JP2022007369A - Polyamide resin composition - Google Patents

Abstract

To provide a polyamide resin composition which is formed into a blow molding that is excellent in blow moldability, can maintain mechanical characteristics under low temperatures, and is excellent in dimensional stability under high temperatures.SOLUTION: A polyamide resin composition contains 40-65 mass% of an aliphatic homopolyamide resin (A-1), 2-20 mass% of an aliphatic copolymer polyamide resin (A-2), 0-5 mass% of an aromatic polyamide resin (A-3), 5-25 mass% of an olefinic ionomer (B), 0-15 mass% of an impact-resistant material (C), and 1-50 mass% of an inorganic filler (D), in 100 mass% of the polyamide resin composition. Relative viscosity of the aliphatic homopolyamide resin (A-1) is 3.5 or more, and an MFR measured at 190°C and a load of 2.16 kg according to JIS K7210 of the olefinic ionomer (B) is less than 5.5 g/10 min.SELECTED DRAWING: None

Description

The present invention relates to a polyamide resin composition.

Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are therefore used as engineering plastics in various applications and are used by various molding methods. Among them, the use as a blow molded product by blow molding is also advancing. FCVs (fuel cell vehicles), which are expected to expand rapidly in the future, are required to have large blow-molded products for fuel. Further, it is required that the blow molded product can be used in various environments.

As a polyamide resin composition used for blow molded products, a polyamide resin composition containing an aromatic polyamide resin, an impact modifier, a stabilizer and an inorganic filler has been proposed, which has excellent blow moldability and a smooth surface. It is said that a blow molded article having an appearance and not deteriorating impact resistance even at high temperatures can be obtained (see, for example, Patent Document 1). Further, it is known that a polyamide resin composition obtained by adding a polyphenylene sulfide resin, an ethylene ionomer resin and an olefin elastomer resin to a polyamide resin is excellent in blow moldability, low temperature toughness and barrier property (for example, Patent Document 2). reference).

Japanese Patent Publication No. 2006-523763 Japanese Unexamined Patent Publication No. 2007-204675

As described above, although it has been confirmed that the conventional polyamide resin composition has excellent blow moldability and mechanical properties from low temperature to high temperature, the blow molded product, which is often exposed to low temperature to high temperature, has the original dimensions. The means for maintaining the condition were not disclosed.
An object of the present invention is to provide a polyamide resin composition which is excellent in blow moldability, can maintain mechanical properties even at low temperature, and is a blow molded article having excellent dimensional stability at high temperature.

The present invention is, for example, the following [1] to [6].
[1] In 100% by mass of the polyamide resin composition, 40 to 65% by mass of the aliphatic homopolyamide resin (A-1), 2 to 20% by mass of the aliphatic copolymerized polyamide resin (A-2), and aromatic. Polyamide resin (A-3) is 0 to 5% by mass, olefin-based ionomer (B) is 5 to 25% by mass, impact-resistant material (C) is 0 to 15% by mass, and inorganic filler (D) is 1 to 50%. Including% by mass
The relative viscosity of the aliphatic homopolyamide resin (A-1) is 3.5 or more, and the relative viscosity is 3.5 or more.
A polyamide resin composition having an MFR of less than 5.5 g / 10 minutes measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K7210 of an olefin ionomer (B).
[2] The polyamide resin composition of [1], wherein the aliphatic copolymerized polyamide (A-2) is at least one selected from the group consisting of polyamide 6/66, polyamide 6/12 and polyamide 6/66/12. thing.
[3] The polyamide resin composition according to [1] or [2], wherein the inorganic filler (D) is at least one selected from the group consisting of talc and glass milled fiber.
[4] The arithmetic mean value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction measured in accordance with ISO11359-2 is 8.5 × 10 ^-5 cm / cm / ° C or less [1]. The polyamide resin composition according to any one of [3].
[5] A blow-molded product of the polyamide resin composition according to any one of [1] to [4].
[6] A molded product of the polyamide resin composition according to any one of [1] to [4], which is a molded product that comes into contact with a high-pressure gas having a shape selected from the group consisting of a tank, a tube, a hose, and a film.

The polyamide resin composition of the present invention is excellent in blow moldability, and the blow molded article obtained from the polyamide resin composition of the present invention can maintain mechanical properties even at low temperatures, and has dimensional stability at high temperatures. Excellent.

In the present invention, 40 to 65% by mass of the aliphatic homopolyamide resin (A-1), 2 to 20% by mass of the aliphatic copolymerized polyamide resin (A-2), and fragrance in 100% by mass of the polyamide resin composition. Group polyamide resin (A-3) is 0 to 5% by mass, olefin-based ionomer (B) is 5 to 25% by mass, impact-resistant material (C) is 0 to 15% by mass, and inorganic filler (D) is 1 to 1 to Contains 50% by mass,
The relative viscosity of the aliphatic homopolyamide resin (A-1) is 3.5 or more, and the relative viscosity is 3.5 or more.
It relates to a polyamide resin composition having an MFR of less than 5.5 measured at 190 ° C. and a load of 2.16 kg according to JIS K7210 of an olefin ionomer (B).

(Aliphatic homopolyamide (A-1))
The polyamide resin composition contains an aliphatic homopolyamide resin (A-1).
The aliphatic homopolyamide (A-1) is a polyamide resin composed of one kind of structural unit derived from an aliphatic monomer. The aliphatic homopolyamide (A-1) may be composed of at least one of one kind of lactam and aminocarboxylic acid which is a hydrolyzate of the lactam, and one kind of diamine and one kind of dicarboxylic acid. It may consist of a combination of. Here, the combination of diamine and dicarboxylic acid is regarded as one kind of monomer by the combination of one kind of diamine and one kind of dicarboxylic acid.

Examples of the lactam include ε-caprolactam, enantractum, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. Among these, one selected from the group consisting of ε-caprolactam, undecane lactam and dodecane lactam is preferable from the viewpoint of polymerization productivity.
Examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

Examples of diamines include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptidemethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, and tetradecanediamine. , Pentadecanediamine, Hexamethylenediamine, Hexamethylenediamine, Octadecandiamine, Nonadecandiamine, Eikosandiamine, 2-Methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, etc. Hexamethylenediamine; 1,3- / 1,4-cyclohexamethylenediamine, bis (4-aminocyclohexamethylene) methane, bis (4-aminocyclohexamethylene) propane, bis (3-methyl-4-aminocyclohexamethylene) methane, (3) -Methyl-4-aminocyclohexamethylene) propane, 1,3- / 1,4-bisaminomethylcyclohexane, 5-amino-2,2,2-trimethyl-1-cyclopentanmethylamine, 5-amino-1,3 , 3-trimethylcyclohexamethylenediamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, alicyclic diamines such as norbornandimethylenediamine and the like can be mentioned.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, and pentadecane. Aliphatic dicarboxylic acids such as dionic acid, hexadecandionic acid, octadecandionic acid, and eicosandionic acid; 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornandicarboxylic acid Examples thereof include alicyclic dicarboxylic acids and the like.

Specific examples of the aliphatic homopolyamide (A-1) include polycaprolactam (polyamide 6), polyenantractum (polyamide 7), polyundecanelactam (polyamide 11), polylauryllactam (polyamide 12), and polyhexamethylene azimuth. Pamide (polyamide 66), polytetramethylene dodecamide (polyamide 412), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexa Methylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), Polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecamethylene decamide (polyamide 1010) ), Polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1210). Polyamide 1212), polyamide 122 and the like can be mentioned. These aliphatic homopolyamides (A-1) can be used alone or as a mixture of two or more kinds.
Among these aliphatic homopolyamides (A-1), polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, and polyamide 12 are preferable, and polyamide 6 and polyamide 66 are particularly preferable.

The aliphatic homopolyamide resin (A-1) contains 40 to 65% by mass, preferably 45 to 60% by mass, and more preferably 45 to 55% by mass in 100% by mass of the polyamide resin composition from the viewpoint of moldability. Is done.

The aliphatic homopolyamide resin (A-1) conforms to JIS K-6920, 1 g of the polyamide resin is dissolved in 100 ml of 96% concentrated sulfuric acid, and the relative viscosity measured at 25 ° C. is the fluidity of the polyamide resin composition. From the viewpoint of moldability, it is 3.5 or more, preferably 3.5 to 5.0, and more preferably 3.5 to 4.5.

When the aliphatic homopolyamide resin (A-1) contains two or more kinds of polyamide resins having different relative viscosities, it is preferable that the relative viscosity of the aliphatic homopolyamide resin (A-1) is measured by the above contents. If the relative viscosity of each polyamide resin and its mixing ratio are known, the average value calculated by multiplying each relative viscosity by the mixing ratio is calculated as the aliphatic homopolyamide resin (A-). It may be the relative viscosity of 1).

(Aliphatic Copolymerized Polyamide (A-2))
The polyamide resin composition contains an aliphatic copolymerized polyamide (A-2).
The aliphatic copolymerized polyamide (A-2) is a polyamide resin composed of two or more kinds of constituent units derived from an aliphatic monomer. The aliphatic copolymerized polyamide (A-2) is two or more copolymers selected from the group consisting of a combination of diamine and dicarboxylic acid, lactam and aminocarboxylic acid. Here, the combination of diamine and dicarboxylic acid is regarded as one kind of monomer by the combination of one kind of diamine and one kind of dicarboxylic acid.

Examples of the diamine include those similar to those exemplified as the raw material of the aliphatic homopolyamide. Can be mentioned.

Examples of the dicarboxylic acid include the same as those exemplified as the raw material of the aliphatic homopolyamide.

Examples of the lactam include those similar to those exemplified as the raw material of the aliphatic homopolyamide.
Further, examples of the aminocarboxylic acid include the same as those exemplified as the raw material of the aliphatic homopolyamide.
These diamines, dicarboxylic acids, lactams, and aminocarboxylic acids may be used alone or in combination of two or more.

Specific examples of the aliphatic copolymerized polyamide (A-2) include caprolactam / hexamethylene diaminoadipic acid copolymer (polyamide 6/66), caprolactam / hexamethylene diaminoazeline acid copolymer (polyamide 6/69), and the like. Caprolactam / hexamethylene diaminosevacinic acid copolymer (polyamide 6/610), caprolactam / hexamethylene diaminoundecanedicanoic acid copolymer (polyamide 6/611), caprolactam / hexamethylene diaminododecanedecanoic acid copolymer (polyamide 6 / 612), caprolactam / aminoundecanoic acid copolymer (polyamide 6/11), caprolactam / lauryllactam copolymer (polyamide 6/12), caprolactam / hexamethylenediaminoadipic acid / lauryllactam copolymer (polyamide 6/66) / 12), caprolactam / hexamethylene diaminoadipic acid / hexamethylene diaminosevacinic acid copolymer (polyamide 6/66/610), caprolactam / hexamethylene diaminoadipic acid / hexamethylene diaminododecandicanolic acid copolymer (polyamide 6 / Examples thereof include aliphatic copolymerized polyamides such as 66/612). These aliphatic copolymerized polyamides (A-2) can be used alone or as a mixture of two or more kinds.
Among these aliphatic copolymerized polyamides (A-2), caprolactam / hexamethylene diaminoadipic acid copolymer (polyamide 6/66), caprolactam / lauryllactam copolymer (polyamide 6/12), caprolactam / hexamethylene. A diaminoadipic acid / lauryl lactam copolymer (polyamide 6/66/12) is preferable.

The aliphatic copolymerized polyamide (A-2) is 2 to 20% by mass, preferably 5 to 20% by mass, and more preferably 7 to 15 in 100% by mass of the polyamide resin composition from the viewpoint of mechanical properties at low temperature. Contains% by mass.

The aliphatic copolymerized polyamide (A-2) conforms to JIS K-6920, 1 g of the polyamide resin is dissolved in 100 ml of 96% concentrated sulfuric acid, and the relative viscosity measured at 25 ° C. is the fluidity of the polyamide resin composition. From the viewpoint of the above, 1.8 to 5.0 is preferable, 2.9 to 5.0 is more preferable, and 3.0 to 4.5 is further preferable.

When the aliphatic copolymerized polyamide (A-2) contains two or more kinds of polyamide resins having different relative viscosities, the relative viscosities are increased by the same method as described in the section of the aliphatic homopolyamide resin (A-1). Desired.

(A-3) Aromatic Polyamide The polyamide resin composition may contain an aromatic polyamide (A-3).
The aromatic polyamide resin is an aromatic polyamide resin containing at least one aromatic monomer component, and is, for example, an aliphatic dicarboxylic acid and an aromatic diamine, an aromatic dicarboxylic acid and an aliphatic diamine, or an aromatic diamine and an aromatic. It is a polyamide resin obtained by polycondensation of dicarboxylic acid as a raw material.

Examples of the aliphatic diamine and the aliphatic dicarboxylic acid as raw materials include those similar to those exemplified in the above description of the aliphatic copolymerized polyamide resin.
Examples of the aromatic diamine include methoxylylenediamine and paraxylylenediamine, and examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid.
These aromatic diamines and aromatic dicarboxylic acids may be used alone or in combination of two or more.

Specific examples include polynonane methylene terephthalamide (polyamide 9T), polyhexamethylene terephthalamide (polyoxide 6T), polyhexamethylene isophthalamide (polyamide 6I), and polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer. (Polyamide 66 / 6T), Polyhexamethylene terephthalamide / Polycaproamide copolymer (Polyamide 6T / 6), Polyhexamethylene adipamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6I), Polyhexamethylene isophthalamide / Polycaproamide copolymer (polyamide 6I / 6), polydodecamide / polyhexamethylene terephthalamide copolymer (polyamide 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexamethylene adipamide / polycaproamide / polyhexamethylene isophthalamide copolymer (polyamide 66/6 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), Examples thereof include polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T) and polyxylylene adipamide (polyamide MXD6). These aromatic polyamides (A-3) can be used alone or as a mixture of two or more kinds.
Among these, an aromatic copolymerized polyamide containing at least two monomer components is preferable, and a semi-aromatic polyamide obtained by copolymerizing one or more aromatic monomer components and one or more aliphatic monomer components is more preferable, and polyhexa is more preferable. Methylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I) and polyxylylene adipamide (polyamide MXD6) are more preferable.

As the aromatic polyamide (A-3) used in the present invention, particularly useful ones include an amorphous partially aromatic copolymerized polyamide resin containing at least two aromatic monomer components. As the amorphous partially aromatic copolymerized polyamide resin, an amorphous polyamide having a glass transition temperature of 100 ° C. or higher obtained by the peak temperature of the loss elastic modulus at the time of absolute drying obtained by measuring the dynamic viscoelasticity is used. preferable.
Here, amorphous means that the amount of heat of crystal melting measured by a differential scanning calorimeter (DSC) is 1 cal / g or less.

The degree of polymerization of the aromatic polyamide resin (A-3) in the present invention is not particularly limited, but the relative viscosity measured at 20 ° C. with a 0.5% metacresol solution according to ISO307 is 0.5 to 4.0. It is preferably 1.0 to 2.0, more preferably 1.0 to 2.0.
When the aromatic polyamide (A-3) is contained in the polyamide resin (A), the aromatic polyamide (A-3) is preferably 0 to 5% by mass in 100% by mass of the polyamide resin (A) from the viewpoint of moldability. %included.

(Manufacturing of polyamide resin)
Polyamide resin manufacturing equipment includes batch type reaction kettles, single-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruders, kneading reaction extruders such as twin-screw kneading extruders, etc. A known polyamide production apparatus can be mentioned. As a polymerization method, a known method such as melt polymerization, solution polymerization or solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure and pressurization operations. These polymerization methods can be used alone or in combination as appropriate.

Among the polyamide resins, at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 6/66 and polyamide 6T / 6I is preferable from the viewpoint of mechanical properties and moldability of the polyamide resin, and polyamide 6 and polyamide 6 are preferable. At least one selected from the group consisting of / 66 and polyamide 6T / 6I is more preferable, and a mixture of polyamide 6, polyamide 6/66 and polyamide 6T / 6I, or a mixture of polyamide 6 and polyamide 6/66 is more preferable. ..

The terminal amino group concentration of the polyamide resin is preferably 30 μmol / g or more, and is in the range of 30 μmol / g or more and 110 μmol / g or less, as the terminal amino group concentration obtained by neutralization titration by dissolving in a mixed solvent of phenol and methanol. Is more preferable, and a range of 30 μmol / g or more and 70 μmol / g or less is further preferable. Within the above range, the molding processability of the molded product using the polyamide resin composition is good.

When the polyamide resin contains two or more kinds of polyamide resins having different terminal amino group concentrations, the terminal amino group concentration in the polyamide resin is preferably measured by the above neutralization pruning, but the terminal amino of each polyamide resin is preferable. When the base concentration and its mixing ratio are known, the average value calculated by multiplying each terminal amino group concentration by the mixing ratio may be used as the terminal amino group concentration of the polyamide resin.

(B) Olefin-based ionomer The polyamide resin composition contains an olefin-based ionomer (B). The olefin-based ionomer is a polymer obtained by neutralizing an olefin with an α, β-unsaturated carboxylic acid and / or an α, β-unsaturated carboxylic acid ester with a metal or a metal ion. When the olefin ionomer (B) is blended, the parison characteristics at the time of blow molding are significantly improved, but the melt viscosity is not significantly increased, so that the productivity is improved.

Examples of the resin of the olefin ionomer (B) include (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid ester) polymer. These may be used alone or in combination of two or more. The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid ester) polymer is ethylene and / or propylene and α, β-unsaturated carboxylic acid. And / or a polymer obtained by copolymerizing with an α, β-unsaturated carboxylic acid ester monomer. Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. Examples of the α, β-unsaturated carboxylic acid ester monomer include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, and nonyl of these α, β-unsaturated carboxylic acids. Examples thereof include esters and decyl esters. These may be used alone or in combination of two or more. Examples of the metal and the metal ion used for the ionomer include Na, K, Cu, Mg, Ca, Ba, Zn, Cd, Al, Fe, Co and Ni, and their ions. These may be used alone or in combination of two or more, but preferably contain at least Zn (also referred to as "zinc" in the present specification). Among these, an ionomer of an ethylene-methacrylic acid copolymer is preferable. Examples of commercially available olefin ionomers include the Hymilan (registered trademark) series manufactured by Mitsui Dow Polychemical Co., Ltd.

The MFR measured at 190 ° C. and a load of 2.16 kg according to JIS K7210 (1999) of the olefin ionomer (B) is less than 5.5 g / 10 minutes, and is 0.1 to 5.0 g / 10. Minutes are preferable, and 0.5 to 2.0 g / 10 minutes are more preferable. When the MFR of the olefin ionomer (B) is in the above range, it is preferable from the viewpoint of blow moldability and dimensional stability.

The olefin ionomer (B) has a melting point of 75 to 100 ° C. measured by a differential scanning calorimeter (DSC) in a nitrogen atmosphere at 20 ° C./min according to ISO11357-3. It is preferably 80 to 95 ° C., more preferably 80 to 95 ° C.
The density of the olefin ionomer (B) measured by JIS K7112 is preferably 940 to 980 kg / m ³ , and more preferably 950 to 970 kg / m ³ .

Further, the metal ion contained in the olefin ionomer (B) preferably contains at least zinc.
When the melting point and the density are in the above ranges, it is preferable from the viewpoint of compatibility with polyamide and wall thickness stability by suppressing swell expansion during blow molding.

The olefin-based ionomer (B) is contained in an amount of 5 to 25% by mass, preferably 7 to 25% by mass, and more preferably 10 to 25% by mass in 100% by mass of the polyamide resin composition. When the content ratio of the olefin ionomer (B) is in the above range, the blow moldability and the dimensional stability are improved.

(C) Impact-resistant material The polyamide resin composition preferably contains an impact-resistant material (C). Examples of the impact resistant material include rubber-like polymers. The impact resistant material preferably has a surface hardness (shore A) of 80 or less as measured in accordance with ASTM D2240.

Specifically, as the impact resistant material (C), (ethylene and / or propylene) / α-olefin-based copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or α, Β-Unsaturated carboxylic acid ester) -based copolymers and the like can be mentioned. These can be used alone or in combination of two or more. The impact-resistant material (C) is preferably an ethylene / α-olefin copolymer.

The (ethylene and / or propylene) / α-olefin-based copolymer is a copolymer obtained by copolymerizing ethylene and / or propylene with an α-olefin having 3 or more or 4 or more carbon atoms.
Examples of α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene, and 1 -Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-Pentene, 4-Methyl-1-Pentene, 4-Methyl-1-Hexene, 4,4-dimethyl-1-Hexene, 4,4-dimethyl-1-Pentene, 4-Ethyl-1-Hexene, 3 -Ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like can be mentioned. These may be used alone or in combination of two or more.

Further, the copolymer may be a copolymer of a polyene such as a non-conjugated diene. Non-conjugated dienes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadien, 1,6-octadien, 1,7-octadien, 2-. Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadene, 4-ethylidene-8-methyl-1,7-norbornene, 4,8-dimethyl-1, 4,8-Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyridene-2-norbornene, 6-Chloromethyl-5-isopropenl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropyridene-5-norbornene, 2-propenyl-2,5-norbornene, etc. Will be. These may be used alone or in combination of two or more.

The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid ester) polymer is ethylene and / or propylene and α, β-unsaturated carboxylic acid. And / or a polymer obtained by copolymerizing with an α, β-unsaturated carboxylic acid ester monomer. Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. Examples of the α, β-unsaturated carboxylic acid ester monomer include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, and nonyl of these α, β-unsaturated carboxylic acids. Examples thereof include esters and decyl esters. These may be used alone or in combination of two or more.

Further, the (ethylene and / or propylene) / α-olefin-based copolymer used as the impact-resistant material (C) has at least a part having a functional group that reacts with the terminal amino group of the polyamide resin (A). Is preferable. The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid ester) -based polymer already has the above functional groups, but further different said functional groups. You may have it.

Examples of the functional group include a carboxy group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group.

Examples of compounds containing these functional groups are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxyl. Acid, endobicyclo- [2.2.1] -5-hepten-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itacone, methyl acrylate, ethyl acrylate, butyl acrylate , 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracon anhydride Acid, Endobicyclo- [2.2.1] -5-hepten-2,3-dicarboxylic acid anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylic acid, acrylic acid Examples thereof include glycidyl, glycidyl methacrylate, glycidyl etacrilate, glycidyl itaconate, glycidyl citraconate and the like. These can be used alone or in combination of two or more. Among these, maleic anhydride, itaconic anhydride, and citraconic anhydride are preferable.

As a method for introducing these functional groups into the polymer used as the impact-resistant material (C), (i) a method for copolymerizing a copolymerizable monomer having a functional group at the time of polymerizing the polymer, (Ii) A method of introducing a functional group into a molecular chain or a molecular terminal of a polymer using a polymerization initiator, a chain transfer agent, or the like, (iii) a compound having a functional group and a functional group capable of grafting (graft compound). Examples thereof include a method of grafting the polymer onto the polymer. These introduction methods can be used alone or in combination as appropriate.

When the impact resistant material (C) contains a functional group such as an acid anhydride group or a carboxylic acid ester group, the content of the functional group in the impact resistant material (C) is preferably more than 25 μmol / g and less than 100 μmol / g, preferably 35 μmol. It is more preferably / g or more and less than 95 μmol, and further preferably 40 μmol / g or more and 90 μmol / g or less. When the content exceeds 25 μmol / g, a composition having a high melt viscosity can be obtained, and a target wall thickness dimension can be obtained in blow molding. Further, when the content is less than 100 μmol / g, the melt viscosity is not too high, and the load on the extruder can be suppressed and the molding process can be performed satisfactorily. The content of the functional group of the impact resistant material (C) is, for example, phenol when it has a carboxyl group, an acid anhydride group, and a carboxylic acid ester group, using a sample solution prepared with toluene or ethanol. It is measured by neutralization titration with 0.1 KOH ethanol solution using phthalein as an indicator.

The impact resistant material (C) preferably has an MFR of 2 g / 10 minutes or less measured at a temperature of 190 ° C. and a load of 2.16 kg in accordance with ASTM D1238. Is suppressed from becoming unstable, and the thickness of the molded product tends to be more uniform. In addition, the amount of sagging of the parison does not become too large, and good blow moldability tends to be obtained.

The impact resistant material (C) is contained in an amount of 0 to 15% by mass, preferably 0 to 13% by mass, and more preferably 0 to 12% by mass in 100% by mass of the polyamide resin composition. When the content ratio of the impact resistant material (C) is within the above range, blow moldability and dimensional stability are good.

(D) Inorganic Filler The polyamide resin composition contains an inorganic filler.
Examples of the inorganic filler include glass fiber, glass milled fiber, wallastnite, potassium silicate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone wool fiber, metal fiber and the like. , Kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swellable layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, etc. Metal compounds, carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate, barium sulfate, glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica. Is preferably at least one selected from the group consisting of talc and glass milled fiber. These may be used alone or in combination of two or more.

The average particle size of talc is preferably 2 to 18 μm, more preferably 4 to 16 μm. The average particle size of talc is the average particle size by the particle size distribution measuring method by the laser diffraction / scattering method. Examples of the measuring device include a laser diffraction type particle size distribution measuring device SALD-7000 manufactured by Shimadzu Corporation. When a commercially available product is used as talc, the catalog value of the commercially available product is adopted as the average particle size of talc.

The average fiber length of the glass milled fiber is measured after pulverizing each fiber, and is preferably 10 to 200 μm, more preferably 30 to 150 μm. The average fiber length can be obtained by, for example, a glass fiber length measuring machine, but when a commercially available product is used as the glass milled fiber, the catalog value of the commercially available product is used. The fiber diameter of the glass milled fiber is preferably 2 to 30 μm, more preferably 5 to 15 μm. The fiber diameter of the glass milled fiber can be obtained by an image analyzer using, for example, observation with an optical microscope, but when a commercially available product is used as the glass milled fiber, the value is the catalog value of the commercially available product.

The inorganic filler (D) is contained in 100% by mass of the polyamide resin composition in an amount of 1 to 50% by mass, preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. When the content ratio of the inorganic filler (D) is in the above range, the low temperature mechanical properties are good. Further, if it is less than 1% by mass, the effect of the present invention cannot be obtained, and if it exceeds 50% by mass, there is a risk of bleeding out.

(E) Heat Resistant Agent The polyamide resin composition preferably contains the heat resistant agent (E). As the heat resistant agent, one that can improve the heat resistance of the polyamide resin can be used, and an organic or inorganic heat resistant agent can be used according to the purpose.

From the viewpoint of heat welding characteristics and heat resistance characteristics, the polyamide resin composition more preferably contains at least one organic antioxidant as a heat resistant agent. By containing an organic antioxidant, it is possible to further improve the heat weldability while maintaining the normal heat aging property, physical properties, melt viscosity and the like even when the interval time is long during blow molding. It is considered that this is because, for example, the addition of an organic antioxidant suppresses gelation due to thermal deterioration of the impact resistant agent, thereby suppressing the nucleation action.

(Organic heat resistant agent)
Examples of the organic antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.

Preferred examples of the phenolic antioxidant include hindered phenolic antioxidants. As used herein, the hindered phenol refers to a compound having a substituent at the ortho position (hereinafter, also referred to as “o position”) of the hydroxyl group of the phenol. The substituent at the o-position is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an amino group, and a halogen. Among these, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group and tert-butyl group are preferable, and bulky i-. Propyl group, sec-butyl group, i-butyl group and tert-butyl group are more preferable, and tert-butyl group is most preferable. Further, as for the o-position, it is preferable that both of the two o-positions with respect to the hydroxyl group of phenol have a substituent.

Specifically, the hindered phenol having a tert-butyl group at the o-position is N, N'-(hexane-1,6-diyl) bis [4-hydroxy-3,5-bis (tert-butyl) benzene. Propanamide, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-) m-tolyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4 8,10-Tetraoxaspiro [5.5] undecane, N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), etc. Can be mentioned. These may be used alone or in combination of two or more. Examples of commercially available products of these heat resistant agents include "Irganox 1010", "Irganox 1098" (BASF), and "Sumilizer GA-80" (Sumitomo Chemical Co., Ltd.).

As the phosphorus-based antioxidant, a subphosphate ester compound of hinderedphenol and a hypophosphite ester compound of hinderedphenol are preferable, and a subphosphate ester compound of hinderedphenol having a tert-butyl group at the o-position, o. A hypophosphite ester compound of hindered phenol having a t-butyl group at the position is more preferable, and a subphosphate ester compound of hindered phenol having a t-butyl group at the o-position is further preferable. Specific examples of the hindered phenol sub-phosphate ester compound having a t-butyl group at the o-position include tris (2,4-di-tert-butylphenyl) phosphite and bis (2,6-di-tert). -Butyl-4-methylphenyl) Pentaelthritol diphosphite and the like can be mentioned. The hypophosphite ester compound of hindered phenol having a tert-butyl group at the o-position is specifically p, p, p', p'-tetrakis (2,4-di-tert-butylphenoxy)-. Examples thereof include reaction products of biphenyl containing 4,4-biphenyldiphosphine as a main component, phosphorus trichloride and 2,4-di-tert-butylphenol. Examples of commercially available products of these heat resistant agents include "Irgafos 168" (BASF) and "hostanoxP-EPQ" (Clariant Chemicals). These may be used alone or in combination of two or more.
Examples of the sulfur-based antioxidant include distearyl-3,3-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), and zidodecyl (3,3'-thiodipropionate). Can be done. These may be used alone or in combination of two or more.
These organic antioxidants may be used alone or in combination of two or more.

(Inorganic heat resistant agent)
Examples of the type of the inorganic heat-resistant agent for the heat-resistant agent include a copper compound and potassium halide, and examples of the copper compound include cuprous iodide, cuprous bromide, cupric bromide, and copper acetate. .. Copper iodide is preferable from the viewpoint of heat resistance and suppression of metal corrosion. Examples of potassium halide include potassium iodide, potassium bromide, potassium chloride and the like. Potassium iodide and / or potassium bromide is preferable from the viewpoint of heat resistance and suppression of metal corrosion. These may be used alone or in combination of two or more.
The organic heat-resistant agent and the inorganic heat-resistant agent may be used in combination.

Further, it is more effective to use a nitrogen-containing compound such as melamine, benganamine, dimethylolurea or cyanuric acid in combination.
From the viewpoint of heat-welding property, the polyamide resin composition preferably contains at least one phenolic antioxidant, and contains at least one phenolic antioxidant and at least one phosphorus antioxidant. It is more preferable to contain a hindered phenol having a tert-butyl group at the o-position and a subphosphate ester compound of the hinderedphenol having a tert-butyl group at the o-position or a hinder having a tert-butyl group at the o-position. It is more preferable to contain a hypophosphite ester compound of dophenol, and further preferably contains a hindered phenol having a tert-butyl group at the o-position and a subphosphate ester compound of a hindered phenol having a tert-butyl group at the o-position. Is particularly preferred.

The heat resistant agent (E) is preferably contained in an amount of 0.1 to 3% by mass, more preferably 0.5 to 2% by mass, based on 100% by mass of the polyamide resin composition. When the content ratio of the heat resistant agent (E) is within the above range, it is possible to suppress burning of the appearance of the molded product, non-uniformity of the wall thickness of the inner surface, and yellowing of the entire molded product, and the appearance can be improved.

<Other resins>
The polyamide resin composition may contain a thermoplastic resin other than the polyamide resin and the impact resistant material (C) as long as the object of the present invention is not impaired. The thermoplastic resin other than the polyamide resin is preferably 2% by mass or less, more preferably 0 to 1.5% by mass, based on 100% by mass of the polyamide resin composition.

<Other ingredients>
The polyamide resin composition is a dye, a pigment, a fibrous reinforcing material, a particulate reinforcing material, a plasticizer, an antioxidant, a foaming agent, a weather resistant agent, and a crystal nucleating agent other than the above-mentioned components, as long as the object of the present invention is not impaired. , A crystallization accelerator, a mold release agent, a lubricant, an antistatic agent, a flame retardant, a flame retardant aid, a functionalizing agent such as a colorant, and the like may be appropriately contained.
The content of the arbitrary component is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on 100% by mass of the polyamide resin composition.

[Manufacturing method of polyamide resin composition]
The method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
A commonly known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll is used for mixing the raw materials of each component.

For example, when using a twin-screw extruder, a method of blending all raw materials and then melt-kneading, a method of blending some raw materials, then melt-kneading, and then blending the remaining raw materials and melt-kneading, or one. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder after blending the raw materials of the portion, but a method of blending all the raw materials and then melt-kneading is preferable.

(MFR of Polyamide Resin Composition)
According to ISO 1133 of the polyamide resin composition, the MFR measured at a temperature of 280 ° C. and a load of 10 kg is preferably 20 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, still more preferably 5 g / 10 minutes or less. When the MFR is in this range, it can be suitably used for the production of a molded product, particularly a blow-molded molded product.

(Dimensional stability of polyamide resin composition)
The added average value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction measured by measuring the molded product of the polyamide resin composition in accordance with ISO11359-2 is 8.5 × 10 ^-5 cm / cm / cm. It is preferably ℃ or less. When the arithmetic mean value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction is in this range, the dimensions are stable in an environment from low temperature to high temperature.

[Use of polyamide resin composition]
The polyamide resin composition can be suitably used for producing a blow-molded product by blow molding, an extrusion-molded product by extrusion molding, an injection-molded product by injection molding, and a rotation-molded product by rotation molding. Since the polyamide resin composition has good blow moldability, it can be more preferably used as a blow molded product by blow molding.
The method for producing a blow-molded product from the polyamide resin composition by blow molding is not particularly limited, and a known method can be used. Generally, blow molding may be performed after forming a parison using a normal blow molding machine. The preferable resin temperature at the time of forming the parison is preferably in the temperature range of 10 ° C. to 70 ° C. higher than the melting point of the polyamide resin composition.

The method for producing an extruded product from the polyamide resin composition by extrusion molding is not particularly limited, and a known method can be used.
It is also possible to obtain a multilayer structure by co-extruding with a polyolefin such as polyethylene or another thermoplastic resin and then performing blow molding. In that case, it is also possible to provide an adhesive layer between the polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of a multilayer structure, the polyamide resin composition of the present invention can be used for both an outer layer and an inner layer.

The method for producing an injection-molded product by injection molding from the polyamide resin composition is not particularly limited, and a known method can be used. For example, the method described in Japanese Patent Application Laid-Open No. 2019-155624 is referred to.

The method for producing a rotation-molded product by rotation molding from the polyamide resin composition is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2019/054109 is referred to.

The blow-molded product by blow molding, the extrusion-molded product by extrusion molding, the injection-molded product by injection molding, and the rotary-molded product by rotary molding are not particularly limited, but are not particularly limited, but are spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, and gas tanks. , Hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, other automobile parts such as hoses, tubes and tanks, electric tool housings, mechanical parts such as pipes, and electricity such as tanks, tubes, hoses and films. Various uses such as electronic parts, household / office supplies, building material-related parts, furniture parts, etc. are preferably mentioned.

Further, since the polyamide resin composition has excellent gas barrier properties, it is suitably used for molded products that come into contact with high-pressure gas, for example, tanks, tubes, hoses, films and the like that come into contact with high-pressure gas. The type of the gas is not particularly limited, and examples thereof include hydrogen, nitrogen, oxygen, helium, methane, butane, and propane. Gases having a small polarity are preferable, and hydrogen, nitrogen, and methane are particularly preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The materials used in the examples and comparative examples are as follows.
Aliphatic homopolyamide polyamide 6 (1): manufactured by Ube Industries, Ltd., relative viscosity: 4.08
Polyamide 6 (2): manufactured by Ube Industries, Ltd., relative viscosity: 3.37
Aliphatic Copolymerized Polyamide Polyamide 6/66: Made by Ube Industries, Ltd., Product Name: 5034, Relative Viscosity: 4.05
The relative viscosity of the above-mentioned polyamide resin is a value measured at 25 ° C. in accordance with JIS K-6920 by dissolving 1 g of the polyamide resin in 100 ml of 96% concentrated sulfuric acid.
Aromatic Polyamide Polyamide 6T / 6I: EMS-CHEMIE (Japan) Co., Ltd., product name "Grivory (registered trademark) G21")

Ionomer (1): Zn-EM Ionomer: Density 960 kg / m ³ , Melting point 88 ° C., MFR 0.9 g / 10 min, Ethylene-methacrylic acid copolymer, Metal ion: Zinc, Product name "Himilan (registered trademark)" 1706 ”Ionomer manufactured by Mitsui Dow Polychemical Co., Ltd. (2): Zn-EMIonomer: Density 950 kg / m ³ , Melting point 95 ° C., MFR 5.5 g / 10 minutes, Ethylene-methacrylic acid copolymer, Metal ion: Zinc , Product name "Himilan (registered trademark) 1557" Ionomer manufactured by Mitsui Dow Polychemical Co., Ltd. (3): Zn-EMIonomer: Density 950 kg / m ³ , Melting point 90 ° C., MFR 16 g / 10 minutes, Ethylene-methacrylic acid Polymer, metal ion: zinc, product name "Himilan (registered trademark) 1702" Ionomer MFR manufactured by Mitsui Dow Polychemical Co., Ltd. is a load of 190 ° C and 2.16 kg in accordance with JIS K7210 (1999). Measured at.

Impact resistant material Toughmer MH5020: Maleic anhydride-modified ethylene-butene copolymer, product name "Toughmer (registered trademark) MH5020" manufactured by Mitsui Chemicals, Inc., acid anhydride concentration: 100 μeq / g, 190 ° C. according to ASTM D1238. , MFR measured with a load of 2.16 kg: 0.6 g / 10 minutes

Inorganic filler talc: Product name "KHP-400" manufactured by Hayashi Kasei Co., Ltd., average particle diameter 11 μm
Glass milled fiber: Product name "80M-10A" manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 10.5 μm, average fiber length 80 μm
Average particle size of talc, fiber diameter of glass milled fiber, average fiber length, catalog value.

Heat-resistant agent Irganox1098: Hindered phenol-based heat-resistant agent (N, N'-(hexane-1,6-diyl) bis [4-hydroxy-3,5-bis (tert-butyl) benzenepropaneamide], product name "Irganox1098"BASF's Irganox 1010: Hindered phenolic heat resistant agent (pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], product name "Irganox 1010" manufactured by BASF)
Irgafos 168: Phosphorus-based heat resistant agent (Tris (2,4-di-tert-butylphenyl) phosphite), product name "Irgafos 168" manufactured by BASF)

[Examples 1 to 7, Comparative Examples 1 to 6]
Each component shown in Table 1 is melt-kneaded with a twin-screw kneader TEX44HCT, a cylinder diameter of 44 mm L / D35 at a cylinder temperature of 250 ° C., a screw rotation of 160 rpm, and a discharge rate of 50 kg / hrs, and the desired polyamide resin composition pellets are melt-kneaded. Was produced.
The unit of the composition in the table is mass%, and the entire resin composition is 100% by mass.

The physical property evaluation methods in Examples and Comparative Examples are shown below.
(1) Blow moldability Using a blow molding machine DA-50 type with an accumulator manufactured by Placo Co., Ltd., a cylinder temperature of 240 ° C., a screw rotation speed of 40 rpm, a die diameter of 50 mm, a cylindrical 3 liter bottle mold, and a mold temperature of 60. At ° C., 1 m of parison was injected at a constant thickness, and the amount of sagging after 3 seconds was measured to evaluate blow moldability. The smaller the amount of sagging, the better the blow moldability. Specifically, when the amount of sagging is less than 50 mm, the blow moldability is excellent, so the evaluation was made according to the following criteria.
◯: The amount of sagging is less than 50 mm, and the blow moldability is good.
X: The amount of sagging is 50 mm or more, and the blow moldability is poor.

(2) Dimensional stability
Using FAS-T100D manufactured by FANUC Corporation, injection molding was performed at a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., and an injection speed of 80 mm / sec to form a 40 × 200 × 5 mm plate.
A 5 × 10 × 5 mm (MD direction) and 10 × 5 × 5 (TD direction) test pieces are machined from a location 10 mm to the left and right from the center of the 40 × 200 × 5 mm plate.
In accordance with ISO11359-2, it was held at 150 ° C. for 5 minutes, annealed, and then the linear expansion coefficient in the MD and TD directions (-) at a heating rate of 5 ° C./min at -100 to 100 ° C. (Calculated from the inclination in the range of 70 to 50 ° C.) was measured and evaluated according to the following criteria.
〇: The arithmetic mean value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction is 8.5 × 10 ^-5 cm / cm / ° C or less.
X: The arithmetic mean value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction is more than 8.5 × 10 ^-5 cm / cm / ° C.

(3) Low-temperature machine characteristics Using SE100D-C160S manufactured by Sumitomo Heavy Industries, Ltd., injection molding was performed at a cylinder temperature of 290 ° C, a mold temperature of 80 ° C, and an injection speed of 32 mm / sec to form an ISO Type-A test piece. The test was performed according to ISO 527-1 and 2 at -60 ° C. using an ISO Type-A test piece having a thickness of 4.0 mm.
The tensile fracture nominal strain at low temperature (-60 ° C.) was evaluated according to the following.
⊚: Tensile fracture nominal strain exceeds 15%, and low temperature mechanical properties are excellent.
〇: The tensile fracture nominal strain is 10 to 15%, and the low temperature mechanical properties are good.
X: The nominal strain at tensile fracture is less than 10%, and the low temperature mechanical properties are poor.

実施例１及び７と比較例１とを比較すると、無機充填材を含まない場合は、ブロー成形性及び寸法安定性が劣ることがわかる。
また、実施例１と比較例２とを比較すると、脂肪族ホモポリアミド樹脂として、相対粘度が３．５未満のものを使用した場合は、ブロー成形性が実施例１より劣ることがわかる。
実施例１と比較例３とを比較すると、アイオノマーを使用しないと、ブロー成形性および寸法安定性が実施例１よりも劣ることがわかる。
実施例１と比較例４とを比較すると、脂肪族共重合ポリアミド樹脂を含まないと、ブロー成形性及び低温機械特性が実施例１よりも劣ることがわかる。
実施例１と比較例５及び６とを比較すると、オレフィン系アイオノマーのＭＦＲが、５．５ｇ／１０分以上であると、ブロー成形性が劣り、よりＭＦＲの値が高くなると、低温機械特性も劣ることがわかる。

Comparing Examples 1 and 7 with Comparative Example 1, it can be seen that the blow moldability and dimensional stability are inferior when the inorganic filler is not contained.
Further, when Example 1 and Comparative Example 2 are compared, it can be seen that when an aliphatic homopolyamide resin having a relative viscosity of less than 3.5 is used, the blow moldability is inferior to that of Example 1.
Comparing Example 1 and Comparative Example 3, it can be seen that the blow moldability and dimensional stability are inferior to those of Example 1 without the use of ionomers.
Comparing Example 1 and Comparative Example 4, it can be seen that the blow moldability and low temperature mechanical properties are inferior to those of Example 1 when the aliphatic copolymerized polyamide resin is not contained.
Comparing Example 1 with Comparative Examples 5 and 6, when the MFR of the olefin ionomer is 5.5 g / 10 minutes or more, the blow moldability is inferior, and when the MFR value is higher, the low temperature mechanical properties are also obtained. It turns out to be inferior.

Claims (6)

40 to 65% by mass of the aliphatic homopolyamide resin (A-1), 2 to 20% by mass of the aliphatic copolymerized polyamide resin (A-2), and an aromatic polyamide resin (A-1) in 100% by mass of the polyamide resin composition. A-3) is contained in an amount of 0 to 5% by mass, an olefin-based ionomer (B) is contained in an amount of 5 to 25% by mass, an impact resistant material (C) is contained in an amount of 0 to 15% by mass, and an inorganic filler (D) is contained in an amount of 1 to 50% by mass. ,
The relative viscosity of the aliphatic homopolyamide resin (A-1) is 3.5 or more, and the relative viscosity is 3.5 or more.
A polyamide resin composition having an MFR of less than 5.5 g / 10 minutes measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K7210 of an olefin ionomer (B). The polyamide resin composition according to claim 1, wherein the aliphatic copolymerized polyamide (A-2) is at least one selected from the group consisting of polyamide 6/66, polyamide 6/12 and polyamide 6/66/12. .. The polyamide resin composition according to claim 1 or 2, wherein the inorganic filler (D) is at least one selected from the group consisting of talc and glass milled fiber. ³ . The polyamide resin composition according to any one item. A blow-molded product of the polyamide resin composition according to any one of claims 1 to 4. The molded product of the polyamide resin composition according to any one of claims 1 to 4, which is a molded product that comes into contact with a high-pressure gas having a shape selected from the group consisting of a tank, a tube, a hose, and a film.