JP6814039B2 - Polyamide resin composition and molded article - Google Patents

Description

The present invention relates to a polyamide resin composition having a particularly excellent balance of moldability, flexibility, slidability, abrasion resistance, and water absorption resistance, and a molded product obtained from the resin composition.

Polyamide has features such as excellent heat resistance, oil resistance, moldability, rigidity, and toughness, so power tools, general industrial parts, mechanical parts, electronic parts, automobile interior / exterior parts, engine room parts, etc. It is widely used as various functional parts such as automobile electrical parts.

However, polyamide has a high coefficient of friction and insufficient slidability as compared with metal materials and the like. Therefore, attempts have been made to improve slidability by blending additives such as polyolefin components.

For example, Patent Document 1 describes from 30 to 100 mol% of a terephthalic acid component unit and 0 to 40 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid and / or 0 to 70 mol% of an aliphatic dicarboxylic acid component unit. A semi-aromatic polyamide having an aromatic dicarboxylic acid component unit (a) and an aliphatic and / or alicyclic alkylenediamine component unit (B), and an ultimate viscosity [η] of 0.8 to 35 dl / g. A polyamide composition comprising a modified polyethylene is disclosed.

Further, Patent Document 2 states that ultra-high molecular weight polyethylene having an ultimate viscosity [η] of 6 dl / g or more and an ultra-high molecular weight polyethylene having an ultimate viscosity [η] of 0.1 An example of a slidability improver containing ~ 5 dl / g of polyethylene and obtained by modifying the ultrahigh molecular weight polyethylene and / or polyethylene with an unsaturated carboxylic acid.

Japanese Unexamined Patent Publication No. 3-285952 Japanese Unexamined Patent Publication No. 4-351647

According to the study of the present inventor, when the slidability improver shown in the patent document is added to a polyamide such as nylon 6 in a region where the amount of ultra-high molecular weight polyolefin is large, the slidability and resistance Although the wear resistance is slightly improved, on the other hand, other mechanical properties and moldability of the polyamide may be impaired.

The present invention solves these problems, and provides a polyamide resin composition and a molded product having improved slidability and abrasion resistance without impairing various properties of the polyamide.

As a result of diligent studies, the present inventor has found that the above problems can be solved by using a resin composition containing a polyamide resin (A) and a specific ethylene / α-olefin copolymer (A) in a specific ratio. We have found and completed the present invention.

That is, the resin composition according to the present invention relates to the following [1] to [4].
[1] Polyamide resin (A) is 50 to 99.9% by mass, and ethylene / α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3) is 0.1 to 5% by mass. %, Polyamide resin composition.
(b-1) The kinematic viscosity at 100 ° C. is 90 to 5000 mm ² / s.
(b-2) The content of ethylene-derived skeletal units is 30 to 80 mol%.
(b-3) No melting point (Tm) is observed by the differential scanning calorimetry (DSC).
[2] The polyamide resin composition according to [1], wherein the ethylene / α-olefin copolymer (B) has a kinematic viscosity of 500 to 2500 mm ² / s at 100 ° C.
[3] The polyamide resin composition according to [1] or [2], wherein the polyamide resin (A) is selected from nylon 6, nylon 12, nylon 6 elastomer and nylon 12 elastomer.
[4] A molded product obtained by using the polyamide resin composition according to any one of [1] to [3] in part or in whole.

According to the present invention, it is possible to provide a polyamide resin composition having properties such as moldability, flexibility and water absorption resistance, and further having excellent slidability and abrasion resistance, and a molded product thereof.

Hereinafter, the present invention will be specifically described.
[Polyamide resin composition]
The polyamide resin composition of the present invention contains the polyamide resin (A) and the ethylene / α-olefin copolymer (B), and the content of the polyamide resin (A) is 50 to 99.9% by mass, preferably 55. ~ 99% by mass, more preferably 60 to 98% by mass, and the content of the ethylene / α-olefin copolymer (B) is 0.1 to 5% by mass, preferably 0.1 to 4% by mass. It is preferably 1 to 3% by mass.

It is preferable that the content of the ethylene / α-olefin copolymer (B) is at least the above lower limit value in terms of slidability and wear resistance, and that it is at least the above upper limit value, which is the inherent mechanical property of the polyamide. It is preferable to maintain.

It is preferable that the content of the polyamide resin (A) is at least the above lower limit value in order to maintain the original mechanical properties of the polyamide, and at least the above upper limit value is at least the above ethylene / α-olefin copolymer. It is preferable to ensure the action of (B).

[Polyamide resin (A)]
Examples of the polyamide resin (A) include hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis. Diamines such as (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), aliphatic diamines such as m- or p-xylylene diamine, alicyclic diamines or aromatic diamines, and adipic acids, sveric acids, and sebacins. Polyamide obtained by polycondensation with an aliphatic dicarboxylic acid such as acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and other dicarboxylic acids; ε-aminocaproic acid, 11-aminoundecane Polyamides obtained by condensation of aminocarboxylic acids such as acids; polyamides obtained from lactams such as ε-caprolactam and ω-laurolactam; or copolymerized polyamides composed of these components; and mixtures of these polyamides can be mentioned. .. Specific examples of this polyamide include nylon 6, nylon 66, nylon 6110, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, aromatic nylon, and the like.

Further, the polyamide resin (A) may be a polyamide-based thermoplastic elastomer, and typical examples thereof include a block copolymer having a hard segment made of polyamide and a soft segment made of polyester or polyol. Be done. Specific examples of this polyamide-based thermoplastic elastomer include the above-mentioned elastomers of specific examples of polyamide such as nylon 6 elastomer and nylon 12 elastomer, and more specifically, nylon 12 / polyether block polymer and the like.

[Ethylene / α-olefin copolymer (B)]
The ethylene / α-olefin copolymer (B) satisfies the following requirements (b-1) to (b-3).
Requirement (b-1) The kinematic viscosity at 100 ° C. is 90 to 5000 mm ² / s.

Kinematic viscosity at 100 ° C. of the ethylene · alpha-olefin copolymer (B) is preferably 500~3500mm ² / s, more preferably 500~2500mm ² / s, more preferably from 500 to 1000 mm ² / s. It is preferable that the kinematic viscosity of the ethylene / α-olefin copolymer (B) at 100 ° C. is in the above range from the viewpoint of improving the slidability of the obtained composition.
Requirement (b-2) The content of ethylene-derived skeletal units is 30 to 80 mol%.

The content of the ethylene / α-olefin copolymer (B) is preferably 40 to 75 mol%, more preferably 40 to 60 mol%. When the content of ethylene-derived skeletal units is in the above range, the slidability of the obtained composition is improved, which is preferable. When the content is in the above range, the ethylene / α-olefin copolymer (B) becomes amorphous or low crystallinity, and it is considered that the slidability of the obtained composition is improved.

The ethylene content of the ethylene / α-olefin copolymer (B) can be measured by the ¹³ C-NMR method, and is described in, for example, the method described later and the "Polymer Analysis Handbook" (P163-170 published by Asakura Shoten). Peak identification and quantification can be performed according to the method. It is also possible to measure the sample obtained by this method as a known sample by using Fourier transform infrared spectroscopy (FT-IR).

The α-olefins constituting the ethylene / α-olefin copolymer (B) include propylene, butene-1, penten-1, hexene-1, heptene-1, octene-1, decene-1, and undecene. 1. Dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eikosen-1, and other α-olefins having 3 to 20 carbon atoms. It can be exemplified. Two or more of these α-olefins may be used in combination. Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferable, and propylene is particularly preferable, from the viewpoint of giving the polymer composition good flexibility, vibration damping property, and weather resistance.

Requirement (b-3) No melting point (Tm) is observed by the differential scanning calorimetry (DSC).
Here, the fact that the melting point (Tm) is not observed means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. The fact that the heat of fusion (ΔH) is not substantially measured means that no peak is observed in the differential scanning calorimetry (DSC) measurement, or the amount of heat of fusion observed is 1 J / g or less. The melting point (Tm) and heat of fusion (ΔH) of the α-olefin (co) polymer are measured by differential scanning calorimetry (DSC), cooled to -100 ° C, and then heated to 150 ° C at a heating rate of 10 ° C / min. The DSC curve was analyzed and obtained with reference to JIS K7121 when the temperature was raised to. If the melting point (Tm) of the ethylene / α-olefin copolymer (B) is not observed, it is preferable in that mixing with the polyamide resin becomes easy.
The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (B) is not particularly limited, but is usually 1.0 to 3.0, preferably 1.4 to 2.5. ..

[Method for producing ethylene / α-olefin copolymer (B)]
The ethylene / α-olefin copolymer (B) can be produced by using a known method. For example, a method of copolymerizing ethylene and α-olefin in the presence of a catalyst composed of a transition metal compound such as vanadium, zirconium, or titanium and an organoaluminum compound (organoaluminium oxy compound) and / or an ionized ionic compound. Can be mentioned. Such a method is described in, for example, International Publication No. 00/34420 Pamphlet and Japanese Patent Application Laid-Open No. 62-121710. It can also be manufactured by a method as described in the pamphlet of International Publication No. 15/147215.

As the ethylene / α-olefin copolymer (B), two or more kinds of ethylene / α-olefin copolymers (B) may be used in combination.
In the present invention, the ethylene / α-olefin copolymer (B) may be imparted with some polar group by graft modification or the like.

[Other ingredients]
The polyamide resin composition of the present invention, and the polyamide resin (A) and the ethylene / α-olefin copolymer (B) constituting the same can be used as ordinary thermoplastic resins as long as the object of the present invention is not impaired. Additives to be added, such as stabilizers such as heat-resistant stabilizers and weather-resistant stabilizers, cross-linking agents, cross-linking aids, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, fillers, It may contain a mineral oil-based softener, a petroleum resin, a wax, or the like. The polyamide resin composition of the present invention may contain a polymer other than the ethylene / α-olefin copolymer (B), for example, modified polyethylene obtained by graft-modifying polyethylene with maleic anhydride or the like. ..

The polyamide resin composition of the present invention may contain, for example, 1 to 49.9% by mass, preferably 5 to 40% by mass, and more preferably 10 to 30% by mass of an inorganic filler. Such a filler-containing polyamide resin composition is useful when it is desired to further improve the mechanical strength of the molded product or when a molded product having an adjusted linear expansion coefficient (molding shrinkage rate) is required.

Examples of the filler include fillers such as fibrous fillers, granular fillers, and plate-like fillers. Specific examples of the fibrous filler include glass fibers, carbon fibers, aramid fibers and the like, and suitable examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm. Specific examples of the granular or plate-like filler include calcium carbonate, mica, glass flakes, glass balloons, magnesium carbonate, silica, talc, clay, crushed carbon fibers and aramid fibers, and the like.

[Manufacturing method of polyamide resin composition]
Examples of the method for producing the polyamide resin composition of the present invention include a method of melt-kneading the polyamide resin (A) and the ethylene / α-olefin copolymer (B). In this method, the polyamide resin (A) and the ethylene / α-olefin copolymer (B) may be kneaded at a temperature at which both are melted, and the temperature is not particularly limited, but is usually 200 to 300 ° C. , Preferably melt-kneading at a temperature of 200 to 270 ° C. Kneading can be performed using a single-screw extruder, a twin-screw extruder, a Bambari mixer or the like.

[Molded product]
The polyamide resin composition of the present invention can be used in various conventionally known methods, specifically, for example, an injection molding method, a deformed extrusion molding method, a pipe molding method, a tube molding method, a coating molding method for different types of molded products, and injection blow molding. By molding methods such as method, direct blow molding method, T-die sheet or film molding method, inflation film molding method, press molding method, etc., it can be used for container-shaped, tray-shaped, sheet-shaped, rod-shaped, film-shaped, or coatings of various molded bodies. Can be molded. The obtained molded product can be widely used for various purposes, but is particularly suitable for applications requiring these because it has an excellent balance of characteristics such as wear resistance and impact strength.

Examples of molded products containing the polyamide resin composition of the present invention in part or in whole include radiator grills, rear spoilers, wheel covers, wheel caps, cowl vent grills, air outlet louvers, air scoops, hood bulges, and fenders. And automotive exterior parts such as back doors; cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, water pump inlets, water pump outlets, thermostat housings, etc. Automotive engine room parts such as cooling fans, fan shrouds, oil pans, oil filter housings, oil filler caps, oil level gauges, timing belts, timing belt covers and engine covers; fuel caps, fuel fillers Automotive fuel system components such as tubes, automotive fuel tanks, fuel sender modules, fuel cutoff valves, quick connectors, canisters, fuel delivery pipes and fuel filler necks; automotive such as shift lever housings and propeller shafts Drive system parts; Automotive chassis parts such as stabilizer bars and linkage rods; Window regulators, door locks, door handles, outside door mirror stays, accelerator pedals, pedal modules, seal rings, bearings, bearing retainers, gears Automotive functional parts such as actuators; Automotive electronics components such as wire harness connectors, relay blocks, sensor housings, encapsulations, ignition coils and distributor caps; instrument panel covers, air conditioner outlets, various operation panels, etc. Interior parts for automobiles such as housings; Fuel system parts for general-purpose equipment such as fuel tanks for general-purpose equipment (cutting machines, lawn mowers, chainsaws, etc.); Electrical and electronic parts such as connectors and LED reflectors, electrical and electronic parts, Examples include building material parts, various housings, and exterior parts.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The method for measuring the physical property values in the examples and comparative examples of the present invention is as follows.
<MFR>
Melt flow rate (MFR) was measured according to ASTM D1234 under conditions of 230 ° C. and a 2.16 kg load.

<Content rate of skeletal unit derived from ethylene (mol%)>
Using JASCO Corp. Fourier transform infrared spectrophotometer FT / IR-610 or FT / IR-6100, 1155cm-based absorption and skeletal vibration of propylene around 721cm ^-1 based on the roll vibration of the long chain methylene group ^- Calculate the absorbance ratio (D1155cm ^-1 / D721cm ^-1 ) with absorption near ¹ and the content of ethylene-derived skeletal units from the calibration curve prepared in advance (prepared using the standard sample at ATM D3900). (By weight%) was calculated. Next, using the obtained ethylene-derived skeletal unit content (% by weight), the ethylene-derived skeletal unit content (mol%) was determined according to the following formula.

<Molecular weight distribution>
The molecular weight distribution was measured using HLC-8320GPC of Tosoh Corporation as follows. As a separation column, TSKgel SuperMultipore HZ-M (4 pieces) was used, the column temperature was 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the developing speed was 0.35 ml / min, and the sample concentration was set to 0.35 ml / min. The sample injection volume was 5.5 g / L, the sample injection volume was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, one manufactured by Tosoh Corporation (PStQuick MP-M) was used. According to the general-purpose calibration procedure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and the molecular weight distribution (Mw / Mn) was calculated from these values.

<Viscosity characteristics>
The kinematic viscosity at 100 ° C. was measured and calculated by the method described in JIS K2283.

<Amount of unsaturated bond>
1H-NMR using o-dichlorobenzene-d ₄ as a measurement solvent under measurement conditions of a measurement temperature of 120 ° C., a spectrum width of 20 ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 6.15 μsec (45 ° pulse). The spectrum (400 MHz, JEOL ECX400P) was measured. The solvent peak (orthodichlorobenzene 7.1 ppm) was used as the chemical shift criterion, and it was derived from the main peak observed at 0 to 3 ppm and vinyl, vinylidene, disubstituted olefins and trisubstituted olefins observed at 4 to 6 ppm. The amount of unsaturated bonds per 1000 carbon atoms (pieces / 1000C) was calculated from the ratio of the integrated values of the peaks.

<Melting point>
Using Seiko Instruments Inc. X-DSC-7000, put about 8 mg of ethylene-α-olefin copolymer in an aluminum sample pan that can be easily sealed and place it in the DSC cell, and place the DSC cell in a nitrogen atmosphere from room temperature. The temperature was raised to 150 ° C. at 10 ° C./min, then held at 150 ° C. for 5 minutes, then lowered to 10 ° C./min, and the DSC cell was cooled to −100 ° C. (lowering process). Then, after holding at 100 ° C. for 5 minutes, the temperature is raised at 10 ° C./min, the temperature at which the enthalpy curve obtained in the temperature raising process shows the maximum value is set as the melting point (Tm), and the total amount of heat absorption accompanying melting is melted. The amount of heat (ΔH) was used. If no peak was observed or the value of heat of fusion (ΔH) was 1 J / g or less, the melting point (Tm) was considered not to be observed. The melting point (Tm) and the heat of fusion (ΔH) were determined based on JIS K7121.

<Bending test>
According to ASTM D790, the shape of the test piece is 12.7 mm (width) x 3.2 mm (thickness) x 127 mm (length), and the bending span is 48.0 mm and the test speed is 5.0 mm / min. And the flexural modulus (FM) (MPa) was determined.

<Charpy impact strength>
Charpy impact strength was measured using a notched multipurpose test piece in accordance with ISO-179.

<Friction coefficient and specific wear amount>
The friction coefficient and the specific wear amount were measured using a Matsubara-type friction and wear tester in accordance with JIS K 7218 “Plastic slip wear test method A”. The test conditions were mating material: S45C, speed: 50 cm / sec, distance: 3 km, load: 15 kg (friction coefficient) or 2.5 kg (specific wear amount), measurement environment temperature: 23 ° C., 150 ° C.

<Limited PV value>
The limit PV value was evaluated by the stepwise method [JIS K7218 (SUS ring / resin sheet)]. Specifically, the sliding speed is 0.2 m / s, the test load is 0.25 to 25 MPa (steps every 0.25 MPa), and the test temperature is 23 ° C., due to fusion and deformation of the resin due to the test load. The limit PV value was calculated from the test load and sliding speed until the friction coefficient increased and the heat generation temperature increased.

[Production of ethylene / α-olefin copolymer (B)]
The ethylene / α-olefin copolymer (B) was produced according to Production Examples 1 and 2 below. The hydrogenation operation of the ethylene / α-olefin copolymer (B) was carried out by the following method.

<Hydrogenation operation>
To a stainless steel autoclave having an internal volume of 1 L, 100 mL of a hexane solution of 0.5 mass% Pd / alumina catalyst and 500 mL of a 30 mass% hexane solution of an ethylene-α-olefin copolymer (B) were added, the autoclave was sealed, and then nitrogen was added. Substitution was performed. Then, the temperature was raised to 140 ° C. with stirring, the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.

<Synthesis of metallocene compounds>
<Synthesis example 1>
[Methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl) Synthesis of zirconium dichloride (i) 6- methyl-6-phenyl fulvene nitrogen atmosphere Below, 7.3 g (101.6 mmol) of lithium cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask and stirred. The solution was cooled in an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. Then, the mixture was stirred at room temperature for 20 hours, and the obtained solution was quenched with a dilute aqueous hydrochloric acid solution. 100 mL of hexane was added to extract the soluble component, and the organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off, and the obtained viscous liquid was separated by column chromatography using hexane as a mobile phase to obtain the target product, 6-methyl-6-phenylfulvene, as a red viscous liquid.

(Ii) Synthesis of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane Under a nitrogen atmosphere, 2,7-di-t-butylfluorene in a 100 mL three-necked flask 2. 01 g (7.20 mmol) and 50 mL of dehydrated t-butyl methyl ether were added. 4.60 mL (7.59 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added while cooling in an ice bath, and the mixture was stirred at room temperature for 16 hours. After adding 1.66 g (9.85 mmol) of 6-methyl-6-phenylfluven, the mixture was stirred under heating under reflux for 1 hour. 50 mL of water was gradually added while cooling in an ice bath, and the resulting two-layer solution was transferred to a 200 mL separatory funnel. After adding 50 mL of diethyl ether and shaking several times, the aqueous layer was removed, and the organic layer was washed 3 times with 50 mL of water and once with 50 mL of saturated brine. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. When a small amount of hexane was added and ultrasonic waves were applied to the obtained solution, a solid was precipitated. Therefore, this was collected and washed with a small amount of hexane. Drying under reduced pressure gave 2.83 g of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane as a white solid.

(Iii) [methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl)] Under nitrogen atmosphere zirconium dichloride, methyl (cyclopenta in 100mL Schlenk tube 1.50 g (3.36 mmol) of dienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane, 50 mL of dehydrated toluene and 570 μL (7.03 mmol) of THF were added in sequence. 4.20 mL (6.93 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added while cooling in an ice bath, and the mixture was stirred at 45 ° C. for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated diethyl ether was added to prepare a red solution. 728 mg (3.12 mmol) of zirconium tetrachloride was added while cooling in a methanol / dry ice bath, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature, and a red-orange slurry was obtained. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After distilling off the solvent under reduced pressure and concentrating, a small amount of hexane was added and left at −20 ° C. to precipitate a red-orange solid. After washing the solid with a small amount of hexane, and dried under reduced pressure, as a red-orange solid [methylphenylmethylene (eta ⁵ - cyclopentadienyl) (η ⁵ -2,7- di -t- Buchirufuru Olenyl)] 1.20 g of zirconium dichloride was obtained.

[Production Example 1] Production of Polymer 1 After charging 250 mL of decan into a glass polymerizer having an internal volume of 1 L sufficiently substituted with nitrogen and raising the temperature in the system to 130 ° C., ethylene was added to 25 L / hr. Propylene was continuously supplied into the polymer at a flow rate of 75 L / hr and hydrogen at a flow rate of 100 L / hr, and the mixture was stirred at a stirring speed of 600 rpm. Next was charged triisobutylaluminum 0.2mmol the polymerization vessel, followed MMAO1.213mmol and [methylphenylmethylene (eta ⁵ - cyclopentadienyl) (η ⁵ -2,7- di -t- butyl fluorenyl )] Polymerization was started by premixing 0.00402 mmol of zirconium dichloride in toluene for 15 minutes or more and charging the polymer. Then, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of isobutyl alcohol into the system, the unreacted monomer was purged. The obtained polymer solution was washed 3 times with 100 mL of 0.2 mol / l hydrochloric acid and then 3 times with 100 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained polymer was dried under reduced pressure at 80 ° C. overnight to obtain 0.77 g of an ethylene / propylene copolymer (polymer 1). The content of the ethylene-derived skeletal unit of the polymer 1 was 48.8 mol%, the Mw / Mn was 1.6, and the kinematic viscosity at 100 ° C. was 102 mm ² / s. The amount of unsaturated bonds of the polymer 1 after the hydrogenation operation was less than 0.1 / 1000C. In addition, the melting point (Tm) of the polymer 1 by DSC was not observed.

[Production Example 2] Production of Polymer 2 710 mL of heptane and 145 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system was raised to 150 ° C., and then 0.40 MPa of hydrogen was used. , Ethylene 0.27 MPa was supplied to bring the total pressure to 3 MPaG. Then triisobutylaluminum 0.4 mmol, [methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl)] zirconium dichloride 0.0001mmol and N, N- Polymerization was started by press-fitting 0.001 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 400 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 3 MPaG, and polymerization was carried out at 150 ° C. for 5 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000 mL of 0.2 mol / L hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained polymer was dried under reduced pressure at 80 ° C. overnight to obtain 52.2 g of an ethylene-propylene copolymer (polymer 2). The content of the ethylene-derived skeletal unit of the polymer 2 was 53.1 mol%, the Mw / Mn was 1.8, and the kinematic viscosity at 100 ° C. was 605 mm ² / s. In addition, the amount of unsaturated bonds of the polymer 2 after the hydrogenation operation was less than 0.1 / 1000C. In addition, the melting point (Tm) of the polymer 2 by DSC was not observed.

[Production Example 3] Production of modified polyethylene (polymer 3) <Preparation of solid titanium catalyst component>
95.2 g of anhydrous magnesium chloride, 398.4 g of decane and 306 g of 2-ethylhexyl alcohol were heated and reacted at 140 ° C. for 6 hours to form a uniform solution, and then 17.6 g of ethyl benzoate was added to this solution. Stirring and mixing was performed at 130 ° C. for 1 hour.

After cooling the uniform solution thus obtained to room temperature, 50 mL of this uniform solution was added dropwise to 200 mL of titanium tetrachloride kept at 0 ° C. for 1 hour while stirring at a constant stirring rate. After the charging is completed, the temperature of this mixed solution is raised to 80 ° C. over 2.5 hours, and when it reaches 80 ° C., 2.35 g of ethyl benzoate is added to the mixed solution and kept at the same temperature for 2 hours. It was held under stirring. After completion of the reaction for 2 hours, the solid part was collected by hot filtration, the solid part was resuspended in 100 mL of titanium tetrachloride, and then the heating reaction was carried out at 90 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and thoroughly washed with decane and hexane at a temperature of 90 ° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component prepared by the above operation was stored as a decan slurry.

When analyzed by the ICP method, 3.5% by mass of the Ti component was contained in the solid titanium catalyst component. The average particle size of the catalyst particles measured by a laser diffraction / scattering method particle size distribution measuring device manufactured by Beckman Coulter was 7 μm, and the maximum particle size was 18 μm.

<Polyethylene polymerization>
After adding 12 L of purified n-decane to a 24 L autoclave with a sufficiently nitrogen-substituted stirrer, add 14 mmol of triethylaluminum in terms of aluminum and 0.3 mmol of the above solid titanium catalyst component in terms of titanium, and stir well. While raising the temperature to 45 ° C., ethylene was supplied at a rate of 4.2 L / min to initiate polymerization. The internal pressure of the autoclave was maintained at 6 kg / cm ² · G. The polymerization temperature was maintained at 45-46 ° C. When 880 L of ethylene was supplied, the supply of ethylene was temporarily stopped, the temperature was kept constant until the internal pressure reached 3 kg / cm ² · G, and then the pressure was quickly depressurized to normal pressure. At this stage, a small amount of the obtained slurry was sampled and washed with decane and hexane to obtain a white solid sample (1). Next, 41 L of hydrogen was introduced, and while raising the temperature to 85 ° C. and supplying ethylene at a rate of 11.6 L / min, the second stage polymerization was started. The total pressure was maintained at 6.4 kg / cm ² · G and the temperature was maintained at 85 ° C.

When 3800 L of ethylene was supplied, the supply of ethylene was stopped, the temperature was maintained at 85 ° C. until the internal pressure reached 3 kg / cm ² · G, and then depressurized and cooled to normal pressure and normal temperature to complete the polymerization. ..

After completion of the polymerization, a solid white solid was separated from the obtained slurry, washed with decane and hexane, and dried under reduced pressure at 80 ° C. The density of the obtained white solid (polyethylene (PE-1)) measured according to ASTM D1505 was 967 kg / cm ³ , and the ultimate viscosity [η] was 5.73 dl / g.

On the other hand, the white solid sample (1) had an ultimate viscosity [η] of 28 dl / g. Further, the content of the ultra-high molecular weight polyethylene produced in the first stage is 19.0% by mass based on the supply amount of ethylene. The ultimate viscosity of the polymer produced in the second stage was 0.5 dl / g when estimated from the following formula.
[Η] all = [η] A × wtA + [η] B × wtB
[Η] all: Extreme viscosity (dl / g) of the entire polymer (polyethylene PE-1)
[Η] A: Extreme viscosity of ultra-high molecular weight polyethylene (dl / g)
wtA: Content of ultra-high molecular weight polyethylene (mass%)
[Η] B: Extreme viscosity of low molecular weight or high molecular weight polyethylene (dl / g)
wtB: Content of low molecular weight or high molecular weight polyethylene (% by mass)

The ultimate viscosity [η] is a value measured at 135 ° C. using a decalin solvent. That is, a sample (about 20 mg) was dissolved in a decalin solvent (15 mL), and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding a decalin solvent (5 mL) to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner as described above. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) of the olefin polymer was extrapolated to 0 was defined as the ultimate viscosity [η] of the olefin polymer.
Extreme viscosity [η] = lim (ηsp / C) (C → 0)

<Manufacturing of modified polyethylene (polymer 3)>
100 parts by mass of polyethylene (PE-1), 0.8 parts by mass of maleic anhydride, and 0.07 parts by mass of organic peroxide [manufactured by Nippon Oil & Fats Co., Ltd., trade name Perhexin-25B] obtained above. Modified polyethylene (polymer 3) was obtained by mixing with a shell mixer and melt-grafting the obtained mixture with a 100 mmφ twin-screw extruder set at 270 ° C. with a kneading time of about 1 minute and 30 seconds.
[PTFE]
As the PTFE, PTFE KTL610 manufactured by Kitamura Co., Ltd. was used.

[Examples 1 to 4]
PA6 (manufactured by Toray Co., Ltd., Amylan, CM1007), which is a polyamide resin, and polymer 1 or polymer 2 which is an ethylene / α-olefin copolymer (B), or PA6 and polymer 1 or polymer. 2 and polymer 3, which is another resin, are blended in the mass ratio shown in Table 1, and melt-mixed using a 46 mmφ bent type twin-screw extruder under cylinder temperature conditions of 200 to 240 ° C., and polyamide. Pellets of the resin composition were produced. An injection molding test piece was prepared using the pellets thus obtained, and the above physical property values were measured. The results are shown in Table 1.

[Comparative Example 1]
An injection molding test piece was prepared using a PA6 carrier, and the above physical property values were measured. The results are shown in Table 1.

[Comparative Example 2]
PA6 and the polymer 3 were blended in the mass ratio shown in Table 1 to produce pellets in the same manner as in Example 1. Injection molding test pieces were prepared using these pellets, and the above physical characteristics were measured. The results are shown in Table 1.

[Comparative Example 3]
PA6 and PTFE were blended in the mass ratio shown in Table 1 to produce pellets in the same manner as in Example 1. Injection molding test pieces were prepared using these pellets, and the above physical characteristics were measured. The results are shown in Table 1.

As shown in Table 1, the polyamide resin compositions of Examples 1 to 4 containing the ethylene / α-olefin copolymer (B) did not impair the mechanical properties as compared with the polyamide resin alone of Comparative Example 1. , The coefficient of friction and the amount of specific wear could be significantly reduced. Comparing Example 1 and Comparative Example 2, the polyamide resin composition of Example 1 has a higher flow rate than the polyamide resin composition composed of the polyamide resin of Comparative Example 2 and the modified polyethylene (polymer 3). I was able to maintain my sex. As the results of Examples 2 to 4 show, the mixing ratio of the ethylene / α-olefin copolymer (B) and the modified polyethylene is changed, or the ethylene / α-olefin copolymer combined with the modified polyethylene is operated at 100 ° C. The fluidity could be adjusted arbitrarily by changing the viscosity.

Further, it is known that the polyamide resin composition composed of the polyamide resin and PTFE shown in Comparative Example 3 can realize a low friction coefficient, but in comparison with this, the polyamide resin composition of Examples has a reduced friction coefficient. In addition, the amount of wear could be reduced.

Claims (3)

Polyamide resin (A) 50 to 99.9 wt%, meets the following requirements (b-1) ~ (b -3), ethylene · alpha-olefin kinematic viscosity at 100 ° C. is 500 to 1000 mm ² / s A polyamide resin composition containing 0.1 to 5% by mass of the copolymer (B).
(b-1) The kinematic viscosity at 100 ° C. is 90 to 5000 mm ² / s.
(b-2) The content of ethylene-derived skeletal units is 30 to 80 mol%.
(b-3) No melting point (Tm) is observed by the differential scanning calorimetry (DSC). The polyamide resin composition according to claim 1 , wherein the polyamide resin (A) is selected from nylon 6, nylon 12, nylon 6 elastomer, and nylon 12 elastomer. A molded product obtained by using the polyamide resin composition according to claim 1 or 2 in part or in whole.