016] (2) The fiber-reinforced polyamide resin composition as described in (1), characterized in that the fiber-reinforced polyamide resin composition contains a copper compound (C) and alkali metal and / or alkaline earth metal halides (D).

[0017] (3) The fiber-reinforced polyamide resin composition as described in (1) or (2), characterized in that the copper compound (C) is a copper halide.

[0018] (4) The fiber-reinforced polyamide resin composition as described in (2) or (3) is characterized in that the molar ratio of the content of halogen elements in the copper compound (C) and the alkali metal and / or alkaline earth metal halide (D) to the content of copper elements in the copper compound (C) is halogen element / copper element = 3 / 1 to 50 / 1.

[0019] (5) The fiber-reinforced polyamide resin composition as described in any one of (1) to (4), characterized in that the average fiber diameter of the glass fiber (B) is 5 μm to 9 μm.

[0020] (6) The fiber-reinforced polyamide resin composition as described in any one of (1) to (5), characterized in that, relative to 100 parts by weight of the crystalline polyamide (A), the fiber-reinforced polyamide resin composition comprises 1 to 100 parts by weight of the glass fiber (B).

[0021] (7) The fiber-reinforced polyamide resin composition as described in any one of (1) to (6), characterized in that the formic acid relative viscosity of the soluble component of the fiber-reinforced polyamide resin composition is 130 or higher.

[0022] (8) A molded body, wherein the molded body is obtained by molding the fiber-reinforced polyamide resin composition of any one of (1) to (7).

[0023] (9) A sliding member comprising any one of (1) to (7) a fiber-reinforced polyamide resin composition, wherein the sliding member is a molded body comprising the fiber-reinforced polyamide resin composition, characterized in that the coefficient of variation of the tensile strength of the sliding member as determined according to ISO 527 is 1.0 or less.

[0024] (10) A sliding member comprising any one of (1) to (7) a fiber-reinforced polyamide resin composition, wherein the sliding member is a molded body comprising the fiber-reinforced polyamide resin composition, characterized in that the coefficient of variation of the simply supported beam impact strength of the sliding member as determined according to ISO 179 is 15.0 or less.

[0025] (11) A sliding member comprising any one of (1) to (7) a fiber-reinforced polyamide resin composition.

[0026] (12) A gear, wherein the gear comprises any one of (1) to (7) a fiber-reinforced polyamide resin composition.

[0027] (13) A worm gear, wherein the worm gear comprises any one of (1) to (7) a fiber-reinforced polyamide resin composition.

[0028] Invention Effects

[0029] According to the present invention, fiber-reinforced polyamide resin compositions and molded articles that possess sufficient mechanical properties and reduced property variations can be obtained. Detailed Implementation

[0030] The following describes in detail the method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiment, and can be implemented with various modifications within its scope.

[0031] <Fiber-reinforced polyamide resin composition>

[0032] The fiber-reinforced polyamide resin composition of this embodiment is a fiber-reinforced polyamide resin composition comprising crystalline polyamide (A) and glass fiber (B), characterized in that the formic acid relative viscosity of the soluble component of the fiber-reinforced polyamide resin composition is 90 or more, and the boron concentration of the glass fiber (B) is 1000 ppm or less.

[0033] The fiber-reinforced polyamide resin composition of this embodiment has the above-described composition, which can impart sufficient mechanical properties and reduce property variations.

[0034] The formic acid relative viscosity of the soluble component in the fiber-reinforced polyamide resin composition of this embodiment is 90 or higher. With a formic acid relative viscosity of 90 or higher, it is desirable to obtain fiber-reinforced polyamide resin molded articles with superior mechanical and sliding properties. Preferably, the formic acid relative viscosity is 130 or higher.

[0035] The relative viscosity of the formic acid described above can be determined by the method according to ASTM D789 as shown in the examples.

[0036] The constituent elements of the fiber-reinforced polyamide resin composition of this embodiment will be described in detail below.

[0037] <(A) Ingredient: Crystalline polyamide>

[0038] In this specification, "crystalline polyamide" refers to a polyamide whose heat of fusion of crystals is 4 J / g or more, as measured using a differential scanning calorimeter at 20°C / min. Examples of crystalline polyamides include, but are not limited to, polyamides obtained by ring-opening polymerization of lactams (Aa), polyamides obtained by self-condensation of ω-aminocarboxylic acids (Ab), polyamides obtained by condensation of diamines and dicarboxylic acids (Ac), and copolymers thereof. A single crystalline polyamide may be used, or two or more may be used in combination.

[0039] Examples of lactams used in the manufacture of (Aa) polyamides include, but are not limited to, pyrrolidone, caprolactam, undecylactam, dodecalactam, etc.

[0040] Examples of ω-aminocarboxylic acids used in the manufacture of (Ab) polyamides include, but are not limited to, ω-amino fatty acids, which are open-ring compounds obtained from water as the aforementioned lactams.

[0041] In addition, the above-mentioned lactam or ω-aminocarboxylic acid can be condensed together with two or more monomers.

[0042] Examples of diamines (monomers) used in the manufacture of (Ac) polyamides include, but are not limited to, linear aliphatic diamines, branched aliphatic diamines, alicyclic diamines, aromatic diamines, etc.

[0043] Examples of linear aliphatic diamines include, but are not limited to, hexamethylenediamine and pentamethylenediamine.

[0044] Examples of branched aliphatic diamines include, but are not limited to, 2-methylpentanediamine and 2-ethylhexamethylenediamine.

[0045] Examples of alicyclic diamines include cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine, but they are not limited to these.

[0046] Examples of aromatic diamines include, but are not limited to, p-phenylenediamine and m-phenylenediamine.

[0047] Dicarboxylic acids (monomers) used in the manufacture of (Ac) polyamides can be, for example, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, etc., but are not limited to these.

[0048] Examples of aliphatic dicarboxylic acids include, but are not limited to, adipic acid, pimelic acid, sebacic acid, etc.

[0049] Examples of alicyclic dicarboxylic acids include, but are not limited to, cyclohexanedicarboxylic acid, etc.

[0050] Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid and isophthalic acid.

[0051] The aforementioned diamines and dicarboxylic acids, which are monomers, can be used individually or in combination of two or more for condensation.

[0052] It should be noted that crystalline polyamides may also contain units derived from tricalcium or higher polycarboxylic acids, such as trimellitic acid, pyromellitic acid, and pyromellitic tetroxide, as needed. A single tricalcium or higher polycarboxylic acid may be used alone, or two or more may be used in combination.

[0053] Specifically, examples of crystalline polyamides contained in the fiber-reinforced polyamide resin composition of this embodiment include: polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polyhexamethylenediamine), polyamide 11 (polyundecanoamide), polyamide 12 (polydodecanoamide), polyamide 46 (poly(butylene adipamide), polyamide 56 (polypentylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacyldiamine), polyamide 612 (polyhexamethylene dodecanoyldiamine), polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonyl terephthalamide), and copolyamides containing these polyamides as constituent components.

[0054] Among these, polyamides 66 (PA66), 46 (PA46), or 610 (PA610) are preferred from the viewpoint of sliding properties. In particular, PA66 is the most preferred material because it is suitable for automotive parts due to its excellent heat resistance, formability, and toughness.

[0055] There are no particular limitations on the polymerization methods for polyamides. Examples include hot melt polymerization, solid-state polymerization, and solution polymerization. Hot melt polymerization, for example, involves adding an antifoaming agent, etc., to hexamethylene adipamide (hexamethylene adipamide), a raw material for polyamide 66, and concentrating it at a temperature of 40°C to 300°C. The resulting water vapor pressure is maintained between atmospheric pressure and 20 atmospheres. Finally, the pressure is removed, and polymerization is carried out under atmospheric or reduced pressure. Solid-state polymerization involves polymerization at a temperature below the melting point of the diamine or dicarboxylate solid salt and the polymerization product. Solution polymerization involves polycondensing the dicarboxylate acyl halide component and the diamine component in a solution. These methods can be combined as needed. Furthermore, polymerization can be batch or continuous. There are no particular limitations on the polymerization equipment; for example, autoclave reactors, drum reactors, extruder-type reactors such as kneaders, etc., can be used.

[0056] To obtain a polyamide with a specified relative viscosity RV, one may use, for example, the above-described hot melt polycondensation method and adjust the polymerization time, or a solid-state polymerization method at a temperature below the melting point of the polycondensation product, and there are no particular limitations.

[0057] The terminal amine concentration [NH2] of the polyamide is preferably 10 mEq / kg or more and 100 mEq / kg or less, more preferably 20 mEq / kg or more and 90 mEq / kg or less, and even more preferably 30 mEq / kg or more and 80 mEq / kg or less. With the terminal amine concentration within the above range, the polyamide resin composition exhibits a superior color tone and further suppresses the tendency for yellowing caused by deterioration. It should be noted that a method for determining the terminal amine concentration can be as follows: a specified amount of polyamide sample is dissolved in a 90% aqueous phenol solution, titrated with 1 / 50N hydrochloric acid at 25°C, and the terminal amine concentration is calculated.

[0058] The terminal carboxyl group concentration [COOH] of the polyamide is preferably 10 mE / kg or more and 150 mE / kg or less, more preferably 20 mE / kg or more and 140 mE / kg or less, and even more preferably 30 mE / kg or more and 130 mE / kg or less. When the terminal carboxyl group concentration is within the above range, the molded article of the fiber-reinforced polyamide resin composition tends to have a better appearance. It should be noted that a method for determining the terminal carboxyl group concentration can be as follows: a specified amount of polyamide sample is dissolved in benzyl alcohol at 160°C, titrated with a 1 / 10N potassium hydroxide solution in ethylene glycol using phenolphthalein as an indicator, and the terminal carboxyl group concentration is calculated. It should be noted that items related to the appearance of the molded article can include, but are not limited to, roughness, smoothness, and silver streaks caused by exposed glass fibers.

[0059] The terminal carboxyl group ratio of the polyamide is preferably 55% to 85%, more preferably 57% to 80%, and even more preferably 60% to 75%. A terminal carboxyl group ratio within the above range tends to result in less yellowing and better long-term color stability. Here, the terminal carboxyl group ratio refers to a value obtained by expressing the ratio of the terminal carboxyl group concentration to the sum of the terminal carboxyl group concentration [COOH] and the terminal amino group concentration [NH2] as a percentage.

[0060] <(B) Composition: Glass fiber>

[0061] The fiber-reinforced polyamide resin composition of this embodiment comprises glass fibers. Preferably, at least a portion of the surface of the glass fibers is covered with a surface treatment agent. Because the polyamide resin composition comprises glass fibers with at least a portion of their surface covered by a surface treatment agent, the glass fibers in the polyamide resin composition exhibit excellent defibrillability and processability.

[0062] There is no particular limitation on the average fiber diameter of the glass fibers, but it is preferably 4 μm to 30 μm, more preferably 5 μm to 9 μm, and particularly preferably 5 μm to 8 μm. Here, the average fiber diameter is a value obtained by observation using an electron microscope or the like. With an average fiber diameter within the above range, there is a tendency to achieve superior mechanical strength, rigidity, and formability in the polyamide resin composition, as well as a reduction in variations in mechanical properties. For example, any commercially available glass fiber that can be obtained in the form of chopped glass fibers, glass fiber rovings, ground glass fibers, etc., can be used.

[0063] In this embodiment, the boron content of the glass fiber is 1000 ppm or less. With a boron content within the aforementioned range, there is a tendency for excellent mechanical strength, mechanical property variation, and wear characteristics; particularly, a polyamide resin composition exhibiting excellent vibration fatigue and wear characteristics under special conditions can be obtained. The aforementioned boron content is preferably 500 ppm or less.

[0064] The boron content is the concentration of boron in the glass fiber, which can be determined using ICP-MS (inductively coupled plasma mass spectrometry) as shown in the examples.

[0065] The surface treatment agent for glass fiber may also contain a bundler, without particular limitation. Examples include: polyurethane resin, polycarbodiimide compound, acrylic homopolymer, copolymer of acrylic acid and copolymerizable monomer, salts of homopolymer (acrylic homopolymer) or copolymer (polymer of acrylic acid and copolymerizable monomer) and amine, epoxy resin, and copolymers containing carboxylic anhydride unsaturated vinyl monomers and unsaturated vinyl monomers, etc. These substances can be used alone or in combination of two or more.

[0066] There are no particular restrictions on the polyurethane resins used as surface treatment agents or bundlers for glass fibers. For example, polyurethane resins synthesized from isocyanates such as isophthalic diisocyanate (XDI), 4,4'-methylene bis(cyclohexyl isocyanate) (HMDI), and isophorone diisocyanate (IPDI) with polyester diols or polyether diols can be appropriately used.

[0067] There are no particular limitations on the aforementioned polycarbodiimide compounds. For example, polycarbodiimide compounds obtained by condensing a compound containing one or more carbodiimide groups (-N=C=N-) can be listed.

[0068] The weight-average molecular weight of the above-mentioned acrylic homopolymer is preferably 1,000 to 90,000, more preferably 1,000 to 50,000, and even more preferably 1,000 to 25,000. It should be noted that the weight-average molecular weight in this specification can be determined by GPC (gel permeation chromatography).

[0069] The copolymerizable monomers constituting the copolymers of acrylic acid and copolymerizable monomers described above are not particularly limited, and examples include monomers having hydroxyl and / or carboxyl groups, and ester monomers. Such copolymerizable monomers are not particularly limited, and examples include one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinyl acetate, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesoconic acid, and their ester compounds (however, except in the case of acrylic acid alone). Among the above monomers, it is preferable to have one or more ester monomers.

[0070] The amine that forms a salt with the homopolymer or copolymer of the aforementioned acrylic acid is not particularly limited and can be a primary, secondary, or tertiary amine. Specifically, examples include triethylamine, triethanolamine, and glycine. From the viewpoint of improving the stability of the mixed solution with other chemical reagents (such as silane coupling agents) and reducing amine odor, the degree of neutralization is preferably 20% to 90%, more preferably 30% to 80%, and even more preferably 40% to 60%.

[0071] There is no particular limitation on the weight-average molecular weight of the homopolymer or copolymer of acrylic acid that forms the above-mentioned salt, but it is preferably 3,000 to 50,000. With a weight-average molecular weight of 3,000 or higher, there is a tendency to further improve the bundled properties of the glass fibers. Furthermore, with a weight-average molecular weight of 50,000 or lower, there is a tendency to further improve the mechanical properties of the resulting molded article.

[0072] There are no particular limitations on the epoxy resin used, but compounds having at least two glycidyl groups are preferred, and epoxy resins obtained by reacting bisphenol with epihalools are suitable. It should be noted that, considering the bundle properties of glass fibers, the epoxy equivalent of the epoxy resin is preferably 180 g / equivalent or more, more preferably 450 g / equivalent to 1900 g / equivalent.

[0073] In the glass fiber reinforced polyamide resin composition of this embodiment, a copolymer of a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer is preferably included as the surface treatment agent or bundler for the glass fibers. Including such a copolymer tends to result in a more superior mechanical property of the molded article. There are no particular limitations on the aforementioned carboxylic anhydride-containing unsaturated vinyl monomer; examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. Maleic anhydride is preferred. On the other hand, there are no particular limitations on the unsaturated vinyl monomer; examples include styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Ethylene, styrene, and butadiene are preferred.

[0074] Among combinations of unsaturated vinyl monomers containing carboxylic anhydride and unsaturated vinyl monomers, copolymers of maleic anhydride and butadiene, copolymers of maleic anhydride and ethylene, copolymers of maleic anhydride and styrene, and mixtures thereof are more preferred.

[0075] Furthermore, the weight-average molecular weight of the copolymer comprising a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer is preferably 2,000 or more, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 500,000. With a weight-average molecular weight within the above range, the flowability of the glass fiber reinforced polyamide resin composition tends to be further improved.

[0076] Silane coupling agents are also suitable as surface treatment agents for glass fibers. There are no particular limitations on the silane coupling agent used; examples include: aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; and vinylsilanes. Preferably, one or more of the above-listed components are used, and aminosilanes are more preferred.

[0077] When preparing surface treatment agents for glass fibers, the use of lubricants is suitable. There are no particular limitations on the lubricant used; for example, any commonly used liquid or solid lubricant material suitable for the purpose can be used. Examples of such lubricants include: animal, plant, or mineral waxes such as carnauba wax and lanolin wax; surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or aromatic ethers.

[0078] (Method of coating the surface of glass fiber with a surface treatment agent)

[0079] In this embodiment, the glass fiber is preferably a glass fiber whose surface is covered by a surface treatment agent at least a portion thereof. There are no particular limitations on the method of applying the surface treatment agent; for example, in a known glass fiber manufacturing process, a known method such as a roller coater can be used to apply the surface treatment agent onto the glass fiber to produce glass fiber filaments, and the produced glass fiber filaments can be dried, thereby allowing the reaction to proceed continuously.

[0080] It should be noted that there are no particular restrictions on the state of the glass fiber. For example, the glass fiber filaments can be used directly in the form of rovings, or they can be further processed into chopped glass filaments. It should also be noted that the drying of the filaments can be carried out after the cutting process, or the filaments can be dried before cutting.

[0081] The amount of surface treatment agent adhering to the glass fiber relative to 100 parts by weight, in terms of solid content, is preferably 0.1 to 1.0 parts by weight, more preferably 0.2 to 1.0 parts by weight, even more preferably 0.2 to 0.8 parts by weight, and most preferably 0.2 to 0.6 parts by weight. By having an amount of surface treatment agent adhering to the glass fiber relative to 100 parts by weight, in terms of solid content, of 0.1 parts by weight or more, there is a tendency to further maintain the coverage of the surface treatment agent on the glass fiber. On the other hand, by having an amount of surface treatment agent used relative to 100 parts by weight, in terms of solid content, of 1.0 parts by weight or less, there is a tendency to further improve the thermal stability of the glass fiber reinforced polyamide resin composition.

[0082] <(C) Component: Copper compound>

[0083] Examples of copper compounds include, but are not limited to, copper halides, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, and copper stearate; and copper complexes obtained by coordination with chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid. These copper compounds can be used alone or in mixtures of two or more. Among them, copper halides are preferred, and from the viewpoint of suppressing the decrease in molecular weight and / or heat aging resistance during melt mixing, cuprous iodide, cuprous bromide, cuprous bromide, cuprous chloride, and copper acetate are further preferred.

[0084] <(D) Composition: Halides of alkali metals and / or alkaline earth metals>

[0085] Examples of alkali metal and / or alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride, as well as mixtures thereof. These substances may be used alone or in combination with two or more. As component (D), only alkali metal halides may be used, only alkaline earth metal halides may be used, or both alkali metal halides and alkaline earth metal halides may be used.

[0086] From the perspective of improving heat resistance and inhibiting metal corrosion, potassium iodide and / or potassium bromide are preferred, and potassium iodide is more preferred.

[0087] By combining copper compounds with alkali metal and / or alkaline earth metal halides, not only can better thermal stability be achieved, but it is also more preferable from the viewpoint of suppressing changes in mechanical properties and improving wear characteristics. Preferably, the polyamide resin composition contains copper compounds and alkali metal and / or alkaline earth metal halides in a molar ratio (halogen / copper) of 3 / 1 to 50 / 1 when used in combination. A molar ratio (halogen / copper) of 4 / 1 to 40 / 1 is more preferable, and even more preferably 5 / 1 to 30 / 1. It should be noted that "halogen" as used herein refers to "halogen elements" such as Br and I. Furthermore, when using copper halides as copper compounds, it refers to the total halogen content from copper halides and the halogen content from alkali metal and / or alkaline earth metal halides.

[0088] When the molar ratio of halogen content to copper content is within the above range, it is preferred from the viewpoint of suppressing copper precipitation and metal corrosion, as well as suppressing changes in mechanical strength and improving wear characteristics.

[0089] <Heat stabilizer>

[0090] It is preferable to add a heat stabilizer to the polyamide resin composition. There are no particular limitations on the heat stabilizer; examples include phenolic stabilizers such as hindered phenolic compounds, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, and sulfur-containing stabilizers. One or more of the above-mentioned heat stabilizers can be used. The presence of a heat stabilizer tends to further suppress heat-induced degradation. In this embodiment, the content of the heat stabilizer is not particularly limited, but from the viewpoint of effectively suppressing heat-induced degradation, preventing discoloration, and maintaining mechanical properties, the content of the heat stabilizer relative to 100 parts by weight of polyamide resin is preferably 0.005 parts by weight to 5 parts by weight, more preferably 0.01 parts by weight to 3 parts by weight, and even more preferably 0.015 parts by weight to 2 parts by weight.

[0091] Phenolic stabilizers are molecules containing phenolic groups, and there are no particular restrictions. Examples include Irganox (registered trademark) 1098 (manufactured by BASF).

[0092] Phosphite stabilizers are molecules containing phosphorus, and there are no particular restrictions. For example, PEP (registered trademark) 36 (manufactured by ADEKA).

[0093] <Other Additives>

[0094] Other additives may be added to the polyamide resin composition as needed, within a range that does not impair the purpose of this embodiment. There are no particular limitations on the aforementioned other additives; for example, inorganic fillers other than glass fiber, antioxidants, ultraviolet absorbers, anti-light degradation agents, plasticizers, lubricants, release agents, nucleating agents, flame retardants, and colorants may be added, and other thermoplastic resins may also be mixed. Here, since the properties of the aforementioned additives vary greatly, the appropriate content of each component that does not significantly impair the effects of this embodiment varies widely and can be appropriately set for each.

[0095] <Fiber-reinforced polyamide resin composition>

[0096] The fiber-reinforced polyamide resin composition of this embodiment comprises crystalline polyamide (A) and glass fiber (B), and preferably comprises 1 to 100 parts by weight of glass fiber (B) relative to 100 parts by weight of crystalline polyamide (A).

[0097] <Method for manufacturing fiber-reinforced polyamide resin composition>

[0098] The method for manufacturing the fiber-reinforced polyamide resin composition of this embodiment is not particularly limited, and it can be manufactured by mixing and kneading (A) crystalline polyamide and (B) glass fiber and other components as needed in any order.

[0099] For fiber-reinforced polyamide resin compositions, melt compounding using various commonly used extruders, such as single-screw or twin-screw extruders, is preferred. Considering productivity and versatility, the twin-screw extruder method is particularly preferred. Specifically, when using chopped glass filaments as (B) glass fiber, it is preferable to use a twin-screw extruder with upstream and downstream feed ports, feeding the chopped glass filaments from the upstream feed port and performing melt compounding. Alternatively, when using glass fiber roving, compounding can also be performed using known methods.

[0100] <Molded articles obtained using fiber-reinforced polyamide resin compositions>

[0101] The molded body in this embodiment is a molded body comprising the fiber-reinforced polyamide resin composition of the above embodiment. For example, various parts can be molded by injection molding of the fiber-reinforced polyamide resin composition of the above embodiment, but there are no particular limitations.

[0102] Furthermore, the molded body described in this embodiment is not particularly limited, and can be applied to various components such as those used in automobiles, machinery industries, electrical / electronic applications, industrial materials, and daily / household products. In this way, the molded body of this embodiment can impart sufficient mechanical properties and wear characteristics, as well as low property variability, to the aforementioned various components.

[0103] Examples of physical properties that exhibit low variability include tensile strength and impact strength of a simply supported beam. Examples of variables that represent variability include relative variables such as the coefficient of variation and absolute variables such as the standard deviation.

[0104] In this specification, the coefficient of variation (CV) is the percentage of the standard deviation (σ) relative to the arithmetic mean (μ), and is calculated by CV = (σ / μ) × 100.

[0105] The coefficient of variation of the tensile strength of the above-mentioned molded article, as determined according to ISO 527, is preferably 1.0 or less.

[0106] The coefficient of variation of the impact strength of the simply supported beam of the above-mentioned molded body, as measured according to ISO 179, is preferably 15.0 or less, more preferably 10.0 or less.

[0107] The fiber-reinforced polyamide resin composition of this embodiment is particularly suitable for automotive applications, especially for sliding components such as gears, worm gears, and worm wheels, due to its excellent mechanical and wear properties and low property variability.

[0108] [Example]

[0109] The present invention will now be described in detail with specific embodiments and comparative examples, but the present invention is not limited to the following embodiments. It should be noted that the raw materials used in the embodiments and comparative examples, as well as the methods for determining physical properties, etc., are as described below.

[0110] [raw material]

[0111] (A) Crystalline polyamide

[0112] Manufacturing Example 1(A)-1: Polyamide 66-1

[0113] 15000g of adipic acid and an equimolar salt of hexamethylenediamine, along with an excess of 0.5 mol% adipic acid relative to the total equimolar salt composition, were dissolved in 15000g of distilled water to obtain a 50% by mass aqueous solution of the raw material monomer. The resulting aqueous solution was placed in a 40L autoclave, and the autoclave was purged with nitrogen. The solution was concentrated to a concentration of 70% by mass by stirring at 110℃–150℃ while slowly removing water vapor. The internal temperature was then raised to 220℃. At this point, the autoclave was pressurized to 1.8 MPa. This pressure was maintained until the internal temperature reached 270℃, while the reaction was allowed to proceed for 1 hour by slowly removing water vapor and maintaining the pressure at 1.8 MPa.

[0114] Then, the pressure was reduced to atmospheric pressure over approximately one hour. Once atmospheric pressure was reached, the material was discharged from the lower nozzle in a linear form, and then water-cooled and cut to obtain granules. The resulting granules were dried in a nitrogen stream at 90°C for 4 hours. The granules had a formic acid relative viscosity of 45, a melting point of 265°C, and a crystallization temperature of 220°C.

[0115] Manufacturing Example 2(A)-2: Polyamide 66-2

[0116] 10 kg of the above-mentioned polyamide 66-1 granules were placed in a conical belt vacuum dryer (manufactured by Ōkawahara Seisakusho Co., Ltd., trade name RIBOCONE RM-10V) and thoroughly purged with nitrogen. The granules were heated at 190°C for 6 hours while being stirred, with nitrogen flowing through at a rate of 1 L / min. Then, the temperature was reduced while nitrogen was flowing through, and the granules were removed from the apparatus at approximately 50°C. The formic acid relative viscosity of the granules was 130.

[0117] Manufacturing Example 3(A)-3: Polyamide 66-3

[0118] Except for heating at a pellet temperature of 205°C for 8 hours, pellets were obtained in the same manner as in Manufacturing Example 2. The relative viscosity of the formic acid in this pellet was 250.

[0119] (B) Glass fiber

[0120] Manufacturing Example 4(B)-1: Glass Chopped Fiber-1

[0121] A glass fiber bundle agent was obtained by diluting the polyurethane resin (trade name: VONDIC (registered trademark) 1050, an aqueous solution with a solid content of 50% by mass (manufactured by Dai Nippon Ink Co., Ltd.)) with 2% by mass, γ-aminopropyltriethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) with 0.6% by mass, and lubricant [trade name: carnauba wax (manufactured by Kato Yoko Co., Ltd.)] with 0.1% by mass using water, and adjusting the total mass to 100% by mass.

[0122] Glass raw materials were prepared in accordance with the glass raw material composition 1 described in Table 1, and melt-spun to obtain long glass fibers with an average fiber diameter of 13 μm. The aforementioned glass fiber bundling agent was then applied. Specifically, the glass fiber bundling agent was applied to the glass fibers being wound onto a rotating drum using an applicator positioned at a predetermined location. The fibers were then dried to obtain a roving of glass fiber bundles (glass fiber roving) that had undergone surface treatment with the aforementioned glass fiber bundling agent. At this point, the glass fibers formed a bundle of 1000 fibers. This bundle was cut into 3 mm lengths to obtain chopped glass filaments-1. These chopped filaments were used as glass fibers. The boron content of chopped glass filaments-1 was determined using ICP-MS (inductively coupled plasma mass spectrometry), and the result was 0 ppm.

[0123] Manufacturing Example 5(B)-2: Glass Chopped Filament-2

[0124] Except that the glass raw materials were formulated in the manner described in Table 1 as glass raw material composition 2, the glass chopped strands-2 were manufactured in the same manner as described in Manufacturing Example 4, thereby obtaining glass chopped strands-2. The boron content of glass chopped strands-2 was 600 ppm.

[0125] Manufacturing Example 6(B)-3: Glass Chopped Filament-3

[0126] Glass raw materials were prepared in the manner described in Table 1 as glass raw material composition 1, and melt-spun to obtain long glass fibers with an average fiber diameter of 7 μm. Otherwise, they were manufactured in the same manner as described in Manufacturing Example 4 to obtain glass chopped strands-3. The boron content of glass chopped strands-3 was 0 ppm.

[0127] Manufacturing Example 7(B)-4: Glass Chopped Filament-4

[0128] Except that the glass raw materials were formulated in the manner described in Table 1 as glass raw material composition 3, the glass chopped filaments-4 were manufactured in the same manner as described in Manufacturing Example 4, thereby obtaining glass chopped filaments-4. The boron content of glass chopped filaments-4 was 13,000 ppm.

[0129] Manufacturing Example 8(B)-5: Glass Chopped Filament-5

[0130] Glass raw materials were prepared in the manner described in Table 1 as glass raw material composition 3, and melt-spun to obtain long glass fibers with an average fiber diameter of 7 μm. Otherwise, they were manufactured in the same manner as described in Manufacturing Example 4 to obtain glass chopped strands-5. The boron content of glass chopped strands-5 was 13,000 ppm.

[0131] [Table 1]

[0132] Glass raw material composition 1 Glass raw material composition 2 Glass raw material composition 3 <![CDATA[SiO2]]> weight% 58 57.8 54 <![CDATA[Al2O3]]> weight% 14 14 14 CaO weight% 21 21 21 MgO weight% 2 2 2 <![CDATA[Na2O+K2O]]> weight% 5 5 5 <![CDATA[B2O3]]> weight% 0 0.2 4

[0133] (C) Copper compounds

[0134] Cuprous iodide (I) (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0135] (D) Halides of alkali metals and / or alkaline earth metals

[0136] Potassium iodide (manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.)

[0137] Other ingredients

[0138] Antioxidant: Irganox (registered trademark) 1098 (manufactured by BASF)

[0139] Colorant: Mitsubishi (registered trademark) Carbon Black #2600 (manufactured by Mitsubishi Chemical Corporation)

[0140] [Example 1]

[0141] A twin-screw extruder (ZSK-26MC: manufactured by Coperon GmbH (Germany)) was used as the extruder. This twin-screw extruder has an upstream feed port on the first barrel counting from the upstream side and a downstream feed port on the sixth barrel counting from the upstream side. Furthermore, L / D (barrel length / barrel diameter) = 48 (number of barrels: 12). In this twin-screw extruder, the temperature from the upstream feed port to the die was set to 300°C, the screw speed was set to 200 rpm, and the discharge rate was set to 15 kg / hour. Under these conditions, (A) crystalline polyamide, (C) copper compounds, (D) halides of alkali metals and / or alkaline earth metals, and other components were supplied from the upstream feed port, and (B) glass fiber was supplied from the downstream feed port, and melt-blended to produce granules of the resin composition. Using a PS-40E injection molding machine (manufactured by Nissei Resin Co., Ltd.), the mold temperature was set to 80°C and the barrel temperature to 290°C. The resulting resin composition was granulated into ISO 3167 multipurpose test disc type A test discs. Various mechanical properties, vibration fatigue characteristics, and wear characteristics were evaluated using these test discs. Furthermore, the molar ratio of copper to halogen content was calculated as I / Cu based on the ratio of cuprous iodide (I) and potassium iodide used.

[0142] [Examples 2-10, Examples 12-21, Comparative Examples 1-4]

[0143] Except for changes in (A) crystalline polyamide, (B) glass fiber, (C) copper compound, (D) alkali metal and / or alkaline earth metal halides and other components as shown in Tables 2 to 5, granules and test pieces of Examples 2 to 10, Examples 12 to 21, and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 and were used in each test.

[0144] [Example 11]

[0145] A masterbatch containing components (C) and (D) was pre-manufactured by compounding 80 parts by mass of (A) crystalline polyamide, 1.6 parts by mass of cuprous iodide as component (C), 16 parts by mass of potassium iodide as component (D), and 2.4 parts by mass of ethylene bis-stearamide (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) under the conditions of screw speed of 200 rpm, barrel set temperature of 260°C, discharge rate of 30 kg / h, and screw structure with two kneading screws.

[0146] As the (A) crystalline polyamide used in the masterbatch, the same type of resin (A)-2 as the (A) crystalline polyamide supplied to the extruder in granule form is used.

[0147] (A) crystalline polyamide, the masterbatch containing components (C) and (D) and other components, were supplied from the upstream supply port according to the contents recorded in Table 3, and (B) glass fiber was supplied from the downstream supply port. Otherwise, the granules and test pieces of Example 11 were prepared in the same manner as in Example 1 and were supplied to each test.

[0148] It should be noted that in Tables 2 to 5, masterbatches containing components (C) and (D) are abbreviated as "C·D masterbatch".

[0149] [Example 22]

[0150] Except for changes to (A) crystalline polyamide, (B) glass fiber, (C) copper compound, (D) alkali metal and / or alkaline earth metal halides, and the types or contents of other components as shown in Table 5, granules were prepared in the same manner as in Example 1. 10 kg of the obtained granules were placed in a conical belt vacuum dryer (manufactured by Ōkawahara Seisakusho Co., Ltd., trade name RIBOCONE RM-10V) and thoroughly purged with nitrogen.

[0151] The pellets were heated at 190°C for 6 hours while being stirred, with nitrogen flowing through them at a rate of 1 L / min. Then, the temperature was lowered while nitrogen was flowing through them, and the pellets were removed from the apparatus at approximately 50°C. The resulting pellets were shaped and used in various tests.

[0152] [Example 23]

[0153] The resin composition obtained in Example 2 was injection molded using an injection molding machine α50i-A [manufactured by FANUC Corporation]. The barrel temperature was set to 290°C, and injection molding was performed under the following conditions: mold temperature 80°C, maximum injection pressure 120 MPa, injection time 10 seconds, and cooling time 60 seconds. This resulted in a worm gear with a module of 3.0, 50 teeth, a tooth thickness of 5 mm, and a tooth width of 15 mm. A gear durability test was conducted using this worm gear.

[0154] [Examples 24-26, Comparative Example 5]

[0155] Except that the resin composition used was changed to the granules of the resin composition described in Table 6, the worm gears of Examples 24-26 and Comparative Example 5 were molded in the same manner as in Example 23 and were used in each test.

[0156] [Determination Method]

[0157] <Relative viscosity of formic acid (VR)>

[0158] The relative viscosity (VR) of formic acid was obtained by comparing the viscosity of a solution (soluble component) obtained by adding the fiber-reinforced polyamide resin composition obtained in the Examples and Comparative Examples to formic acid with the viscosity of formic acid itself. Specifically, it was performed according to ASTM-D789. More specifically, the VR was measured at 25°C using a solution obtained by dissolving the fiber-reinforced polyamide resin composition in 90% formic acid (10% water) to achieve a soluble component of 8.4% by mass.

[0159] <Tension Test>

[0160] Using the type A test pieces obtained in Examples 1-22 and Comparative Examples 1-4, tensile tests were performed according to ISO 527 at a test speed of 50 mm / min, and the tensile strength (MPa) was determined.

[0161] In addition, a total of 20 type A test pieces were formed, and their tensile strengths were measured. The coefficient of variation (CV) of the tensile strength was calculated using the following formula. 拉伸 ).

[0162] CV 拉伸 =(σ 拉伸 / μ 拉伸 )×100

[0163] Here, σ 拉伸 The standard deviation of tensile strength, μ 拉伸 This represents the arithmetic mean of tensile strength.

[0164] Impact strength of simply supported beams

[0165] The type A test pieces obtained in Examples 1-22 and Comparative Examples 1-4 were processed into 80mm × 10mm × 4mm pieces, and the impact strength (kJ / m²) of a notched simply supported beam was determined according to ISO 179. 2 ).

[0166] In addition, a total of 20 type A test pieces were manufactured, and their simple beam impact strength was measured. The coefficient of variation (CV) of the simple beam impact strength was calculated using the following formula. 简支梁 ).

[0167] CV 简支梁 =(σ 简支梁 / μ 简支梁 )×100

[0168] Here, σ 简支梁 The standard deviation of the impact strength of a simply supported beam, μ 简支梁 This represents the arithmetic mean of the impact strength of a simply supported beam.

[0169] Vibration fatigue

[0170] Using an injection molding machine PS-40E [manufactured by Nissei Resin Co., Ltd.], the injection + holding time was set to 10 seconds, the mold temperature to 80°C, and the barrel temperature to 290°C. JIS K7139 small ISO test specimens (3 mm thick) were prepared according to ISO 294-1 using resin composition granules obtained in Examples 1-22 and Comparative Examples 1-4. Using these test specimens as the test subjects, vibration fatigue tests were conducted using a Shimadzu servo pulse generator (EHF-FV1OKN-1OLA) manufactured by Shimadzu Corporation. The conditions were set as follows: frequency: 20 Hz, waveform: sine wave, temperature: 120°C, stress ratio: 0.1, clamp spacing: 30 mm, and stress applied to the specimen: 60 MPa. The number of vibrations until the specimen fractured was determined.

[0171] Wear Test

[0172] Wear tests were conducted on the type A test pieces obtained in Examples 1-22 and Comparative Examples 1-4 using a reciprocating dynamic friction and wear testing machine (AFT-15MS type manufactured by Toyo Precision Co., Ltd.) and SUS304 test pieces (balls with a diameter of 5 mm) as the relative material, under the conditions of a linear speed of 30 mm / s, a reciprocating distance of 20 mm, a temperature of 23°C, a humidity of 50%, a load of 1.5 kg, and 5,000 reciprocating cycles. The wear depth at the center of the wear track of the sample after the sliding test was measured using a surface roughness tester (575A-30 manufactured by Toyo Precision Co., Ltd.). The results are expressed as "wear depth (23°C)" in Tables 2-5.

[0173] <Saltwater Wear Test>

[0174] The Type A test pieces obtained in Examples 1-22 and Comparative Examples 1-4 were immersed in a 3.5% by weight sodium chloride aqueous solution at 23°C for 100 hours. After immersion, the test pieces were rinsed with distilled water, and the surface moisture was thoroughly wiped off with a soft cloth. Then, the above-described wear test was performed, and the wear depth at the center of the wear track was measured. The results are expressed as "wear depth under salt water conditions" in Tables 2-5.

[0175] <Gear Durability Test>

[0176] The worm gears obtained in Examples 23-26 and Comparative Example 5 were used, and tests were conducted using a gear durability testing machine manufactured by Toshiba Machine Co., Ltd. A worm made of SUS304 and a resin worm gear were combined, with the worm gear on the driving side and the worm on the driven side. Lubricating grease (manufactured by Kyodo Yushi Co., Ltd., Multemp CPL) was applied to the meshing parts, and the machine was rotated by hand to mix the grease with the worm and worm gear as a whole. Next, the gear on the driving side was rotated under the following conditions, and the number of times it lasted until gear failure (durability cycles) was measured.

[0177] Test conditions: Temperature 23℃, humidity 50%, torque 25 N / m, speed 30 rpm

[0178] After each of the outgoing and returning paths has rotated once, there is a 1-second interval before rotating in the opposite direction.

[0179] <Weight reduction rate after 100,000 rotations>

[0180] Using the worm gears obtained in Examples 23-26 and Comparative Example 5, the gears were rotated 100,000 times (1.0 × 10⁻⁶) using the aforementioned gear durability testing machine. 5 Then, the mass W1 of the worm gear is measured, and the weight reduction rate (wt%) relative to the mass W0 before the start of the test is calculated according to the following formula.

[0181] Weight reduction rate = [(W0-W1) / W0]×100 [Table 2]

[0182]

[0183] [Table 3]

[0184]

[0185] [Table 4]

[0186]

[0187] [Table 5]

[0188]

[0189] [Table 6]

[0190]

[0191] For the granules of Examples 1 to 22 and the worm gears of Examples 23 to 26 that meet the specified range, sufficient mechanical properties are imparted and property variations are reduced.

[0192] On the other hand, the granules of Comparative Examples 1 to 4 and the worm gear of Comparative Example 5 did not impart sufficient mechanical properties to the molded articles, nor did they reduce the variation in physical properties.

[0193] Industrial practicality

[0194] The fiber-reinforced polyamide resin composition and molded articles of the present invention have industrial applicability in the automotive, electrical and electronic, machinery and industrial, office equipment, aerospace and other fields due to their excellent mechanical properties, reduced property variations and excellent wear characteristics.

Claims

1. A fiber-reinforced polyamide resin composition comprising crystalline polyamide (A) and glass fiber (B), characterized in that, The fiber-reinforced polyamide resin composition contains a heat stabilizer. The soluble component of the fiber-reinforced polyamide resin composition has a formic acid relative viscosity of 90 or higher, and The boron concentration in the glass fiber (B) is below 1000 ppm.

2. The fiber-reinforced polyamide resin composition according to claim 1, wherein The crystalline polyamide (A) is selected from one or more of polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 56, polyamide 66, polyamide 610, polyamide 612, polyamide 6T, polyamide 9T, and copolyamides containing these polyamides as constituent components.

3. The fiber-reinforced polyamide resin composition according to claim 1 or 2, characterized in that, The boron concentration in the glass fiber (B) is below 500 ppm.

4. The fiber-reinforced polyamide resin composition according to claim 1 or 2, wherein The glass fiber is a glass fiber whose surface is covered by a surface treatment agent at least a portion thereof.

5. The fiber-reinforced polyamide resin composition according to claim 4, characterized in that, The surface treatment agent contains a clustering agent.

6. The fiber-reinforced polyamide resin composition according to claim 5, wherein The slugging agent is selected from one or more of the following: polyurethane resin, polycarbodiimide compound, acrylic homopolymer, copolymer of acrylic acid and copolymerizable monomer, acrylic homopolymer or copolymer of acrylic acid and copolymerizable monomer with amine salt, epoxy resin, and copolymer of carboxylic anhydride unsaturated vinyl monomer and unsaturated vinyl monomer.

7. The fiber reinforced polyamide resin composition according to claim 5 or 6, wherein The slugging agent comprises a copolymer containing carboxylic anhydride unsaturated vinyl monomers and unsaturated vinyl monomers.

8. The fiber-reinforced polyamide resin composition according to claim 7, wherein The unsaturated vinyl monomer containing carboxylic anhydride is maleic anhydride, itaconic anhydride, or citraconic anhydride.

9. The fiber-reinforced polyamide resin composition according to claim 7, wherein The unsaturated vinyl monomer is styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, or ethyl methacrylate.

10. The fiber-reinforced polyamide resin composition according to Claim 7, wherein The copolymer containing carboxylic anhydride unsaturated vinyl monomers and unsaturated vinyl monomers is a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, or a mixture thereof.

11. The fiber-reinforced polyamide resin composition according to claim 4, wherein The surface treatment agent contains a silane coupling agent.

12. The fiber-reinforced polyamide resin composition according to claim 11, wherein The silane coupling agent is selected from one or more of aminosilanes, mercaptosilanes, epoxysilanes, and vinylsilanes.

13. The fiber-reinforced polyamide resin composition according to claim 12, wherein The aminosilanes are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

14. The fiber-reinforced polyamide resin composition according to Claim 12, wherein The mercaptosilanes are γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane.

15. The fiber reinforced polyamide resin composition according to claim 4, wherein The surface treatment agent contains a lubricant.

16. The fiber reinforced polyamide resin composition according to claim 15, wherein The lubricant is a wax, fatty acid amide, fatty acid ester, fatty acid ether, aromatic ester, or aromatic ether from animal, plant, or mineral sources.

17. The fiber reinforced polyamide resin composition according to claim 16, wherein The plant, animal, or mineral waxes mentioned are carnauba wax or lanolin wax.

18. The fiber reinforced polyamide resin composition according to Claim 4, wherein The amount of the surface treatment agent attached relative to 100 parts by weight of glass fiber is 0.1 to 1.0 parts by weight in terms of solid content.

19. The fiber reinforced polyamide resin composition according to claim 18, wherein The amount of the surface treatment agent attached relative to 100 parts by weight of glass fiber is 0.2 to 0.8 parts by weight in terms of solid content.

20. The fiber reinforced polyamide resin composition according to claim 18 or 19, wherein The amount of the surface treatment agent attached relative to 100 parts by weight of glass fiber is 0.2 to 0.6 parts by weight in terms of solid content.

21. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The fiber-reinforced polyamide resin composition contains a copper compound (C) and alkali metal and / or alkaline earth metal halides (D).

22. The fiber reinforced polyamide resin composition according to claim 21, wherein The copper compound (C) is selected from one or more of copper halides, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, and copper complex salts.

23. The fiber reinforced polyamide resin composition according to claim 21, wherein The copper compound (C) is selected from one or more of cuprous iodide, cuprous bromide, cuprous bromide, cuprous chloride, and copper acetate.

24. The fiber reinforced polyamide resin composition according to Claim 21, wherein The copper compound (C) is a copper halide.

25. The fiber reinforced polyamide resin composition according to claim 21, wherein The alkali metal and / or alkaline earth metal halide is selected from one or more of potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride.

26. The fiber reinforced polyamide resin composition according to claim 21, wherein The molar ratio of the halogen content in the copper compound (C) and the alkali metal and / or alkaline earth metal halide (D) to the copper content in the copper compound (C) is halogen / copper = 3 / 1 to 50 / 1.

27. The fiber reinforced polyamide resin composition according to claim 26, wherein The ratio of halogen element to copper element is 4 / 1 to 40 / 1.

28. The fiber reinforced polyamide resin composition according to claim 26 or 27, wherein The ratio of halogen element to copper element is 5 / 1 to 30 / 1.

29. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The average fiber diameter of the glass fiber (B) is 4 μm to 30 μm.

30. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The average fiber diameter of the glass fiber (B) is 5 μm to 9 μm.

31. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The average fiber diameter of the glass fiber (B) is 5 μm to 8 μm.

32. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The fiber-reinforced polyamide resin composition comprises 1 to 100 parts by weight of the glass fiber (B) relative to 100 parts by weight of the crystalline polyamide (A).

33. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The relative viscosity of the formic acid in the soluble component of the fiber-reinforced polyamide resin composition is 130 or higher.

34. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The heat stabilizer is selected from one or more of phenolic stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, and sulfur-containing stabilizers.

35. The fiber reinforced polyamide resin composition according to claim 1 or 2, wherein The content of the heat stabilizer is 0.005 to 5 parts by weight relative to 100 parts by weight of polyamide resin.

36. The fiber-reinforced polyamide resin composition according to claim 1 or 2, characterized in that, The content of the heat stabilizer is 0.01 to 3 parts by weight relative to 100 parts by weight of polyamide resin.

37. The fiber-reinforced polyamide resin composition according to claim 1 or 2, characterized in that, The content of the heat stabilizer is 0.015 to 2 parts by weight relative to 100 parts by weight of polyamide resin.

38. A molded body, wherein, The molded body is obtained by molding the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37.

39. A sliding member comprising the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37, and the sliding member being a molded body comprising the fiber-reinforced polyamide resin composition, characterized in that, The coefficient of variation of the tensile strength of the sliding member, as determined according to ISO 527, is less than 1.

0.

40. A sliding member comprising the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37, and the sliding member being a molded body comprising the fiber-reinforced polyamide resin composition, characterized in that, The coefficient of variation of the impact strength of the simply supported beam of the sliding member, as determined according to ISO 179, is less than 15.

0.

41. The sliding member as claimed in claim 40, characterized in that, The coefficient of variation of the impact strength of the simply supported beam of the sliding member, as determined according to ISO 179, is less than 10.

0.

42. A sliding member, wherein, The sliding member comprises the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37.

43. A gear, wherein, The gear comprises the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37.

44. A worm gear, wherein, The worm gear comprises the fiber-reinforced polyamide resin composition according to any one of claims 1 to 37.

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