Polyamide resin composition

Abstract

To provide a polyamide resin composition for bonded to acid-modified polyolefin which is excellent in releasability in molding, mechanical characteristics, adhesion and calcium chloride resistance.SOLUTION: A polyamide resin composition for bonded to acid-modified polyolefin contains, in 100 mass% of a polyamide resin composition, 70 mass% or more and 99 mass% or less of an aliphatic polyamide resin (A) having amino group concentration of 46-110 μmol / g, 0 mass% or more and 18 mass% or less of an aromatic polyamide resin (B), 0.01 mass% or more and 0.50 mass% or less of polyalkylene glycol alkylether (C), 0.01 mass% or more and 0.50 mass% or less of polyolefin wax (D), 0.01 mass% or more and less than 0.10 mass% of a crystal nucleus agent (E), 0.01 mass% or more and 0.10 mass% or less of fatty acid bisamide (F), and 0.01 mass% or more and 0.20 mass% or less of ester of an organic acid having 20 to 30 carbon atoms and / or metal salt (G) of the organic acid, and 0 mass% or more and 29.95 mass% or less of a component (H) other than the (A) to (G), wherein an acid modification amount of the acid-modified polyolefin is 8-100 μmol / g.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamide resin composition.

Background Art

[0002] Polyamide resins are known as resins having excellent fuel permeation resistance (low fuel permeability), and polyamide resin compositions having fuel permeation resistance are required for various applications. Patent Document 1 discloses that a fuel component obtained by welding a polyamide 6 resin having an amino terminal group concentration higher than the carboxyl terminal group concentration and a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof is excellent in fuel permeation resistance and fuel resistance of the welded portion.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the composition containing a polyamide resin as disclosed in Patent Document 1 has been required to be further improved in terms of mold release property during molding, mechanical properties, and resistance to calcium chloride used in deicing agents and the like. Further, according to the findings of the present inventors, there is room for further improvement in the adhesiveness when adhering to a polyolefin having a specific amount of acid modification in a composition containing a polyamide resin as disclosed in Patent Document 1.

[0005] Therefore, an object of the present invention is to provide a polyamide resin composition for adhering to an acid-modified polyolefin, which is excellent in mold release property, mechanical properties, adhesiveness, and calcium chloride resistance during molding.

Means for Solving the Problems

[0006] The present invention relates to the following [1] to [9]. [1] A polyamide resin composition for adhering to an acid-modified polyolefin, wherein the polyamide resin composition contains, in 100% by mass of the polyamide resin composition, 70% by mass or more and 99% by mass or less of an aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g, 0% by mass or more and 18% by mass or less of an aromatic polyamide resin (B), 0.01% by mass or more and 0.50% by mass or less of a polyalkylene glycol alkyl ether (C), 0.01% by mass or more and 0.50% by mass or less of a polyolefin wax (D), 0.01% by mass or more and less than 0.10% by mass of a crystal nucleating agent (E), 0.01% by mass or more and 0.10% by mass or less of a fatty acid bisamide (F), and 0.01% by mass or more and 0.20% by mass or less of an ester of an organic acid having 20 to 30 carbon atoms and / or a metal salt of the organic acid (G), and 0% by mass or more and 29.95% by mass or less of a component (H) other than (A) to (G), and the acid modification amount of the acid-modified polyolefin is 8 to 100 μmol / g. [2] The polyamide resin composition according to [1], wherein the aliphatic polyamide resin (A) is an aliphatic homopolyamide resin (A-1). [3] The polyamide resin composition according to [1] or [2], wherein the aromatic polyamide resin (B) is an aromatic copolymer polyamide resin. [4] The polyamide resin composition according to any one of [1] to [3], wherein the polyalkylene glycol alkyl ether (C) is polyethylene glycol monomethyl ether. [5] The polyamide resin composition according to any one of [1] to [4], wherein the number average molecular weight of the polyolefin wax (D) is 1,000 to 5,000. [6] The polyamide resin composition according to any one of [1] to [5], wherein the crystal nucleating agent (E) is at least one selected from the group consisting of talc, silica, and kaolin. [7] The polyamide resin composition according to any one of [1] to [6], wherein the fatty acid bisamide (F) is at least one selected from the group consisting of ethylene bisstearic acid amide, ethylene bisbehenic acid amide, ethylene bisoleic acid amide, and ethylene biserucic acid amide. [8][1] A molded article comprising any one of the polyamide resin compositions of [1] to [7] and an acid-modified polyolefin, wherein at least a part of the polyamide resin composition and at least a part of the acid-modified polyolefin are adhered to each other, and the acid modification amount of the acid-modified polyolefin is 8 to 100 μmol / g. [9] A component that comes into contact with fuel and includes the molded article of [8].

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a polyamide resin composition for adhering to an acid-modified polyolefin, which is excellent in mold release properties, mechanical properties, adhesiveness, and calcium chloride resistance during molding.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0009] In this specification, the content of each component in the composition means the total amount of the plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In this specification, "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value. For example, "70 to 99% by mass" means "70% by mass or more and 99% by mass or less".

[0010] [Polyamide Resin Composition] The polyamide resin composition is a polyamide resin composition for adhering to an acid-modified polyolefin. In 100% by mass of the polyamide resin composition, there are 70% by mass or more and 99% by mass or less of an aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g, 0% by mass or more and 18% by mass or less of an aromatic polyamide resin (B), 0.01% by mass or more and 0.50% by mass or less of a polyalkylene glycol alkyl ether (C), 0.01% by mass or more and 0.50% by mass or less of a polyolefin wax (D), 0.01% by mass or more and less than 0.10% by mass of a crystal nucleating agent (E), 0.01% by mass or more and 0.10% by mass or less of a fatty acid bisamide (F), and 0.01% by mass or more and 0.20% by mass or less of an ester of an organic acid having 20 to 30 carbon atoms and / or a metal salt of the organic acid (G), and 0% by mass or more and 29.95% by mass or less of a component (H) other than (A) to (G). The acid modification amount of the acid-modified polyolefin is 8 to 100 μmol / g. The polyamide resin composition is excellent not only in mold release properties, mechanical properties, adhesiveness, and calcium chloride resistance during molding, but also in fuel permeability resistance. Hereinafter, unless otherwise specified, the term "adhesiveness" means the adhesiveness to an "acid-modified polyolefin having an acid modification amount of 8 to 100 μmol / g".

[0011] ≪Aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g≫ The polyamide resin composition contains an aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g (also simply referred to as "aliphatic polyamide resin (A)" in this specification).

[0012] The aliphatic polyamide resin (A) is an aliphatic polyamide resin having no aromatic ring and alicyclic group. Examples of the aliphatic polyamide resin (A) include an aliphatic homopolyamide resin (A-1) and an aliphatic copolymer polyamide resin (A-2).

[0013] <Aliphatic homopolyamide resin (A-1)> The aliphatic homopolyamide resin (A-1) means a polyamide resin in which the monomer components constituting the aliphatic polyamide resin are of one kind. Here, examples of the monomer components constituting the aliphatic polyamide resin include a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, a lactam, or an aminocarboxylic acid. When the monomer components constituting the aliphatic polyamide resin are a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, it shall be regarded as one kind of monomer component in the combination of one kind of aliphatic diamine and one kind of aliphatic dicarboxylic acid.

[0014] The number of carbon atoms of the aliphatic diamine is preferably 2 to 20, particularly preferably 4 to 12. The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 2 to 20, particularly preferably 6 to 12. The number of carbon atoms of the lactam is preferably 6 to 12. The number of carbon atoms of the aminocarboxylic acid is preferably 6 to 12.

[0015] Examples of the aliphatic diamine include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, etc. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, etc.

[0016] Examples of the combination of an aliphatic diamine and an aliphatic dicarboxylic acid include the combination of hexamethylenediamine and adipic acid, the combination of hexamethylenediamine and sebacic acid, the combination of hexamethylenediamine and dodecanedioic acid, etc. Equimolar salts of these combinations are preferably used.

[0017] Examples of the lactam include ε-caprolactam, enanthlactam, undecalactam, dodecalactam, α-pyrrolidone, α-piperidone, etc. Examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid. From the viewpoint of productivity, the lactam is preferably ε-caprolactam, undecalactam or dodecalactam.

[0018] Specific examples of the aliphatic homopolyamide resin (A-1) include polycaprolactam (polyamide 6), polyenanthlactam (polyamide 7), polyundecanolactam (polyamide 11), polylauryl lactam (polyamide 12), polyhexamethylene adipamide (polyamide 66), polytetramethylene dodecamide (polyamide 412), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene 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 1212), polydodecamethylene oxamide (polyamide 122), and the like.

[0019] <Aliphatic copolyamide resin (A-2)> The aliphatic copolyamide resin (A-2) is an aliphatic polyamide resin in which the monomer components constituting the aliphatic polyamide resin are two or more and which has no aromatic ring or alicyclic group. Therefore, examples of the aliphatic copolyamide resin (A-2) include aliphatic copolyamide resins that are copolymers of two or more monomers selected from the group consisting of aliphatic diamines and aliphatic dicarboxylic acids, lactams, and aminocarboxylic acids.

[0020] Specific examples of the aliphatic copolyamide resin (A-2) include caprolactam / hexamethylenediaminoadipic acid copolymer (polyamide 6 / 66), caprolactam / hexamethylenediaminoazelainic acid copolymer (polyamide 6 / 69), caprolactam / hexamethylenediaminosebacic acid copolymer (polyamide 6 / 610), caprolactam / hexamethylenediaminoundecanoic acid copolymer (polyamide 6 / 611), caprolactam / hexamethylenediaminododecanoic 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 / hexamethylenediaminoadipic acid / hexamethylenediaminosebacic acid copolymer (polyamide 6 / 66 / 610), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedicarboxylic acid copolymer (polyamide 6 / 66 / 612), hexamethylenediaminoadipic acid / caprolactam copolymer (polyamide 66 / 6), and the like.

[0021] <Preferred Embodiment> From the viewpoint of productivity, the aliphatic polyamide resin (A) is preferably an aliphatic homopolyamide resin (A-1), more preferably one or more selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, and polyamide 12, and particularly preferably polyamide 6 and / or polyamide 66.

[0022] <Properties> (Amino Group Concentration) The amino group concentration of the aliphatic polyamide resin (A) is 46 to 110 μmol / g. When the amino group concentration is less than 46 μmol / g, the adhesiveness is poor. Also, when the amino group concentration exceeds 110 μmol / g, the molecular weight cannot be maintained, it is difficult to produce a polyamide resin having such an amino group concentration, and the mechanical properties of the molded product are impaired due to the decrease in molecular weight. The amino group concentration of the aliphatic polyamide resin (A) is preferably 50 to 110 μmol / g, more preferably 60 to 100 μmol / g, and particularly preferably 80 to 99 μmol / g. The amino group concentration is a value determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The amino group concentration can be adjusted by adding an aliphatic mono- or diamine and / or an aliphatic mono- or dicarboxylic acid in the production of the aliphatic polyamide resin (A).

[0023] (Relative viscosity) The relative viscosity of the aliphatic polyamide resin (A) is not particularly limited, but according to JIS K 6920, for the aliphatic polyamide resin (A) with a concentration of 1% by mass in 96% by mass sulfuric acid, the relative viscosity measured at 25 °C is preferably 1.8 to 5.0, and particularly preferably 1.8 to 4.5. The measurement of the relative viscosity is preferably carried out as described above. However, when the relative viscosity of each aliphatic polyamide resin (A) and its mixing ratio are known, the average value calculated by summing the values obtained by multiplying each relative viscosity by its mixing ratio can be used as the relative viscosity of the entire aliphatic polyamide resin (A).

[0024] Examples of the production apparatus for the aliphatic polyamide resin (A) include known polyamide production apparatuses such as batch reactors, single-tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as single-screw kneading extruders and twin-screw kneading extruders. As the polymerization method, known methods such as melt polymerization, solution polymerization, and 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 appropriate combinations.

[0025] As the method for producing the aliphatic polyamide resin (A), there is no particular limitation as long as an aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g can be obtained. Specific examples of the method for producing the aliphatic polyamide resin (A) include, for example, a method including a step of adding an aliphatic diamine compound during or after the polymerization of the aliphatic polyamide resin and / or when the aliphatic polyamide resin is extruded and kneaded. Further, a method of polymerizing by adding an excessive amount of an aliphatic diamine compound at the time of raw material charging, a method of polymerizing by adding a raw material monomer component and an aliphatic diamine compound other than the raw material monomer component at the time of raw material charging, or a method of adding an aliphatic diamine compound in an amount such that the target amino group concentration is reached immediately before extracting the aliphatic polyamide resin from the polymerization tank after polymerizing an aliphatic polyamide resin having a predetermined molecular weight may be used to produce the aliphatic polyamide resin (A). Furthermore, the aliphatic polyamide resin (A) may be produced by a method of melt-kneading the aliphatic polyamide resin after polymerization and the diamine compound so as to obtain the target amino group concentration. As the production conditions of the aliphatic polyamide resin (A) other than those described above, for example, the method described in JP-A-2002-370551 can be mentioned.

[0026] The aliphatic polyamide resin (A) may be one kind or a combination of two or more kinds.

[0027] ≪Aromatic polyamide resin (B)≫ The aromatic polyamide resin (B) is a polyamide resin containing an aromatic ring. Therefore, examples of the aromatic polyamide resin (B) include an aromatic copolyamide resin (B-1) and an aromatic homopolyamide resin (B-2).

[0028] <Aromatic copolyamide resin (B-1)> The aromatic copolyamide resin (B-1) is an aromatic polyamide resin in which the monomer components constituting the aromatic polyamide resin are two or more. Here, examples of the aromatic copolyamide resin (B-1) include aromatic polyamide resins that are copolymers of monomers selected from combinations of aliphatic and / or alicyclic diamines and aromatic dicarboxylic acids, combinations of aromatic diamines and aliphatic and / or alicyclic dicarboxylic acids, and combinations of aromatic diamines and aromatic dicarboxylic acids. Here, when the monomer components constituting the aromatic polyamide resin are a combination of diamine and dicarboxylic acid, it shall be regarded as one monomer component for a combination of one diamine and one dicarboxylic acid. Examples of the aliphatic diamine and aliphatic dicarboxylic acid are as described above.

[0029] Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid. Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid.

[0030] Examples of the aromatic diamine include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether. Examples of the alicyclic diamine include cyclohexanediamine, methylcyclohexanediamine, isophoronediamine.

[0031] Specific examples of the aromatic copolyamide resin (B-1) include poly(tetramethylene terephthalamide / hexamethylene terephthalamide) copolymer (polyamide 4T / 6T), poly(tetramethylene terephthalamide / tetramethylene adipamide) copolymer (polyamide 4T / 46), poly(hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 6T / 6I), poly(hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T), poly(hexamethylene terephthalamide / caprolactam) copolymer (polyamide 6T / 6), poly(hexamethylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 66), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 610), poly(hexamethylene terephthalamide / hexamethylene dodecanamide) copolymer (polyamide 6T / 612), poly(hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 6I / 66), poly(hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 6I / 610), poly(hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene dodecanamide) copolymer (polyamide 6T / 6I / 612), and the like.

[0032] Specific examples of the aromatic copolyamide resin (B-1) include poly(nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 9T / M8T), poly(nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / undecanamide) copolymer (polyamide 9T / M8T / 11), poly(nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / dodecanamide) copolymer (polyamide 9T / M8T / 12), poly(nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / nonomethylene isophthalamide / 2-methyloctamethylene isophthalamide) copolymer (polyamide 9T / M8T / 9I / M8I), poly(nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide) copolymer (polyamide 9N / M8N), poly(nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / undecanamide) copolymer (polyamide 9N / M8N / 11), poly(nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / dodecanamide) copolymer (polyamide 9N / M8N / 12), poly(decamethylene terephthalamide / undecanamide) copolymer (polyamide 10T / 11), poly(decamethylene terephthalamide / dodecanamide) copolymer (polyamide 10T / 12), poly(decamethylene terephthalamide / decamethylene sebacamide) copolymer (polyamide 10T / 1010), poly(decamethylene terephthalamide / decamethylene dodecanamide) copolymer (polyamide 10T / 1012), poly(decamethylene terephthalamide / decamethylene isophthalamide / undecanamide) copolymer (polyamide 10T / 10I / 11), poly(decamethylene terephthalamide / decamethylene isophthalamide / dodecanamide) copolymer (polyamide 10T / 10I / 12), poly(decamethylene terephthalamide / decamethylene isophthalamide / decamethylene sebacamide) copolymer (polyamide 10T / 10I / 1010), poly(decamethylene terephthalamide / decamethylene isophthalamide / decamethylene dodecanamide) copolymer (polyamide 10T / 10I / 1012), poly(decamethylene naphthalamide / undecanamide) copolymer (polyamide 10N / 11),Poly(decamethylene naphthalamide / dodecanamide) copolymer (polyamide 10N / 12), poly(decamethylene naphthalamide / decamethylene sebacamide) copolymer (polyamide 10N / 1010), poly(decamethylene naphthalamide / decamethylene dodecamide) copolymer (polyamide 10N / 1012), poly(decamethylene terephthalamide / decamethylene naphthalamide / undecanamide) copolymer (polyamide 10T / 10N / 11), poly(decamethylene terephthalamide / decamethylene naphthalamide / dodecanamide) copolymer (polyamide 10T / 10N / 12), poly(decamethylene terephthalamide / decamethylene naphthalamide / decamethylene sebacamide) copolymer (polyamide 10T / 10N / 1010), poly(decamethylene terephthalamide / decamethylene naphthalamide / decamethylene dodecamide) copolymer (polyamide 10T / 10N / 1012), etc. can be mentioned.

[0033] Specific examples of the aromatic copolyamide resin (B-1) include poly(dodecamethylene terephthalamide / undecanamide) copolymer (polyamide 12T / 11), poly(dodecamethylene terephthalamide / dodecanamide) copolymer (polyamide 12T / 12), poly(dodecamethylene terephthalamide / dodecamethylene sebacamide) copolymer (polyamide 12T / 1210), poly(dodecamethylene terephthalamide / dodecamethylene dodecanamide) copolymer (polyamide 12T / 1212), poly(dodecamethylene terephthalamide / dodecamethylene isophthalamide / undecanamide) copolymer (polyamide 12T / 12I / 11), poly(dodecamethylene terephthalamide / dodecamethylene isophthalamide / dodecanamide) copolymer (polyamide 12T / 12I / 12), poly(dodecamethylene terephthalamide / dodecamethylene isophthalamide / dodecamethylene sebacamide) copolymer (polyamide 12T / 12I / 1210), poly(dodecamethylene terephthalamide / dodecamethylene isophthalamide / dodecamethylene dodecanamide) copolymer (polyamide 12T / 12I / 1212), poly(dodecamethylene naphthalamide / undecanamide) copolymer (polyamide 12N / 11), poly(dodecamethylene naphthalamide / dodecanamide) copolymer (polyamide 12N / 12), poly(dodecamethylene naphthalamide / dodecamethylene sebacamide) copolymer (polyamide 12N / 1210), poly(dodecamethylene naphthalamide / dodecamethylene dodecanamide) copolymer (polyamide 12N / 1212), poly(dodecamethylene terephthalamide / dodecamethylene naphthalamide / undecanamide) copolymer (polyamide 12T / 12N / 11), poly(dodecamethylene terephthalamide / dodecamethylene naphthalamide / dodecanamide) copolymer (polyamide 12T / 12N / 12), poly(dodecamethylene terephthalamide / dodecamethylene naphthalamide / dodecamethylene sebacamide) copolymer (polyamide 12T / 12N / 1210), poly(dodecamethylene terephthalamide / dodecamethylene naphthalamide / dodecamethylene dodecanamide) copolymer (polyamide 12T / 12N / 1212), and the like.

[0034] <Aromatic Homopolyamide Resin (B-2)> The aromatic homopolyamide resin (B-2) means a polyamide resin in which the monomer components constituting the aliphatic polyamide resin are of one kind. Therefore, examples of the aromatic homopolyamide resin (B-2) include combinations of aliphatic and / or alicyclic diamines and aromatic dicarboxylic acids, combinations of aromatic diamines and aliphatic and / or alicyclic dicarboxylic acids, and combinations of aromatic diamines and aromatic dicarboxylic acids. Here, examples of the aliphatic diamine, alicyclic diamine, aromatic diamine, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid are those described above.

[0035] Specific examples of the aromatic homopolyamide resin (B-2) include polynonamethylene terephthalamide (polyamide 9T), polynonamethylene naphthalamide (polyamide 9N), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene naphthalamide (polyamide 10N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene naphthalamide (polyamide 12N), polymetaxylylene succinamide (polyamide MXD4), polymetaxylylene glutaramide (polyamide MXD5), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene suberamide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutaramide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene suberamide (polyamide PXD8), polyparaxylylene azelamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), etc.

[0036] <Preferred Embodiment> The aromatic polyamide resin (B) is preferably an aromatic copolyamide resin (B-1) composed of 40 to 95 mol% of units derived from terephthalic acid, 5 to 60 mol% of units derived from isophthalic acid, and an aliphatic diamine, or an aromatic homopolyamide resin (B-2) composed of an aliphatic dicarboxylic acid and m- or p-xylenediamine. More preferably, it is an aromatic copolyamide resin (B-1) containing 60 to 99% by weight of units derived from a monomer component composed of an aliphatic diamine, isophthalic acid, and terephthalic acid, and 1 to 40% by weight of units derived from an aliphatic polyamide component, or an aromatic homopolyamide resin (B-2) composed of an aliphatic dicarboxylic acid and m-xylenediamine. Here, the monomer component composed of an aliphatic diamine, isophthalic acid, and terephthalic acid is preferably an equimolar salt of hexamethylenediamine and terephthalic acid and an equimolar salt of hexamethylenediamine and isophthalic acid. Further, from the viewpoint of productivity, the aromatic polyamide resin (B) is more preferably at least one selected from the group consisting of polyamide 6T / 6I, polyamide MXD6, and polyamide PXD6, and particularly preferably polyamide 6T / 6I.

[0037] <Properties> <<Amino group concentration>> The amino group concentration of the aromatic polyamide resin (B) is not particularly limited, but from the viewpoint of productivity, it is preferably 20 to 110 μmol / g, more preferably 30 to 100 μmol / g, and particularly preferably 31 to 49 μmol / g. The amino group concentration can be adjusted by adding mono- or diamine and / or mono- or dicarboxylic acid in the production of the aromatic polyamide resin (B).

[0038] <<Relative viscosity>> The relative viscosity of the aromatic polyamide resin (B) is not particularly limited, but according to JIS K 6920, for the aromatic polyamide resin (B) with a concentration of 1% by weight in 96% sulfuric acid, the relative viscosity measured at 25°C is preferably 1.8 to 5.0, and particularly preferably 1.8 to 4.5. When two or more aromatic polyamide resins (B) are present, the relative viscosity can be as described for the aliphatic polyamide resin (A).

[0039] Examples of the production apparatus and polymerization method of the aromatic polyamide resin (B) include the production apparatus and polymerization method described above for the aliphatic polyamide resin (A).

[0040] The aromatic polyamide resin (B) may be one kind or a combination of two or more kinds.

[0041] ≪Polyalkylene glycol alkyl ether (C)≫ The polyalkylene glycol alkyl ether (C) is a monoalkyl ether or dialkyl ether of a polyalkylene glycol having an alkylene chain.

[0042] The number of carbon atoms in the alkylene chain of the polyalkylene glycol is preferably 1 to 6, and particularly preferably 2 to 4. The alkylene chain of the polyalkylene glycol may be either linear or branched, and may be a combination of one kind or two or more kinds. Specific examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Also, the number of carbon atoms in the alkyl group in the alkyl ether is preferably 1 to 6, and particularly preferably 1 to 4.

[0043] Therefore, the polyalkylene glycol alkyl ether (C) is preferably a monoalkyl ether having 1 to 6 carbon atoms in the alkylene chain of the polyalkylene glycol and having 1 to 6 carbon atoms, and particularly preferably the monomethyl ether of polyethylene glycol.

[0044] The number average molecular weight of the polyalkylene glycol alkyl ether (C) is preferably from 500 to 10,000, more preferably from 1,000 to 5,000, from the viewpoint of moldability. Here, the number average molecular weight of the polyalkylene glycol alkyl ether (C) can be measured by gel permeation chromatography (GPC).

[0045] Examples of commercially available polyalkylene glycol alkyl ethers (C) include M-PEG CP400, CP500, CP2500, CP5000, etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and Uniox M-400, M-550, M-1000, M-2000, M-4000, etc. manufactured by NOF Corporation.

[0046] The polyalkylene glycol alkyl ether (C) may be used alone or in combination of two or more.

[0047] ≪Polyolefin wax (D)≫ Examples of the polyolefin wax (D) include polyethylene wax, polypropylene wax, polyethylene copolymer wax, oxidized polyethylene wax, acid-modified polyethylene wax, acid-modified polypropylene wax, etc. Here, the polyethylene copolymer includes copolymers of polyethylene and α-olefins other than ethylene.

[0048] As the polyolefin wax (D), polyethylene wax or modified polyethylene wax obtained by introducing a polar group by oxidizing or acid-modifying polyethylene wax is preferable.

[0049] Further, from the viewpoint of improving the dispersibility in the polyamide resin, the polyolefin wax (D) is preferably a polyolefin wax having a polar group introduced by acid modification. Acid modification is as described below for acid-modified polyolefins.

[0050] The number average molecular weight of the polyolefin wax (D) is preferably from 1,000 to 5,000, particularly preferably from 1,500 to 4,000. Here, the number average molecular weight of the polyolefin wax can be measured by gel permeation chromatography (GPC).

[0051] The melting point of the polyolefin wax (D) is not particularly limited, but is preferably from 60 to 145°C.

[0052] Examples of commercially available polyolefin waxes (D) include Hi-Wax 200P, 320P, 400P, 420P, 405MP, 320MP, 4051E, 2203A, NL800, etc. manufactured by Mitsui Chemicals, Inc. The polyolefin wax (D) may be one kind or a combination of two or more kinds.

[0053] ≪Nucleating Agent (E)≫ Examples of the nucleating agent (E) include inorganic nucleating agents and organic nucleating agents.

[0054] Examples of the inorganic nucleating agents include talc, mica, synthetic mica, glass flakes, non-swelling mica, fullerene, carbon nanotubes, carbon black, graphite, metal foils, ceramic beads, clay, sericite, zeolite, bentonite, aluminum hydroxide, dolomite, kaolin, silica, fine silica, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, magnesium hydroxide, gypsum, novaculite, dacite, clay, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, slag fiber, zonolite, eleolite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber, etc.

[0055] The average particle diameter of the inorganic nucleating agent is preferably 0.5 to 20 μm, more preferably 1 to 15 μm, and particularly preferably 2 to 10 μm. When the average particle diameter is within the above range, the gas barrier property tends to be excellent. The average particle diameter of the inorganic nucleating agent can be measured by a particle size distribution measurement method using a laser diffraction / scattering method. As a measurement device, the laser diffraction type particle size distribution measurement device SALD-7000 manufactured by Shimadzu Corporation can be mentioned. When using a commercially available product as the inorganic nucleating agent, the average particle diameter of the inorganic nucleating agent adopts the catalog value of the commercially available product.

[0056] Examples of the organic nucleating agent include organic nucleating agents having a weight average molecular weight of 5000 or less. Specific examples of the organic nucleating agent include carboxylic acid amides, aliphatic carboxylates, aliphatic alcohols, carboxylic acid esters, etc. having the above weight average molecular weight. Here, the weight average molecular weight of the organic nucleating agent can be measured by gel permeation chromatography (GPC). The weight average molecular weight of the organic nucleating agent can be measured, for example, by the method described in paragraph 18 of JP-A-2016-104846.

[0057] In addition to this, the crystal nucleating agent can refer to the descriptions in JP-A-2021-70712 and JP-A-2016-104846. From the viewpoint of suppressing the gas permeability of nitrogen and hydrogen, the crystal nucleating agent (E) is preferably an inorganic nucleating agent, more preferably at least one selected from the group consisting of talc, silica, and kaolin, and particularly preferably talc. The crystal nucleating agent (E) may be one kind or a combination of two or more kinds.

[0058] ≪Fatty acid bisamide (F)≫ The fatty acid bisamide (F) is a compound represented by the following general formula (1) and / or general formula (2), wherein R 1 is a divalent hydrocarbon group, R 2 and R 3 are monovalent hydrocarbon groups, R 4 and R 5 represent a hydrogen atom or a monovalent hydrocarbon group.

[0059] [Chem.]

[0060] [Chem.]

[0061] The fatty acid bisamide represented by the general formula (1) is obtained by the reaction of an aliphatic or aromatic diamine with a fatty acid (i.e., a monocarboxylic acid having a straight-chain, saturated or unsaturated hydrocarbon chain), and typically includes alkylene bisfatty acid amide, arylene bisfatty acid amide, etc. Examples of the diamine as the raw material include the aliphatic diamines described above in the aliphatic polyamide resin (A) and the aromatic diamines described above in the aromatic polyamide resin (B), and alkylene diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, etc., arylene diamines such as phenylenediamine, naphthalenediamine, etc., and arylene alkyl diamines such as xylylenediamine, etc. are preferred. Examples of the fatty acid as the raw material include stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, alkylidic acid, behenic acid, oleic acid, elaidic acid, montanic acid, etc.

[0062] The fatty acid bisamide represented by the general formula (2) is obtained by the reaction of an aliphatic or aromatic monoamine with an aliphatic or aromatic dicarboxylic acid (excluding the reaction of an aromatic monoamine with an aromatic dicarboxylic acid). Examples of the raw material monoamine include alkylamines such as ethylenediamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, dodecylamine, etc., arylamines such as aniline, naphthylamine, etc., aralkylamines such as benzylamine, etc., and cycloalkylamines such as cyclohexylamine, etc. Examples of the raw material dicarboxylic acid include the aliphatic dicarboxylic acid described above in the aliphatic polyamide resin (A) and the aromatic dicarboxylic acid described above in the aromatic polyamide resin (B), and it is preferably terephthalic acid, p-phenylenedipropionic acid, succinic acid, adipic acid, etc. Examples of the fatty acid bisamide represented by the general formula (2) include dioctadecyl dibasic acid amide, etc., and dioctadecyl adipic acid amide is preferably used.

[0063] The fatty acid bisamide (F) is preferably a fatty acid bisamide represented by the general formula (1), and it is particularly preferably at least one selected from the group consisting of ethylene bisstearic acid amide, ethylene bisbehenic acid amide, ethylene bisoleic acid amide, and ethylene biserucic acid amide. The fatty acid bisamide (F) may be one kind or a combination of two or more kinds.

[0064] ≪Ester of an organic acid having 20 to 30 carbon atoms and / or metal salt of the organic acid (G)≫ Examples of the organic acid having 20 to 30 carbon atoms include saturated fatty acids having 20 to 30 carbon atoms. Here, the saturated fatty acid is a monovalent carboxylic acid having a linear saturated hydrocarbon chain, and examples include arachidic acid (C20), heneicosylic acid (C21), behenic acid (C22), lignoceric acid (C24), cerotic acid (C26), montanic acid (C28), melissic acid (C30), etc. Here, the numbers in parentheses indicate the number of carbon atoms of each saturated fatty acid.

[0065] Examples of the ester include unsubstituted linear or branched alkyl esters, linear or branched alkyl esters substituted with a hydroxyl group, and the like. Specific examples of the alkyl ester substituted with a hydroxyl group include polyhydric alcohol esters such as ethylene glycol ester and glycerol ester.

[0066] The metal salt is not particularly limited as long as it is a metal capable of forming a salt with the organic acid having 20 to 30 carbon atoms, but is preferably an alkali metal salt (for example, lithium salt, sodium salt, potassium salt), an alkaline earth metal salt (for example, magnesium salt, calcium salt, barium salt, strontium salt), or a salt with a transition metal or other metal (for example, zinc salt, aluminum salt), more preferably an alkaline earth metal salt, and particularly preferably a magnesium salt, a calcium salt, or a barium salt.

[0067] The ester of the organic acid having 20 to 30 carbon atoms and / or the metal salt (G) of the organic acid may be one kind or a combination of two or more kinds.

[0068] ≪Component (H) other than (A) to (G)≫ The polyamide resin composition may contain a component (H) other than (A) to (G) as long as the effects of the present invention are not impaired. Examples of such a component (H) include polyamide resins other than the aliphatic polyamide resin (A) and the aromatic polyamide resin (B); diamines; functional additives such as plasticizers, heat-resistant materials, foaming agents, weather-resistant agents, antioxidants, crystallization accelerators, mold release agents, lubricants, antistatic agents, flame retardants, flame retardant aids, pigments, and dyes.

[0069] Examples of the polyamide resin other than the aliphatic polyamide resin (A) and the aromatic polyamide resin (B) include an aliphatic polyamide resin having an amino group concentration of less than 46 μmol / g and an aliphatic polyamide resin having an amino group concentration exceeding 110 μmol / g.

[0070] Diamine is a component that can increase the amino group concentration of the polyamide resin. When the polyamide resin composition contains diamine as component (E), the adhesiveness can be improved. The diamine includes the above-described components, and is preferably an aliphatic diamine.

[0071] The pigment is added to adjust the color of the polyamide resin composition. Examples of the pigment include inorganic pigments and organic pigments, such as titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, perylene pigments, and the like.

[0072] Examples of the functional additive other than the pigment include the components described in JP-A-2002-370551.

[0073] Component (H) may be each one kind or a combination of two or more kinds. For example, component (H) may be a combination of one or more pigments and one or more organic antioxidants.

[0074] The polyamide resin composition preferably does not contain a polyamide resin other than the aliphatic polyamide resin (A) and the aromatic polyamide resin (B). That is, in the polyamide resin composition, the polyamide resin preferably consists only of the aliphatic polyamide resin (A) and the aromatic polyamide resin (B).

[0075] ≪Content≫ The content of each component with respect to the total mass of the polyamide resin composition is as follows. In the polyamide resin composition, the total of (A) to (H) is 100% by mass.

[0076] The content of the aliphatic polyamide resin (A) is 70 to 99% by mass. From the viewpoints of mechanical properties and moldability, the content of the aliphatic polyamide resin (A) with respect to the total mass of the polyamide resin composition is preferably 80 to 97% by mass, and more preferably 85 to 95% by mass. Further, from the viewpoints of mechanical properties and moldability, the content of the aliphatic homopolyamide resin (A-1) with respect to the total mass of the aliphatic polyamide resin (A) is preferably 60 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.

[0077] The content of the aromatic polyamide resin (B) is 0 to 18% by mass. From the viewpoints of mechanical properties and moldability, the content of the aromatic polyamide resin (B) with respect to the total mass of the polyamide resin composition is preferably 5 to 15% by mass, and particularly preferably 8 to 12% by mass.

[0078] The content of the polyalkylene glycol alkyl ether (C) is 0.01 to 0.50% by mass. From the viewpoints of mechanical properties and moldability, it is preferably 0.03 to 0.45% by mass, more preferably 0.05 to 0.40% by mass, and particularly preferably 0.10 to 0.30% by mass.

[0079] The content of the polyolefin wax (D) is 0.01 to 0.50% by mass. From the viewpoints of mechanical properties and moldability, it is preferably 0.02 to 0.45% by mass, more preferably 0.03 to 0.40% by mass, and particularly preferably 0.05 to 0.15% by mass.

[0080] The content of the crystal nucleating agent (E) is 0.01% by mass or more and less than 0.10% by mass. From the viewpoints of mold release property, mechanical properties and moldability during molding, it is preferably 0.02 to 0.08% by mass.

[0081] The content of the fatty acid bisamide (F) is 0.005 to 0.10% by mass. From the viewpoints of mechanical properties and moldability, it is preferably 0.01 to 0.10% by mass.

[0082] The content of the ester of the organic acid having 20 to 30 carbon atoms and / or the metal salt (G) of the organic acid is 0.01 to 0.35% by mass. From the viewpoints of mechanical properties and moldability, it is preferably 0.05 to 0.25% by mass.

[0083] The content of the component (H) other than (A) to (G) is 0 to 29.95% by mass. From the viewpoints of mechanical properties and moldability, it is preferably 0 to 20.00% by mass, more preferably 0 to 15.00% by mass, and particularly preferably 0 to 5.00% by mass.

[0084] (Preferred embodiment) The polyamide resin composition preferably has an elongation at break of 20% or more in the two-color molded product (2) obtained through the following steps 1 to 3. Step 1: A step of obtaining part 1 by injection molding an acid-modified polyolefin having an acid modification amount of 15 μmol / g at a cylinder temperature of 200°C and a mold temperature of 40°C. Step 2: A step of obtaining the two-color molded product (1) by heating the part 1 obtained in Step 1 to 100°C, introducing it into the mold, and then injection molding the polyamide resin composition at a cylinder temperature of 290°C and a mold temperature of 90°C. Step 3: A step of obtaining the two-color molded product (2) by immersing the two-color molded product (1) obtained in Step 2 in a mixed solution of isooctane / toluene / ethanol at 65°C for 1 week, where the volume ratio of isooctane:toluene:ethanol in the mixed solution is 45:45:10. Further, the polyamide resin composition preferably has an elongation at break of 15% or more, and particularly preferably 20% or more, in the two-color molded product (2') obtained through the above Step 1 and Step 2 and the following Step 3'. Step 3': A step of obtaining the two-color molded product (2') by immersing the two-color molded product (1) obtained in Step 2 in a mixed solution of isooctane / toluene / ethanol at 65°C for 3 weeks, where the volume ratio of isooctane:toluene:ethanol in the mixed solution is 45:45:10.

[0085] For the production methods of the two-color molded articles (1), (2) and (2'), the methods described in JP-A-2002-370551 can be employed, except for the methods described later in the applications and examples of the polyamide resin composition.

[0086] ≪Method for producing polyamide resin composition≫ The method for producing the polyamide resin composition is not particularly limited, and for example, the following methods can be applied. For the mixing of the aliphatic polyamide resin (A), aromatic polyamide resin (B), polyalkylene glycol alkyl ether (C), polyolefin wax (D), crystal nucleating agent (E), fatty acid bisamide (F), ester of an organic acid having 20 to 30 carbon atoms and / or metal salt of the organic acid (G), and components (H) other than (A) to (G), commonly known melt kneaders such as single-screw and twin-screw extruders, Banbury mixers, kneaders, and mixing rolls can be used. Specific methods of mixing, which are not limited, include a method of melt kneading after blending all raw materials using a twin-screw extruder; a method of melt kneading after blending some raw materials, further blending the remaining raw materials, and then melt kneading; or a method of mixing the remaining raw materials using a side feeder during the melt kneading after blending some raw materials, etc.

[0087] ≪Acid-modified polyolefin having an acid modification amount of 8 to 100 μmol / g≫ The acid-modified polyolefin having an acid modification amount of 8 to 100 μmol / g (also simply referred to as "acid-modified polyolefin" in this specification) has a predetermined acid modification amount for the polyamide resin composition to exhibit adhesiveness. In the molecule of such a polyolefin, a functional group having an affinity for the polyamide resin (A) is present in an amount such that the polyamide resin composition exhibits adhesiveness.

[0088] The amount of acid modification of the acid-modified polyolefin is 8 to 100 μmol / g, preferably 9 to 100 μmol / g, more preferably 10 to 100 μmol / g, and particularly preferably 12 to 40 μmol / g. When the amount of acid modification of the acid-modified polyolefin is less than 8 μmol / g, the adhesiveness is poor. When the amount of acid modification of the acid-modified polyolefin exceeds 100 μmol / g, the original mechanical properties of the polyolefin may be impaired because the acid-modified polyolefin and the polyamide resin react excessively at the adhesion interface. The amount of acid modification of the acid-modified polyolefin can be measured by titration. Specifically, the amount of acid modification of the acid-modified polyolefin can be measured by the method described in the examples.

[0089] Examples of the polyolefin in the acid-modified polyolefin include (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester) copolymers, etc., and an ethylene / α-olefin copolymer is preferred.

[0090] (Ethylene and / or propylene) / α-olefin copolymers are polymers obtained by copolymerizing ethylene and / or propylene with an α-olefin having 3 or more carbon atoms. Examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 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, etc.

[0091] The copolymer may also be one obtained by copolymerizing a polyene such as a non-conjugated diene. Examples of the non-conjugated diene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, and the like.

[0092] (Ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester) copolymers are polymers obtained by copolymerizing ethylene and / or propylene with α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester monomers. Examples of the α,β-unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid. Examples of the α,β-unsaturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, etc. of α,β-unsaturated carboxylic acids.

[0093] Examples of the compound for acid-modifying polyolefin include carboxylic acids and their derivatives. Examples of the carboxylic acids and their derivatives include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, 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, citraconic anhydride, endo-bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconate, etc.

[0094] The acid-modified polyolefin is preferably an (ethylene and / or propylene) / α-olefin copolymer acid-modified with an unsaturated carboxylic acid or its acid anhydride, and an (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester) copolymer.

[0095] [Use of Polyamide Resin Composition] The polyamide resin composition is not particularly limited and can be used for the production of molded articles using known methods. The molded article using the polyamide resin composition is a molded article containing the polyamide resin composition and an acid-modified polyolefin, and at least a part of the polyamide resin composition and at least a part of the acid-modified polyolefin are adhered. That is, the present invention also relates to the use of the polyamide resin composition for adhering to an acid-modified polyolefin. Further, the present invention also relates to a method of using the polyamide resin composition for adhering to an acid-modified polyolefin. Further, the present invention also relates to the use of the polyamide resin composition as an adhesive for an acid-modified polyolefin. Further, the present invention also relates to a method of using the polyamide resin composition as an adhesive for an acid-modified polyolefin.

[0096] The molded article using the polyamide resin composition can be produced by a method including a step of adhering the polyamide resin composition and the acid-modified polyolefin. Here, the method of adhering the polyamide resin composition and the acid-modified polyolefin is not particularly limited and can be any method. The molded article using the polyamide resin composition is preferably produced by a method including a step of welding the polyamide resin composition and the acid-modified polyolefin. Examples of the method of welding the polyamide resin composition and the acid-modified polyolefin include a method including a step of molding the acid-modified polyolefin and a step of injection molding the polyamide resin composition and welding both molded articles. Therefore, the present invention also relates to a method for producing a molded article, which includes a step of adhering the polyamide resin composition and the acid-modified polyolefin. Here, the method for producing a molded article, which is a preferred embodiment, includes a step of welding the polyamide resin composition and the acid-modified polyolefin.

[0097] As methods for welding a molded article of a polyamide resin composition and a molded article of an acid-modified polyolefin, there may be mentioned a vibration welding method, an injection welding method, an ultrasonic welding method, a spin welding method, a hot plate welding method, a hot wire welding method, a laser welding method, a high-frequency induction heating welding method, etc., which are appropriately selected according to the shape of the desired molded article and / or the purpose of use. Here, as the injection welding method, there may be mentioned die slide injection (DSI), die rotary injection (DRI), and two-color molding.

[0098] The molding resin temperature in the injection welding method is preferably 250°C to 320°C, and particularly preferably 270°C to 300°C. Also, the mold temperature in the injection welding method is preferably 30°C to 120°C, and particularly preferably 50°C to 100°C.

[0099] In addition, the conditions in the step of molding the acid-modified polyolefin are not particularly limited, and any method can be adopted. The molding resin temperature of the acid-modified polyolefin is preferably 190°C to 250°C, and particularly preferably 180°C to 220°C. Also, the mold temperature when molding the acid-modified polyolefin is preferably 10°C to 90°C, and particularly preferably 30°C to 60°C.

[0100] Therefore, the manufacturing method of a molded article using a polyamide resin composition is preferably a manufacturing method of a two-color molded article including the following steps 1-a and 2-a. Step 1-a: A step of obtaining part 1 by injection molding an acid-modified polyolefin having an acid-modified amount of 8 to 100 μmol / g at a cylinder temperature of 180 to 220°C and a mold temperature of 30 to 60°C. Step 2-a: A step of heating part 1 obtained in step 1-a to 90 to 110°C (preferably 100°C) and injecting it into a mold, and then injection molding a polyamide resin composition at a molding resin temperature of 270 to 300°C and a mold temperature of 50 to 100°C to obtain a two-color molded article.

[0101] The shape of the molded article obtained using the polyamide resin composition is arbitrary, and examples include film form, sheet form, hollow form (tube form, hose form, bottle form, etc.), etc., and it is appropriately set according to the purpose of the molded article.

[0102] The molded article obtained using the polyamide resin composition can be used for various purposes such as automotive parts, railway parts, machine parts, industrial materials, industrial supplies, electrical parts, electronic parts, medical parts, parts for food packaging, household goods, office supplies, building materials-related parts, furniture parts, etc., either as the molded article itself or as a part including the molded article. In parts used for various purposes, members other than the molded article can be appropriately used from known members according to the purpose.

[0103] Also, since the polyamide resin composition is excellent in fuel resistance, the molded article obtained using the polyamide resin composition is preferably used as a part that comes into contact with fuel and as a part including the molded article. Here, the fuel is not particularly limited, but is preferably a fuel for automobiles. Therefore, as a part that comes into contact with fuel, it is preferably an automotive part.

[0104] Here, specific examples of automotive parts include fuel parts (fuel tanks for fuel such as gasoline tanks and oil tanks; fuel transport parts such as fuel delivery pipes, fuel rails, fuel tubes, fuel hoses, etc.; parts attached to parts that come into contact with fuel such as valves attached to fuel tanks, fittings for fuel hoses, nozzles for canister connections, separators, etc.); intake system parts or exhaust system parts (air ducts, intake manifolds, air cleaners, air cleaner boxes, resonators, throttle bodies, pneumatic hoses, pneumatic tubes, etc.); automotive exterior panels and exterior structure members (air spoilers, fenders, bumpers, suspension boots, etc.); or other automotive parts (hose joints, hydraulic tubes, hydraulic hoses, seat covers, etc.). Also, as a part that comes into contact with fuel, it is preferably a part such as valves attached to fuel tanks, fittings for fuel hoses, nozzles for canister connections, separators, etc.

Examples

[0105] 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 content of each component in the table is all in mass%. In addition, the components used in the Examples and Comparative Examples and the physical property evaluation methods of the molded products are shown below.

[0106] [Components Used] 1. Aliphatic polyamide resin (A) (1) PA6(1): Polyamide 6 (manufactured by Ube Industries, Ltd.: amino group concentration = 91 μmol / g) 2. Aromatic polyamide resin (B) (1) PA6T / 6I: Polyamide 6T / 6I copolymer (manufactured by EMS Chemie Japan Co., Ltd., Grivory (registered trademark) G21: amino group concentration = 38 μmol / g) 3. Polyalkylene glycol alkyl ether (C) (1) Polyethylene glycol monomethyl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., M-PEG CP2500: number average molecular weight 2,500) 4. Polyolefin wax (D) (1) Polyethylene wax (manufactured by Mitsui Chemicals, Inc., Hi-Wax 320P, number average molecular weight 3,000) 5. Nucleating agent (E) (1) Talc (manufactured by Nippon Talc Co., Ltd.: Micro Ace L-1, average particle diameter 5 μm) 6. Fatty acid bisamide (F) (1) Ethylene bisstearamide (EBS) (manufactured by NOF Corporation, Alflow HP-50PF) 7. Ester of organic acid having 20 to 30 carbon atoms and / or metal salt of said organic acid (G) (1) Calcium behenate (manufactured by Nitto Kasei Kogyo Co., Ltd., CS-7) (2) Montanic acid ester and calcium montanate (manufactured by Clariant Chemicals, Ltd., LICOWAX OP) 8. Acid-modified polyolefin (1) Maleic anhydride-modified polyethylene Amount of acid modification: 16 μmol / g (by titration method) MFR: 0.6 g / 10 min (at 190 °C, 2,160 g) Density: 0.93 Melting point: 128 °C (by DSC method)

[0107] [Preparation of polyamide resin composition pellets] Each component described in Table 1 was melt-kneaded using a twin-screw kneader ZSK32McPlus (manufactured by Coperion), with L / D 48, screw diameter 32 mm, at a cylinder temperature of 250 °C, screw rotation speed of 200 rpm, and discharge rate of 50 kg / h to prepare pellets of the polyamide resin composition. The obtained pellets were used for the evaluation of the following "mechanical properties".

[0108] [Mechanical properties] (1) Tensile yield stress, tensile fracture elongation, and tensile modulus Using the above pellets, type A test specimens were prepared based on ISO294-1, and a tensile test was carried out at 23 °C in accordance with ISO527-1,2. (2) Flexural strength and flexural modulus Using the above pellets, type B test specimens were prepared based on ISO294-1, and a flexural test was carried out at 23 °C in accordance with ISO178. (3) Charpy impact strength Using the above pellets, type B test specimens were prepared based on ISO294-1, and were V-notch processed by post-processing based on ISO 179 / 1eA. A Charpy impact test was carried out at a hammer capacity of 1 J and at 23 °C. (4) Heat distortion temperature Using the above pellets, type B test specimens were prepared based on ISO294-1, and the temperature until a specified amount of deflection occurred under the condition of a load of 0.45 MPa was measured in accordance with ISO75-2. Note that when the Charpy impact strength is 4.5 KJ / m 2 or more and the heat distortion temperature is 60 °C or more, it was judged that the "mechanical properties" were excellent.

[0109] [Acid modification rate of acid-modified polyolefin] Xylene was added to the acid-modified polyolefin and dissolved while stirring in an oil bath at 125°C. After the acid-modified polyolefin was dissolved, an appropriate amount of thymol blue was added, a burette was set up, and neutralization titration was performed using KOH to determine the acid modification rate of the polyolefin.

[0110] [Adhesion Test with Acid-Modified Polyolefin] (1) Preparation of Test Specimens Through the following Process 1 and Process 2, a two-color injection-molded test specimen (Test Specimen 1) having the shape of an ASTM No. 1 dumbbell-shaped test specimen was obtained. Also, through the following Process 3, a test specimen (Test Specimen 2) after fuel immersion was obtained. FIG. 1 is a plan view showing the shape of the test specimen for evaluating the adhesion test, and FIG. 2 is a side view showing the shape of the test specimen for evaluating the adhesion test. Here, the test specimen is composed of Component 1 (FIGS. 1 and 2: 1) and Component 2 (FIGS. 1 and 2: 2). (1-1) Process 1 Using an injection molding machine (FANUC T-100D, clamping force 100 tons, screw diameter 36 mm), a metal piece in the shape of Component 2 in FIG. 1 was inserted into the mold, and primary molding of maleic anhydride-modified polyolefin was performed under the conditions of a cylinder temperature of 200°C, a mold temperature of 40°C, and an injection speed of 50 mm / sec to obtain a molded product of maleic anhydride-modified polyolefin having the shape of Component 1. (1-2) Process 2 The maleic anhydride-modified polyolefin molded product obtained in Process 1 was sufficiently preheated at 100°C. Then, with the metal piece insert in the shape of Component 2 removed, the maleic anhydride-modified polyolefin molded product was inserted into the mold. Under the conditions of a cylinder temperature of 290°C, a mold temperature of 90°C, and an injection speed of 100 mm / sec, using a polyamide resin composition, the part of Component 2 was secondarily molded to obtain a two-color injection-molded product (Test Specimen 1). In Test Specimen 1, the interface between Component 1 (the molded product of maleic anhydride-modified polyolefin) and Component 2 (the molded product of the polyamide resin composition) is melt-bonded during the injection of the polyamide resin composition.

[0111] (1-3) Process 3 The two-color injection molded product (test piece 1) was placed in an autoclave and sealed until it was completely immersed in a FuelC + ethanol 10% by volume mixed fuel (isooctane:toluene:ethanol = 45:45:10 (volume ratio)). The autoclave was heated to 65 °C and subjected to an immersion treatment for 1 week or 3 weeks. Then, the molded product was taken out, the chemicals were wiped off, and the test piece after fuel immersion (test piece 2) was obtained.

[0112] (2) Physical property test The tensile test of test piece 2 was carried out at room temperature (23 °C), a test speed of 50 mm / sec, and a chuck distance of 140 mm to obtain the elongation at the break point and the maximum stress at the tensile yield point. The values in the table are the average values of the test results for 3 test pieces. Here, when the elongation at the break point of the test piece immediately after production is 20% or more, the elongation at the break point of the test piece after 1-week immersion treatment is 20% or more, and the elongation at the break point of the test piece after 1-week immersion treatment is 20% or more, it was judged that the adhesiveness is excellent.

[0113] [Calcium chloride resistance] Type A test pieces obtained based on ISO 294-1 were pretreated for 24 hours in a thermostatic bath adjusted to 80 °C × 90% RH. A gauze was placed on the central part of the taken-out test piece, and after applying a saturated calcium chloride aqueous solution, the surface appearance after leaving it at 100 °C for 2 hours was observed. When the appearance was good (marked as 〇), it was judged that the calcium chloride resistance was excellent. 〇: Good appearance ×: Poor appearance

[0114] [Release property] A pressure sensor was installed in the ejector part of a mold for release measurement (a box-shaped mold with dimensions of 60 mm × 30 mm × a draw width of 35 mm from the mold). When the molded product was ejected, the ejector resistance was recorded with a data logger, and the maximum peak was taken as the release resistance. An injection molding machine, FANUC T-100D with a clamping force of 100 tons and a screw diameter of 36 mm, was used. Continuous molding was carried out under the injection molding conditions of a cylinder temperature of 270 °C, a mold temperature of 50 °C, and an injection speed of 50 mm / sec. The value at which the release resistance became stable was taken as the resistance value. The evaluation criterion was that when the release resistance was 0.4 kN or less, it was judged that the release property during molding was excellent and the release resistance was low.

[0115] [Fuel permeability] Using an injection molding machine, a flat plate test piece with a diameter of 75 mm and a thickness of 1 mm was molded. At a test temperature of 60 °C, using Fuel C (SAE, J1681) + ethanol 10 vol% mixed fuel (isooctane:toluene:ethanol = 45:45:10 (volume ratio)), the fuel permeability was measured in accordance with JIS Z0208. The permeation area was 1.13×10 -3 m 2 (φ3.8×10 -2 m). The number of test pieces filled with the test fuel was "2", and the number of test pieces not filled with the control test fuel was "1".

[0116] The results are shown in Table 1. The unit of the composition in the table is mass%.

[0117]

Table 1

[0118] As is clear from the results in Table 1, the polyamide resin composition of the example was excellent in release property, mechanical properties, adhesiveness, and calcium chloride resistance during molding. The resin composition of Comparative Example 1 was inferior in release property during molding because it did not contain a crystal nucleating agent (E), a fatty acid bisamide (F), and an ester of an organic acid having 20 to 30 carbon atoms and / or a metal salt of the organic acid (G). Since the resin composition of Comparative Example 2 does not contain a crystal nucleating agent (E) and a fatty acid bisamide (F), it was inferior in mold release properties during molding. Since the resin composition of Comparative Example 3 does not contain a crystal nucleating agent (E), it was inferior in mold release properties during molding. Since the content of the ester of an organic acid having 20 to 30 carbon atoms and / or the metal salt (G) of the organic acid in the resin composition of Comparative Example 4 exceeded 0.20% by mass, it was inferior in adhesiveness. Since the content of the crystal nucleating agent (E) in the resin composition of Comparative Example 5 was 0.10% by mass or more, it was inferior in mechanical properties.

Explanation of Symbols

[0119] 1: Component 1 2: Component 2

Claims

1. A polyamide resin composition for adhesion to an acid-modified polyolefin, wherein in the polyamide resin composition, based on 100% by mass of the polyamide resin composition, an aliphatic polyamide resin (A) having an amino group concentration of 46 to 110 μmol / g is 70% by mass or more and 99% by mass or less, an aromatic polyamide resin (B) is 0% by mass or more and 18% by mass or less, a polyalkylene glycol alkyl ether (C) is 0.01% by mass or more and 0.50% by mass or less, a polyolefin wax (D) is 0.01% by mass or more and 0.50% by mass or less, a crystal nucleating agent (E) is 0.01% by mass or more and less than 0.10% by mass, a fatty acid bisamide (F) is 0.01% by mass or more and 0.10% by mass or less, and an ester of an organic acid having 20 to 30 carbon atoms and / or a metal salt of the organic acid (G) is 0.01% by mass or more and 0.20% by mass or less, and further includes a component (H) other than (A) to (G) in an amount of 0% by mass or more and 29.95% by mass or less, the acid modification amount of the acid-modified polyolefin is 8 to 100 μmol / g, a polyamide resin composition.

2. The polyamide resin composition according to claim 1, wherein the aliphatic polyamide resin (A) is an aliphatic homopolyamide resin.

3. The polyamide resin composition according to claim 1 or 2, wherein the aromatic polyamide resin (B) is an aromatic copolyamide resin.

4. The polyamide resin composition according to any one of claims 1 to 3, wherein the polyalkylene glycol alkyl ether (C) is polyethylene glycol monomethyl ether.

5. The polyamide resin composition according to any one of claims 1 to 4, wherein the number average molecular weight of the polyolefin wax (D) is 1,000 to 5,000.

6. The polyamide resin composition according to any one of claims 1 to 5, wherein the crystal nucleating agent (E) is at least one selected from the group consisting of talc, silica, and kaolin.

7. The polyamide resin composition according to any one of claims 1 to 6, wherein the fatty acid bisamide (F) is at least one selected from the group consisting of ethylene bisstearamide, ethylene bisbehenamide, ethylene bisoleamide, and ethylene biserucamide.

8. A molded article comprising the polyamide resin composition according to any one of claims 1 to 7 and an acid-modified polyolefin, wherein at least a part of the polyamide resin composition and at least a part of the acid-modified polyolefin are adhered to each other, and the amount of acid modification of the acid-modified polyolefin is 8 to 100 μmol / g.

9. A component that comes into contact with fuel, the component comprising the molded article according to claim 8.

Images