JP2003253116A - Crystalline polyamide sliding parts - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystalline polyamide sliding part which is excellent in strength and rigidity, has low friction and abrasion, and also is excellent in anti-fatigue properties as sliding parts. <P>SOLUTION: The sliding parts comprise a polyamide resin and a metal salt and/or a higher alcohol ester of a higher fatty acid, in which &eta;r is 3.5-6.0, and the maximum diameter of a<SB>0</SB>of a spherical crystal in 100 &mu;m surface layer of the said parts and the maximum diameter b<SB>0</SB>in a core of the said parts are a<SB>0</SB>&le;10 and 1&le;b<SB>0</SB>/a<SB>0</SB>&le;10. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sliding part made of crystalline polyamide which is excellent in strength and rigidity, has low friction and wear resistance, and is excellent in fatigue characteristics.

[0002]

2. Description of the Related Art Crystalline polyamide resins are used in various mechanical industrial parts and electric / electronic parts because of their excellent strength, rigidity, toughness and heat resistance. In particular, the replacement of metal materials has been greatly promoted because the effect of reducing the weight by making the parts resin is great. In recent years, from the viewpoint of energy problems, it has been desired to extend the life of crystalline polyamide sliding parts using these crystalline polyamide resins. For example, gears, shoes, guide rails, etc., which are one of the slidable parts, are being made of resin in order to reduce the weight of the parts, but good slidability, that is, low friction There is a need for a material that has low wear and good fatigue properties.

In the prior art, in order to develop low friction and low abrasion, polyamide resin is blended with an inorganic filler such as glass fiber. For example, Japanese Patent Fair 6-6
In 0674, nylon 66, nylon 6 or the like is used as a resin, and a material reinforced by filling glass fiber or carbon fiber in order to improve strength and rigidity is injection-molded to cut the tooth portion of the gear. A resin gear formed by processing is disclosed. However, there has been a problem that the specific gravity increases and the advantage of weight reduction due to the use of resin is weak.

Further, there is a problem that the wear of the cutting tool is remarkable because it is reinforced with the filler. Further, since the reworkability is poor, the above method is not always a preferable means from the viewpoint of recycling. On the other hand, it has been attempted to add various organic slidability improvers such as silicone resin and olefin resin to polyamide resin to achieve low friction and low wear resistance. In some cases, the resin was not well-sewn with each other and mechanical properties, especially tensile strength and elongation properties, were deteriorated, and it caused cracks in parts under high load atmosphere, resulting in a short life as parts. .

Japanese Patent Laid-Open No. 61-174259 discloses a method for producing a polyamide resin molded article having excellent abrasion resistance, which is obtained by sprinkling calcium stearate on the surface of the polyamide resin pellets and then molding. However, in gears where dimensional accuracy of parts is required, the molded product may be cut to adjust the accuracy, and in this method, if the surface of the molded product is cut, the effect of improving wear resistance becomes weak. There was a point.

Further, Japanese Patent Application Laid-Open No. 11-270655 discloses a synthetic resin gear having wear resistance and good fatigue characteristics by making the crystalline morphology of a crystalline polymer molded product uniform. However, molding a gear having a uniform crystal structure requires a special device and has a problem of lacking versatility. Further, with respect to sliding characteristics and fatigue characteristics, the effect is not sufficient for a gear to which a high load is applied. From the above problems, low specific gravity, excellent mechanical properties,
There has been a demand for a long-life crystalline polyamide sliding component that exhibits good slidability and good fatigue properties at the same time.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, a crystalline polyamide slide having excellent strength and rigidity, low friction, low wear and excellent fatigue characteristics. It is to provide moving parts.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a crystalline polyamide resin and a metal salt of a higher fatty acid and / or an ester compound of a higher fatty acid and a higher alcohol are used. The inventors have found that a crystalline polyamide sliding component having a controlled crystal morphology can solve the above problems, and have completed the present invention. That is, the present invention is: Made of crystalline polyamide in which at least one selected from the group consisting of metal salts of higher fatty acids and ester compounds of higher fatty acids and higher alcohols is contained in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the crystalline polyamide resin. A sliding part having a 98% sulfuric acid relative viscosity (1 g / 100 ml) ηr of 3.5 or more and 6.0 or less in the slidable part, and having a maximum spherulite at a depth of 100 μm from the surface layer of the part. When the particle size is a ₀ μm and the maximum particle size of spherulites in the core part of the component is b ₀ μm, a ₀ ≦ 10 and 1 ≦ b
₀ / a ₀ ≦ 10, a sliding part made of crystalline polyamide,

2. The crystalline polyamide resin is polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), polyhexamethylene isophthalamide (nylon 6I), and at least two of them 2. A crystalline polyamide sliding component as described in 1 above, which is a polyamide copolymer containing different polyamide forming components and a mixture thereof.

The present invention will be described in detail below. The present invention relates to a sliding part made of crystalline polyamide, which has excellent strength and rigidity, low friction, low wear resistance, and excellent fatigue characteristics. The crystalline polyamide used in the present invention,
It refers to a polyamide having a heat of fusion of crystals of 4 J / g or more when measured by a differential scanning calorimeter at 10 degrees / min, and is not particularly limited as long as it is a known crystalline polyamide. For example, polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612) ), Polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon 11), polydodecaractam (nylon 12),
Polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I), polynonane methylene terephthalamide (9T), polyhexamethylene terephthalamide (6
T).

Further, polybis (4-aminocyclohexyl) methandodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methandodecamide (nylon dimethyl PACM12), polymethaxylylene adipamide (nylon MXD6), poly Undecamethylene hexahydroterephthalamide (nylon 1
1T (H)), and a polyamide copolymer containing at least two different polyamide forming components,
And mixtures thereof. Among these crystalline polyamides, preferred crystalline polyamides from the viewpoint of manufacturing cost are polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), polyhexamethylene. Mention may be made of isophthalamide (nylon 6I), polyamide copolymers containing at least two different polyamide forming components, and mixtures thereof.

The raw material of the crystalline polyamide is not particularly limited, and known amino acids, lactams,
And salts of diamine and dicarboxylic acid and oligomers thereof. An end-capping agent may be added to the above-mentioned polyamide raw material in order to control the molecular weight and improve hot water resistance. The endcapping agent is preferably monocarboxylic acid or monoamine. Other examples include acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters and monoalcohols.

The monocarboxylic acid that can be used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and capryl. Acids, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, aliphatic monocarboxylic acids such as isobutyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α- Examples thereof include naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acids such as phenylacetic acid, and the like. In the present invention, one type of these monocarboxylic acids may be used, or two or more types may be used in combination.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine and hexylamine.
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine, cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine Can be mentioned. In the present invention, one type of these monoamines may be used, or two or more types may be used in combination.

The method for producing the crystalline polyamide is not particularly limited, and a general melt polymerization method can be used, for example, a batch polymerization method or a continuous polymerization method. it can. The higher fatty acid metal salt used in the present invention is not particularly limited,
In order to show excellent sliding characteristics, it is preferable that the carbon number is 1
It is a metal salt of a carboxylic acid of 0 to 30. Specific examples thereof include palmitic acid, stearic acid, montanic acid, and other lithium salts, sodium salts, calcium salts, aluminum salts, and the like. In the present invention, these metal salts of higher fatty acids may be used alone or in combination of two or more.

The ester compound of higher fatty acid and higher alcohol used in the present invention is not particularly limited, but preferably 10 carbon atoms in order to exhibit excellent sliding properties.
To 30 metal salts of carboxylic acids and 10 to 3 carbon atoms
It is an ester compound of a higher alcohol which is 0. Specific examples include stearyl stearate, which is an ester compound of stearic acid and stearyl alcohol, and behenyl behenate, which is an ester compound of behenic acid and behenyl alcohol. In the present invention, these ester compounds of higher fatty acids and higher alcohols may be used alone or in combination of two or more.

In the crystalline polyamide sliding component of the present invention, the metal salt of the higher fatty acid and the ester compound of the higher fatty acid and the higher alcohol may be used alone or in combination. The crystalline polyamide sliding part of the present invention means crystalline polyamide resin 1
A sliding part made of crystalline polyamide, which comprises 0.01 to 5 parts by mass of a metal salt of a higher fatty acid and / or an ester compound of a higher fatty acid and a higher alcohol with respect to 00 parts by mass. In 98% sulfuric acid relative viscosity (1 g / 100 ml) ηr is 3.5 or more and 6.0 or less, and the maximum grain size of spherulites at a depth of 100 μm from the surface layer of the component is a ₀ μm, and the core of the component is When the maximum grain size of spherulites in the part is b ₀ μm, a ₀ ≦ 10 and 1 ≦ b
It is a crystalline polyamide sliding part characterized in that ₀ / a ₀ ≦ 10.

The crystalline polyamide sliding component of the present invention refers to a component having a portion where resin and resin or resin and metal are in contact with each other and rub against each other.
Gears, shoes, guide rails, cams, etc. can be mentioned. The molding method for obtaining the crystalline polyamide sliding part of the present invention is a known molding method, for example, press molding,
Generally-known plastic molding methods such as injection molding, gas-assisted injection molding, fusion molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, foam molding, and melt spinning can be used.

Further, it is also possible to form a part such as a gear by cutting after it is obtained by molding, and for example, a cylindrical molded product is cut into a desired thickness if necessary, and further the outer periphery is cut. There may be mentioned a method in which the tooth having a concave shape is intermittently formed along the outer circumference by a method such as cutting the resin of (1). In the sliding part made of crystalline polyamide of the present invention, the compounding ratio of the metal salt of higher fatty acid and / or the ester compound of higher fatty acid and higher alcohol exhibits excellent slidability, and when reworking the part, From the viewpoint of decreasing the viscosity, it is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the crystalline polyamide resin.
Parts by mass.

Further, it is preferable that the metal salt of higher fatty acid and / or the ester compound of higher fatty acid and higher alcohol is uniformly dispersed in the crystalline polyamide resin. With such uniform dispersion, the crystals in the resin composition are finer and more easily dispersed, tending to exhibit excellent mechanical properties, slidability, and good fatigue strength. Actually, the surface layer (skin portion) and the deep layer portion (core portion) of the molded product are cut out and metal salts of higher fatty acids and / or ester compounds of higher fatty acids and higher alcohols are extracted to compare the component amounts. You can see the uniformity.

The 98% sulfuric acid relative viscosity (1 g / 100 ml) ηr of the crystalline polyamide sliding part of the present invention is 3.5 or more and 6.0 or less, but preferably from the viewpoint of fatigue characteristics and fluidity. It is 8 or more and 5.5 or less, and most preferably 4.2 or more and 5.2 or less. In the crystalline polyamide sliding part of the present invention, 10 parts from the surface layer
When the maximum grain size of spherulites at a depth of ₀ μm is a ₀ μm and the maximum grain size of spherulites in the core of the component is b ₀ μm,
a ₀ ≦ 10 and 1 ≦ b ₀ / a ₀ ≦ 10. here,
From the viewpoint of superior strength and rigidity and excellent sliding characteristics, a ₀ ≦ 5 and 1 ≦ b ₀ / a ₀ ≦ 8 are preferable, and a ₀ ≦ 3 and 1 ≦ b ₀ / a are more preferable. ₀ ≤
5, most preferably a ₀ ≤1 and 1 ≤b ₀ / a ₀ ≤3.

Here, confirmation of a ₀ and b ₀ was carried out by cutting out from the surface layer portion (skin portion) of the molded product at a portion of 100 μm and the deepest innermost layer portion (core portion) in the molded product, and measuring the thickness with a microtome. A ₀ and b ₀ can be obtained by making a 30 μm section and observing it with a polarizing microscope using a magnification of 40 to 500 times and measuring the size of at least 100 spherulites. As a preferred method for producing a crystalline polyamide resin composition for obtaining the crystalline polyamide sliding part of the present invention, for example, 100 parts by mass of a crystalline polyamide resin powder having an average particle diameter of 3 μm obtained by freeze pulverization and a higher fatty acid are used. A method in which 0.01 to 5 parts by mass of an ester compound of a metal salt and / or a higher fatty acid and a higher alcohol are blended in a Henschel mixer and then melt-kneaded using a twin-screw extruder or the like, or further solid-phase polymerization is performed. And a method for obtaining a resin composition having a high viscosity can be given.

In addition, a method of previously preparing a masterbatch containing a high concentration of a metal salt of a higher fatty acid and / or an ester compound of a higher fatty acid and a higher alcohol, and melt-kneading the obtained masterbatch and the crystalline polyamide resin again I can give you. The crystalline polyamide sliding part of the present invention, if necessary, within the range not impairing the object of the present invention, thermal deterioration, prevention of discoloration at the time of heat, heat aging resistance, deterioration suppression for the purpose of improving weather resistance There is no problem even if an agent is added. The deterioration inhibitor is a copper stabilizer such as copper acetate or copper iodide or a phenol stabilizer such as an organic hindered phenol compound, a phosphite stabilizer, a hindered amine stabilizer, a triazine stabilizer, and sulfur. A system stabilizer etc. can be mentioned.

A coloring agent may be added to the crystalline polyamide sliding part of the present invention. The colorant is
Dyes such as nigrosine, pigments such as titanium oxide or carbon black, or aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide,
It is at least one colorant selected from metal particles such as stainless steel and titanium, pearl pigments made of mica, color graphite, color glass fibers, metallic pigments such as color glass flakes, and the like.

Conductive carbon black may be added to the crystalline polyamide sliding part of the present invention. The conductive carbon black is at least one carbon black selected from acetylene black, Ketjen black, carbon nanotubes, etc.,
Among them, those having a good chain structure and a large aggregation density are preferable. A flame retardant may be added to the sliding parts made of crystalline polyamide of the present invention. The flame retardant is preferably a non-halogen flame retardant or a bromine flame retardant.

The non-halogen flame retardant is a phosphorus flame retardant such as red phosphorus, ammonium phosphate, or ammonium polyphosphate, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide. , Basic magnesium carbonate, zirconium hydroxide, tin oxide, zinc stannate, hydrates of inorganic metal compounds such as zinc hydroxystannate, zinc borate, zinc metaborate, barium metaborate, etc. Inorganic compound-based flame retardants such as boric acid compounds, melamine, melam, melem, melon (product of deammonification of 3 to 3 molecules of melem at 300 ° C or higher), melamine cyanurate, melamine phosphate, melamine polyphosphate, sac Sinoguanamine, Adipoguanamine, Methylglutaloganamin Triazine-based flame retardant such as melamine resins, at least one flame retardant selected from silicone-based flame retardants such as silicone resin, silicone oil, silica.

The brominated flame retardant is at least one flame retardant selected from compounds consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer and brominated crosslinked aromatic polymer. . The crystalline polyamide sliding part of the present invention is excellent in strength and rigidity, has low friction, low wear, and is excellent in fatigue characteristics. Is expected to be applied.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The evaluations described in the following examples and comparative examples were carried out by the following methods. (1) Sulfuric Acid Relative Viscosity Measurement In 100 g of 98% concentrated sulfuric acid, 1.00 g of a resin composition cut out from a pellet or a molded product is dissolved,
It was measured at 25 ° C. according to JIS K6810.

(2) Mechanical characteristics Using an injection molding machine (PS40E manufactured by Nissei Plastic Co., Ltd.),
A cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. were set, and dumbbell pieces for evaluation and strips were obtained under the injection molding conditions of injection for 14 seconds and cooling for 15 seconds. (2-1) Flexural modulus (GPa) and flexural strength (MP
a) Performed according to ASTM D790. (23 ° C, 50%
Humidity) (2-2) Tensile Strength (MPa) and Tensile Elongation (%) It was measured according to ASTM D638. (23 ° C, 50%
Humidity) (2-3) Notched Izod impact strength (J / m) It was measured according to ASTM D256. (23 ° C, 50%
Humidity)

(3) Observation of spherulite size Using an injection molding machine (FN3000 manufactured by Nissei Plastic Co., Ltd.), the cylinder temperature was set to 290 ° C. and the mold temperature was set to 80 ° C., injection for 14 seconds and cooling for 15 seconds. A plate (a × b × c = 90 mm × 60 mm × 3 mm) was obtained under the molding conditions.
Here, the ab surface is a surface in contact with the mold. Next, a 30 μm-thick section (a × b ×
c = 30 μm × 10 mm × 3 mm) was cut out to obtain a spherulite size measurement sample. The spherulites were observed with a polarizing microscope using a magnification of 40 to 500, and the surface layer (a
The maximum spherulite size in the part from the (b-side) to 100 μm is a ₀ , and the core layer is 1.0 mm from both surface layers (ab-side)
The maximum spherulite size at the depth of was observed as b ₀ .

(4) Sliding Characteristics (Measurement of Friction Coefficient and Amount of Abrasion) The friction and abrasion test is conducted in the following two ways: (a) a plate after molding and (b) a plate after cutting the surface after molding. Evaluation was performed by type. (4-1) Using a plate injection molding machine (FN3000 manufactured by Nissei Plastic Co., Ltd.) after molding, setting the cylinder temperature to 290 ° C. and the mold temperature to 80 ° C., injection molding conditions of injection 14 seconds and cooling 15 seconds. Then, an evaluation plate (a × b × c = 90 mm × 60 mm × 3 mm) was obtained and tested. Here, the ab surface is the mold surface,
The test was performed on the ab plane.

(4-2) Plate after Surface Cutting The plate after molding was cut with a microtome from the ab surface to a depth of 100 μm, and a test was conducted using the surface after cutting. The friction / wear test was performed under the following conditions using a pin / plate tester AFT-15MS manufactured by Toseki Seimitsu Co., Ltd. Pin SUS314 Reciprocating speed 30mm / s Reciprocating distance 20mm Load 0.20MPa Temperature 25 ° C Humidity 50%

(5) Bending vibration fatigue test Using an injection molding machine (PS40E manufactured by Nissei Plastic Co., Ltd.),
Cylinder temperature 280 ° C, mold temperature 80 ° C, injection type 14 seconds injection, cooling 15 seconds evaluation type type
A bending vibration fatigue test piece was obtained. The test was performed using a constant stress vibration fatigue tester (manufactured by Toyo Seiki Seisakusho) under the following conditions. Test speed 1800 times / min Set stress 30, 40, 50 MPa Temperature 23 ° C Humidity 50%

Production Example 1-1 Production of Polyamide (I) 30 kg of an aqueous solution of 50% by weight of a raw material of polyamide 66 (equimolar salt of hexamethylenediamine and adipic acid).
It was prepared and sufficiently stirred. The aqueous solution of the polyamide 66 raw material was charged into a 70 liter autoclave having a stirrer and a discharge nozzle at the bottom, and sufficiently stirred at a temperature of 50 ° C. After purging with nitrogen, the temperature was raised from 50 ° C. to about 270 ° C. with stirring. At this time, the pressure inside the autoclave is a gauge pressure of about 1.77M.
Although Pa was reached, heating was continued for about 1 hour while removing water outside the system so that the pressure did not exceed 1.77 MPa. After that, it takes about 1 hour, the pressure is reduced to atmospheric pressure, and the mixture is further held at about 270 ° C. and atmospheric pressure for about 1 hour, then stirring is stopped, and the polymer is discharged in a strand form from the lower nozzle,
Water cooling and cutting were performed to obtain pellets. The 98% sulfuric acid relative viscosity (1 g / 100 ml) ηr of this pellet was 3.0.

Production Example 1-2 Production of Polyamide (II) 50 kg of the pellet obtained in Production Example 1 was put into a 150 L solid-state polymerization apparatus, and nitrogen substitution was sufficiently performed. Then, the heater temperature was set to 220 ° C. using a steam line, and solid phase polymerization was performed while flowing nitrogen at 8 L / min. At that time, the internal temperature rose to 200 ° C. After 28 hours, the heating was stopped and the pellets were taken out after cooling. The pellet-shaped resin composition thus obtained had an ηr of 5.1.

Production Example 1-3 Production of Polyamide (III) Calcium stearate (hereinafter referred to as St-Ca)
And stearyl stearate (esterification product of stearic acid and stearyl alcohol) (hereinafter referred to as St-St) were mixed in equal amounts to prepare a mixture of lubricants.
The melting point of this lubricant mixture was 160 ° C. This mixture of lubricants was heated to 180 ° C to create a uniform melt. This melt was added by injection in the continuous polymerization process of nylon 66 (Ny66). First, a 50% aqueous solution of AH salt consisting of adipic acid and hexamethylenediamine is pre-concentrated to 80%, and then 250% in a polymerization tank.
The mixture was heated to 0 ° C. and condensed water was removed under pressure to 17 atm to form a prepolymer. Then, the pressure was reduced to atmospheric pressure and heated to 280 ° C., and further the condensation water was removed to complete polycondensation, and 98% sulfuric acid relative viscosity (1 g / 100 ml) ηr.
= 2.8 nylon 66 polymer was obtained. The water content in the polymer at this stage was 1% or less.

An amount of 0.3 parts by mass of St-Ca and St-St melt, which was heated and melted, was applied to 100 parts by mass of the resin (using a plunger pump) in the discharge line of the molten polymer of nylon 66. St-Ca, St-St, each corresponding to 0.15 parts by mass) are added by injection to add St-Ca, S
A polyamide resin composition containing t-St was prepared.
Next, it was formed into a strand, cut, and then dried to obtain a pellet. The pelletized resin composition thus obtained had ηr of 2.8.

Production Example 1-4 Production of Polyamide (IV) 50 kg of the pellet obtained in Production Example 1-3 was put into a 150 L solid-state polymerization apparatus, and nitrogen substitution was carried out sufficiently. afterwards,
The heater temperature was set to 220 ° C. using a steam line, and solid phase polymerization was carried out while flowing nitrogen at 8 L / min.
At that time, the internal temperature rose to 200 ° C. After 28 hours, the heating was stopped and the pellets were taken out after cooling. The pellet-shaped resin composition thus obtained had an ηr of 5.1.

Production Example 2-1 Production of Masterbatch (I) The polyamide (I) obtained in Production Example 1-1 was freeze-pulverized to give a powder. To 100 parts by mass of this powdery polyamide, 10 parts by mass of calcium montanate (hereinafter referred to as CaV) as a higher fatty acid metal salt was blended with a Henschel mixer, and a twin-screw extruder (TEM3 manufactured by Toshiba Machine Co., Ltd.) was blended.
In 5), the discharge rate is 40 kg / h, the rotation speed is 300 rpm,
A masterbatch (I) was obtained by melt-kneading at a temperature of 280 ° C. The ηr of this masterbatch was 2.7.

Production Example 2-2 Production of Masterbatch (II) Masterbatch (II) was treated in the same manner as in Production Example 2-1 except that the polyamide (II) obtained in Production Example 1-2 was used.
Got The ηr of this masterbatch was 3.7. Production Example 2-3 Production of Masterbatch (III) Polyamide (II) obtained in Production Example 1-2 was freeze-pulverized to give a powder. To 100 parts by mass of this powdery polyamide, 10 parts by mass of aluminum stearate (hereinafter referred to as St-Al) as a higher fatty acid metal salt was blended with a Henschel mixer, and a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) was blended. ), Discharge rate 40 kg / h, rotation speed 300
A masterbatch (III) was obtained by melt-kneading at rpm and a temperature of 280 ° C. The ηr of this masterbatch was 3.7.

Production Example 2-4 Production of Masterbatch (IV) The polyamide (II) obtained in Production Example 1-2 was freeze-pulverized to give a powder. To 100 parts by mass of this powdery polyamide, 5 parts by mass of calcium stearate (hereinafter referred to as St-Ca) as a higher fatty acid metal salt and stearyl stearate (hereinafter referred to as St-St) as an ester compound of a higher fatty acid and a higher alcohol. 5 parts by mass were blended with a Henschel mixer, and melt-kneaded with a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) at a discharge rate of 40 kg / h, a rotation speed of 300 rpm, and a temperature of 280 ° C. to prepare a masterbatch (III). Obtained. The ηr of this masterbatch was 3.8.

[0042]

Example 1 Polyamide (II) 1 obtained in Production Example 1-2
00.5 parts by mass and 0.55 parts by mass of the masterbatch (I) obtained in Production Example 2-1 were blended with a Henschel mixer, and 0.05 part by mass of calcium montanate (CaV) was added to 100 parts by mass of polyamide. Part and This mixed pellet was evaluated as an injection molded product. The evaluation results are shown in Tables 1 and 2.
Shown in.

[0043]

Example 2 The masterbatch (I
Example 1 was repeated except that I) was used. The evaluation results are shown in Tables 1 and 2.

[0044]

Example 3 Polyamide (II) 1 obtained in Production Example 1-2
05 parts by mass and the masterbatch (I
I) blending 5.5 parts by mass with a Henschel mixer,
The amount of calcium montanate (CaV) was 0.5 part by mass with respect to 100 parts by mass of polyamide. This mixed pellet was evaluated as an injection molded product. The evaluation results are shown in Tables 1 and 2.

[0045]

Example 4 The masterbatch (II obtained in Production Example 2-3
It carried out like Example 1 except having used I). The evaluation results are shown in Tables 1 and 2.

[0046]

Example 5 The masterbatch (I
Example 1 was repeated except that V) was used. The evaluation results are shown in Tables 1 and 2.

[0047]

Example 6 The polyamide (IV) obtained in Production Example 1-4 was evaluated as an injection molded product. The evaluation results are shown in Tables 1 and 2.

[0048]

Comparative Example 1 The polyamide (I) obtained in Production Example 1-1 was evaluated as an injection molded product. The evaluation results are shown in Tables 3 and 4.

[0049]

Comparative Example 2 The polyamide (II) obtained in Production Example 1-2 was evaluated as an injection molded product. The evaluation results are shown in Tables 3 and 4.

[0050]

Comparative Example 3 Polyamide (III) obtained in Production Example 1-3
Was evaluated as an injection molded product. The evaluation results are shown in Tables 3 and 4.

[0051]

Comparative Example 4 Polyamide (II) 1 obtained in Production Example 1-2
Calcium montanate (CaV) for 100 parts by mass
0.05 parts by mass were mixed and blended with a cone-type blender to adhere to the pellet surface. This mixed pellet was evaluated as an injection molded product. The evaluation results are shown in Tables 3 and 4.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

INDUSTRIAL APPLICABILITY The present invention is a crystalline polyamide slide having excellent strength and rigidity as a sliding part in various machine industries and electric and electronic fields, low friction, low wear and excellent fatigue characteristics. The present invention relates to moving parts, and the molded product of the present invention is expected to be applied to various sliding parts in the fields of automobiles, electric / electronic fields, mechanical / industrial fields, office equipment, aerospace, etc.

Continued front page    F term (reference) 3J030 AC10 BC01                 4F071 AA54 AA55 AA55X AA56                       AA56X AA57 AA57X AC09A                       AC10A AE11 AF22 AH17                       BA01 BB05 BC07                 4J002 CL001 CL011 CL031 CL051                       CL081 EG026 EG036 EG046                       FD176 GM00

Claims (2)

[Claims] 1. At least one selected from the group consisting of metal salts of higher fatty acids and ester compounds of higher fatty acids and higher alcohols is contained in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the crystalline polyamide resin. A sliding part made of crystalline polyamide, the sliding part being 98%
Sulfuric acid relative viscosity (1 g / 100 ml) ηr is 3.5 or more and 6.0 or less, and the maximum grain size of spherulites at a depth of 100 μm from the surface layer of the part is a ₀ μm, and spherulite in the core part of the part When the maximum particle size of b is ₀ μm, a ₀ ≦ 1
A crystalline polyamide sliding component characterized in that 0 and 1 ≦ b ₀ / a ₀ ≦ 10. 2. The crystalline polyamide resin is polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), polyhexamethylene isophthalamide (nylon 6I), and these. The crystalline polyamide sliding component according to claim 1, which is a polyamide copolymer containing at least two different polyamide forming components, and a mixture thereof.