Polyamide resin composition, molded body, and sliding member

Abstract

The invention relates to a polyamide resin composition, a molded body, and a sliding member. Provided is a polyamide resin composition which has more excellent sliding characteristics and mechanical characteristics, and which has stable sliding characteristics without relying on an injection molding step, which is one of the processes of the production method thereof, or a sliding environment for a wide range of industrial applications. A polyamide resin composition containing component (A): a polyamide resin and component (B): a modified polyorganosiloxane copolymer having at least a reactive moiety in a side chain thereof, the mass of the component (B) being 0.1-15 parts by mass per 100 parts by mass of the component (A), the component (B) being dispersed in the polyamide resin composition, and the content of the component (B) being 0.1-15 parts by mass per 100 parts by mass of the component (A). And the number average dispersion diameter of the dispersed component (B) is 5 [mu] m or less.

Description

Technical Field

[0001] The present invention relates to a polyamide resin composition, a molded body, and a sliding member. Background Art

[0002] Polyamide resins have excellent sliding properties, moldability, mechanical properties, and chemical resistance. They have long been used as component materials for industrial materials, automobiles, electrical and electronic devices, and other industrial applications.

[0003] In recent years, the use of resins in metal components has been advancing in the automotive, electrical, and electronic fields. Recently, in the automotive field, there is a growing demand for molding materials with superior sliding properties and mechanical properties such as toughness and impact resistance, driven by weight reduction, cost reduction, and streamlined assembly processes to improve fuel economy.

[0004] As a method for further improving the sliding properties of polyamide resins, it is known to mix and knead a solid lubricant such as a fluorine-containing resin, graphite, or molybdenum disulfide into the polyamide resin.

[0005] Patent Documents 2 to 4 disclose polyamide resin compositions having improved sliding properties by blending a fluorine-containing resin into a polyamide resin. Patent Document 1 discloses a power transmission guide sliding member obtained by dispersing a polyolefin resin in a polyamide resin.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-117842

[0009] Patent Document 2: International Publication No. 2013 / 047625

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2011-084679

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 2012-102189 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] As a technique for improving sliding properties, a solution has been proposed for blending fluororesins into polyamide resins. Examples of such fluororesins include polytetrafluoroethylene (PTFE). When using PTFE, melt-kneading under high shear conditions at a temperature above its melting point is necessary to microdisperse it. This melt-kneading process can lead to degradation of the polyamide resin and reduced mechanical strength.

[0014] In addition, as the technology that improves sliding properties, the scheme of coordinating polyolefin resin in polyamide resin has been proposed.But the melt viscosity, SP value of polyamide resin and polyolefin resin are different.In addition, according to the shear rate applied when manufacturing, the melt viscosity of polyamide resin and polyolefin resin also changes significantly.As the result that the melt viscosity of polyamide resin and polyolefin resin is very different, there is the problem that the morphological state of polyolefin resin is unstable, mechanical properties and sliding properties are caused to have a big influence.In addition, according to the difference of various conditions such as sliding component and / or test environment, exposure condition, can't bring into play stable sliding properties.

[0015] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyamide resin composition having more excellent sliding properties and mechanical properties, and having stable sliding properties and mechanical properties even under various conditions such as sliding parts and / or test environments and exposure conditions.

[0016] Means used to solve problems

[0017] The present invention includes the following aspects.

[0018] [1] A polyamide resin composition comprising:

[0019] (A) Component: polyamide resin, and

[0020] Component (B): a modified polyorganosiloxane copolymer having at least a reactive portion in its side chain, wherein

[0021] The mass of the component (B) is 0.1 to 15 parts by mass relative to 100 parts by mass of the component (A).

[0022] The (B) component is dispersed in the polyamide resin composition, and

[0023] The number average dispersion diameter of the dispersed component (B) is 5 μm or less.

[0024] [2] The polyamide resin composition according to [1], wherein the reactive portion is at least one selected from the group consisting of a glycidyl group, an acryloyl group, a methacryloyl group, a structural unit derived from a carboxylic anhydride, and a structural unit of an amino group.

[0025] [3] The polyamide resin composition according to [1], wherein the component (A) has a terminal carboxyl group and a terminal amino group,

[0026] The difference (CA) between the concentration C (mmol / kg) of the terminal carboxyl groups in the component (A) and the concentration A (mmol / kg) of the terminal amino groups in the component (A) is within a range of 30 mmol / kg to 130 mmol / kg.

[0027] [4] The polyamide resin composition according to [3], wherein, when B is the mass fraction of the component (B) minus the siloxane component, B and the concentration C satisfy the relationship of C×B=50 to 300.

[0028] [5] The polyamide resin composition according to [1], wherein the component (B) is a graft copolymer.

[0029] [6] The polyamide resin composition according to [1], wherein the number average dispersion diameter is 2 μm or less.

[0030] [7] The polyamide resin composition according to [1], wherein the ratio of the siloxane component in the component (B) is 50% to 90%.

[0031] [8] A molded article, wherein the molded article is a molded article of the polyamide resin composition according to any one of [1] to [7].

[0032] [9] A sliding member comprising the polyamide resin composition according to any one of [1] to [7].

[0033]

[10] The sliding member according to [9], wherein the sliding member is used in a liquid lubrication environment.

[0034]

[11] The sliding member according to

[10] , wherein the material of the contact object of the sliding member is a material other than thermoplastic resin.

[0035] Effects of the Invention

[0036] According to the present invention, a polyamide resin composition can be obtained which has more excellent sliding properties and mechanical properties and has stable sliding properties independent of the shear rate applied in the injection molding step in its production method. DETAILED DESCRIPTION

[0037] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiments are for illustration of the present invention and are not intended to limit the present invention to the following contents. The present invention can be implemented by appropriately modifying the present invention within the scope of its purpose.

[0038] In this specification, "polyamide" refers to a polymer having an amide (-NHCO-) group in the main chain.

[0039] In this specification, unless otherwise specified, numerical ranges are intended to include both the lower and upper limits of the range. For example, "0.1 to 15 parts by mass" means 0.1 parts by mass or more and 15 parts by mass or less.

[0040] <Polyamide resin composition>

[0041] The polyamide resin composition of this embodiment contains:

[0042] (A) component: polyamide resin; and

[0043] Component (B): a modified polyorganosiloxane copolymer having at least a reactive portion in its side chain,

[0044] The mass of the component (B) is 0.1 to 15 parts by mass relative to 100 parts by mass of the component (A).

[0045] The (B) component is dispersed in the polyamide resin composition, and

[0046] The number average dispersion diameter of the dispersed component (B) is 5 μm or less.

[0047] Hereinafter, each component of the polyamide resin composition according to the present embodiment will be described.

[0048] (A) Polyamide resin

[0049] Examples of the polyamide resin (A) in the present embodiment include, but are not limited to, (a-1) polyamides obtained by ring-opening polymerization of lactams, (a-2) polyamides obtained by self-condensation of ω-aminocarboxylic acids, (a-3) polyamides obtained by condensation of diamines and dicarboxylic acids, and copolymers thereof.

[0050] As the (A) polyamide resin, one of the above-mentioned polyamides may be used alone, or two or more thereof may be used as a mixture.

[0051] Examples of the lactam used for producing the polyamide (a-1) include pyrrolidone, caprolactam, undecanolactam, and laurolactam, but are not limited thereto.

[0052] Examples of the ω-aminocarboxylic acid used for producing the polyamide (a-2) include, but are not limited to, ω-amino fatty acids that are ring-opening compounds of the lactams described above obtained with water.

[0053] Furthermore, as the above-mentioned lactam or the above-mentioned ω-aminocarboxylic acid, two or more monomers may be used in combination for condensation.

[0054] Examples of the diamine (monomer) used for producing the polyamide (a-3) include, but are not limited to, linear aliphatic diamines, branched aliphatic diamines, alicyclic diamines, and aromatic diamines.

[0055] Examples of the linear aliphatic diamine include hexamethylenediamine and pentamethylenediamine, but are not limited thereto.

[0056] Examples of the branched aliphatic diamine include, but are not limited to, 2-methylpentanediamine and 2-ethylhexamethylenediamine.

[0057] Examples of the alicyclic diamine include cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine, but are not limited thereto.

[0058] Examples of the aromatic diamine include p-phenylenediamine and m-phenylenediamine, but are not limited thereto.

[0059] Examples of the dicarboxylic acid (monomer) used for producing the polyamide (a-3) include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

[0060] Examples of the aliphatic dicarboxylic acid include adipic acid, pimelic acid, sebacic acid, and the like, but are not limited thereto.

[0061] Examples of the alicyclic dicarboxylic acid include cyclohexanedicarboxylic acid, but are not limited thereto.

[0062] Examples of the aromatic dicarboxylic acid include phthalic acid and isophthalic acid, but are not limited thereto.

[0063] The diamines and dicarboxylic acids as the above monomers may be condensed alone or in combination of two or more.

[0064] Examples of the polyamide of component (A) include polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polybutylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecanoamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 2Me5T (poly(2-methylpentamethylene terephthalamide) (hereinafter, the methyl group may be referred to as Me)), polyamide MXD6 (poly(m-phenylene adipamide), polyamide PXD12 (poly(p-phenylene dodecanoamide), and copolymer polyamides containing at least one of these as a constituent component, but are not limited thereto.

[0065] (Composition ratio of component (A))

[0066] From the viewpoint of improving sliding properties, the polyamide resin (A) of this embodiment preferably contains as a main component polyamide 66, polyamide 46, polyamide 4T, polyamide 6T, polyamide 9T, polyamide 6, or polyamide 610. Hereinafter, "main component" means that the content ratio of the polyamide resin as the main component is 50% by mass or more relative to the total mass of the polyamide resin (A).

[0067] From the viewpoint of improving heat resistance, the polyamide resin (A) is preferably a polyamide resin containing polyamide 66, polyamide 46, polyamide 4T, polyamide 6T, polyamide 9T, or polyamide PXD12 as a main component, and more preferably a polyamide resin containing polyamide 66 as a main component.

[0068] In one embodiment, the component (A) has a terminal carboxyl group and a terminal amino group.

[0069] (Terminal amino group concentration)

[0070] The terminal amino group concentration of the polyamide resin (A) is not particularly limited, but is preferably 20 mmol / kg or greater, more preferably 30 mmol / kg or greater, even more preferably 40 mmol / kg or greater, particularly preferably 60 mmol / kg or greater, and most preferably 80 mmol / kg or greater. The upper limit of the terminal amino group concentration of the polyamide resin (A) is not particularly limited, but may be, for example, 120 mmol / kg.

[0071] The terminal carboxyl concentration of the polyamide resin (A) is not particularly limited. A high terminal carboxyl concentration can improve compatibility with the component (B). Therefore, by increasing the terminal carboxyl concentration, the number average dispersion diameter of the component (B) can be reduced, which can improve the sliding properties. It is desirable to increase the terminal carboxyl concentration relative to the terminal amino concentration of the polyamide resin (A). The difference between the terminal carboxyl concentration and the terminal amino concentration is preferably 80 mmol / kg ± 50 mmol / kg or less, more preferably 80 mmol / kg ± 40 mmol / kg or less, further preferably 80 mmol / kg ± 30 mmol / kg or less, and most preferably 80 mmol / kg ± 20 mmol / kg or less.

[0072] The terminal group concentration of the polyamide resin (A) can be measured by neutralization titration, nuclear magnetic resonance analysis, etc. Specifically, it can be measured by the method described in the examples below.

[0073] (Relative viscosity of sulfuric acid of component (A))

[0074] The relative viscosity in sulfuric acid of the polyamide resin (A) is preferably 2.0 or greater, more preferably 2.1 or greater, further preferably 2.3 or greater, and most preferably 3.2 or greater. Furthermore, the relative viscosity in sulfuric acid of the polyamide resin (A) is preferably 4.5 or less, more preferably 4.4 or less, and most preferably 4.3 or less.

[0075] When the sulfuric acid relative viscosity is 2.0 or higher, a polyamide resin composition having better mechanical properties tends to be obtained. When the sulfuric acid relative viscosity is 4.5 or lower, a polyamide resin composition having better fluidity and processability tends to be obtained.

[0076] The sulfuric acid relative viscosity can be measured by the method described in JIS-K6920 described in the Examples below.

[0077] As the component (A) in the polyamide resin composition of the present embodiment, a known substance may be used, or a commercially available product may be used.

[0078] (B) Modified polyorganosiloxane copolymer having at least a reactive portion in its side chain

[0079] The modified polyorganosiloxane copolymer (B) having a reactive portion in this embodiment is not particularly limited as long as it is a modified polyorganosiloxane copolymer having a reactive portion. Preferred examples of component (B) include components having at least one reactive portion selected from the group consisting of a glycidyl group, an acryloyl group, a structural unit derived from a carboxylic anhydride, and a structural unit consisting of an amino group. More preferably, the modified polyorganosiloxane copolymer having a reactive portion is a graft copolymer.

[0080] By including the component (B), the sliding properties of the obtained polyamide resin composition are improved.

[0081] [Method for preparing component (B)]

[0082] The preparation method of component (B) is not limited to the following method, but preferably a modified polyorganosiloxane having a reactive moiety is obtained by further adding a silane coupling agent during the polymerization of a cyclic organosiloxane to prepare (i) a polyorganosiloxane represented by general formula (1), and then subjecting a mixture of (i) the polyorganosiloxane, (ii) an acrylate monomer or a methacrylate monomer, and (iii) a monomer copolymerizable therewith having a carboxyl group, an amide group, and / or a hydroxyl group, a glycidyl group, or a structural unit derived from a carboxylic anhydride as a reactive moiety to emulsion graft polymerization. Alternatively, a modified polyorganosiloxane having a reactive moiety is obtained by subjecting a mixture of the polyorganosiloxane as a component, (ii) an acrylate monomer, and (iii) a functional group-containing monomer copolymerizable therewith to emulsion graft polymerization.

[0083]

[0084] (In formula (1), R represents the same or different substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms, X represents the same or different substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, or hydroxyl groups, Y represents X or the same or different group represented by [O—Si(X)₂]₇X, and at least two of X and Y represent hydroxyl groups. a represents a number from 0 to 1000, b represents a positive number from 100 to 10,000, and c represents a positive number from 1 to 1000.)

[0085] Here, R represents, for example, the same or different substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms. Specific examples include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, and naphthyl. Examples of substituted alkyl groups include, but are not limited to, halogen atoms, acryloyloxy groups, methacryloyloxy groups, carboxyl groups, alkoxy groups, alkenyloxy groups, amino groups, amino groups substituted with alkyl, alkoxy, or (meth)acryloyloxy groups, carboxyl groups, amide groups, and / or hydroxyl groups, glycidyl groups, and alkyl groups substituted with structural units derived from carboxylic anhydrides. R is preferably methyl.

[0086] X is, for example, the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Specifically, in addition to hydroxyl group, examples include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, naphthyl, methoxy, ethoxy, propoxy, butoxy, hexyl, heptyl, octyloxy, decyloxy, and tetradecyloxy. Examples of substituted alkyl groups include the same substituted alkyl groups as described above.

[0087] Y is X or a group of the same or different kind represented by, for example, [O-Si(X)2]cX, but is not limited thereto.

[0088] a is not limited to the following numbers. For example, if a is greater than 1000, the strength of the resulting film is insufficient. Therefore, a is a number from 0 to 1000, preferably from 0 to 200. If b is less than 100, the flexibility of the film is poor. If b is greater than 10,000, the tear strength of the film decreases. Therefore, b is a positive number from 100 to 10,000, preferably from 1,000 to 5,000. c is a positive number from 1 to 1000, preferably from 1 to 200. In addition, from the perspective of crosslinking properties, a substance having at least two, preferably from 2 to 4, hydroxyl groups in one molecule, with the hydroxyl groups formed at both ends, can be used.

[0089] Component (i) can be obtained, for example, by ring-opening polymerization of a cyclic organosiloxane, but is not limited thereto. Examples of the cyclic organosiloxane used as a raw material include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7-tetrakis(3-methacryloyloxypropyl)tetramethylcyclotetrasiloxane Tetrasiloxane, 1,3,5,7-tetrakis(3-acryloyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane, etc.

[0090] Furthermore, a silane coupling agent represented by the following general formula (2) can be copolymerized with the cyclic organosiloxane. Copolymerization of the silane coupling agent can assist in bonding the organosiloxane to the monomer of component (ii) or (iii).

[0091] R 3 (4-d-e) R 5 e Si(OR 4 ) d (2)

[0092] (In formula (2), R 3 R represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloyloxy group or a methacryloyloxy group. 4 represents an alkyl group having 1 to 4 carbon atoms, R 5 represents an alkyl group having 1 to 4 carbon atoms, d represents an integer of 1 to 3, e represents an integer of 0 to 2, and e+d=1 to 3.

[0093] Specific examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the cyclic organosiloxane.

[0094] The polymerization catalyst used in the polymerization of the cyclic organosiloxane is preferably a strong acid, and examples thereof include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid having emulsifying ability is preferred.

[0095] In addition, examples of anionic surfactants used in polymerizing cyclic organosiloxanes include sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyl taurates, fatty soaps, and alkyl phosphates. Among these, surfactants that are readily soluble in water and do not have a polyethylene oxide chain are preferred. N-acylamino acid salts, N-acyl taurates, fatty soaps, and alkyl phosphates are more preferred, and sodium lauroyl methyl taurate and sodium myristoyl methyl taurate are particularly preferred.

[0096] The polymerization temperature of the cyclic organosiloxane is preferably 50° C. to 75° C., and the polymerization time is preferably 10 hours or longer, more preferably 15 hours or longer. Furthermore, aging at 5° C. to 30° C. for 10 hours or longer after polymerization is particularly preferred.

[0097] The (ii) acrylate or methacrylate (hereinafter sometimes referred to as the acrylic component) used in the present invention refers to an acrylate monomer or methacrylate monomer that does not have a functional group such as a hydroxyl group, an amide group, or a carboxyl group. Preferably, it is an acrylate or methacrylate having an alkyl group having 1 to 10 carbon atoms. More preferably, the acrylic component polymer has a glass transition temperature (hereinafter sometimes referred to as Tg) of 40°C or higher, preferably 60°C or higher. Examples of such monomers include butyl acrylate, methyl methacrylate, isopropyl methacrylate, ethyl methacrylate, and cyclohexyl methacrylate. The upper limit of Tg is preferably 200°C or lower, more preferably 150°C or lower.

[0098] The glass transition temperature can be measured in accordance with JIS K7121.

[0099] The functional group-containing monomer (iii) copolymerizable with the component (ii) is a monomer having an unsaturated bond such as a carboxyl group, an amide group, a hydroxyl group, a vinyl group, or an allyl group. Specific examples thereof include methacrylic acid, acrylic acid, acrylamide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. By copolymerizing these, compatibility can be improved.

[0100] Regarding the component (B) of the present invention, a mixture of (ii) an acrylate or methacrylate monomer and (iii) a functional group-containing monomer copolymerizable therewith is subjected to emulsion graft polymerization on the (i) polyorganosiloxane obtained in the above manner.

[0101] Examples of the free radical initiator used herein include persulfates such as potassium persulfate and ammonium persulfate, aqueous sulfuric acid-hydrogen peroxide mixtures, tert-butyl hydroperoxide, and hydrogen peroxide. Redox free radical initiators using a reducing agent such as sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, sugars, or amines may also be used as needed.

[0102] Graft polymerization can be fully carried out using the surfactant already present in the polyorganosiloxane emulsion. However, to improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyltaurates, fatty soaps, and alkyl phosphates may be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether may also be added.

[0103] The graft polymerization temperature of the components (ii) and (iii) is preferably 25° C. to 55° C., more preferably 25° C. to 40° C. The polymerization time is preferably 2 hours to 8 hours, more preferably 3 hours to 6 hours.

[0104] Furthermore, a chain transfer agent may be added to adjust the molecular weight and graft ratio of the graft polymer.

[0105] The modified polyorganosiloxane (B) obtained in this manner is a polymer in which components (ii) and (iii) are randomly grafted. In this case, the solids content of the acrylic modified polyorganosiloxane is preferably 35% to 50% by mass. Furthermore, the viscosity (25°C) is preferably 500 mPa·s or less, more preferably 50 mPa·s to 500 mPa·s. The viscosity can be measured using a rotational viscometer. The average particle size is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm).

[0106] The modified polyorganosiloxane of the present invention is granulated into a powder by the methods listed below. Examples include spray drying and airflow drying. A spray dryer is preferred for productivity. Powderization is preferably performed by thermal drying, preferably at 80°C to 150°C. The average particle size of the resulting powder particles is preferably as small as possible, preferably 50 μm or less. More preferably, it is 1 μm to 30 μm. It should be noted that the particle size of the emulsion and powder can be measured as the cumulative mass average value D50 using a laser diffraction particle size analyzer.

[0107] The modified polyorganosiloxane (B) of the present invention, when incorporated into the polyamide resin (A), can be used, without particular limitation, as a raw material for sliding parts in a wide range of applications, including electrical / electronic components, automotive parts, construction parts, and industrial parts. In daily necessities, it can be used as fasteners, fans, and speed reducer gears. In vehicles, it can be used as gear components, radiator tanks (including intake manifolds), tanks, engine hoods, bearing retainers, gears, doorstops, chain guides, sliding parts around electric power steering systems, combination valves within thermal management modules, engine peripheral components such as actuator gears, and exterior parts such as fender mirrors. In particular, it can be used in gears, bearing retainers, and chain guides where improved slidability and wear resistance are desired.

[0108] (Content ratio of the silicone component in component (B))

[0109] The component (B) preferably contains at least 50% by mass or more of a siloxane component relative to 100% by mass of the component (B).

[0110] (Composition ratio of component (B))

[0111] The ratio of the siloxane component constituting the component (B) is preferably 50% by mass or more, and particularly preferably 60% by mass to 90% by mass.

[0112] By satisfying the above ratio, the sliding properties of the obtained polyamide resin composition are improved.

[0113] When B is the mass of component (B) minus the siloxane component, B and the concentration C are preferably within the range of C×B=10 to 1000. More preferably, C×B is within the range of 20 to 500, more preferably within the range of 50 to 300, and most preferably within the range of 30 to 300. When C×B is within these ranges, sliding properties can be significantly improved.

[0114] (Average dispersion diameter of component (B))

[0115] The number average dispersion diameter of the (B) component dispersed in the polyamide resin composition is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, and most preferably 1 μm or less. By having the number average dispersion diameter of the (B) component be 5 μm or less, in particular, the sliding properties can be improved. In addition, when the number average dispersion diameter is outside the above-mentioned specified range, the sliding properties and mechanical properties are greatly reduced. There is no particular restriction on the determination of the number average dispersion diameter of the (B) component, and it can be obtained by observing the dispersion diameter of at least 50 particles using a scanning electron microscope (SEM). Here, the dispersion diameter is defined as the longer diameter of the short diameter and the long diameter.

[0116] (Ratio of component (B))

[0117] Relative to 100% by mass of the (A) polyamide resin, the content of the (B) component in the polyamide resin composition of the present embodiment is preferably 0.1% by mass to 15% by mass, more preferably 1% by mass to 12% by mass, and further preferably 2% by mass to 7% by mass. By having the content of the (B) component being above the above lower limit, the sliding properties of the obtained polyamide resin composition can be effectively exerted. In addition, by having the content of the (B) component being below the above upper limit, the wear resistance and mechanical properties of the obtained polyamide resin composition are improved.

[0118] As the component (B) in the polyamide resin composition of the present embodiment, any known modified polyorganosiloxane copolymer having a reactive portion may be used, and a commercially available product may also be used.

[0119] (Compatibilizer)

[0120] The compatibilizer in this embodiment is not limited to the following substances. However, from the perspective of achieving superior sliding properties, mechanical properties, heat resistance, long-term heat resistance, moldability, and processability, there are no particular limitations on the compatibility of the compound containing a silicone component and / or an acrylic component with the polyamide resin. Examples of the compound capable of improving the compatibility of the compound containing a silicone component and / or an acrylic component with the polyamide resin include, but are not limited to, at least one compound selected from compounds having reactive functional groups capable of reacting with terminal groups and / or main chain amide groups of the polyamide resin, and compounds having amide bonds, such as polyamides and / or copolymers thereof.

[0121] (Proportion of compatibilizer)

[0122] The content of the compatibilizer in the polyamide resin composition of the present embodiment is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 15 parts by mass, further preferably 0.1 to 12 parts by mass, and most preferably 1 to 7 parts by mass, relative to 100 parts by mass of the polyamide resin (A). When the content of the compatibilizer is above the lower limit, sliding properties, moldability, processability, etc. can be effectively exerted. When the content of the compatibilizer is below the upper limit, sliding properties, mechanical properties, heat resistance, long-term heat resistance, moldability, processability, etc. are improved.

[0123] From the viewpoint of improving sliding properties, mechanical properties, heat resistance, long-term heat resistance, moldability, and processability, it is preferred to use a compatibilizer that improves the compatibility between (A) the polyamide resin and (B) the modified polyorganosiloxane copolymer having a reactive portion.

[0124] (Copper compounds)

[0125] Examples of the copper compound used in this embodiment 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 coordinated with chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid.

[0126] These copper compounds may be used alone or in combination of two or more.

[0127] Among these, preferred copper compounds are cuprous iodide, cuprous bromide, cupric bromide, cuprous chloride, and cupric acetate, with cuprous iodide being more preferred. Furthermore, from the perspective of sliding properties, the above copper compounds are preferably used in a masterbatch with a halide of a metal selected from the group consisting of alkali metals and alkaline earth metals.

[0128] (Amount of copper compound added)

[0129] The amount of the copper compound added is 0.01 to 5 parts by mass, preferably 0.01 to 4 parts by mass, and more preferably 0.03 to 3 parts by mass, relative to 100 parts by mass of the component (A).

[0130] By incorporating the copper compound in an amount within the above range, heat aging resistance can be improved, copper precipitation and corrosion can be suppressed, and the friction coefficient and wear depth can be reduced.

[0131] (Metal halide selected from the group consisting of alkali metals and alkaline earth metals)

[0132] Examples of metal halides selected from the group consisting of alkali metals and alkaline earth metals (hereinafter sometimes referred to simply as "metal halides") used in this embodiment include potassium iodide, sodium iodide, potassium bromide, potassium chloride, sodium chloride, etc. Among these, potassium iodide is preferred.

[0133] These metal halides may be used alone or in combination of two or more.

[0134] (Metal halide content)

[0135] The amount of the metal halide to be added is 0.05 to 5 parts by mass, preferably 0.1 to 4 parts by mass, and more preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the (A) polyamide resin.

[0136] By adding a metal halide in an amount within the above range, heat aging resistance can be improved, copper precipitation and corrosion can be suppressed, and the friction coefficient and wear depth can be reduced.

[0137] (Particle size of copper compounds and metal halides)

[0138] Furthermore, the maximum particle size of the copper compound and the metal halide to be blended is preferably 50 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less.

[0139] In the present invention, particle size refers to the biaxial average diameter, i.e., the average of the minor diameter and the major diameter. Here, the minor diameter and the major diameter are the short side and the long side, respectively, of the rectangle circumscribing the particle with the smallest area. The maximum particle size of the copper compound and metal halide can be determined by observing at least 50 particles using a scanning electron microscope (SEM).

[0140] By having a maximum particle size within the above range, the copper compound and the metal halide can be finely dispersed in the polyamide resin (A) even when the water content of the polyamide resin (A) is low. As a result, metal precipitation and corrosion can be suppressed, and the toughness, heat aging resistance, appearance, and color tone of the resulting polyamide resin composition can be further improved. Furthermore, the friction coefficient and wear depth can be reduced.

[0141] (Molar ratio of halogen to copper)

[0142] When a copper compound and a metal halide are prepared into a masterbatch, the molar ratio of halogen to copper (halogen / copper) in the masterbatch is preferably 3-30, more preferably 4-25, and even more preferably 5-23.

[0143] When the molar ratio of halogen to copper is above the above lower limit, copper precipitation and metal corrosion can be suppressed. In addition, when the molar ratio of halogen to copper is below the above upper limit, corrosion of the screw of the molding machine can be suppressed without compromising mechanical properties such as toughness.

[0144] (Organic compound having at least one amide group)

[0145] In this embodiment, an organic compound having at least one amide group (excluding polyamide) may be present in the masterbatch.

[0146] The inclusion of an organic compound having at least one amide group (excluding polyamides) can prevent the copper compound and metal halide from dissolving in the water in component (A) and forming a complex during melt kneading. Furthermore, the copper compound and metal halide can be stabilized in component (A) without adversely affecting component (A), thereby preventing precipitation and deterioration.

[0147] The organic compound having at least one amide group used in this embodiment is a compound having at least one amide group in its molecular chain. Examples of the organic compound having at least one amide group include, but are not limited to, monoamides, substituted amides, hydroxymethylamides, and bisamides.

[0148] Monoamides are represented by the general formula R-CONH2 (wherein R is a saturated aliphatic group, an unsaturated aliphatic group, an aromatic group having 8 to 30 carbon atoms, or a group in which a part of the -H groups thereof is substituted with -OH).

[0149] Examples of the monoamides include, but are not limited to, laurylamide, palmitamide, stearylamide, behenylamide, hydroxystearylamide, oleylamide, erucylamide, and ricinoleylamide.

[0150] Substituted amides are composed of the general formula R 1 -CONH-R 2 Indicates (where R 1 and R 2 Each independently represents a saturated aliphatic group, an unsaturated aliphatic group, an aromatic group having 8 to 30 carbon atoms, or a group in which a part of -H groups thereof is substituted with -OH).

[0151] Examples of the substituted amides include, but are not limited to, N-lauryl lauramide, N-palmityl palmitamide, N-stearyl stearamide, N-oleyl oleamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide, N-oleyl palmitamide, N-stearyl 12-hydroxystearamide, and N-oleyl 12-hydroxystearamide.

[0152] Hydroxymethylamides are represented by the general formula R-CONHCH2OH (wherein R is a saturated aliphatic group, an unsaturated aliphatic group, an aromatic group having 8 to 30 carbon atoms, or a group in which a part of the -H groups thereof is substituted with -OH).

[0153] Examples of the methylolamides include methylolstearamide and methylolbehenamide.

[0154] Bisamides are represented by the general formula (R-CONH)2(CH2)n (wherein R is a saturated aliphatic group, an unsaturated aliphatic group, an aromatic group having 8 to 30 carbon atoms, or a group in which a portion of -H is substituted by -OH, and n is 1 to 8).

[0155] Examples of the bisamides include, but are not limited to, methylenebislauramide, methylenebishydroxystearamide, ethylenebisoctylamide, ethylenebislauramide, ethylenebisstearamide, ethylenebisisostearamide, ethylenebishydroxystearamide, ethylenebisbehenamide, hexamethylenebisstearamide, hexamethylenebisbehenamide, hexamethylenebishydroxystearamide, butylenebishydroxystearamide, N,N'-distearyl adipamide, N,N'-distearyl sebacamide, methylenebisoleamide, ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-dioleyl adipamide, N,N'-dioleyl sebacamide, isophthalylenebisstearamide, and N,N'-distearylisophthalamide.

[0156] These organic compounds having at least one amide group may be used alone or in combination of two or more.

[0157] Among them, preferred examples include bisamides.

[0158] (Amount of organic compound having at least one amide group)

[0159] The amount of the organic compound having at least one amide group is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass per 100 parts by mass of the (A) polyamide resin.

[0160] By incorporating the organic compound having at least one amide group within the above range, the dispersibility of the copper compound and metal halide in component (A) can be improved, further enhancing heat aging resistance. Consequently, copper precipitation and metal corrosion can be suppressed, reducing the friction coefficient and wear depth.

[0161] (Water content of masterbatch)

[0162] The moisture content of the masterbatch is preferably 0.06% by mass to 1.0% by mass, more preferably 0.10% by mass to 0.75% by mass, and even more preferably 0.15% by mass to 0.75% by mass, relative to the total mass of the masterbatch.

[0163] The moisture in the masterbatch may be present in the form of moisture bound to the polyamide molecules or in the form of moisture adhering to the surface of the masterbatch, such as the surface of masterbatch pellets or masterbatch powder.

[0164] By keeping the moisture content within the above range, the aggregation of copper compounds and metal halides can be suppressed, thereby improving mechanical properties such as toughness and heat aging resistance, suppressing copper precipitation and metal corrosion, and reducing the friction coefficient and wear depth.

[0165] The moisture content of the masterbatch can be adjusted by controlling the degree of pressure reduction in the extruder, the immersion time and length of the strands in the bath during cooling, or the amount of water sprayed.

[0166] (Water content of polyamide resin composition)

[0167] The water content of the polyamide resin composition in this embodiment is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, and even more preferably 0.05 to 0.30% by mass, relative to the total mass of the polyamide resin composition.

[0168] The water in the polyamide resin composition may be present as water bound to the polyamide molecules or as water adhering to the surface of the polyamide resin composition, such as the surface of particles or powder. From the viewpoint of enhancing the effects of the present invention, it is more preferably present as water bound to the polyamide molecules.

[0169] By keeping the water content of the polyamide resin composition within the above range, the aggregation of copper compounds and metal halides can be suppressed. As a result, mechanical properties such as toughness and heat aging resistance can be improved, copper precipitation and metal corrosion can be suppressed, and the friction coefficient and wear depth can be reduced.

[0170] The water content of the polyamide resin composition can be adjusted by controlling the degree of pressure reduction in the extruder, the immersion time and length of the strands in the bath during cooling, or the amount of water sprayed.

[0171] (Hindered phenolic heat stabilizer)

[0172] It is preferred to further add a heat stabilizer to the polyamide resin composition.

[0173] The heat stabilizer is not particularly limited, and examples thereof include phenolic stabilizers such as hindered phenol compounds, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, and sulfur-containing stabilizers.

[0174] Preferred are hindered phenol compounds as phenol stabilizers.

[0175] These heat stabilizers are also effective in reducing the friction coefficient and wear depth.

[0176] The content of the hindered phenol-based heat stabilizer is preferably 0.01 to 5 parts by mass, more preferably 0.015 to 3 parts by mass, relative to 100 parts by mass of the component (A).

[0177] (Fiber filler)

[0178] Examples of the fibrous filler include carbon fibers, glass fibers, calcium silicate fibers, potassium titanate fibers, aluminum borate fibers, wollastonite, and carbon nanotubes, but are not limited thereto.

[0179] Among them, carbon fibers and glass fibers are preferred. Glass fibers are preferred from the viewpoint of increasing the strength of the polyamide resin composition, and carbon fibers are preferred from the viewpoint of improving sliding properties.

[0180] As the carbon fibers, for example, either polyacrylonitrile (PAN)-based carbon fibers or pitch-based carbon fibers can be used, but PAN-based carbon fibers are preferably used from the viewpoint of mechanical properties.

[0181] The above-mentioned fibrous fillers may be used alone or in combination of two or more.

[0182] From the viewpoint of improving sliding properties, the amount of the fibrous filler relative to 100 parts by mass of the component (A) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 10 parts by mass or less.

[0183] For carbon fibers, it is preferred to add them in the form of short fibers of about 3 mm to about 10 mm by melt kneading in an extruder from the viewpoint of productivity. In this case, it is preferred to add the carbon fibers from a side feeder to prevent breakage of the carbon fibers.

[0184] From the viewpoint of affinity with the polyamide resin, the carbon fibers are preferably coated with a urethane sizing agent, a maleic anhydride sizing agent, an acrylic sizing agent, or a polyamide sizing agent.

[0185] From the viewpoint of physical properties and sliding properties, the diameter of the carbon fibers is preferably 5 μm or more and 10 μm or less.

[0186] (Moldability Improver)

[0187] A moldability improver may be added to the polyamide resin composition as needed within a range that does not impair the purpose of the present invention.

[0188] The moldability improver is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

[0189] Examples of higher fatty acids include, but are not limited to, saturated or unsaturated linear or branched aliphatic monocarboxylic acids having 8 to 40 carbon atoms, such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid.

[0190] Among them, stearic acid and montanic acid are preferred.

[0191] The higher fatty acid metal salt is a metal salt of the above-mentioned higher fatty acid.

[0192] The metal element of the metal salt is preferably an element of Group 1, Group 2, or Group 3 of the periodic table, zinc, or aluminum, and more preferably an element of Group 1 or Group 2 such as calcium, sodium, potassium, or magnesium, or aluminum.

[0193] Examples of higher fatty acid metal salts include, but are not limited to, metal salts of stearic acid such as calcium stearate, aluminum stearate, zinc stearate, and magnesium stearate; metal salts of montanic acid such as calcium montanate and sodium montanate; and metal salts of palmitic acid such as calcium palmitate.

[0194] Among them, metal salts of montanic acid and metal salts of stearic acid are preferred.

[0195] The higher fatty acid ester refers to an esterification product of the above-mentioned higher fatty acid and an alcohol.

[0196] Preferred are esters of aliphatic carboxylic acids having 8 to 40 carbon atoms and aliphatic alcohols having 8 to 40 carbon atoms.

[0197] Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, and lauryl alcohol.

[0198] Examples of the higher fatty acid ester include stearyl stearate and behenyl behenate.

[0199] The higher fatty acid amide refers to an amide compound of the above-mentioned higher fatty acid.

[0200] Examples of higher fatty acid amides include, but are not limited to, stearamide, oleamide, erucamide, ethylenebisstearamide, ethylenebisoleamide, N-stearyl stearamide, and N-stearyl erucamide.

[0201] These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides may be used alone or in combination of two or more.

[0202] (colorant)

[0203] A colorant may be added to the polyamide resin composition as needed within a range that does not impair the purpose of the present invention.

[0204] The colorant is not particularly limited, and examples thereof include dyes such as aniline black; pigments such as titanium oxide and carbon black; metal particles such as aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide, stainless steel, and titanium; and metallic pigments such as mica pearlescent pigments and colored graphite.

[0205] (Other resins)

[0206] To the polyamide resin composition, other resins may be added as needed within a range that does not impair the purpose of the present invention.

[0207] Such a resin is not particularly limited, and examples thereof include thermoplastic resins and rubber components described below.

[0208] Examples of thermoplastic resins include, but are not limited to, polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS (acrylonitrile-styrene) resin, and ABS (acrylonitrile-butadiene-styrene) resin; acrylic resins such as polyacrylic acid, polyacrylate, and polymethyl methacrylate; and halogen-containing vinyl compound resins such as polyvinyl chloride and polyvinylidene chloride.

[0209] These thermoplastic resins may be used alone or in combination of two or more.

[0210] Examples of the rubber component include natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, and styrene-isoprene block copolymer. Ethylene-ethylene-propylene random copolymer, styrene-ethylene-butene random copolymer, ethylene-propylene copolymer (EPR), ethylene-(1-butene) copolymer, ethylene-(1-hexene) copolymer, ethylene-(1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM), butadiene-acrylonitrile-styrene core-shell rubber (ABS), methyl methacrylate-butadiene-styrene core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene core-shell rubber (MAS), octyl acrylate-butadiene-styrene core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene core-shell rubber (SBR), silicone-containing core-shell rubber headed by methyl methacrylate-butyl acrylate siloxane, and other core-shell types.

[0211] These rubber components may be used alone or in combination of two or more.

[0212] The polyamide resin composition of the present invention is not particularly limited as long as the application requires mechanical and sliding properties, and can be widely used as a raw material for sliding parts such as electrical / electronic components, automotive parts, building parts, and industrial parts. Examples of sliding parts include bearings, gears, door checkers, chain guides, and the like, which are generally used as injection-molded articles.

[0213] [Method for producing polyamide resin composition]

[0214] The polyamide resin composition of the present embodiment can be obtained by mixing and kneading (A) a polyamide resin, (B) a modified polyorganosiloxane copolymer having a reactive portion, and (C) a compatibilizer, a copper compound, a metal halide, and other components as needed.

[0215] The copper compound and metal halide are preferably prepared in advance as a masterbatch, which is then melt-kneaded together with component (A) and component (B). Alternatively, the copper compound, metal halide, and component (A) are preferably prepared in advance as a masterbatch, which is then melt-kneaded together with component (B).

[0216] When producing the polyamide resin composition, the raw material of the component (C) may be added while mixing and kneading the component (A) with the copper compound and metal halide as needed and other components, and the mixture may be prepared in a twin-screw extruder.

[0217] [Masterbatch preparation process]

[0218] The masterbatch is prepared by melt-kneading the copper compound and the metal halide.

[0219] It is preferred that the above-mentioned organic compound having at least one amide group (excluding polyamide) be blended in addition to the above-mentioned copper compound and metal halide.

[0220] It is preferred to mix the component (A) in addition to the organic compound having at least one amide group (excluding polyamide).

[0221] When an organic compound having at least one amide group (excluding polyamides) is mixed with the component (A), the copper compound, the metal halide, and the organic compound having at least one amide group (excluding polyamides) may each be separately mixed into the component (A). Alternatively, at least two of the three compounds may be premixed and then mixed into the component (A). Alternatively, at least two of the three compounds may be premixed and ground into powder and then mixed into the component (A). Alternatively, at least two of the three compounds may be premixed, ground into powder, and then mixed into the component (A).

[0222] As a method for mixing the compounds, a known method can be used. Examples of the method for mixing the compounds include a method of mixing using a tumbler, a Henschel mixer, a plowshare mixer, a Nauta mixer, a jet mixer, and the like.

[0223] The compound can be pulverized by a known method, for example, by using a hammer mill, knife mill, ball mill, jaw crusher, cone crusher, roller mill, jet mill, stone mill, or the like.

[0224] As a method for forming the compound into a tablet, a known method can be used. Examples of methods for forming the compound into a tablet include compression granulation, tablet molding, dry extrusion granulation, and melt extrusion granulation.

[0225] As the device for carrying out melt mixing, there is no particular limitation, and known devices can be used. As the device for carrying out melt mixing, for example, melt mixing machines such as single screw or twin screw extruders, Banbury mixers and mixing rollers are preferably used. Wherein, twin screw extruders are preferably used. In addition, in the device for carrying out melt mixing, a degassing mechanism (vent) device and a side feeder device can be equipped.

[0226] The temperature of melt kneading in this embodiment is preferably in the range of 1°C higher than the melting point or softening point of component (A) determined by differential scanning calorimetry (DSC) according to JIS K7121 to 310°C, more preferably in the range of 10°C higher than the melting point or softening point of component (A) to 300°C, and further preferably in the range of 15°C higher than the melting point or softening point of component (A) to 295°C. In this embodiment, the temperature of melt kneading refers to the set temperature of the barrel of the extruder. The shear rate in the kneader is preferably about 100 (seconds) -1 ) or more. In addition, the average residence time during kneading is preferably about 1 minute to about 15 minutes.

[0227] (Masterbatch, Component (A), Component (B) Melt-Kneading Step)

[0228] The polyamide resin composition of this embodiment can be produced by melt-kneading the masterbatch, component (A), and component (B). When the masterbatch contains component (A), the polyamide resin composition of this embodiment can be produced by melt-kneading component (B) into the masterbatch.

[0229] (Total mass of the copper compound and metal halide)

[0230] The total mass of the copper compound and the metal halide is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the (A) polyamide resin.

[0231] By keeping the combined mass of the copper compound and the metal halide within the above range, metallic copper precipitation and metal corrosion within the extruder or molding machine can be suppressed, thereby improving stability during processing. As a result, heat aging resistance can be further improved without compromising the mechanical properties of the product, while the friction coefficient and wear depth can be further reduced, and color changes due to water absorption can be further suppressed.

[0232] The mixing ratio of the component (B) relative to 100% by mass of the polyamide resin (A) is as described above.

[0233] The masterbatch, the component (A), the component (B), and other components as needed are melt-kneaded together.

[0234] The melt-kneading step is preferably carried out using various commonly used extruders such as single-screw or twin-screw extruders. From the viewpoints of productivity and versatility, it is particularly preferred to use a twin-screw extruder. In this case, the melt-kneading temperature depends on the type of component (A), but is preferably adjusted so that the temperature of the molten resin discharged from the extruder outlet reaches a temperature above the melting point of components (A) and (B).

[0235] By adjusting the melt-kneading temperature within the above range, extrusion kneading defects are less likely to occur, and fine dispersion of the component (B) can be achieved.

[0236] In the case of a twin-screw extruder, the extruder screw preferably has at least two kneading zones combined with kneading disks. The kneading zone is a region that applies high shear to efficiently knead the molten resin while suppressing its progress in the extrusion direction.

[0237] In the melt-kneading step, a method is preferably used in which component (A), component (B), and a masterbatch (copper compound and metal halide), as well as other components (hindered phenolic heat stabilizer, etc.) as needed, are supplied from the upstreammost supply port of a twin-screw extruder and melt-kneaded in a first kneading zone to obtain a first melt-kneaded product. Furthermore, a fibrous filler is supplied from a side feed port located downstream of the first kneading zone as needed, and the non-melted fibrous filler is dispersed in the first melt-kneaded product in a second kneading zone located downstream of the side feed port.

[0238] It is preferred that the extruder conditions (barrel temperature, screw speed, discharge rate, etc.) be set so that the resin temperature of the polyamide resin composition discharged from the extruder outlet after the melt-kneading step is higher than the crystallization temperature of component (A) and is 280°C to 400°C. By adjusting the temperature of the polyamide resin composition at the discharge outlet to 280°C to 400°C, components (A) and (B) can be further finely dispersed. As a result, a polyamide resin composition having excellent sliding properties and mechanical properties can be obtained.

[0239] The temperature of the polyamide resin composition is preferably measured, for example, by bringing the detection portion of a commonly available commercial thermocouple thermometer into direct contact with the molten polyamide resin composition discharged from the outlet of the extruder.

[0240] The temperature setting of the extruder for achieving the above-mentioned temperature of the polyamide resin composition is preferably 280° C. or higher and 400° C. or lower.

[0241] The molded article of the polyamide resin composition according to the present embodiment is obtained by molding the polyamide resin composition.

[0242] There are no particular restrictions on the method for obtaining a molded body, and a known molding method can be used.

[0243] Examples of molding methods include extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, heterogeneous material molding, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin-wall injection molding (ultra-high-speed injection molding), and in-mold composite molding (insert molding, injection molding on a substrate).

[0244] The set temperature of the molding machine when molding the polyamide resin composition of this embodiment is preferably in the range of 5°C higher than the melting point of the component (A) used to 340°C, more preferably in the range of 10°C higher than the melting point of the component (A) used to 300°C, and further preferably in the range of 15°C higher than the melting point of the component (A) used to 295°C.

[0245] By setting the set temperature of the molding machine within the above-mentioned temperature range, the polyamide resin composition can be efficiently kneaded during molding, and the component (B) in the polyamide resin composition can be further finely dispersed.

[0246] The polyamide resin composition of the present invention is not particularly limited as long as the application requires mechanical and sliding properties, and can be widely used as a raw material for sliding parts such as electrical / electronic components, automotive parts, building components, and industrial parts. Examples of sliding parts include conventional injection-molded products such as bearings, gears, door checkers, and chain guides.

[0247] The polyamide resin composition of the present invention is not particularly limited as long as its application requires mechanical properties and sliding properties, and can exhibit stable sliding properties even under a wide range of sliding conditions, such as sliding mechanisms, the presence or absence of a lubricated environment, the influence of the type of the partner material, and exposure conditions.

[0248] The lubricating environment is not particularly limited, and commercially available products can be used as long as they can improve lubricity. Examples of lubricants include engine oil, silicone oil, electric motor oil, rust-proof / penetrating lubricants, and grease.

[0249] Example

[0250] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. It should be noted that the raw materials and measurement methods such as physical property tests used in the examples and comparative examples are as follows.

[0251] (Manufacturing Example 1) Preparation of polyamide 66

[0252] 15,000 g of an equimolar salt of adipic acid and hexamethylenediamine, along with a 0.5 mol% excess of adipic acid relative to the total equimolar salt components, were dissolved in 15,000 g of distilled water to obtain a 50% by mass aqueous solution of the raw monomers. The resulting aqueous solution was placed in a 40 L autoclave, and the interior of the autoclave was purged with nitrogen. The aqueous solution was stirred at 110°C to 150°C, and water vapor was slowly removed to concentrate the solution to a concentration of 70% by mass. The internal temperature was then raised to 220°C. At this point, the autoclave pressure was increased to 1.8 MPa. The reaction was continued in this state for one hour while slowly removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 270°C. The pressure was then reduced to atmospheric pressure over approximately one hour. Once atmospheric pressure was reached, the strands were discharged from a lower nozzle, water-cooled, and cut to obtain pellets. The resulting pellets were dried at 90°C for four hours under a stream of nitrogen. The relative viscosity of the pellets in 98% sulfuric acid is 2.71, the melting point is 265°C, and the crystallization temperature is 220°C.

[0253] ((A) Polyamide resin)

[0254] (A-1) Polyamide resin (Production Example 1)

[0255] (A-2) Polyamide resin: "REONA 1500-X31", manufactured by Asahi Kasei Corporation

[0256] (A-3) Polyamide resin: "REONA 3100-001", manufactured by Asahi Kasei Corporation

[0257] (A-4) Polyamide resin (Production Example 4)

[0258] (A-5) Polyamide resin: Stanyl (registered trademark) TW341-J, manufactured by DSM Co., Ltd.

[0259] (A-6) Polyamide resin: Maranyl Nylon 66 A125J, manufactured by UNITIKA Co., Ltd.

[0260] ((B) Modified polyorganosiloxane copolymer having a reactive moiety in the side chain)

[0261] (B-1) Modified polyorganosiloxane copolymer having a reactive portion (Production Example 5)

[0262] (Production Example 5)

[0263] A solution obtained by dissolving 499.6 g of octamethylcyclotetrasiloxane, 0.4 g of 3-methacryloyloxypropyldimethoxysilane, and 5 g of sodium lauryl sulfate in 45 g of pure water and a solution obtained by dissolving 5 g of dodecylbenzenesulfonic acid in 45 g of pure water were placed in a 2 L polyethylene beaker and uniformly emulsified using a homomixer. 400 g of water was then slowly added for dilution and the mixture was stirred at a pressure of 300 kgf / cm. 2 The mixture was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. The emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50°C for 24 hours. It was then aged at 10°C for 24 hours and then neutralized to pH 6.2 with 12 g of a 10% aqueous sodium carbonate solution. The nonvolatile content of the emulsion after drying at 105°C for 3 hours was 45.4%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. In this manner, an emulsion containing approximately 45% of component (i) was obtained.

[0264] For this emulsion, methyl methacrylate, butyl acrylate, and acrylamide were graft copolymerized at a mass ratio of (89 / 1 / 10) using peroxide and vitamin C by a 4-hour redox reaction at room temperature, thereby obtaining an acrylic modified silicone resin emulsion (acrylic modified polyorganosiloxane) of about 45%. This acrylic modified silicone resin emulsion is obtained by random graft polymerization of acrylic monomers. It is designed to be 22.5 parts of (ii) acrylic ester and 2.5 parts of (iii) monomers copolymerizable therewith with respect to 100 parts of polyorganosiloxane (i). It should be noted that the Tg of the acrylic component as component (ii) is 102°C. The emulsion viscosity (25°C) is 100mPa·s, and the average particle size of the emulsion is 220nm. It is spray-dried (100°C) to obtain a powder with an average particle size of 30μm (Manufacturing Example 5).

[0265] (B-2) Modified polyorganosiloxane copolymer having a reactive portion (Production Example 6)

[0266] (Production Example 6)

[0267] A solution obtained by dissolving 499.6 g of octamethylcyclotetrasiloxane, 0.4 g of 3-methacryloyloxypropyldimethoxysilane, and 5 g of sodium lauryl sulfate in 45 g of pure water and a solution obtained by dissolving 5 g of dodecylbenzenesulfonic acid in 45 g of pure water were placed in a 2 L polyethylene beaker and uniformly emulsified using a homomixer. 400 g of water was then slowly added for dilution and the mixture was stirred at a pressure of 300 kgf / cm.2 The mixture was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. The emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50°C for 24 hours. It was then aged at 10°C for 24 hours and then neutralized to pH 6.2 with 12 g of a 10% aqueous sodium carbonate solution. The nonvolatile content of the emulsion after drying at 105°C for 3 hours was 45.4%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. In this manner, an emulsion containing approximately 45% of component (i) was obtained.

[0268] This emulsion was graft-copolymerized with methyl methacrylate, butyl acrylate, and acrylic acid at a ratio of (89 / 1 / 10) using peroxide and vitamin C via a 4-hour redox reaction, yielding an approximately 45% acrylic-modified silicone resin emulsion. The emulsion was designed to contain 22.5 parts of (ii) acrylate and 2.5 parts of a copolymerizable monomer (iii) per 100 parts of polyorganosiloxane (i). The Tg of the acrylic component (ii) was the same as that in Production Example 1. The emulsion viscosity was 150 mPa·s, and the average particle size was 210 nm.

[0269] This was spray-dried to obtain a powder having an average particle size of 30 μm (Production Example 6).

[0270] (B-3) CHALINE R-200, manufactured by Nissin Chemical Co., Ltd., a modified polyorganosiloxane copolymer having a reactive moiety

[0271] ((C) Other Slip Additives)

[0272] (C-1) MODIPER-A1100, manufactured by NOF Corporation, polyethylene-polystyrene graft copolymer

[0273] (C-2) DOWSIL SH200 FLUID (10000 cSt), manufactured by Dow Toray Industries, Ltd., silicone oil

[0274] (C-3) FUSABOND N416, manufactured by The Dow Chemical Company, maleic anhydride-modified polyolefin polymer

[0275] Cuprous iodide: Copper (I) iodide, manufactured by Wako Pure Chemical Industries, Ltd.

[0276] Potassium iodide: Potassium iodide, manufactured by Wako Pure Chemical Industries, Ltd.

[0277] Hindered phenolic heat stabilizer: manufactured by BASF, IRGANOX 1098

[0278] Spreader: PEG400 manufactured by Sanyo Chemical Industries, Ltd.

[0279] Azine dye: Nigrosine, manufactured by Orient Chemical Industry Co., Ltd., NUBIAN (registered trademark) BLACKTH-807

[0280] (Manufacturing Example 2) Preparation of Masterbatch

[0281] 1.5 parts by mass of a copper compound and 32.5 parts by mass of a 40% by mass aqueous solution of a metal halide were added to 100 parts by mass of the polyamide resin (A-1) obtained in (Production Example 1). The mixture was melt-kneaded using a twin-screw extruder (manufactured by the Institute of Plastics Engineering, twin co-rotating screws, L / D = 60 (D = 30φ)) at a screw speed of 100 rpm and a barrel temperature of 280°C to obtain a masterbatch containing the polyamide resin (A-1), the copper compound, and the metal halide.

[0282] (Production Example 3) Polystyrene-polyamide polymer

[0283] 10 wt% of the compatibilizer (C-3-1) was added to the polyamide resin (A), and the mixture was melt-kneaded using a twin-screw extruder (manufactured by the Plastics Engineering Research Institute, twin-shaft co-rotating screw type, L / D = 60 (D = 30φ)) at a screw speed of 300 rpm and a barrel temperature of 280°C to obtain a polystyrene-polyamide polymer containing the polyamide resin (A) and 10 wt% of the compatibilizer (C-3-1).

[0284] (Production Example 4) Crystalline Semi-Aromatic Polyamide Resin

[0285] 15kg of 4T / 6T salt (39 / 61 mol / mol) was loaded into a 50-liter rotary dryer. The rotary dryer was vented to 50 mbar and then filled with nitrogen, which was repeated 5 times. The mixture was heated to a temperature of 220°C in 5 hours while the reaction water was discharged from the rotary dryer, and then heated to 255°C in 15 hours. A low nitrogen purge was used during the reaction. The mixture was cooled to 235°C in 19 hours, and then a mixture of 650kg of 1,6-hexamethylenediamine, 300kg of 1,4-butylene diamine and 1.0kg of water was added in 7 hours while the temperature was maintained at 235°C. The mixture was then reacted for 29 hours at 235°C. Subsequently, a nitrogen gas stream was added, and the material was then cooled to room temperature. A white powder was obtained.

[0286] [Molding method]

[0287] Unless otherwise specified, pellets of the polyamide resin compositions obtained in the Examples and Comparative Examples were prepared using an injection molding machine NEX50IV-5EG (manufactured by Nissei Plastics Co., Ltd., with a screw diameter of 26 mm and an injection volume of 49 cm). 3 ), set the following conditions: injection + holding time is 25 seconds, cooling time is 15 seconds, mold temperature is 80°C, barrel temperature = (melting point of polyamide resin + 20)°C, and molded into a multi-purpose test piece type A test piece in accordance with ISO 3167.

[0288] [Formic acid viscosity VN]

[0289] The measurement was performed in accordance with ISO 307 (JIS-K6933).

[0290] [Determination of Carboxyl Terminal Concentration of Polyamide Resin]

[0291] Neutralization titration was performed as follows. First, 4.0 g of the obtained polyamide resin was dissolved in 50 mL of benzyl alcohol. The resulting solution was then titrated with 0.1 N NaOH to determine the concentration C (mmol / kg). The endpoint was determined by the color change of the phenolphthalein indicator.

[0292] The terminal concentration was evaluated on a scale of 1 to 6, and the results are shown in the table.

[0293] 1: 80 mmol / kg ± 20 mmol / kg

[0294] 2: 80 mmol / kg ± 30 mmol / kg

[0295] 3: 80 mmol / kg ± 40 mmol / kg

[0296] 4: 80 mmol / kg ± 50 mmol / kg

[0297] 5: <30 mmol / kg

[0298] 6: >130 mmol / kg

[0299] [Determination of terminal amino group concentration of polyamide resin]

[0300] 3.0 g of a polyamide resin was dissolved in 100 mL of a 90% by mass phenol aqueous solution, and the resulting solution was titrated with 0.025 N hydrochloric acid to determine the amino terminal amount (microequivalents / g). The endpoint was determined by the pH meter reading.

[0301] [Evaluation of sliding characteristics]

[0302] (friction coefficient, wear depth)

[0303] Sliding tests were conducted using a reciprocating friction and wear tester (AFT-15MS, manufactured by Toyo Seimitsu Co., Ltd.) and a SUS304 test piece (5mm diameter ball) as the target material at a linear velocity of 50 mm / s, a reciprocating distance of 20 mm, a temperature of 23°C, and a humidity of 50%. A friction coefficient test was then conducted under the conditions of a load of 4 kg and 10,000 reciprocating cycles. Furthermore, the maximum wear depth of the wear scar on the samples after the sliding test was measured using a surface roughness meter (575A-30, manufactured by Toyo Seimitsu Co., Ltd.).

[0304] The evaluation samples were obtained by molding under the conditions of samples 1 to 4 described later, and multi-purpose test piece type A test pieces were molded according to ISO 3167. Since the injection speeds of the conditions of samples 1 to 3 were greatly different, it was confirmed that the flow rate (shear rate) of the molten resin was also greatly different, and the morphological state of the polyorganosiloxane resin changed greatly. Sample conditions with a wide range of shear rates during evaluation processing were established. In addition, regarding the conditions of sample 4, when molding a multi-purpose test piece type A test piece according to ISO 3167, it was retained in the barrel of the injection molding machine for 60 minutes. Then, the multi-purpose test piece type A test piece was molded in the same manner as in the above-mentioned [molding method] to produce a sample.

[0305] The evaluation samples were molded under the conditions of Samples 5 and 6 described below, and were molded into test pieces of Multipurpose Test Piece Type A in the same manner as in the above [Molding Method] according to ISO 3167. Samples 5 and 6 were then prepared.

[0306] Sample 5: (High temperature exposure test: 150°C x 500 hours)

[0307] A high-temperature exposure test was performed by placing each multipurpose test piece (Type A) in an oven according to ISO 188 and heating it at 150°C for 500 hours. After 500 hours, each multipurpose test piece (Type A) was removed from the oven and cooled at 23°C for 24 hours.

[0308] Sample 6: (High temperature oil immersion test: 150°C x 500 hours)

[0309] A multi-purpose test piece type A was immersed in oil (Magnatec 0W-20 manufactured by Castrol) in an autoclave. The autoclave was then heated to 150° C. After 500 hours, the test piece was removed from the autoclave and wiped with hexane for degreasing.

[0310] Sample 1: The same procedure as in the above-mentioned [Molding Method] was carried out except that the injection speed was set to 5 mm / sec.

[0311] Sample 2: The same procedure as in the above-mentioned [Molding Method] was carried out except that the injection speed was set to 30 mm / sec.

[0312] Sample 3: The same procedure as in the above-mentioned [molding method] was carried out except that the injection speed was set to 100 mm / sec.

[0313] Sample 4: The same procedure as in the above [molding method] was followed except that the sample was retained in the molding machine cylinder for 60 minutes.

[0314] Sample 5: A sample molded in the same manner as in the above-mentioned [Molding Method] was subjected to a high-temperature exposure test and then taken out.

[0315] Sample 6: A sample molded in the same manner as in the above-mentioned [Molding Method] was subjected to a high-temperature oil exposure test and then taken out.

[0316] [Evaluation of mechanical properties]

[0317] (Tensile test)

[0318] Using type A test pieces molded from the compositions obtained in Examples and Comparative Examples under the conditions described in [Molding Method], tensile tests were performed at a test speed of 50 mm / min in accordance with ISO 527 to measure tensile strength.

[0319] In addition, the ratio of the displacement amount of the distance between the chucks at the time of fracture to the distance between the chucks before the test was defined as the tensile elongation (%).

[0320] Tensile elongation (%) = 100 × breaking point displacement (mm) / initial chuck distance (mm)

[0321] In addition, the value obtained by dividing the tensile strength by the tensile elongation is defined as the tensile elastic modulus.

[0322] Tensile modulus = tensile strength / tensile elongation

[0323] (Charpy impact strength)

[0324] The compositions obtained in the examples and comparative examples were molded under the conditions shown in [Molding Method] to obtain type A test pieces with a size of 80 mm × 10 mm × 4 mm. The notched Charpy impact strength (kJ / m 2 ).

[0325] (Examples 1 to 7, 11)

[0326] (A) Polyamide resin and (B) modified polyorganosiloxane copolymer were mixed in the amounts listed in Tables 1 and 2 and fed at 25 kg / hour from the upstream supply port of a twin-screw extruder (manufactured by Coperion Corporation, trade name "ZSK26MC18") with a screw diameter of 26 mm. Subsequently, the extruder barrel temperature was set at (melting point of polyamide resin + 20)° C., and extrusion was performed while melt-kneading at a screw speed of 300 rpm to obtain pellets of a polyamide resin composition.

[0327] Using the obtained polyamide resin composition pellets, test pieces were produced by the method described in [Molding Method], and the sliding properties and mechanical properties were evaluated.

[0328] (Example 8)

[0329] Pellets of a polyamide resin composition were obtained and evaluated in the same manner as in Example 1 except that the formulation was changed as shown in Table 2 and the cylinder temperature of the extruder and the cylinder temperature of the molding machine were changed to 340°C.

[0330] (Example 9)

[0331] In addition to adding 100 parts by mass of the polyamide resin (A-1), 30 parts by mass of the polyamide resin (A-4) were added, the barrel temperature of the extruder was set to 320°C, and the amount was increased as described in Table 2 below. Pellets of the polyamide resin composition were obtained and evaluated using the same method as in Example 1, except that the amount was increased as described in Table 2 below.

[0332] (Example 10)

[0333] Pellets of a polyamide resin composition were prepared in the same manner as in Example 3. 10 kg of the obtained pellets were placed in a conical belt vacuum dryer (manufactured by Ohkawara Seisakusho Co., Ltd., trade name: Ribocone RM-10V), and the atmosphere was thoroughly purged with nitrogen.

[0334] The pellets were heated at 190°C for 6 hours while stirring while flowing nitrogen at 1 L / min. The temperature was then lowered while nitrogen was flowing, and the pellets were removed from the apparatus when the temperature reached approximately 50°C. The resulting pellets and test pieces were prepared.

[0335] (Comparative Examples 1, 4 to 7)

[0336] Except for changing the compounding ratio as described in Table 3, pellets of a polyamide resin composition were obtained by the same method as in Example 1 and evaluated.

[0337] (Comparative Example 2)

[0338] In Comparative Example 1, except that the screw rotation speed was changed to 120 rpm, pellets of a polyamide resin composition were obtained and evaluated by the same method as in Comparative Example 1.

[0339] (Comparative Example 3)

[0340] In Comparative Example 1, the same method as in Comparative Example 1 was used except that the cylinder temperature of the extruder was set to 230° C. However, the motor torque of the twin-screw extruder reached the upper limit, and pellets of the polyamide resin composition could not be obtained.

[0341] [Table 1]

[0342]

[0343] [Table 2]

[0344]

[0345] [Table 3]

[0346]

[0347] The results of the Examples demonstrate that the polyamide resin compositions of the present invention exhibit excellent sliding properties (friction coefficient, wear depth), moldability, long-term heat resistance, and mechanical properties (tensile strength, elastic modulus, impact resistance, and heat resistance). In particular, compared to the Comparative Examples, it is clear that the combination of components (A) and (B) yielded excellent sliding properties in all of the evaluation results for Samples 1 to 6. These results demonstrate that polyamide resin compositions have been obtained that are independent of injection speed (the shear rate applied to the molten resin) or residence time, and exhibit stable, excellent sliding properties even after thermal aging.

[0348] On the other hand, the results of the comparative examples show that, while some polyamide resin compositions with excellent properties were obtained, the balance of sliding properties, long-term heat resistance, moldability, and mechanical properties was poor. In particular, the sliding properties were significantly worse than those of the examples, and the sliding properties varied significantly depending on the sample conditions. Furthermore, in Comparative Examples 1 and 2, which did not incorporate component (C), all properties were poor. From the perspective of moldability, during injection molding, molten resin leaked from the nozzle tip of the injection molding machine, making continuous injection molding difficult, resulting in low industrial practicality. Furthermore, in Comparative Examples 5 to 7, which did not incorporate component (B), the sliding properties were significantly worse.

[0349] Industrial Applicability

[0350] The polyamide resin composition of the present invention has excellent sliding characteristics and mechanical properties and is therefore useful in the automotive field, electrical and electronic field, mechanical and industrial field, office equipment field, aviation and aerospace field, and the like.

Claims

1. A polyamide resin composition, comprising: (A) Component: polyamide resin, and Component (B): a modified polyorganosiloxane copolymer having at least a reactive portion in its side chain, wherein The mass of the component (B) is 0.1 to 15 parts by mass relative to 100 parts by mass of the component (A). The (B) component is dispersed in the polyamide resin composition, and The number average dispersion diameter of the dispersed component (B) is 5 μm or less.

2. The polyamide resin composition according to claim 1, wherein The reactive portion is at least one selected from the group consisting of a glycidyl group, an acryloyl group, a methacryloyl group, a structural unit derived from a carboxylic anhydride, and a structural unit of an amino group.

3. The polyamide resin composition according to claim 1, wherein The component (A) has a terminal carboxyl group and a terminal amino group, The difference (CA) between the concentration C (mmol / kg) of the terminal carboxyl groups in the component (A) and the concentration A (mmol / kg) of the terminal amino groups in the component (A) is within a range of 30 mmol / kg to 130 mmol / kg.

4. The polyamide resin composition according to claim 3, wherein When B is the mass part after excluding the siloxane component from the mass part of the component (B), B and the concentration C satisfy the relationship of C×B=50-300.

5. The polyamide resin composition according to claim 1, wherein The component (B) is a graft copolymer. The polyamide resin composition according to claim 1, wherein The number average dispersion diameter is 2 μm or less.

7. The polyamide resin composition according to claim 1, wherein The ratio of the silicone component in the component (B) is 50% to 90%.

8. A molded article, wherein The molded article is a molded article of the polyamide resin composition according to any one of claims 1 to 7.

9. A sliding member, wherein: The sliding member comprises the polyamide resin composition according to any one of claims 1 to 7.

10. The sliding member according to claim 9, wherein The sliding member is used in a liquid lubrication environment. The sliding member according to claim 10 , wherein: The material of the contact object of the sliding member is a material other than thermoplastic resin.

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