CN114302916B - Polyamide resin composition for sliding member and sliding member - Google Patents
Polyamide resin composition for sliding member and sliding member Download PDFInfo
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- CN114302916B CN114302916B CN202080059795.7A CN202080059795A CN114302916B CN 114302916 B CN114302916 B CN 114302916B CN 202080059795 A CN202080059795 A CN 202080059795A CN 114302916 B CN114302916 B CN 114302916B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
The present invention aims to provide a polyamide resin composition which is suitable for molding a sliding member required to have excellent moldability and heat resistance stability, and also excellent sliding characteristics, particularly abrasion resistance and sliding stability across particles having high hardness (hereinafter also referred to as "dust"). The polyamide resin composition for sliding parts of the present invention comprises: crystalline polyamide resin (A); a modified polyolefin resin (B) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A); a thermoplastic elastomer (C) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A); an antioxidant (D); and a release agent (E) in which the modified polyolefin resin (B) and the thermoplastic elastomer (C) are dispersed in a matrix of the polyamide resin (A) in a region having a particle diameter of 5 μm or less.
Description
Technical Field
The present invention relates to a polyamide resin composition, and more particularly, to a polyamide resin composition suitable for molding sliding parts.
Background
Polyamide resins are crystalline and have excellent sliding properties, but in order to obtain more excellent sliding properties, solid lubricants such as molybdenum disulfide, graphite and fluororesin, liquid lubricants such as various lubricating oils and silicone oils, and the like are known.
Among these slip improvers, the solid lubricant needs to be mixed in a large amount, and has a disadvantage that toughness of the polyamide resin as a base material is significantly lowered. Although the liquid lubricant can impart high-efficiency sliding properties in a relatively small amount, in many cases, compatibility with a resin as a base material is poor, and the surface of a molded article is easily contaminated with the liquid lubricant, which has a drawback that the use thereof is limited.
As a method for improving the disadvantages caused by the mixing of the above-described various lubricants, a method of mixing a modified vinyl polymer and a modified high-density polyethylene having a molecular weight in a specific range has been proposed (patent document 1); a method of mixing a modified polyolefin resin with a crystalline polyamide resin having a high viscosity (patent document 2).
According to the polyamide resin composition, a molded article having excellent sliding properties and free from the above-mentioned drawbacks can be provided. However, in recent years, due to the trend of weight reduction of molded articles, complexity of the molded article shape, and the like, higher level characteristics such as improvement of moldability, improvement of heat resistance stability, improvement of sliding characteristics, and the like have been demanded.
Prior art literature
Patent literature
Japanese patent application laid-open No. 8-157714
Patent document 2, WO2008/075699
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a polyamide resin composition which is suitable for molding a sliding member required to have excellent moldability and heat resistance stability, and also required to have excellent sliding characteristics, particularly abrasion resistance and sliding stability across particles having high hardness (hereinafter also referred to as dust (durt)).
Technical proposal for solving the problems
The present inventors have made intensive studies to achieve the above-mentioned problems, and as a result, have found that an antioxidant and a release agent added to improve moldability and heat resistance can improve sliding properties, and have completed the present invention.
That is, the present invention has the following configuration.
[1]
A polyamide resin composition for sliding parts, comprising: crystalline polyamide resin (A); a modified polyolefin resin (B) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A); a thermoplastic elastomer (C) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A); an antioxidant (D); and a release agent (E) in which the modified polyolefin resin (B) and the thermoplastic elastomer (C) are dispersed in a matrix of the polyamide resin (A) in a region having a particle diameter of 5 μm or less.
[2]
The polyamide resin composition for sliding parts according to [1], wherein the antioxidant (D) and the release agent (E) are compounds which inhibit deactivation of the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C). [3]
The polyamide resin composition for sliding parts according to [1] or [2], wherein the reactive functional group is an acid anhydride.
[4]
The polyamide resin composition for sliding parts according to any one of [1] to [3], wherein the antioxidant (D) is a hindered phenol antioxidant.
[5]
The polyamide resin composition for sliding parts according to any one of [1] to [4], wherein the release agent (E) is a higher fatty acid ester compound.
[6]
The polyamide resin composition for sliding parts according to any one of [1] to [5], wherein the thermoplastic elastomer (C) is a styrene-based and/or olefin-based thermoplastic elastomer.
[7]
A sliding member obtained from the polyamide resin composition for sliding members described in any one of [1] to [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The polyamide resin composition of the present invention is not only excellent in moldability and heat resistance stability, but also has improved abrasion resistance and further improved sliding properties with less variation in coefficient of friction.
Drawings
Fig. 1 is an image obtained by observing a cross section of the evaluation sample prepared in example 1 with a differential interference microscope.
Fig. 2 is an image obtained by observing a cross section of the evaluation sample prepared in comparative example 6 with a differential interference microscope.
Detailed Description
The present invention will be specifically described below. The polyamide resin composition for sliding parts of the present invention comprises: crystalline polyamide resin (A); a modified polyolefin resin (B) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (a) (hereinafter, also referred to as a modified polyolefin resin (B)); a thermoplastic elastomer (C) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A) (hereinafter, also referred to as a thermoplastic elastomer (C)); an antioxidant (D); a release agent (E).
The mixing amount of each component is represented by mass parts, where 100 mass parts are the total amount of the total resin components of the crystalline polyamide resin (a), the modified polyolefin resin (B), and the thermoplastic elastomer (C). The amount to be blended in the polyamide resin composition of the present invention may be directly set to the content in the polyamide resin composition.
The crystalline polyamide resin (a) is not particularly limited as long as it is a crystalline polymer having an amide bond (-NHCO-) in the main chain, and examples thereof include polyamide 6 (NY 6), polyamide 66 (NY 66), polyamide 46 (NY 46), polyamide 11 (NY 11), polyamide 12 (NY 12), polyamide 610 (NY 610), polyamide 612 (NY 612), poly (m-xylylenediamine adipamide) (MXD 6), hexamethylenediamine-terephthalic acid polymer (6T), hexamethylenediamine-terephthalic acid and adipic acid polymer (66T), hexamethylenediamine-terephthalic acid-epsilon-caprolactam copolymer (6T/6), trimethylhexamethylenediamine-terephthalic acid polymer (TMD-T), m-xylylenediamine and adipic acid-isophthalic acid copolymer (MXD-6/I), trimethylhexamethylenediamine and terephthalic acid-epsilon-caprolactam copolymer (TMD-T/6), diaminodicyclohexylmethane (CA), and isophthalic acid-laurolactam copolymer, and the like. The number of these may be 1 or 2 or more. Among them, polyamide 6 (NY 6) and polyamide 66 (NY 66) are preferably used.
The relative viscosity of the crystalline polyamide resin (A) is not particularly limited, but is preferably 2.0 to 5.0, more preferably 2.0 to 3.5, as measured in 96% sulfuric acid solution (polyamide resin concentration 1g/dl, temperature 25 ℃).
The modified polyolefin resin (B) is a resin obtained by modifying a polyolefin resin. Examples of the polyolefin resin include high-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, linear low-density polyethylene, polypropylene, poly (1-butene), and poly (4-methylpentene). The number of these may be 1 or 2 or more. Among them, high-density polyethylene is preferably used.
In order to improve the compatibility with the crystalline polyamide resin (a), the modified polyolefin resin (B) has a reactive functional group capable of reacting with the terminal group (amino group or carboxyl group) and/or the main chain amide group of the polyamide resin (a). Examples of the reactive functional group include a carboxyl group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group. Among them, an acid anhydride group is preferable from the viewpoint of high reactivity with the polyamide resin (a).
The content of the reactive functional group in the modified polyolefin resin (B) is preferably 0.05 to 8 mass%, more preferably 0.1 to 5 mass%. The method for producing the modified polyolefin resin (B) having the reactive functional group is not particularly limited, and examples thereof include a method in which a compound having the reactive functional group is reacted in a step of producing a polyolefin resin; and a method in which pellets of the polyolefin resin are mixed with a compound having the above reactive functional group, etc., and reacted by kneading with an extruder, etc.
The blending amount of the modified polyolefin resin (B) is not particularly limited as long as the modified polyolefin resin (B) can be dispersed in a region having a particle diameter of 5 μm or less in the matrix of the polyamide resin (A), and is usually 0.5 to 10% by mass, preferably 1 to 8% by mass, and more preferably 2 to 6% by mass relative to 100% by mass of the total resin component.
The thermoplastic elastomer (C) is not particularly limited, and examples thereof include styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer. The number of these may be 1 or 2 or more.
The styrene-based thermoplastic elastomer is not particularly limited, and examples thereof include styrene/butadiene/styrene block copolymer (SBS), styrene/ethylene-butylene/styrene block copolymer (SEBS) as its hydride, styrene/butadiene copolymer (SBR), styrene/ethylene/butylene copolymer (HSBR) as its hydride, styrene/isoprene/styrene block copolymer (SIS), and styrene/ethylene-propylene/styrene block copolymer (SEPS) as its hydride.
The olefinic thermoplastic elastomer is not particularly limited, and examples thereof include rubbers such as ethylene/propylene/diene rubber (EPDM), ethylene/propylene rubber (EPR), and butyl rubber (IIR), dynamically crosslinked olefinic thermoplastic elastomers, and ethylene copolymers having flexibility.
The polyamide-based thermoplastic elastomer is not particularly limited, and examples thereof include polyether ester amides and polyester amides in which polyamide having a high crystalline melting temperature is used as a hard segment and polyether or polyester having a low glass transition temperature is used as a soft segment.
The polyester-based thermoplastic elastomer is not particularly limited, and examples thereof include a block copolymer of a polyether polyester and a polyester, wherein a polyester having a high crystalline melting temperature is used as a hard segment and a polyether or a polyester having a low glass transition temperature is used as a soft segment.
The polyurethane-based thermoplastic elastomer is not particularly limited, and examples thereof include polyether polyurethane and polyester polyurethane in which a polyester having a high crystalline melting temperature is used as a hard segment and a polyether or polyester having a low glass transition temperature is used as a soft segment.
Among these thermoplastic elastomers, from the viewpoint of balance between the toughness improvement effect and the elastic modulus, styrene-based and/or olefin-based thermoplastic elastomers are preferable, styrene-based thermoplastic elastomers are more preferable, and SEBS is further preferable.
In order to improve the compatibility with the crystalline polyamide resin (a), the thermoplastic elastomer (C) has a reactive functional group capable of reacting with the terminal group (amino group or carboxyl group) and/or the main chain amide group of the polyamide resin (a). Examples of the reactive functional group include a carboxyl group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group. Among them, an acid anhydride group is preferable from the viewpoint of high reactivity with the polyamide resin (a).
The content of the reactive functional group in the thermoplastic elastomer (C) is preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass. The method for producing the thermoplastic elastomer (C) having the reactive functional group is not particularly limited, and examples thereof include a method in which a compound having the reactive functional group is reacted in a step of producing the thermoplastic elastomer; and a method in which pellets of a thermoplastic elastomer and a compound having the above reactive functional group are mixed and reacted by kneading with an extruder or the like.
The mixing amount of the thermoplastic elastomer (C) is not particularly limited as long as the thermoplastic elastomer (C) can be dispersed in the matrix of the polyamide resin (A) in a region having a particle diameter of 5 μm or less, and is usually 0.1 to 10% by mass, preferably 1 to 7% by mass, relative to 100% by mass of the total resin component.
The antioxidant (D) is preferably a compound that inhibits deactivation of the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C). By "inhibiting deactivation of reactive functional groups" is meant "not reacting with reactive functional groups". That is, the antioxidant (D) is a compound which does not inhibit fine dispersion of the modified polyolefin resin (B) and the thermoplastic elastomer (C) in the matrix of the polyamide resin (A).
The antioxidant (D) is not particularly limited, and examples thereof include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants and phosphorus antioxidants, and heat stabilizers, and the like, and preferably hindered phenol antioxidants, when the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C) are acid anhydride groups, and do not have functional groups reactive with acid anhydride groups. The number of these may be 1 or 2 or more. Examples of the functional group that reacts with an acid anhydride group include an amino group and a hydroxyl group. The phenolic hydroxyl group of the hindered phenol structure is not a functional group that reacts with an acid anhydride group. Amine antioxidants are not preferable because they react with the reactive functional groups to deactivate them.
The mixing amount of the antioxidant (D) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, relative to 100 parts by mass of the total resin component. The mixing amount of the antioxidant (D) is within the above range, and not only contributes to improvement of the sliding property and toughness of the polyamide resin composition, but also can be formulated in an amount corresponding to the amount of the polyamide resin composition to prevent oxidative deterioration with time.
The release agent (E) is preferably a compound that suppresses deactivation of the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C). By "inhibiting deactivation of reactive functional groups" is meant "not reacting with reactive functional groups". That is, the release agent (E) is a compound which does not inhibit fine dispersion of the modified polyolefin resin (B) and the thermoplastic elastomer (C) in the matrix of the polyamide resin (A).
The release agent (E) is not particularly limited, and examples thereof include higher fatty acid ester compounds, amide compounds, polyethylene waxes, silicones, polyethylene oxides, and the like. The number of these may be 1 or 2 or more. When the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C) are acid anhydride groups, the release agent (E) is preferably a higher fatty acid ester compound. The higher fatty acid is a fatty acid having more than 10 carbon atoms, preferably a fatty acid having 11 to 30 carbon atoms. The metal salt compound is not preferable because it reacts with the reactive functional group to deactivate the same.
The mixing amount of the release agent (E) is preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.8 part by mass, relative to 100 parts by mass of the total resin component. The amount of the release agent (E) to be mixed is within the above range, and thus not only can the slidability and toughness of the polyamide resin composition be improved, but also an appropriate releasability can be ensured.
The antioxidant (D) and the release agent (E) do not inhibit fine dispersion of the modified polyolefin resin (B) and the thermoplastic elastomer (C) in the matrix of the polyamide resin (A). Accordingly, the modified polyolefin resin (B) and the thermoplastic elastomer (C) effectively react with the polyamide resin (A), and finely disperse in the matrix of the polyamide resin (A) in the region of a particle diameter of 5 μm or less. As a result, it is considered that the effect of improving the sliding property by the modified polyolefin resin (B) and the effect of improving the toughness by the thermoplastic elastomer (C) effectively act, and the characteristic effect of the present invention is exhibited. The particle diameter is preferably 4 μm or less, more preferably 3.5 μm or less. The lower limit of the particle diameter is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of fluidity.
The polyamide resin composition of the present invention may contain, in addition to the components (a) to (E), additives such as carbon black or copper oxide, alkali metal halides, light stabilizers or heat stabilizers, crystal nucleus agents, lubricants, antistatic agents, pigments, dyes, coupling agents, and the like, which are conventionally mixed in polyamide resin compositions, as weather resistance improvers, as long as the modified polyolefin resin (B) and the thermoplastic elastomer (C) are not inhibited from finely dispersing in the matrix of the polyamide resin (a). Further, by mixing the filler, the strength and rigidity of the molded article can be greatly improved. Examples of the filler include glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. The total of the components (a) to (E) in the polyamide resin composition of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
The polyamide resin composition of the present invention is produced, for example, by kneading the components using a single screw extruder, a twin screw extruder, or a pressure kneader. The kneading apparatus is preferably a twin-screw extruder. In one embodiment, the above components (a) to (E) and pigments and the like added according to the use are mixed and added to a twin-screw extruder. The polyamide resin composition excellent in slidability can be produced by uniformly kneading using a twin-screw extruder. The kneading temperature of the twin-screw extruder is preferably 220 to 300℃and the kneading time is preferably about 2 to 15 minutes.
The polyamide resin composition of the present invention can be widely used as a raw material for sliding parts such as electric/electronic parts, automobile parts, building members, industrial parts, and the like, which require slidability. The sliding member may be a bearing, a gear, a door system, or a chain guide.
Examples (example)
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the polyamide resin molded articles obtained in the examples below were measured by the following test methods.
The raw materials used in the examples and comparative examples are as follows.
As the crystalline polyamide resin (a), the resins (A1) to (A3) are used.
(A1) Polyamide 66 (rv=3.4): EPR34W (manufactured by Shanghai Trojan plastics science, inc.), melting point 265 DEG C
(A2) Polyamide 66 (rv=2.8): vydyne 21FSR (manufactured by Assetnd Co., ltd.) melting point 265 DEG C
(A3) Polyamide 66 (rv=2.4): EPR24 (manufactured by Shanghai Mars plastics technology Co., ltd.) with melting point 265 DEG C
As the modified polyolefin resin (B), the modified polyolefin resins (B1) and (B2) were used.
(B1) Maleic anhydride modified polyethylene: modic DH0200 (Mitsubishi chemical Co., ltd.)
(B2) Unmodified polyethylene: HI-ZEX 6203B (Pu Rui Man Polymer Co., ltd.)
As the thermoplastic elastomer (C), the thermoplastic elastomers (C1) and (C2) are used.
(C1) Maleic anhydride modified SEBS: tuftec M-1943 (manufactured by Asahi Kasei Co., ltd.)
(C2) Unmodified SEBS: tuftec H-1221 (manufactured by Asahi Kasei Co., ltd.)
As the antioxidant (D), the antioxidants (D1) and (D2) were used.
(D1) Hindered phenol-based antioxidants: triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (SONGWON, inc. SONGNOX 2450)
(D2) Amine-based antioxidants: nonflex DCD (manufactured by Seiko chemical Co., ltd.)
As the release agent (E), the release agents (E1) to (E3) were used.
(E1) Aliphatic esters: licolub WE-40 (Clariant Japan Co., ltd.)
(E2) Magnesium stearate: N.P.1500-S (manufactured by Milkinson chemical Co., ltd.)
(E3) Calcium montanate: licom Cav102 (Clariant Japan Co., ltd.)
Examples 1 to 7 and comparative examples 1 to 8
The evaluation samples were produced by weighing the respective raw materials in accordance with the mixing ratio of the polyamide-based resin compositions shown in tables 1 and 2, mixing the raw materials with a drum (screw), and feeding the mixture into a twin-screw extruder. The set temperature of the twin-screw extruder is 250-300 ℃, and the mixing time is 5-10 minutes. The obtained pellets were molded into various evaluation samples by an injection molding machine. The temperature of the charging barrel of the extrusion molding machine is 250-290 ℃ and the temperature of the die is 80 ℃.
Various evaluation methods are described below. The evaluation and measurement results are shown in tables 1 and 2.
1. Relative viscosity of Polyamide resin (96% sulfuric acid solution method)
The measurement was performed at a polyamide resin concentration of 1g/dl in a 96 mass% sulfuric acid solution at 25℃using an Ubbelohde viscosity tube.
2. Melting Point of Polyamide resin
The endothermic peak temperature was obtained by measuring with a differential scanning calorimeter (SEIKO INSTRUMENTS Co., ltd., EXSTAR 6000) at a heating rate of 20℃per minute
3. Tensile strength, tensile elastic modulus, and tensile elongation
Measured on the basis of ISO 178.
4. Impact resistance
Measured on the basis of ISO 179-1.
5. Slidability of the slide
The weight ratio of grease, silica sand, and pozzolan, which were uniformly coated with a molybdenum disulfide formulation on the surface in a certain amount, was 1:1:1, contacting a polyamide resin plate with a cylindrical shaped article made of Polyoxymethylene (POM) and under a load of 30kgf/cm 2 And sliding continuously at a speed of 40mm/sec for 30 minutes. Thereafter, the dynamic friction coefficient was calculated from the difference in weight before and after abrasion and the convergence load value at the time of abrasion test.
6. Particle size
The formed evaluation samples were cut and cross sections were prepared using a microtome equipped with a glass knife. The prepared sections were observed with a differential interference microscope to take photographs. In the photomicrographs, 10 regions having the largest dispersion diameter were arbitrarily selected from the regions of the modified polyolefin resin (B) and the thermoplastic elastomer (C), and the long diameters of the selected regions were measured and the average value thereof was used as the particle diameter.
TABLE 1
TABLE 2
The Charpy impact strength of each of examples 1 to 7 was 6kJ/m 2 As described above, a composition having higher toughness than the unmodified polyamide was obtained. In addition, there is no great loss in tensile modulus of elasticity and tensile elongation. The abrasion resistance and dynamic friction coefficient after the sliding test with dust were also good as compared with those of comparative examples 1 to 8. In comparative examples 1 and 2, the toughness was insufficient to suppress the breakage of the brittle surface during sliding, and the amount of wear was increased. In comparative example 3, although toughness was sufficient, it was difficult to exert the sliding modifying effect of the polyolefin resin. In comparative example 4, since an unmodified thermoplastic elastomer was mixed, it was difficult to form a finely dispersed region, and particle diameters which hardly exhibited excellent physical properties were not preferable. In comparative examples 5, 6 and 7, amine antioxidants and fatty acid metal salts were used, respectively, and the amine antioxidants and fatty acid metal salts reacted with reactive functional groups of the modified polyolefin resin or the thermoplastic elastomer to deactivate the reactive functional groups, so that finely dispersed domains could not be formed. In comparative example 8, since the unmodified polyolefin resin was mixed, it was difficult to form finely dispersed regions, the sliding modifying effect was not exhibited on the surface, and the abrasion amount became large.
Fig. 1 is an image obtained by observing a cross section of example 1 using a differential interference microscope. It is known that the polyolefin resin and the thermoplastic elastomer are finely dispersed uniformly in the matrix of the polyamide resin in the region having a particle diameter of 5 μm or less. On the other hand, fig. 2 is an image obtained by observing a cross section of comparative example 6 using a differential interference microscope. The 2 modifiers are unevenly dispersed in the matrix of the polyamide resin, and cannot form finely dispersed domains. In addition, since the region exists as a coarse region, stress is concentrated during wear, and this may become a starting point for wear.
Industrial applicability
The polyamide resin composition of the present invention is a molding material having both excellent toughness and sliding properties. In particular, the present invention is applicable to sliding members having excellent wear resistance and sliding stability, which are required to have particles having high hardness, and is expected to contribute significantly to the industry as engineering plastics that can be used in a wide range of fields.
Claims (7)
1. A polyamide resin composition for sliding parts, comprising:
crystalline polyamide resin (A);
a modified polyolefin resin (B) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (a);
a thermoplastic elastomer (C) having a reactive functional group capable of reacting with a terminal group and/or a main chain amide group of the polyamide resin (A);
an antioxidant (D); and
a release agent (E),
the modified polyolefin resin (B) and the thermoplastic elastomer (C) are dispersed in a matrix of the polyamide resin (A) in a region having a particle diameter of 5 μm or less.
2. The polyamide resin composition for sliding parts according to claim 1, wherein the antioxidant (D) and the release agent (E) are compounds that inhibit deactivation of the reactive functional groups of the modified polyolefin resin (B) and the thermoplastic elastomer (C).
3. The polyamide resin composition for sliding parts according to claim 1, wherein the reactive functional group is an acid anhydride.
4. The polyamide resin composition for sliding parts according to claim 1, wherein the antioxidant (D) is a hindered phenol-based antioxidant.
5. The polyamide resin composition for sliding parts according to claim 1, wherein the release agent (E) is a higher fatty acid ester compound.
6. The polyamide resin composition for sliding parts according to any one of claims 1 to 5, wherein the thermoplastic elastomer (C) is a styrene-based and/or olefin-based thermoplastic elastomer.
7. A sliding part obtained from the polyamide resin composition for sliding parts according to any one of claims 1 to 6.
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|---|---|---|---|
| JP2019177690 | 2019-09-27 | ||
| JP2019-177690 | 2019-09-27 | ||
| PCT/JP2020/034549 WO2021060030A1 (en) | 2019-09-27 | 2020-09-11 | Polyamide resin composition for sliding components, and sliding component |
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| CN114302916A CN114302916A (en) | 2022-04-08 |
| CN114302916B true CN114302916B (en) | 2023-07-14 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6872155B1 (en) | 2021-05-19 |
| WO2021060030A1 (en) | 2021-04-01 |
| CN114302916A (en) | 2022-04-08 |
| TW202118830A (en) | 2021-05-16 |
| JPWO2021060030A1 (en) | 2021-10-07 |
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