JP2017190405A - Polyamide resin composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition excellent in heat aging resistance, having efficiently suppressed metal corrosion resistance and suppressed copper deposition property.SOLUTION: There is provided a polyamide resin composition containing (A) a polyamide resin, (B) a copper compound, and (C) bromide of an alkali metal and/or alkali earth metal, at least a part of the (A) polyamide resin is a polyamide resin having (a1) at least amino group terminals and carboxyl group terminals and the number of amino terminals are larger than that of carboxyl groups.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition and a molded body.

  Polyamide resins have excellent mechanical properties (mechanical strength, rigidity, impact resistance, etc.), toughness, heat resistance, chemical resistance, and chemical resistance, so traditionally clothing, industrial materials, automobiles, and electricity・ Used in various industrial fields such as electronics and other industries.

In particular, the polyamide resin is excellent in heat aging resistance as compared with other resins, and thus is suitably used as a material for parts in parts that are extremely heated, such as in an automobile engine room.
Recently, as the density of parts in the car engine room has increased and the engine output has increased, the environmental temperature in the car engine room has become increasingly higher. The polyamide resin is required to have characteristics capable of maintaining long-term heat aging resistance.

Conventionally, as a technique for improving the heat aging resistance of a polyamide resin, a technique of adding a copper compound (copper oxide or salt) and a halogen compound is known.
Among the halogen compounds, it is common to add an iodine compound, and a polyamide resin composition containing a polyamide resin, a copper compound, an iodine compound, and an aliphatic carboxylic acid derivative is disclosed (for example, Patent Documents). 1).
However, iodine is a resource mined from the ground, and the area where it can be mined efficiently is limited. Therefore, the price of iodine compounds has increased in recent years, and using iodine compounds results in high costs. Has the problem.
On the other hand, bromine is a resource that can be collected from seawater and the like, so it is very inexpensive and industrially useful compared to iodine. Therefore, a technique of adding a bromine compound instead of an iodine compound in order to improve the heat aging resistance of the polyamide resin is also disclosed (for example, see Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 7-18176 International Publication No. 2013-143858 Pamphlet Special table 2011-511097 gazette

  However, since bromine compounds are more susceptible to metal corrosion than iodine compounds, if a polyamide resin composition containing bromine compounds is used as a material for automobile engine compartment parts, processing of extruders, molding machines, etc. There is a concern about the corrosion of metal parts of machines, and it is necessary to consider the conditions for use, and therefore, there is a need for a polyamide resin composition with further reduced metal corrosivity than before.

  Therefore, an object of the present invention is to provide a polyamide resin composition that is excellent in heat aging resistance, effectively suppresses metal corrosiveness, and suppresses copper precipitation.

As a result of intensive studies to solve the above problems, the inventors of the present invention are polyamide resin compositions containing a polyamide resin, a copper compound, and an alkali metal and / or alkaline earth metal bromide, It has been found that a polyamide resin composition in which at least a part is a polyamide resin having a specific end group in a specific ratio can solve the above problems, and has completed the present invention.
That is, the present invention is as follows.

[1]
(A) a polyamide resin;
(B) a copper compound;
(C) an alkali metal and / or alkaline earth metal bromide;
A polyamide resin composition comprising:
A polyamide resin composition in which at least a part of the (A) polyamide resin is (a-1) a polyamide resin having at least an amino group end and a carboxyl group end, and having more amino group ends than carboxyl group ends.
[2]
The polyamide resin composition according to [1], wherein the (a-1) polyamide resin has an amino terminal group concentration of 50 to 80 mmol / kg.
[3]
A masterbatch in which the (B) copper compound, and the (C) alkali metal and / or alkaline earth metal bromide are blended in advance in the (a-1) polyamide resin;
(A-2) a polyamide resin other than (a-1),
The polyamide resin composition according to the above [1] or [2].
[4]
(D) one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts,
The polyamide resin composition according to any one of [1] to [3], wherein the acid value of the (D) fatty acid compound is 10 mg / g or less.
[5]
The master batch contains (D) one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts,
In the above [3] or [4], the (B) copper compound and the (C) alkali metal and / or alkaline earth metal bromide are blended in advance in the (a-1) polyamide resin. The polyamide resin composition as described.
[6]
The polyamide resin composition according to any one of [1] to [5], wherein the (B) copper compound is a copper halide compound.
[7]
The proportion of copper element contained in the polyamide resin composition is
The polyamide resin composition according to any one of [1] to [6], which is 0.005% by mass or more with respect to 100% by mass of the polyamide resin composition.
[8]
(E) The polyamide resin composition according to any one of [1] to [7], further including an inorganic filler.
[9]
[1] to [8], wherein when (A) the polyamide resin is brought into contact with the rolled steel (SS400) for 8 hours at a temperature of the melting point of the polyamide resin + 30 ° C., no precipitation of copper element occurs on the surface of the rolled steel. The polyamide resin composition as described in any one.
[10]
The molded object containing the polyamide resin composition as described in any one of said [1] thru | or [9].

  According to the present invention, it is possible to provide a polyamide resin composition that is excellent in heat aging resistance, effectively suppresses metal corrosiveness, and suppresses copper precipitation.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
In addition, the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A) a polyamide resin;
(B) a copper compound;
(C) an alkali metal and / or alkaline earth metal bromide;
Containing,
At least a part of the (A) polyamide resin is (a-1) a polyamide resin having at least an amino group end and a carboxyl group end, and having more amino group ends than carboxyl group ends.
Hereinafter, each component of the polyamide resin composition will be described in detail.

((A) Polyamide resin)
The polyamide resin composition of the present embodiment contains (A) a polyamide resin (hereinafter sometimes referred to as “component (A)”).
The polyamide resin means a polymer compound having a —CO—NH— (amide) bond in the main chain.
(A) The polyamide resin is not limited to the following, but includes, for example, a polyamide resin obtained by ring-opening polymerization of lactam, a polyamide resin obtained by self-condensation of ω-aminocarboxylic acid, a diamine and a dicarboxylic acid. Examples thereof include polyamide resins obtained by condensation, and copolymers thereof.
These polyamide resins may be used alone or as a mixture of two or more.

Hereinafter, the raw material of (A) polyamide resin is demonstrated.
Examples of the lactam as a monomer that is a constituent component of the polyamide resin include, but are not limited to, pyrrolidone, caprolactam, undecaractam, and dodecaractam. These may be used alone or in combination of two or more.
Examples of the ω-aminocarboxylic acid include, but are not limited to, ω-amino fatty acids which are ring-opening compounds of the lactam with water. In addition, as lactam or ω-aminocarboxylic acid, two or more monomers may be used together and condensed.

Then, the polyamide resin obtained by condensing diamine and dicarboxylic acid is demonstrated.
First, examples of the diamine (monomer) include, but are not limited to, linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine; 2-methylpentane diamine and 2-ethyl. Examples include branched aliphatic diamines such as hexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine.
On the other hand, examples of the dicarboxylic acid (monomer) include, but are not limited to, aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid. Acid; Alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid is exemplified.
The diamine and dicarboxylic acid as the monomers described above may be used alone or in combination of two or more.

(A) The polyamide resin is not limited to the following, but, for example, polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecane) Amide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide) And polyamide 6I (polyhexamethylene isophthalamide) and copolymerized polyamides containing these as constituents.
The above polyamide resins may be used alone or in combination of two or more.

Among the polyamide resins listed above, as the (A) polyamide resin used in the polyamide resin composition of the present embodiment, a polyamide resin having a melting point of 200 ° C. or higher is preferable from the viewpoint of improving heat resistance.
Preferred polyamide resins having such properties are not limited to the following, but include, for example, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 46, polyamide 6T, polyamide 6I and polyamide 9T, and these. 1 or more types selected from the group which consists of the copolyamide included as a structural component are mentioned.
In addition, the melting point of the polyamide resin in this specification refers to that obtained by a differential scanning calorimetry method (DSC method) based on JIS K7121.

  In addition, the ratio of carbon number / nitrogen number (C / N ratio) in the polymer chain of the (A) polyamide resin is preferably more than 5 from the viewpoint of heat aging resistance. More preferably, it is more than 5 and 15 or less, and more preferably more than 5 and 12 or less.

  Examples of the copolyamide include, but are not limited to, for example, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide; a copolymer of hexamethylene adipamide and hexamethylene isophthalamide; and Examples thereof include one or more copolymers selected from the group consisting of a copolymer of hexamethylene terephthalamide and 2-methylpentanediamine terephthalamide.

The (A) polyamide resin generally has an amino group or a carboxyl group as a terminal group.
The ratio of the terminal groups in the polyamide resin (A) contained in the polyamide resin composition of the present embodiment is preferably 9/1 to 1/9, more preferably 6 as amino group concentration / carboxyl group concentration. / 4 to 1/9, more preferably 5/5 to 1/9. When the ratio of the terminal groups is within the above range, the mechanical strength of the polyamide resin composition of the present embodiment can be further improved.

(A) The density | concentration of the amino group terminal in a polyamide resin becomes like this. Preferably it is 10-100 micromol / g, More preferably, it is 15-80 micromol / g, More preferably, it is 30-80 micromol / g.
(A) When the amino group terminal concentration in the polyamide resin is within the above range, the mechanical strength of the polyamide resin composition of the present embodiment can be further improved.
(A) The density | concentration of the carboxyl group terminal in a polyamide resin becomes like this. Preferably it is 20 micromol / g or more, More preferably, it is 50 micromol / g or more, More preferably, it is 50-120 micromol / g, More preferably, it is 50-100 micromol. / G.
(A) When the density | concentration of the carboxyl group terminal in a polyamide resin is in the said range, the heat-resisting aging property of the polyamide resin composition of this embodiment can be improved further.

  In addition, the density | concentration of the terminal group of (A) polyamide resin mentioned above is an average value per unit mass also when the (A) polyamide resin is a mixture of 2 or more types.

In the polyamide resin composition of this embodiment, (A) at least a part of the polyamide resin has (a-1) at least an amino group end and a carboxyl group end, and the amino group end is larger than the carboxyl group end. It is a polyamide resin (hereinafter referred to as (a-1) polyamide resin having more amino group ends than carboxyl group ends, (a-1) polyamide resin, and (a-1) component).
(A-1) The ratio of the terminal groups in the polyamide resin is preferably 9/1 to 5.1 / 4.9, more preferably 8/2 to 5.5, as amino group concentration / carboxyl group concentration. /4.5, more preferably 7/3 to 6/4.
When the ratio of the terminal groups is within the above range, the metal corrosivity of the polyamide resin composition of the present embodiment can be further suppressed.

The concentration of the amino group terminal of the (a-1) polyamide resin is preferably 50 to 100 mmol / kg, more preferably 50 to 90 mmol / kg, still more preferably 50 to 80 mmol / kg, and still more preferably. Is 60-80 mmol / kg.
(A-1) When the concentration of the amino group terminal of the polyamide resin is within the above range, the metal corrosivity of the polyamide resin composition of the present embodiment can be further suppressed.
The concentration of the carboxyl group terminal of the (a-1) polyamide resin is preferably 100 mmol / kg or less, more preferably 80 mmol / kg or less, still more preferably 20 to 80 mmol / kg, and even more preferably 20-60 mmol / kg.
(A-1) When the carboxyl group terminal density | concentration in a polyamide resin is in the said range, the metal corrosivity of the polyamide resin composition of this embodiment can be suppressed further.

(A) The polyamide resin includes (a-2) a polyamide resin other than (a-1) (hereinafter, may be referred to as (a-2) polyamide resin, (a-2) component). May be.
(A-2) The polyamide resin is not particularly limited, but a polyamide resin having more carboxyl group ends than amino group ends is preferable.
(A-2) The ratio of the terminal groups in the polyamide resin is preferably 1/9 to 4.9 / 5.1, more preferably 2/8 to 4.5 as amino group concentration / carboxyl group concentration. /5.5, more preferably 3/7 to 4/6.
When the ratio of the terminal groups is within the above range, the copper depositability of the polyamide resin composition of this embodiment can be further suppressed.

The concentration of the amino group terminal of the (a-2) polyamide resin is preferably 20 to 60 μmol / g, more preferably 20 to 50 μmol / g, and further preferably 30 to 50 μmol / g.
(A-2) When the concentration of the amino group terminal of the polyamide resin is within the above range, the copper precipitation of the polyamide resin composition of the present embodiment can be further suppressed.
The concentration of the carboxyl group terminal of the (a-2) polyamide resin is preferably 20 μmol / g or more, more preferably 50 μmol / g or more, still more preferably 50 to 100 μmol / g, and even more preferably 60-90 μmol / g.
(A-2) When the carboxyl group terminal concentration in the polyamide resin is within the above range, the copper precipitation of the polyamide resin composition of the present embodiment can be further suppressed.

In the present specification, the concentrations of the amino group terminal and the carboxyl group terminal of each polyamide resin of the component (A), the component (a-1) and the component (a-2) are measured by ¹ H-NMR. It can be determined by the integral value of the characteristic signal corresponding to the end group, and the ratio of these concentrations can be calculated.

The concentration of terminal groups of (A) polyamide resin, (a-1) polyamide resin, and (a-2) polyamide resin can be adjusted by a known method.
Although the terminal group adjustment method is not limited to the following, for example, a method using a terminal adjusting agent can be mentioned.
Specifically, (A) at least one selected from the group consisting of a monoamine compound, a diamine compound, a monocarboxylic acid compound, and a dicarboxylic acid compound is added so as to have a predetermined terminal concentration during polymerization of the polyamide resin. Can be adjusted.
The timing of addition of these components to the polymerization solvent is not particularly limited as long as it functions as a terminal adjuster. For example, a method of adding the above-mentioned polyamide resin raw material to the polymerization solvent Is mentioned.
Examples of the monoamine compound include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Aliphatic monoamines such as alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and any mixtures thereof.
These may be used alone or in combination of two or more.
In particular, the monoamine compound is selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline from the viewpoints of reactivity, boiling point, sealing end stability, and price. One or more selected from the above are preferred.
Examples of the diamine compound include, but are not limited to, linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine, and branched branches such as 2-methylpentane diamine and 2-ethyl hexamethylene diamine. Type aliphatic diamines; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine.
These may be used alone or in combination of two or more.
Examples of the monocarboxylic acid compound include, but are not limited to, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid. , Aliphatic monocarboxylic acids such as pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenyl Aromatic monocarboxylic acids such as acetic acid can be mentioned.
These monocarboxylic acid compounds may be used alone or in combination of two or more.
Examples of the dicarboxylic acid compound include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2, Aliphatic dicarboxylic acids such as 2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; alicyclics such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Dicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, Diphenic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′- Units derived from an aromatic dicarboxylic acid such as carboxylic acid and 4,4'-biphenyl dicarboxylic acid (unit) and the like.
These dicarboxylic acid compounds may be used alone or in combination of two or more.

The (a-1) polyamide resin and the (a-2) polyamide resin may be the same type of polyamide resin (for example, both the (a-1) component and the (a-2) component are polyamide 66). Different types of polyamide resins (for example, the component (a-1) is polyamide 6 and the component (a-2) is polyamide 66) may be used.
In the case of different types of polyamide resins, (a-1) the ratio of carbon number / nitrogen number in the polymer chain of the polyamide resin (C / N ratio) and (a-2) carbon in the polymer chain of the polyamide resin The difference in the number / nitrogen number ratio (C / N ratio) is preferably a combination of 3 or less from the viewpoint of suppression of metal corrosivity and suppression of copper precipitation. 2 or less is more preferable, and it is more preferable that they are the same without difference.

Moreover, it is preferable that the melting point of the (a-1) polyamide resin is lower than the melting point of the (a-2) polyamide resin from the viewpoint of suppressing metal corrosiveness and copper precipitation.
The combination of these (a-1) polyamide resin and (a-2) polyamide resin is not limited to the following. For example, (a-1) the polyamide resin is polyamide 6, and (a- 2) The polyamide resin is at least one selected from the group consisting of polyamide 46, polyamide 56, polyamide 66, and a copolyamide containing these as constituents, more preferably (a-1) the polyamide resin is polyamide 6 (A-2) The polyamide resin is polyamide 46 and / or polyamide 66, more preferably (a-1) the polyamide resin is polyamide 6, and (a-2) the polyamide resin is polyamide 66. These combinations tend to improve hydrolysis resistance in addition to suppressing metal corrosiveness and copper precipitation.

((B) Copper compound)
The polyamide resin composition of the present embodiment contains (B) a copper compound (hereinafter sometimes referred to as “component (B)”).
(B) As a copper compound, although not limited to the following, for example, a copper halide compound (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate , Copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex with copper coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid Is mentioned.
These may be used alone or in combination of two or more.
Among the copper compounds (B) listed above, preferably selected from the group consisting of copper halide compounds (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.) and copper acetate. More preferably, it is a copper halide compound, more preferably copper iodide and / or cuprous bromide.
Polyamide resin composition that is excellent in heat aging resistance and can effectively suppress metal corrosion of the screw and cylinder during extrusion (hereinafter also simply referred to as “metal corrosion”) when the compounds listed as the preferred copper compounds are used. A thing is obtained.

The content of the (B) copper compound contained in the polyamide resin composition of the present embodiment is preferably 0.001 to 0.2% by mass with respect to 100% by mass of the polyamide resin composition of the present embodiment, More preferably, it is 0.005-0.15 mass%, More preferably, it is 0.01-0.1 mass%.
When the content of the (B) copper compound in the polyamide resin composition is within the above range, the heat aging resistance can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.
The content of copper element in the polyamide resin composition is preferably 0.001% by mass with respect to 100% by mass of the polyamide resin composition of the present embodiment, from the viewpoint of improving the heat aging resistance of the polyamide resin composition. It is above, More preferably, it is 0.005 mass% or more, More preferably, it is 0.005-0.05 mass%, More preferably, it is 0.007-0.03 mass%.

((C) Alkali metal and / or alkaline earth metal bromide)
The polyamide resin composition of this embodiment contains (C) an alkali metal and / or alkaline earth metal bromide (hereinafter sometimes referred to as component (C)).
(C) Alkali metal and / or alkaline earth metal bromides include, but are not limited to, for example, potassium bromide, sodium bromide, lithium bromide, calcium bromide and magnesium bromide, and These mixtures are mentioned.
In particular, potassium bromide and / or sodium bromide is preferable, and potassium bromide is more preferable from the viewpoint of improving the heat aging resistance of the polyamide resin composition of the present embodiment and suppressing metal corrosion.

The content of (C) alkali metal and / or alkaline earth metal bromide in the polyamide resin composition of the present embodiment is preferably 0.05 to 100 mass% of the polyamide resin composition of the present embodiment. It is 5 mass%, More preferably, it is 0.1-2 mass%, More preferably, it is 0.1-0.5 mass%.
(C) When the content of alkali metal and / or alkaline earth metal bromide is within the above range, the polyamide resin composition of the present embodiment is further improved in heat aging resistance and is effective in copper precipitation and metal corrosion. Can be suppressed.

In the polyamide resin composition of the present embodiment, the content ratio of the copper compound (B) and the bromide of the alkali metal and / or alkaline earth metal (C) is a molar ratio of halogen element to copper element (halogen). Element / copper element), preferably 2/1 to 50/1, more preferably 5/1 to 30/1, still more preferably 5/1 to 20/1. is there.
When the content ratio of (halogen element / copper element) is within the above range, the heat aging resistance of the polyamide resin composition of the present embodiment can be further improved.
Here, for example, when the (B) copper compound is a copper halide, the halogen element is a halogen element derived from copper halide and (C) a bromine element derived from a bromide of an alkali metal and / or alkaline earth metal. Mean total.
When the molar ratio of the halogen element to the copper element (halogen element / copper element) is 2/1 or more, in the polyamide resin composition of the present embodiment, copper precipitation and metal corrosion can be effectively suppressed. Therefore, it is preferable.
On the other hand, when the molar ratio (halogen element / copper element) is 50/1 or less, in the polyamide resin composition of the present embodiment, the mechanical properties such as toughness are hardly impaired, and the screw of the molding machine or the like. This is preferable because corrosion can be prevented.

  In the polyamide resin composition of the present embodiment, the (B) copper compound and the (C) alkali metal and / or alkaline earth metal bromide have (a-1) at least an amino group terminal and a carboxyl group terminal. It is a metal containing a masterbatch that is pre-blended in a polyamide resin having more amino group ends than carboxyl group ends and a polyamide resin other than (a-2) (a-1) described above. It is preferable from the viewpoints of suppressing corrosivity, suppressing copper precipitation, and further improving hydrolysis resistance.

  In the polyamide resin composition of the present embodiment, in addition to the components (A) to (C) described above, (D) one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts (hereinafter referred to as ( D) Fatty acid compound and (D) component may be described.), (E) Inorganic filler (hereinafter also referred to as (E) component) may be further contained in the polyamide resin composition. May be.

((D) fatty acid compound)
The (D) fatty acid compound preferably contains one or more fatty acid compounds selected from the group consisting of (D) fatty acid esters, fatty acid amides, and fatty acid metal salts from the viewpoint of further improving the heat aging resistance. .
(D) A fatty acid compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) The fatty acid which comprises a fatty acid compound shows aliphatic monocarboxylic acid.
In particular, fatty acids having 8 or more carbon atoms are preferable, and fatty acids having 8 to 40 carbon atoms are more preferable.
Examples of the fatty acid include, but are not limited to, a saturated or unsaturated, linear or branched aliphatic monocarboxylic acid.
Examples of fatty acids include, but are not limited to, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid.

The fatty acid ester is an ester compound of the fatty acid and alcohol.
Examples of the alcohol include, but are not limited to, 1,3-butanediol, trimethylolpropane, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.
Examples of fatty acid esters include, but are not limited to, stearyl stearate, behenyl behenate, montanic acid-1,3-butanediol ester, montanic acid-trimethylolpropane ester, trimethylolpropane trilaurate. And butyl stearate.

The fatty acid amide is an amidated product of the fatty acid.
Examples of the fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Examples include amides. In particular, stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucamide are preferable, and ethylene bisstearyl amide and N-stearyl erucamide are more preferable.

The said fatty acid metal salt is the metal salt of the fatty acid mentioned above.
Examples of metal elements that form salts with fatty acids include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), Group 3 elements, zinc, and aluminum in the Periodic Table of Elements.
As the metal element, alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; aluminum are preferable.
Examples of the fatty acid metal salt include, but are not limited to, for example, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, aluminum montanate, zinc montanate, Examples include magnesium montanate, calcium behenate, sodium behenate, zinc behenate, calcium laurate, zinc laurate, and calcium palmitate.
As the fatty acid metal salt, a metal salt of montanic acid, a metal salt of behenate and a metal stearate are preferably used, and in particular, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, and montanic acid. Zinc, magnesium montanate, calcium behenate, zinc behenate are preferred, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, zinc montanate, calcium behenate, zinc behenate are more preferred, calcium montanate More preferred are zinc montanate and zinc behenate.
These fatty acid metal salts may be used alone or in combination of two or more.
The metal content in the fatty acid metal salt is 3.5 to 11.5% by mass with respect to 100% by mass of the fatty acid metal salt, thereby suppressing metal corrosion and copper deposition of the polyamide resin composition of the present embodiment. From the viewpoint of further improving the appearance and releasability. More preferably, it is 3.5-10.0 mass%, More preferably, it is 4.0-9.0 mass%.

  From the viewpoint of suppressing metal corrosion and copper deposition of the polyamide resin composition of the present embodiment, the (D) fatty acid compound is an acid value measured according to JIS K 0070 (free fatty acid contained in 1 g of sample, resin acid, etc.). The number of mg of potassium hydroxide required for neutralization is preferably 10 mg / g or less. More preferably, it is 0.01-10 mg / g, More preferably, it is 0.01-5 mg / g, Most preferably, it is 0.01-3 mg / g.

  The fatty acid compound (D) is preferably a fatty acid amide or a fatty acid metal salt from the viewpoint of further improving moldability, and in particular, the appearance and releasability of the polyamide resin composition of the present embodiment are further improved. From the viewpoint, a fatty acid metal salt is more preferable.

The melting point of the (D) fatty acid compound is preferably 110 to 150 ° C., more preferably 115 to 145 ° C., from the viewpoint of further improving the appearance and releasability of the polyamide resin composition of the present embodiment. More preferably, it is 115-140 degreeC.
(D) The melting point of the fatty acid compound can be measured by differential scanning calorimetry (DSC) or the like.

The content of the (D) fatty acid compound is preferably 0.01 to 10% by mass, and 0.03 to 5% by mass with respect to 100% by mass of the polyamide resin composition of the present embodiment. More preferably, it is 0.05-2 mass%.
(D) By making content of a fatty acid compound into the said range, the polyamide resin composition which is further excellent in an external appearance, mold release property, mechanical strength, and plasticization property is obtained.

In the polyamide resin composition of the present embodiment, the content ratio of the (C) alkali metal and / or alkaline earth metal bromide and the (D) fatty acid compound is a mass ratio ((C) component / (D ) Component) is preferably 2/1 to 1/10, more preferably 2/1 to 1/5, still more preferably 1/1 to 1/5, and even more preferably 1/1. ~ 1/3.
When the mass ratio (component (C) / component (D)) is within the above range, in the polyamide resin composition of the present embodiment, the heat aging resistance can be further improved, and metal corrosion and copper deposition can be prevented. Further suppression can be achieved.

  In the polyamide resin composition of the present embodiment, (D) the fatty acid compound, together with the (B) copper compound, and the (C) alkali metal and / or alkaline earth metal bromide, in the master batch described above. (A-1) is pre-blended in a polyamide resin having at least an amino group end and a carboxyl group end and having more amino group ends than the carboxyl group end, and the polyamide resin composition of the present embodiment comprises the master The batch and (a-2) a polyamide resin other than the above (a-1) are mixed to suppress metal corrosiveness, copper precipitation, and further improve hydrolysis resistance. It is preferable from the viewpoint.

((E) inorganic filler)
(E) As an inorganic filler, although not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, flaky glass, talc, kaolin, Mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, Sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluoromica and Apatite, and the like.
These may be used alone or in combination of two or more.
Among those exemplified above, from the viewpoint of increasing the mechanical strength and rigidity of the polyamide resin composition of the present embodiment, glass fiber, carbon fiber, flaky glass, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, One or more selected from the group consisting of wollastonite, silica, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swellable fluorine mica and apatite are preferred. More preferably, it is at least one selected from the group consisting of glass fiber, carbon fiber, wollastonite, talc, mica, kaolin and silicon nitride.

  Among the glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical properties to the polyamide resin composition, the polyamide resin composition has a number average fiber diameter of 3 to 30 μm and a weight average fiber length of 100 to 100. More preferably, it is 750 μm, and the aspect ratio of the weight average fiber length to the number average fiber diameter (value obtained by dividing the weight average fiber length by the number average fiber diameter) is 10 to 100.

  Of the wollastonite, the polyamide resin composition has a number average fiber diameter of 3 to 30 μm and a weight average fiber length of 10 from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition. It is more preferable that it is ˜500 μm and the aspect ratio is 3 to 100.

  In addition, among the talc, mica, kaolin, and silicon nitride, the number average particle size in the polyamide resin composition is 0.1 to 10 μm from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition. More preferred.

Here, the number average fiber diameter, number average particle diameter, and weight average fiber length in the present specification can be measured by the following methods.
The polyamide resin composition is put in an electric furnace, the contained organic matter is incinerated, for example, 100 or more inorganic fillers are arbitrarily selected from the residue, and observed by SEM, and the fiber diameters of these inorganic fillers And the number average fiber diameter and the number average particle diameter are measured by measuring the particle diameter. In addition, the weight average fiber length is determined by measuring the fiber length using an SEM photograph at a magnification of 1000 times.

The (E) inorganic filler may be surface-treated with a silane coupling agent or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Aminosilanes such as dimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
In particular, at least one selected from the above listed components is preferable, and aminosilanes are more preferable.

In addition, for the glass fiber and the carbon fiber, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are further used as a sizing agent. Copolymers, epoxy compounds, polycarbodiimide compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary, and tertiary thereof It may contain a salt with an amine. These may be used alone or in combination of two or more.
The glass fiber and carbon fiber containing a sizing agent can be obtained by continuously reacting the sizing agent in a known glass fiber and carbon fiber production process.
Specifically, the glass fiber and the carbon fiber are obtained by drying a fiber strand produced by applying the sizing agent to the glass fiber and the carbon fiber using a known method such as a roller type applicator.
The fiber strands may be used as rovings as they are, or may be used as chopped glass strands after further cutting.

The sizing agent preferably imparts (adds) a solid content of 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, with respect to 100% by mass of glass fiber or carbon fiber. Apply (add).
From the viewpoint of maintaining the bundling of the glass fiber and the carbon fiber, the addition amount of the sizing agent is preferably equivalent to 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or the carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition of the present embodiment, it is preferably equivalent to 3% by mass or less. Moreover, drying of a strand may be performed after a cutting process, or a cutting process may be performed after drying of a strand.

  The content of the (E) inorganic filler in the polyamide resin composition of the present embodiment is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, from the viewpoint of improving moldability and mechanical strength. %, And more preferably 20 to 65% by mass.

(Other ingredients)
In addition to the components (A) to (E) described above, the polyamide resin composition of the present embodiment may further contain other components as necessary within a range not impairing the effects of the present invention.
Other components include, but are not limited to, for example, antioxidants, ultraviolet absorbers, heat stabilizers, photodegradation inhibitors, plasticizers, lubricants, mold release agents, nucleating agents, flame retardants, Coloring agents, dyeing agents, pigments and the like may be added, or other thermoplastic resins may be mixed.
Here, since the properties of the other components are greatly different from each other, there are various suitable contents for each component that hardly impair the effects of the present embodiment. A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of polyamide resin composition]
Although it does not restrict | limit to the following as a manufacturing method of the polyamide resin composition of this embodiment, For example, in the state which melted (A) polyamide resin with the single screw or the multi-screw extruder, the said (B) component, ( A method of kneading the component (C) and, if necessary, the component (D) can be used.
(E) When using an inorganic filler, a twin screw extruder provided with an upstream supply port and a downstream supply port is used, and (A) the polyamide resin, the component (B), (C It is preferable to use a method in which the component (D) and the component (D) are supplied and melted, and then the (E) inorganic filler is supplied from the downstream supply port and melt-kneaded. Moreover, also when using rovings, such as glass fiber and carbon fiber, it can compound by a well-known method.

[Characteristics of polyamide resin composition]
In the polyamide resin composition of the present embodiment, precipitation of copper element occurs on the surface of the rolled steel material when it is brought into contact with the rolled steel material (SS400) for 8 hours at a temperature of (A) the melting point of the polyamide resin + 30 ° C. It is preferable not to.
In the polyamide resin composition of the present embodiment, (a-1) copper precipitation can be effectively suppressed by using a polyamide resin having more amino terminal groups than carboxyl terminal groups. Moreover, copper precipitation can be effectively suppressed by using a fatty acid compound having an acid value of 10 mg / g or less as the (D) fatty acid compound. Further, (B) a copper compound and (C) an alkali metal compound and / or an alkaline earth metal bromide are blended in advance as a masterbatch with (a-1) a polyamide resin having more amino terminal groups than carboxyl terminal groups. Copper deposition can be more effectively suppressed by using a polyamide resin composition in which the master batch and (a-2) a polyamide resin other than (a-1) are combined.
That is, by appropriately applying these methods, when (A) the polyamide resin is brought into contact with the rolled steel material (SS400) for 8 hours at a temperature of the melting point of the polyamide resin + 30 ° C., copper element is deposited on the surface of the rolled steel material. It may not occur.
About the copper precipitation of the polyamide resin composition of this embodiment, it can verify by the method described in the Example mentioned later.

[Molded body]
The molded body of the present embodiment includes the polyamide resin composition of the present embodiment described above.
The molded body of the present embodiment can be obtained, for example, by injection molding a polyamide resin composition.

[Use]
The molded body of this embodiment can be suitably used, for example, as various molded bodies and parts for automobiles, machine industries, electrical / electronics, industrial materials, industrial materials, daily / household goods, and the like.

  Hereinafter, although a specific Example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited to the following examples.

〔Evaluation method〕
Hereinafter, evaluation methods performed in Examples and Comparative Examples will be described.
<Heat aging resistance (tensile strength retention after heat aging)>
The pellets of the polyamide resin composition obtained in the examples and comparative examples were obtained by using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.) while conforming to ISO 3167 and using a multipurpose test piece (A type). Molded pieces were produced.
At that time, the injection and pressure holding time were set to 25 seconds, the cooling time was set to 15 seconds, the mold temperature was 80 ° C., and the molten resin temperature was 290 ° C.
Using the obtained multipurpose test piece (A type), a tensile test was performed at a tensile speed of 5 mm / min in accordance with ISO 527, and a tensile strength (MPa) was measured.
Moreover, the multipurpose test piece (A type) was heat-aged at 180 ° C. for 2,000 hours in a hot-air circulating oven.
After cooling this at 23 ° C. for 24 hours or more, a tensile test was conducted at a tensile speed of 5 mm / min in accordance with ISO 527, and the tensile strength (MPa) after heat aging for 2,000 hours was measured. The tensile strength retention rate (%) relative to the tensile strength was evaluated.

<Metal corrosion>
20 g of pellets of the polyamide resin compositions obtained in the examples and comparative examples were put into a SUS314 autoclave having a pressure resistance of 2.0 MPa and an internal volume of 100 mL, and the surface was polished by # 2000 on a rolled steel material (SS400) of 10 mm × 20 mm × 2 mm. A test piece was put, and 20 g of a polyamide resin composition pellet was further put, and the rolled steel material test piece was buried.
The inside of the autoclave was purged with nitrogen and sealed, and when the polyamide resin used in the polyamide resin composition was PA66, it was heated at 290 ° C., and when PA6 was 250 ° C., it was heated for 8 hours.
Subsequently, the autoclave was opened by cooling to room temperature under running water.
A rolled steel material test piece is taken out from the pellet of the melted and solidified polyamide resin composition, and after removing the polyamide resin composition adhering to the surface of the rolled steel material test piece using HFIP (hexafluoropropanol), the mass of the rolled steel material test piece is obtained. Was precisely weighed to the nearest 0.01 mg and divided by the mass of the pre-test rolled steel specimen previously measured to obtain the mass reduction rate in mass ppm.

<Copper deposition>
The surface of the rolled steel material test piece after the metal corrosion test was observed, and the state of copper element precipitation was visually observed and evaluated as follows.
A: No precipitation of copper element was observed.
○: Precipitation of copper element was less than 5% with respect to the surface area of the rolled steel.
Δ: Precipitation of copper element was 5% or more and less than 10% with respect to the surface area of the rolled steel material.
X: Precipitation of copper element was 10% or more with respect to the surface area of the rolled steel material.

<Hydrolysis resistance (tensile strength retention after immersion in LLC solution)>
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the polyamide resin composition pellets obtained in the examples and comparative examples were injected and held for 10 seconds, cooled for 15 seconds, and mold temperature. A dumbbell molded piece of small tensile test piece type 4 type (3 mmt) conforming to ISO 8256 was formed at 80 ° C. and a molten resin temperature of 290 ° C. The obtained test piece was immersed in pure water / long life coolant liquid (LLC liquid; G48 manufactured by BASF) = 50/50 at 130 ° C. for 24 hours and 500 hours using an autoclave.
The test piece after immersion was subjected to a tensile test at a distance between chucks of 30 mm and a tensile speed of 1 mm / min.
The tensile strength retention (%) after 500 hours immersion was evaluated with respect to the tensile strength after 24 hours immersion.

[Preparation of raw materials]
(1. (A) Polyamide resin)
(1-1) Polyamide 66 (hereinafter abbreviated as “PA-1”)
VN (sulfuric acid): 143 ml / g, amino end group: 48 mmol / kg,
Carboxylic acid end group: 79 mmol / kg
(1-2) Polyamide 66 (hereinafter abbreviated as “PA-2”)
VN (sulfuric acid): 140 ml / g, amino end group: 80 mmol / kg,
Carboxylic acid end group: 46 mmol / kg
(1-3) Polyamide 6 (hereinafter abbreviated as “PA-3”)
VN (sulfuric acid): 141 ml / g, amino end group: 45 mmol / kg,
Carboxylic acid end group: 82 mmol / kg
(1-4) Polyamide 6 (hereinafter abbreviated as “PA-4”)
VN (sulfuric acid): 140 ml / g, amino end group: 70 mmol / kg,
Carboxylic acid end group: 49 mmol / kg

(2. (B) Copper iodide (hereinafter abbreviated as “CuI”))
A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.

(3. (C) Potassium bromide (hereinafter abbreviated as “KBr”))
A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.

(4. (D) Fatty acid compound)
(4-1) Calcium montanate (hereinafter abbreviated as “MonCa”)
Acid value: 0.8 mg / g, Melting point: 120 ° C.
(4-2) Montanic acid-1,3-butanediol ester (hereinafter abbreviated as “MonEs”)
Acid value: 15 mg / g, melting point: 80 ° C.

(5. (E) inorganic filler: glass fiber (hereinafter abbreviated as “GF”))
Product name: ECS 03T-275H (manufactured by Nippon Electric Glass Co., Ltd.) was used.

[Example 1]
L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = 48 (number of barrels: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used.
In the twin-screw extruder, the temperature from the upstream supply port to the die was set to 250 ° C., the screw rotation speed 250 rpm, and the discharge amount 25 kg / hour.
Under such conditions, the polyamide resin (PA-4) is 80 parts by mass, the CuI is 2 parts by mass, the KBr is 12 parts by mass, and the calcium montanate is 6 parts by mass. A polyamide resin composition PA-MB was obtained.
About the obtained polyamide resin composition PA-MB, when metal corrosivity was evaluated, the mass reduction | decrease rate was 75 ppm and precipitation of copper was not observed.

[Examples 2 to 5], [Comparative Examples 1 and 2]
L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = 48 (number of barrels: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used.
In the twin-screw extruder, the distance from the upstream supply port to the die was set to 280 ° C., the screw rotation speed 250 rpm, and the discharge amount 25 kg / hour.
Under such conditions, the polyamide resin (PA), CuI, KBr, and fatty acid compound are respectively supplied from the upstream supply port and GF is supplied from the downstream supply port according to the ratio described in the upper column of Table 1 below. did.
These were melt-kneaded to produce polyamide resin composition pellets.
In Example 5, the polyamide resin composition PA-MB produced in Example 1 was used, and the polyamide resin and the polyamide resin composition PA-MB were supplied from the upstream supply port, and GF was supplied from the downstream supply port. Supplied.
The obtained polyamide resin composition was molded at the above-mentioned molten resin temperature and mold temperature, and heat aging resistance, metal corrosion resistance, copper precipitation, and hydrolysis resistance were evaluated.
The evaluation (counting) results are shown in Table 1 below.

How to read Table 1 will be described.
The higher the tensile strength retention after heat aging, the better the heat aging resistance.
Furthermore, it shows that metal corrosivity is suppressed effectively, so that the mass reduction amount of a metal corrosion test is small.
Moreover, it shows that it is excellent in hydrolysis resistance, so that the intensity | strength retention rate after LLC liquid immersion is high.

As shown in Table 1, in Examples 2 to 5, although the type of polyamide resin having more amino terminal groups than the carboxyl terminal groups and the acid value of the fatty acid compound are different, the heat aging resistance is high, metal corrosion and A polyamide resin composition having excellent thermal stability and excellent balance in suppressing copper deposition was obtained.
Among Examples 2-5, when the acid value of (D) fatty acid compound is 10 mg / g or less by contrast of Example 2, 3 and Example 4, it is especially excellent in metal corrosivity and copper precipitation. I understood that. In addition, Example 5 in which the copper compound and bromide are blended in advance as a masterbatch with (a-1) a polyamide resin having more amino terminal groups than carboxyl terminal groups is particularly excellent in metal corrosivity and copper precipitation, It was found to be excellent in hydrolysis resistance.
On the other hand, (a-1) Comparative Examples 1 and 2 which are polyamide resins having more amino terminal groups than carboxyl terminal groups (PA-2) and (PA-4) are not corrosive to metal or copper precipitated. It turned out to be inferior.
From the above, it has been found that the polyamide resin composition of the present invention is excellent in heat aging resistance, can effectively suppress metal corrosion, and can obtain a remarkable suppression effect on copper precipitation.

  The polyamide resin composition of the present invention has industrial applicability as a material for molded products that require high-level mechanical properties such as automobile parts and various electronic parts.

Claims (10)

(A) a polyamide resin;
(B) a copper compound;
(C) an alkali metal and / or alkaline earth metal bromide;
A polyamide resin composition comprising:
A polyamide resin composition in which at least a part of the (A) polyamide resin is (a-1) a polyamide resin having at least an amino group end and a carboxyl group end, and having more amino group ends than carboxyl group ends.   2. The polyamide resin composition according to claim 1, wherein the (a-1) polyamide resin has an amino terminal group concentration of 50 to 80 mmol / kg. A masterbatch in which the (B) copper compound, and the (C) alkali metal and / or alkaline earth metal bromide are blended in advance in the (a-1) polyamide resin;
(A-2) a polyamide resin other than (a-1),
The polyamide resin composition according to claim 1 or 2, comprising (D) one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts,
The acid value of the (D) fatty acid compound is 10 mg / g or less,
The polyamide resin composition according to any one of claims 1 to 3. The master batch contains (D) one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts,
The polyamide according to claim 3 or 4, preliminarily blended in the (a-1) polyamide resin together with the (B) copper compound and the (C) alkali metal and / or alkaline earth metal bromide. Resin composition.   The polyamide resin composition according to any one of claims 1 to 5, wherein the (B) copper compound is a copper halide compound. The proportion of copper element contained in the polyamide resin composition is
The polyamide resin composition according to any one of claims 1 to 6, which is 0.005 mass% or more with respect to 100 mass% of the polyamide resin composition.   (E) The polyamide resin composition according to any one of claims 1 to 7, further comprising an inorganic filler. (A) At the temperature of the melting point of the polyamide resin + 30 ° C., when contacted with the rolled steel (SS400) for 8 hours, no precipitation of copper element occurs on the surface of the rolled steel.
The polyamide resin composition according to any one of claims 1 to 8.   The molded object containing the polyamide resin composition as described in any one of Claims 1 thru | or 9.