JP5490648B2 - Auto parts comprising a polyamide composition - Google Patents

Description

  The present invention relates to an automotive part comprising a polyamide composition.

  Polyamides represented by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties or chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

By the way, in the automobile industry, as an environmental measure, there is a demand for weight reduction of the vehicle body by metal replacement in order to reduce exhaust gas. In order to meet such demands, polyamides are increasingly used for exterior materials and interior materials, and the level of required properties such as heat resistance, strength, and appearance for polyamide materials is further improved. Above all, since the temperature in the engine room is also increasing, there is an increasing demand for higher heat resistance for the polyamide material.
In addition, in the electrical and electronic industries such as home appliances, high heat resistance of polyamide materials is required so as to be able to withstand the rise in melting point of solder in order to cope with lead-free surface mount (SMT) solder.
Polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.

In order to solve the above problems of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.
However, since PA6T is a high-melting-point polyamide having a melting point of about 370 ° C., it is difficult to obtain a molded product having sufficient characteristics due to severe pyrolysis of the polyamide even if a molded product is obtained by melt molding.

  In order to solve the above-mentioned problems of PA6T, PA6T may be abbreviated as aliphatic polyamide such as PA6 and PA66 or amorphous aromatic polyamide (hereinafter referred to as “PA6I”) composed of isophthalic acid and hexamethylenediamine. ) And the like, and a high melting point semi-aromatic polyamide mainly composed of terephthalic acid and hexamethylenediamine (hereinafter referred to as “6T copolymer polyamide”) whose melting point is lowered to about 220 to 340 ° C. Have been proposed).

  As a 6T copolymer polyamide, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. May be abbreviated as “PA6T / 2MPDT”).

  Further, in contrast to an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine (hereinafter sometimes abbreviated as “PA46”) or an alicyclic ring. An alicyclic polyamide composed of an aliphatic dicarboxylic acid and an aliphatic diamine has been proposed.

Patent Documents 2 and 3 disclose semialicyclic polyamides of alicyclic polyamides (hereinafter sometimes referred to as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and other polyamides. (Hereinafter, it may be abbreviated as “PA6C copolymer polyamide”).
Further, Patent Document 2 discloses that the heat and heat resistance of semi-alicyclic polyamides containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit is improved in solder heat resistance. 3 discloses that an automobile part is excellent in fluidity and toughness.

Furthermore, Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, lightness, And excellent heat resistance and the like. In addition, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or less to form a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to have a melting point of 311 ° C. The production of polyamides is disclosed.
In Patent Document 5, a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet

  However, although the 6T copolymer polyamide has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low fluidity and insufficient moldability and surface appearance of the molded product, toughness and Inferior in light resistance. Therefore, improvement is desired in applications where the appearance of a molded product such as an exterior part is required or exposed to sunlight. In addition, the specific gravity is large, and improvement in lightness is also desired.

  Further, the PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymer polyamide, but it has fluidity, moldability, toughness, surface appearance of the molded product, and light resistance. However, the level of improvement is insufficient.

  Furthermore, PA 46 has good heat resistance and moldability, but has a high water absorption rate, and has a problem that a dimensional change and a decrease in mechanical properties due to water absorption are remarkably large. There are cases where the requirements cannot be met in terms of dimensional changes.

Furthermore, the PA6C copolymer polyamides disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity. Furthermore, the polyamides disclosed in Patent Documents 4 and 5 also There is a problem that improvement is insufficient in terms of toughness, strength, and fluidity.

  The problem to be solved by the present invention is an automotive part that is excellent in fluidity, strength, rigidity, toughness and low water absorption, and also excellent in high temperature rigidity, heat aging resistance, vibration fatigue resistance, LLC resistance and surface appearance. It is to provide.

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, the above-mentioned problem is solved in an automotive part including a polyamide composition containing a polyamide obtained by polymerizing alicyclic dicarboxylic acid and a diamine having a substituent branched from the main chain as a constituent component and an inorganic filler. The present inventors have found that this can be done and have completed the present invention.

That is, the present invention is as follows.
[1]
(A) (a) a polyamide obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain; ,
(B) an inorganic filler;
An automobile part comprising a polyamide composition containing
[2]
The automobile part according to [1], wherein the diamine having a substituent branched from the main chain is 2-methylpentamethylenediamine.
[3]
The automobile part according to [1] or [2], wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.
[4]
The automobile part according to any one of [1] to [3], wherein (a) the dicarboxylic acid containing at least 50 mol% of the alicyclic dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms. .
[5]
The automobile part according to any one of [1] to [4], wherein the (A) polyamide is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.
[6]
The automotive part according to any one of [1] to [5], wherein the polyamide (A) has a melting point of 270 to 350 ° C.
[7]
The automobile part according to any one of [1] to [6], wherein a trans isomer ratio in a portion derived from the alicyclic dicarboxylic acid in the (A) polyamide is 50 to 85%.
[8]
The automobile according to any one of [1] to [7], wherein the polyamide composition contains 1 to 200 parts by mass of the inorganic filler (B) with respect to 100 parts by mass of the polyamide (A). parts.
[9]
The automobile part according to any one of [1] to [8], wherein the polyamide composition further contains (C) a copper compound and a metal halogen compound.
[10]
The automobile part according to [9], wherein the copper compound is copper acetate and / or copper iodide, and the metal halide compound is potassium iodide.
[11]
(A) The said [9] or [10] containing the said copper compound 0.01-0.6 mass part and the said metal halogen compound 0.05-20 mass part with respect to 100 mass parts of said polyamides. Car parts.
[12]
The automobile component according to any one of [9] to [11], wherein a molar ratio of halogen and copper (halogen / copper) is 2/1 to 50/1.
[13]
Any one of [9] to [12] above, wherein the copper compound is contained so that the content as copper is 50 to 2,000 parts by mass with respect to 10 ⁶ parts by mass of the (A) polyamide. Auto parts as described.
[14]
The automobile part according to any one of [1] to [13], which is an automobile underhood part.
[15]
The automobile part according to any one of [1] to [13], which is an automobile mechanism part.
[16]
The automobile part according to any one of [1] to [13], which is an automobile exterior part.
[17]
The automobile part according to any one of [1] to [13], which is an automobile interior part.
[18]
The automobile part according to any one of [1] to [13], which is an automobile electrical part.

  According to the present invention, it is possible to provide an automotive part which is excellent in fluidity, strength, rigidity, toughness and low water absorption, and also excellent in high temperature rigidity, heat aging resistance, vibration fatigue resistance, LLC resistance and surface appearance. it can.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

(Auto parts)
The automobile part of this embodiment contains a polyamide composition, and the polyamide composition used in this embodiment contains (A) polyamide and (B) an inorganic filler.
Here, “automobile parts” in the present embodiment means automobile parts excluding automobile intake system parts and automobile cooling system parts.

(Polyamide composition)
As described above, the polyamide composition contains (A) polyamide and (B) inorganic filler as essential components.
[(A) Polyamide]
The polyamide (A) contained in the polyamide composition is a polyamide obtained by polymerizing the following (a) and (b).
(A) A dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid.
(B) A diamine containing at least 50 mol% of a diamine having a substituent branched from the main chain.
In the present embodiment, polyamide means a polymer having an amide (—NHCO—) bond in the main chain.

[(A) Dicarboxylic acid]
The (a) dicarboxylic acid that is a polymerization component of the polyamide (A) contains at least 50 mol% of an alicyclic dicarboxylic acid.
(A) When dicarboxylic acid contains alicyclic dicarboxylic acid at least 50 mol%, it can be set as the polyamide which satisfy | fills simultaneously the heat resistance, fluidity | liquidity, toughness, low water absorption, intensity | strength, etc. of the automotive component obtained.

<(A-1) Alicyclic dicarboxylic acid>
(A-1) Examples of alicyclic dicarboxylic acids (also referred to as alicyclic dicarboxylic acids) include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentane. An alicyclic dicarboxylic acid such as a dicarboxylic acid, preferably having 3 to 10 carbon atoms, more preferably 5 to 10 carbon atoms in the alicyclic structure.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

As the alicyclic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of heat resistance, low water absorption and strength.
As alicyclic dicarboxylic acid, you may use individually by 1 type and may be used in combination of 2 or more type.

An alicyclic dicarboxylic acid has a geometric isomer of a trans isomer and a cis isomer.
Either the trans isomer or the cis isomer may be used as the alicyclic dicarboxylic acid as the raw material monomer, or a mixture of various ratios of the trans isomer and the cis isomer may be used.
Alicyclic dicarboxylic acids are isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with diamine than the trans isomer. The ratio of isomer / cis isomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35/65 to 15/85 in terms of molar ratio. .
The trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR). Here, the trans isomer / cis isomer ratio (molar ratio) in the present specification is determined by 1H-NMR.

<(A-2) Dicarboxylic acid other than alicyclic dicarboxylic acid>
Among (a) dicarboxylic acids used in the present embodiment, dicarboxylic acids other than the above-described (a-1) alicyclic dicarboxylic acids (hereinafter referred to as (a-2) dicarboxylic acids other than alicyclic dicarboxylic acids). ) Include, for example, aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, and 2,3-diethyl glutaric acid. , Glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as diacid, eicosane diacid, and diglycolic acid.

Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above substituent.
Examples of the various substituents include, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a halogen group such as a chloro group and a bromo group, and 1 carbon atom. ˜6 silyl groups, and sulfonic acid groups and salts thereof (such as sodium salts).

In the case of copolymerizing a dicarboxylic acid other than the (a-2) alicyclic dicarboxylic acid, it is preferably an aliphatic dicarboxylic acid, more preferably in terms of heat resistance, fluidity, toughness, low water absorption and strength. Is an aliphatic dicarboxylic acid having 6 or more carbon atoms.
Among these, aliphatic dicarboxylic acids having 10 or more carbon atoms are preferable from the viewpoints of heat resistance and low water absorption.
Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.
Of these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.
Dicarboxylic acids other than the (a-2) alicyclic dicarboxylic acid may be used singly or in combination of two or more.

Further, (a) a dicarboxylic acid component may further contain a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid within a range not impairing the object of the present embodiment.
As polyvalent carboxylic acid, you may use individually by 1 type and may be used in combination of 2 or more type.

The proportion (mol%) of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 50 mol%. The proportion of the alicyclic dicarboxylic acid is 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and more preferably 100 mol%. When the ratio of the alicyclic dicarboxylic acid is at least 50 mol%, a polyamide having excellent heat resistance, low water absorption, strength, and the like can be obtained.
(A) The ratio (mol%) of dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 50 mol%, and preferably 0 to 40 mol%.

  When (a) the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 10 or more carbon atoms, (a-1) 50-99.9 mol% of the alicyclic dicarboxylic acid and (a-2) 10 carbon atoms. It is preferable that it is 0.1-50 mol% of the above aliphatic dicarboxylic acid, (a-1) 60-95 mol% of alicyclic dicarboxylic acid, and (a-2) C10 or more aliphatic dicarboxylic acid. More preferably, it is 5-40 mol%, (a-1) alicyclic dicarboxylic acid is 80-95 mol% and (a-2) C10 or more aliphatic dicarboxylic acid is 5-20 mol%. More preferably.

In the present embodiment, the (a) dicarboxylic acid is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids. Can be mentioned.

[(B) Diamine]
The (b) diamine which is a polymerization component of the polyamide (A) contains at least 50 mol% of a diamine having a substituent branched from the main chain.
(B) By containing at least 50 mol% of a diamine having a substituent branched from the main chain as the diamine, a polyamide that simultaneously satisfies fluidity, toughness, strength, and the like can be obtained.
Examples of the substituent branched from the main chain include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. Is mentioned.

<(B-1) Diamine with Substituent Branched from Main Chain>
(B-1) Examples of the diamine having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane) and 2,2,4-. Examples include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine. .
The diamine having a substituent branched from the main chain is preferably 2-methylpentamethylenediamine from the viewpoints of heat resistance and strength.
As the diamine having a substituent branched from the main chain, one kind may be used alone, or two or more kinds may be used in combination.

<(B-2) Diamines other than diamines having substituents branched from the main chain>
Among the (b) diamines used in the present embodiment, diamines other than the diamine having a substituent branched from the above-mentioned (b-1) main chain (hereinafter referred to as (b-2) having a substituent branched from the main chain. Examples of diamines other than diamines include aliphatic diamines, alicyclic diamines, and aromatic diamines.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, And straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as tridecamethylenediamine.

  Examples of the alicyclic diamine (also referred to as alicyclic diamine) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.

  The aromatic diamine is an aromatic diamine, such as metaxylylenediamine.

(B-2) The diamine other than the diamine having a substituent branched from the main chain is preferably an aliphatic diamine or an alicyclic diamine in terms of heat resistance, fluidity, toughness, low water absorption and strength. Yes, more preferably a linear saturated aliphatic diamine having 4 to 13 carbon atoms, still more preferably a linear saturated aliphatic diamine having 6 to 10 carbon atoms, and even more preferably hexamethylene diamine.
(B-2) A diamine other than a diamine having a substituent branched from the main chain may be used singly or in combination of two or more.

(B) As the diamine component, a trivalent or higher polyvalent amine such as bishexamethylenetriamine may be further included within a range not impairing the object of the present embodiment.
A polyvalent amine may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) The ratio (mol%) of the diamine having a substituent branched from the main chain (b-1) in the diamine is at least 50 mol%. The ratio of the diamine having a substituent branched from the main chain is 50 to 100 mol%, and preferably 60 to 100 mol%. More preferably, it is 80-100 mol%, More preferably, it is 85-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is 100 mol%. When the ratio of the diamine having a substituent branched from the main chain is at least 50 mol%, a polyamide having excellent fluidity, toughness, and strength can be obtained.
(B) The ratio (mol%) of diamines other than the diamine having a substituent branched from the main chain (b-2) in the diamine is 0 to 50 mol%, preferably 0 to 40 mol%.

  The addition amount of (a) dicarboxylic acid and the addition amount of (b) diamine are preferably around the same molar amount. The amount of (b) diamine escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and (a) the molar amount of (b) diamine as a whole is 0 It is preferably .90 to 1.20, more preferably 0.95 to 1.10, and still more preferably 0.98 to 1.05.

[(C) Lactam and / or aminocarboxylic acid]
(A) Polyamide can further copolymerize (c) lactam and / or aminocarboxylic acid from a viewpoint of toughness.
(C) A lactam and / or aminocarboxylic acid means a lactam and / or aminocarboxylic acid that can be condensed (condensed).
When (A) polyamide is a polyamide obtained by polymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, (c) lactam and / or aminocarboxylic acid is A lactam having 4 to 14 carbon atoms and / or an aminocarboxylic acid is preferable, and a lactam having 6 to 12 carbon atoms and / or an aminocarboxylic acid is more preferable.

Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
Among these, from the viewpoint of toughness, ε-caprolactam and laurolactam are preferable, and ε-caprolactam is more preferable.
Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which the lactam is ring-opened.
The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, such as 6-aminocaproic acid, 11-aminoundecanoic acid, And 12-aminododecanoic acid. The aminocarboxylic acid may be paraaminomethylbenzoic acid.
(C) A lactam and / or aminocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
(C) The addition amount (mol%) of the lactam and / or aminocarboxylic acid is 0 to 20 mol% with respect to the molar amount of each monomer in (a), (b) and (c). preferable.

(End sealant)
When a polyamide is polymerized from (a) a dicarboxylic acid and (b) a diamine, and (c) a lactam and / or an aminocarboxylic acid, if necessary, a known end-capping agent is further added to adjust the molecular weight. Can do.
Examples of the end-capping agent include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint, monocarboxylic acid and monoamine are preferable.
A terminal blocker may be used individually by 1 type, and may be used in combination of 2 or more type.

The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , Caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluyl And aromatic monocarboxylic acids such as acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
Monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; Etc.
As monoamine, it may be used individually by 1 type and may be used in combination of 2 or more type.

The combination of (a) dicarboxylic acid and (b) diamine is not limited to the following, but 50 mol% or more of (a-1) dicarboxylic acid containing alicyclic dicarboxylic acid and 50 mol% or more of ( b-1) A combination of diamines containing 2-methylpentamethylenediamine is preferred, 50 mol% or more of (a-1) dicarboxylic acid containing 1,4-cyclohexanedicarboxylic acid and 50 mol% or more of (b-1) A combination of diamines containing 2-methylpentamethylenediamine is more preferred.
By polymerizing these combinations as polyamide components, a polyamide having excellent heat resistance, fluidity, toughness, low water absorption and strength can be obtained.

(A) In polyamide, an alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.
(A) In the polyamide, (a-1) the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid is such that the portion derived from the alicyclic dicarboxylic acid in the entire alicyclic dicarboxylic acid in the polyamide is trans. It is expressed as a ratio that is an isomer. The trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 60 to 80 mol%.
(A-1) As the alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100. In (A) polyamide obtained by polymerization of (a) dicarboxylic acid and (b) diamine, the trans isomer ratio in the part derived from (a-1) alicyclic dicarboxylic acid is 50 to 85 mol%. It is preferable.
When the trans isomer ratio is within the above range, the polyamide has a high melting point, toughness and strength, as well as high thermal rigidity due to a high Tg, and fluidity, which is usually opposite to heat resistance. And having a high crystallinity at the same time.
These features consist of a combination of (a) a dicarboxylic acid containing 50 mol% or more of 1,4-cyclohexanedicarboxylic acid and (b) a diamine containing 50 mol% or more of 2-methylpentamethylenediamine, and trans isomerism This is particularly remarkable for polyamides having a body ratio of 50 to 85 mol%.
In the present embodiment, the trans isomer ratio can be measured by the method described in the following examples.

[(A) Polyamide production method]
(A) Polyamide is not particularly limited, but (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of an aliphatic having a substituent branched from the main chain. It can manufacture with the manufacturing method of polyamide including the process of polymerizing diamine containing diamine.
(A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

(A) As a manufacturing method of polyamide, various methods are mentioned, for example so that it may illustrate below.
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to as “hot melt polymerization method”).
2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter, sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”). .
3) A method in which an aqueous solution or a suspension of water of a diamine / dicarboxylate salt or a mixture thereof is heated and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as “pre-polymerization”). It may be abbreviated as “polymer / extrusion polymerization method”).
4) A method of heating an aqueous solution or a suspension of water of a diamine dicarboxylate or a mixture thereof and increasing the degree of polymerization while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide (hereinafter, (It may be abbreviated as “prepolymer / solid phase polymerization method”).
5) A method of polymerizing a diamine dicarboxylate or a mixture thereof while maintaining a solid state (hereinafter, sometimes abbreviated as “solid phase polymerization method”).
6) A method of polymerizing using a dicarboxylic acid halide component equivalent to dicarboxylic acid and a diamine component (hereinafter also referred to as “solution method”).

(A) In the polyamide production method, from the viewpoint of polyamide fluidity, the trans isomer ratio in the part derived from (a-1) alicyclic dicarboxylic acid is maintained at 85% or less in (A) polyamide. Polymerization is preferred, and in particular, by maintaining it at 80% or less, a polyamide having a higher color tone and tensile elongation and a high melting point can be obtained.
In the polyamide production method, it is necessary to increase the heating temperature and / or lengthen the heating time in order to increase the degree of polymerization and increase the melting point of the polyamide. However, in that case, the polyamide may be colored by heating or the tensile elongation may be lowered due to thermal degradation. In addition, the rate at which the molecular weight increases may decrease significantly.
From the viewpoint of effectively preventing a decrease in tensile elongation due to coloration or thermal deterioration of polyamide, it is preferable to perform polymerization while maintaining the trans isomer ratio at 80% or less.

  (A) As a method for producing polyamide, (a-1) it is easy to maintain the trans isomer ratio in the portion derived from alicyclic dicarboxylic acid at 85% or less, and the color tone of the resulting polyamide From an excellent viewpoint, it is preferable to produce a polyamide by 1) a hot melt polymerization method and 2) a hot melt polymerization / solid phase polymerization method.

(A) In the production method of polyamide, the polymerization form may be a batch type or a continuous type.
The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.
The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a batch-type hot melt polymerization method described below.
Examples of the batch-type hot melt polymerization method include, for example, a polyamide component ((a) dicarboxylic acid, (b) diamine, and, if necessary, (c) lactam and / or aminocarboxylic acid) using water as a solvent. About 40 to 60% by mass of the contained solution is concentrated to about 65 to 90% by mass in a concentration tank operated at a temperature of 110 to 180 ° C. and a pressure of about 0.035 to 0.6 MPa (gauge pressure). To obtain a concentrated solution. The concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the container is about 1.5-5.0 MPa (gauge pressure). Thereafter, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while draining water and / or gas components, and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure (gauge pressure is , 0 MPa). By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, pressurization is performed with an inert gas such as nitrogen to extrude the polyamide melt as a strand. The strand is cooled and cut to obtain pellets.

Moreover, it does not specifically limit as a manufacturing method of polyamide, Polyamide can be manufactured also in the continuous hot melt polymerization method described below.
As the continuous hot melt polymerization method, for example, a solution of about 40 to 60% by mass containing water and a polyamide component as a solvent is preheated to about 40 to 100 ° C. in a container of a preliminary apparatus, and then a concentration tank / Concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. to obtain a concentrated solution. The concentrated solution is discharged into a flasher maintained at a temperature of about 200 to 350 ° C., and then the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure to atmospheric pressure, reduce the pressure as necessary. Thereafter, the polyamide melt is extruded into strands, cooled and cut into pellets.

(A) The molecular weight of the polyamide can be determined using a relative viscosity ηr at 25 ° C. as an index.
The molecular weight of the polyamide (A) is preferably 1.5% in terms of mechanical properties such as toughness and strength, moldability, and the like, in a relative viscosity ηr of 98% sulfuric acid concentration of 1% and 25 ° C. measured according to JIS-K6920. It is -7.0, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.
The measurement of the relative viscosity at 25 ° C. can be performed according to JIS-K6920 as described in the following examples.

(A) The melting point of polyamide is preferably 270 to 350 ° C. as Tm2 from the viewpoint of heat resistance. Melting | fusing point Tm2 becomes like this. Preferably it is 270 degreeC or more, More preferably, it is 275 degreeC or more, More preferably, it is 280 degreeC or more. The melting point Tm2 is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
(A) By setting the melting point Tm2 of the polyamide to 270 ° C. or higher, a polyamide having excellent heat resistance can be obtained. Moreover, (A) By making polyamide melting | fusing point Tm2 into 350 degrees C or less, the thermal decomposition of the polyamide in melt processing, such as extrusion and shaping | molding, can be suppressed.

(A) From the viewpoint of heat resistance, the heat of fusion ΔH of polyamide is preferably 10 J / g or more, more preferably 14 J / g or more, still more preferably 18 J / g or more, and even more preferably 20 J. / G or more.
(A) The measurement of the melting point (Tm1 or Tm2) of polyamide and the heat of fusion ΔH can be performed according to JIS-K7121 as described in the following examples.
Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

(A) The glass transition temperature Tg of the polyamide is preferably 90 to 170 ° C. The glass transition temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. Further, the glass transition temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A) By setting the glass transition temperature of polyamide to 90 ° C. or higher, a polyamide having excellent heat resistance and chemical resistance can be obtained. Moreover, the molded article with a favorable external appearance can be obtained by making the glass transition temperature of (A) polyamide 170 degrees C or less.
The glass transition temperature can be measured according to JIS-K7121 as described in the following examples.
Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.

[(B) Inorganic filler]
The polyamide composition contained in the automobile part of the present embodiment contains the (A) polyamide and (B) an inorganic filler.
(B) By containing an inorganic filler, it is excellent in heat resistance, fluidity, toughness and low water absorption without impairing the properties of polyamide excellent in heat resistance, fluidity, toughness and low water absorption. In addition, a polyamide composition having excellent rigidity and vibration fatigue resistance can be obtained.
The (B) inorganic filler is not particularly limited. For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica , Clay, 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, swelling fluorine Mother, and apatite, and the like.
(B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the above-mentioned inorganic fillers (B), from the viewpoint of improving rigidity and strength, glass fiber, carbon fiber, glass flake, talc, kaolin, mica, clay, calcium carbonate, calcium monohydrogen phosphate, wollastonite Silica, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swellable fluorine mica and apatite are preferred.

(B) As an inorganic filler, glass fiber and carbon fiber are more preferable, and a number average fiber diameter is 3-30 micrometers from a viewpoint that the outstanding mechanical strength can be provided to a polyamide composition among glass fiber and carbon fiber. More preferably, the fiber has a weight average fiber length of 100 to 750 μm and an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D).
Here, for the number average fiber diameter and the weight average fiber length in this specification, the polyamide composition is put in an electric furnace, the contained organic matter is incinerated, and 100 or more glass fibers or carbon fibers are arbitrarily selected from the residue. The number average fiber diameter is measured by observing with a scanning electron microscope (SEM) and measuring the fiber diameter of these glass fibers or carbon fibers, and an SEM photograph at a magnification of 1,000 times is used. The weight average fiber length is obtained by measuring the fiber length.

The cross section of the glass fiber or carbon fiber may be a perfect circle or a flat shape. Examples of such a flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction. Here, the “flattening ratio” in the present specification refers to a value represented by D2 / D1 when the major axis of the fiber cross section is D2 and the minor axis of the fiber cross section is D1. The rate is about 1.) When a perfect circular glass fiber or carbon fiber is used, the flatness is preferably 1.5 to 10.
(B) As the inorganic filler, wollastonite is also preferably used. Among the wollastonites, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 10 to 500 μm, and the aspect ratio Those having (L / D) of 3 to 100 are more preferably used.

Furthermore, as the (B) inorganic filler, talc, mica, kaolin and silicon nitride are more preferable, and among them, those having a number average fiber diameter of 0.1 to 3 μm are more preferably used.
The inorganic filler may be surface treated with a silane coupling agent or the like. Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

In addition, the inorganic filler includes, as a sizing agent, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units. Copolymers, epoxy compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary and tertiary amines, and carvone A copolymer containing an unsaturated vinyl monomer excluding the acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer may be further included. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among them, from the viewpoint of the mechanical strength of the polyamide composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as structural units. A copolymer, an epoxy compound, and a polyurethane resin, and a combination thereof, and a unsaturated vinyl monomer except the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer More preferred are copolymers and polyurethane resins containing a polymer as a structural unit, and combinations thereof.

Among the copolymers containing the above carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units, the carboxylic acid anhydride The product-containing unsaturated vinyl monomer is not particularly limited, and examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Among them, maleic anhydride is preferable. On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. The unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer is not particularly limited. For example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2, 3 -Dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Of these, styrene and butadiene are preferred.
Among these combinations described above, from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. More preferably, it is at least one selected.

  In addition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight of 2 1,000 or more. Further, from the viewpoint of improving the fluidity of the polyamide composition, the weight average molecular weight is more preferably 2,000 to 1,000,000, and further preferably 2,000 to 500,000. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC).

  Although it does not restrict | limit especially as an epoxy compound, For example, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, dodecene oxide, pentadecene Aliphatic epoxy compounds such as oxide and eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1, 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene oxide Alicyclic epoxy compounds such as epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide, m-chlorostyrene oxide; epoxidized soybean oil; And epoxidized linseed oil.

  The polyurethane resin is not particularly limited as long as it is generally used as a sizing agent. For example, m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone. Those synthesized from an isocyanate such as diisocyanate (IPDI) and a polyester or polyether diol can be suitably used.

  The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The polyacrylic acid may be in a salt form. Such polyacrylic acid salts include primary, secondary or tertiary amines. Although it does not restrict | limit in particular, For example, a triethylamine, a triethanolamine, glycine etc. are mentioned. The degree of neutralization is preferably 20 to 90% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and from the viewpoint of reducing amine odor, and is preferably 40 to 60%. More preferably.

  The weight average molecular weight of the polyacrylic acid forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less are preferable from the viewpoint of improving mechanical properties when a resin composition is obtained.

  The acrylic acid polymer may be a copolymer of acrylic acid and other copolymerizable monomers. The monomer that forms the copolymer with acrylic acid is not particularly limited, and examples thereof include acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotonic acid among monomers having a hydroxyl group and / or a carboxyl group. And at least one selected from the group consisting of fumaric acid, itaconic acid, citraconic acid, and mesaconic acid (except for acrylic acid only). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

  The acrylic acid polymer (copolymer) may be in the form of a salt. The polymer salt of acrylic acid is not particularly limited, and examples thereof include primary, secondary, and tertiary amines. Although not particularly limited, specific examples include triethylamine, triethanolamine, and glycine. The degree of neutralization is preferably 20 to 90%, preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer (copolymer) forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. That is, 3,000 or more is preferable from the viewpoint of improving the converging property of the inorganic filler, and 50,000 or less is preferable from the viewpoint of improving mechanical properties when the resin composition is obtained.

  (B) Glass fiber or carbon fiber as an inorganic filler was produced by applying the sizing agent to the fiber using a known method such as a roller-type applicator in the known fiber production process. By drying the fiber strand, it is obtained by continuously reacting. The fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step. The sizing agent preferably imparts (adds) 0.2 to 3% by mass, more preferably 0.3 to 2% by mass (as a solid fraction), with respect to 100% by mass of glass fiber or carbon fiber. Added. From the viewpoint of maintaining the bundling of the fibers, the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fibers or carbon fibers. On the other hand, from the viewpoint of improving the thermal stability of the polyamide composition, it is preferably 3% by mass or less. The strand may be dried after the cutting step, or may be cut after the strand is dried.

[(C) Copper compound and metal halide compound]
The automobile part of the present embodiment includes the polyamide composition described above, and the polyamide composition preferably further includes (C) a copper compound and a metal halogen compound.

Among the above, examples of the copper compound include copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, and copper stearate. And copper complex salts coordinated to chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid.
As a copper compound, you may use individually by 1 type and may be used in combination of 2 or more type.

Among the above, metal halide compounds exclude copper halides.
The metal halide is a salt of a group 1 or 2 metal element of the periodic table of elements and a halogen, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride. Of these, potassium iodide and potassium bromide are preferred.
A metal halogen compound may be used individually by 1 type, and may be used in combination of 2 or more type.
Among metal halide compounds, potassium iodide is more preferable from the viewpoint of excellent vibration fatigue resistance and suppression of metal corrosion.

The polyamide composition further contains (C) a copper compound and a metal halogen compound, so that the properties of the polyamide excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, etc. are not impaired, and the fluidity, toughness, A polyamide composition having excellent low water absorption, strength and rigidity, and excellent heat resistance and vibration fatigue resistance can be obtained.
The present embodiment provides an automotive part that is excellent in fluidity, toughness, low water absorption, strength and rigidity, and is also excellent in heat resistance and vibration fatigue resistance by being an automotive part including such a polyamide composition. Can do.

  From the viewpoint of being excellent in vibration fatigue resistance and capable of suppressing metal corrosion of the screw and cylinder part during extrusion (hereinafter sometimes abbreviated as “metal corrosion”) as the copper compound. Copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred, and copper iodide and / or copper acetate are more preferred.

The content of the copper compound in the polyamide composition containing the (C) copper compound and the metal halide is preferably 0.01 to 0.6 parts by mass with respect to 100 parts by mass of the (A) polyamide. Preferably it is 0.02-0.4 mass part.
By setting the content of the copper compound within the above range, vibration fatigue resistance can be sufficiently improved, and copper precipitation and metal corrosion can be suppressed.

(C) copper compound and the polyamide composition containing a metal halide compound, to ¹⁰⁶ parts by weight polyamide are contained in the polyamide composition, as copper, preferably 50 to 2,000 parts by weight, more preferably The copper compound of (C) is contained so that it may become 100-1500 mass parts, More preferably, it is 150-1,000 mass parts.
When it is within the above range, a polyamide composition having excellent vibration fatigue resistance can be obtained.

The content of the metal halide compound in the polyamide composition containing the (C) copper compound and the metal halide compound is preferably 0.05 to 20 parts by mass, more preferably 100 parts by mass of the polyamide (A). Is 0.20 to 10 parts by mass.
By setting the content of the metal halogen compound within the above range, vibration fatigue resistance can be sufficiently improved, and copper precipitation and metal corrosion can be suppressed.

The polyamide composition preferably contains (C) a copper compound and a metal halogen compound so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 50/1. Halogen / copper is more preferably 2/1 to 40/1, and further preferably 5/1 to 30/1.
When halogen / copper is 2/1 or more, copper deposition and metal corrosion can be suppressed. On the other hand, when the halogen / copper is 50/1 or less, corrosion of the screws of the molding machine can be further prevented without impairing mechanical properties such as toughness, strength and rigidity.
Even if each of the copper compound and the metal halide is contained alone, a certain effect can be obtained. However, it is preferable to contain both a copper compound and a metal halogen compound from the viewpoint of improving the performance of the resulting polyamide composition.

[Heat stabilizer]
The polyamide composition is a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, an amine-based heat stabilizer, and groups Ib, IIb, and IIIa of the periodic table as long as the object of this embodiment is not impaired One or more thermal stabilizers selected from the group consisting of metal salts of elements of Group IIIb, Group IVa and Group IVb, and alkali metal and alkaline earth metal halides.

<Phenolic heat stabilizer>
Although it does not restrict | limit especially as a phenol type heat stabilizer, For example, a hindered phenol compound is mentioned. Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.
The hindered phenol compound is not particularly limited. For example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), penta Erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydro Cinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl- 4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di- -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3,3 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. These may be used alone or in combination of two or more. Among these, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by weight, more preferably 0, with respect to 100 parts by weight of the polyamide composition. 10 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Phosphorus heat stabilizer>
The phosphorus-based heat stabilizer is not particularly limited. Phosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl (tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-) t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis (3-methyl 6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-t-butyl) Phenyl) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite , Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono , Dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis (2-t Butylphenyl) .di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t- Butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) )) 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4,4′-isopropylidene) Bis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2,2- Tylene bis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4- And di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite. These may be used alone or in combination of two or more.

  Among those listed above, pentaerythritol phosphite compounds and / or tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the amount of gas generated. . The pentaerythritol type phosphite compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t-butyl- 4-methylphenyl methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl isodecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl isotridecyl Pentaerythritol diphosphite, 2,6-di-t-butyl-4- Tilphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl benzyl Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol penta Erythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol di Phosphite, bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2,4-di-t-octylphenyl · pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexyl Phenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Rudiphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite Is mentioned. These may be used alone or in combination of two or more.

Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6) is used from the viewpoint of reducing the amount of gas generated. -Di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-) One or more selected from the group consisting of t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is More preferred.
When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by weight, more preferably 0, with respect to 100 parts by weight of the polyamide composition. 10 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Amine heat stabilizer>
The amine heat stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4- Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, -(Ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2 , 6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetra Methyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6- Tramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxy 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propi Nyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. These may be used alone or in combination of two or more.
When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass, more preferably 0 with respect to 100 parts by mass of the polyamide composition. .1 to 1 part by mass. In the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table>
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt. . The copper salt is not particularly limited, and examples thereof include copper halides (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 copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. These may be used alone or in combination of two or more.
Among the copper salts listed above, preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, more preferably Copper iodide and / or copper acetate. When such a preferable copper salt is used, it is possible to obtain a polyamide composition which is excellent in heat aging resistance and can suppress the metal corrosion of the screw or cylinder part during extrusion (hereinafter also simply referred to as “metal corrosion”). .
When using a copper salt, the content of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
Moreover, from the viewpoint of improving the heat aging resistance, the content concentration of the copper element is preferably 10 to 500 ppm by mass, more preferably 30 to 500 ppm by mass, and still more preferably 50 to the total amount of the polyamide composition. It is -300 mass ppm.

<Alkali metal and alkaline earth metal halide>
Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Of these, potassium iodide and potassium bromide, and mixtures thereof are preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion, and potassium iodide is more preferable.
When alkali metal and alkaline earth metal halides are used, the content of alkali metal and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 100 parts by mass of the polyamide composition. 5 parts by mass, more preferably 0.2-2 parts by mass. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
The components of the heat stabilizer described above may be used singly or in combination of two or more. Among them, a copper salt, an alkali metal and an alkaline earth metal halide, A mixture of
The ratio of the copper salt to the alkali metal and alkaline earth metal halide is included in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. Is more preferable, and 5/1 to 30/1 is more preferable. In the above range, the heat aging resistance can be further improved.
When the above halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine and the like can be prevented without substantially impairing mechanical properties such as toughness.

[Other components that may be included in the polyamide composition]
The polyamide composition is an additive conventionally used for polyamide, for example, a colorant such as a pigment or a dye (including a colored masterbatch), a flame retardant, and a fibrillation as long as the object of the present embodiment is not impaired. Agent, lubricant, fluorescent bleaching agent, plasticizer, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, nucleating agent, rubber and reinforcing agent As well as other polymers.

(Production method of polyamide composition)
The manufacturing method of the polyamide composition contained in the automobile part of the present embodiment includes (A) polyamide, (B) inorganic filler, and (C) copper compound, metal halide compound, and other heat stabilizers as required. The method is not particularly limited as long as it is a method of mixing the components.
Examples of the method of mixing (A) polyamide, (B) inorganic filler, (C) copper compound and metal halogen compound include (A) polyamide, (B) inorganic filler, (C) copper compound and metal halogen. The compound is mixed with a Henschel mixer, etc., supplied to a melt kneader and kneaded, or (A) a polyamide and (C) a copper compound and a metal halogen which are melted with a single screw or twin screw extruder Examples thereof include a method of blending the compound with (B) an inorganic filler from the side feeder.
In general, the various heat stabilizers and other components such as additives described above may be added during extrusion kneading, may be added to the pellets after extrusion, or during polymerization of polyamide. It may be added.

In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.
The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.25 to 5 minutes.
The apparatus for performing the melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.

The method for producing the polyamide composition may be a method in which (A) polyamide, and (C) a copper compound and a metal halogen compound are mixed by the following method, and then (B) an inorganic filler is mixed.
Examples of such a mixing method include (A) a method in which (C) a copper compound and a metal halide compound are added individually or as a mixture during the polyamide polymerization step (hereinafter, sometimes referred to as “Production Method 1”). And (A) a polyamide, (C) a copper compound and a metal halide compound are added individually or as a mixture using melt kneading (hereinafter sometimes referred to as “Production Method 2”). .

When (C) a copper compound and a metal halogen compound are added to (A) polyamide, it may be added as a solid or in the form of an aqueous solution.
“In the process of polymerizing polyamide” in the production method 1 is any process from the raw material monomer to the completion of the polymerization of the polyamide, and may be any time as long as it is in between.
The apparatus for melt kneading in production method 2 is not particularly limited, and a known apparatus such as a single- or twin-screw extruder, a Banbury mixer, and a melt kneader such as a mixing roll can be used. . Of these, a twin screw extruder is preferably used.
The temperature of melt kneading is preferably a temperature higher by about 1 to 100 ° C., more preferably a temperature higher by about 10 to 50 ° C. than the melting point of (A) polyamide.
The shear rate in the kneader is preferably about 100 sec ⁻¹ or more, and the average residence time during kneading is preferably about 0.25 to 5 minutes.

In addition, in the manufacturing process of the polyamide composition, other components are added for the purpose of dispersing (C) the copper compound and the metal halogen compound in the polyamide (as a dispersant) to the extent that the object of the present embodiment is not impaired. May be.
Examples of the other components include higher fatty acids such as lauric acid as a lubricant, higher fatty acid metal salts of higher fatty acids and metals such as aluminum, higher fatty acid amides such as ethylenebisstearylamide, and waxes such as polyethylene wax. Is mentioned.
Moreover, the organic compound which has one or more amide groups is also mentioned.

(Molding method of polyamide composition)
Polyamide compositions are various molded products using known molding methods such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. Can be processed.
Molded articles obtained from the polyamide composition are excellent in toughness, moldability and low water absorption, and are also excellent in heat resistance and vibration fatigue resistance.

(Physical properties of polyamide composition and molded product thereof)
The relative viscosity ηr at 25 ° C., the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition can be measured by the same method as that for the polyamide (A). Moreover, the polyamide composition which is excellent in heat resistance, a moldability, and chemical resistance can be obtained because the measured value in a polyamide composition exists in the range similar to a preferable range as a measured value of said (A) polyamide.

The melt shear viscosity ηs of the polyamide composition is preferably 30 to 200 Pa · s, more preferably 40 to 180 Pa · s, and still more preferably 50 to 150 Pa · s.
The melt shear viscosity can be measured by the method described in the following examples.
When the melt shear viscosity is within the above range, a polyamide composition having excellent fluidity can be obtained, and when molded as an automobile part, molding defects are caused for relatively large parts and molded parts having thin portions. Excellent in that it does not occur easily.

The tensile strength of the molded product obtained from the polyamide composition is preferably 180 MPa or more, more preferably 190 MPa or more, and further preferably 200 MPa or more.
The tensile strength can be measured according to ASTM D638 as described in the following examples.
When the tensile strength of the molded product is 180 MPa or more, an automobile part having excellent strength and rigidity can be obtained.

The tensile elongation of the molded product obtained from the polyamide composition is preferably 1.5% or more, more preferably 2.0% or more, and further preferably 2.5% or more.
The tensile elongation can be measured according to ASTM D638 as described in the following examples.
When the tensile elongation of the molded product is 1.5% or more, an automotive part having excellent toughness can be obtained.

The water absorption of the molded product obtained from the polyamide composition is preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.0% or less.
The water absorption rate can be measured by the method described in the following examples.
When the water absorption rate of the molded product is 5.0% or less, an automobile part having excellent low water absorption can be obtained.
The flexural modulus at 100 ° C. of the molded product obtained from the polyamide composition is preferably 5.5 GPa or more, more preferably 6.5 GPa or more, and further preferably 7.5 GPa or more.
When the flexural modulus at 100 ° C. of the molded product is 5.5 GPa or more, an automobile part having excellent high-temperature rigidity can be obtained.

The strength half-life of the molded product obtained from the polyamide composition is preferably 40 days or more, more preferably 45 days or more, and further preferably 50 days or more.
The strength half-life can be measured by the method described in the Examples below.
When the strength half-life of the molded product is 40 days or more, an automotive part having excellent heat resistance, particularly heat aging resistance, can be obtained.

The fracture stress of the molded product obtained from the polyamide composition is preferably 45 MPa or more, more preferably 50 MPa or more, and further preferably 55 MPa or more.
The fracture stress can be measured by the method described in the following examples.
By molding a polyamide composition having a molded article having a fracture stress of 45 MPa or more, an automotive part having excellent vibration fatigue resistance can be obtained.

The tensile strength retention after immersion of the molded product obtained from the polyamide composition is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more.
The tensile strength retention after immersion can be measured by the method described in the following examples.
When the tensile strength retention after immersion of the molded product is 70% or more, an automobile part having excellent LLC resistance can be obtained.

[Auto parts]
Molded articles containing the polyamide composition are used as automobile parts.
The above-mentioned polyamide composition is excellent in fluidity, strength, rigidity, toughness and low water absorption, and is also excellent in high temperature rigidity, heat aging resistance, vibration fatigue resistance, LLC resistance and surface appearance. It can be used suitably. The automobile parts of this embodiment are automobile parts excluding automobile intake system parts and automobile cooling system parts. Examples of such automobile parts include underhood parts, mechanism parts, interior parts, exterior parts, and electrical parts.

In addition, the above-described polyamide composition is excellent in fluidity, strength, rigidity, toughness, low water absorption, high temperature rigidity, heat aging resistance, vibration fatigue resistance and LLC resistance, so it is very suitable as an automobile underhood part. Used.
The underhood parts for automobiles are not particularly limited. For example, front end modules, rocker arm covers, ornament covers, oil pans, surge tanks, power steering oil tanks, cooling pipes, EGR pipes, oil cooler tanks, oil pipes. , Oil pump, oil filter cap, water pump, water pump impeller, water pump housing, water pipe, cooling fan, cylinder head cover, valve, brake piping, fuel piping tube, intake duct, engine cover, air cleaner, inverter case, Converter case, drive motor case, gasoline tank case, fuel tank, fuel tank valve, injector, alternator, clutch master Cylinder, motor brush holders, Ties, intake valve body, the brake cylinder guide and ATF cooling unit, and the like.

Moreover, since the above-mentioned polyamide composition is excellent in strength, rigidity, toughness, high-temperature rigidity, heat aging resistance, and vibration fatigue resistance, it is very suitably used as an automobile mechanism part.
There are no particular limitations on the automotive mechanism parts, such as active mount, torque rod, shift lever bracket, steering lock bracket, electronic throttle gear, mission actuator, oil filter bracket, steering bracket, brake cylinder guide, instrument panel rain. Force, mirror bracket, back door inner, gear, ABS piston, key cylinder, and the like.

Furthermore, since the above-mentioned polyamide composition is excellent in strength, rigidity, toughness, low water absorption, high temperature rigidity, heat aging resistance, and surface appearance, it is very suitably used as an automobile interior part.
The automobile interior parts are not particularly limited, and examples thereof include a steering wheel, a door inner handle, a door handle cowl, an interior mirror bracket, an air conditioner switch, an instrument panel, a console box, a glove box, and a trim. .

Furthermore, since the above-mentioned polyamide composition is excellent in fluidity, strength, rigidity, toughness, low water absorption, high temperature rigidity, heat aging resistance, vibration fatigue resistance, and surface appearance, it is very suitably used as an automobile exterior part. It is done.
The automobile exterior parts are not particularly limited.For example, sunroof deflector, roof rail, door mirror stay, hood, front fender, rear quarter panel, back door panel, outer door handle, molding, lamp housing, front grill, mudguard, Examples include sunroof brackets and side bumpers.
Furthermore, since the above-mentioned polyamide composition is excellent in strength, toughness, low water absorption, high-temperature rigidity, heat aging resistance, and vibration fatigue resistance, it is very suitably used as an automobile electrical component.
There are no particular limitations on automotive electrical components, such as connectors, wire harness connectors, motor components, lamp sockets, sensor on-board switches, and combination switches, stick coil case towers, motor insulators, FPM bobbins, steering wheel steering angles. Examples include sensors, NSS covers, ECU housings, high voltage connectors, AT rotation sensor housings, and the like.

Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples.
The raw materials and measurement methods used in Examples and Comparative Examples are shown below.
In this example, 1 kg / cm ² means 0.098 MPa.

[raw materials]
The following compounds were used in this example.
[(A) Polyamide]
<(A) Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA) manufactured by Eastman Chemical Co., Ltd., trade name 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75)
(2) Terephthalic acid (TPA) Wako Pure Chemical Industries product name Terephthalic acid (3) Adipic acid (ADA) Wako Pure Chemical Industries product name Adipic acid (4) Suberic acid (C8DA) Wako Pure Chemical Industries product name Suberin Acid (5) Azelaic acid (C9DA) Wako Pure Chemical Industries product name Azelaic acid (6) Sebacic acid (C10DA) Wako Pure Chemical Industries product name Sebacic acid (7) Dodecanedioic acid (C12DA) Wako Pure Chemical Industries product Name Dodecanedioic acid (8) Tetradecanedioic acid (C14DA) manufactured by Tokyo Chemical Industry Product name Tetradecanedioic acid (9) Hexadecanedioic acid (C16DA) Product name manufactured by Tokyo Chemical Industry Hexadecanedioic acid

<(B) Diamine>
(10) 2-methylpentamethylenediamine (2MPD) manufactured by Tokyo Chemical Industry Co., Ltd. Product name 2-methyl-1,5-diaminopentane (11) hexamethylenediamine (HMD) manufactured by Wako Pure Chemical Industries, Ltd. product name hexamethylenediamine (12) 1,9-nonamethylenediamine (NMD) Aldrich product name 1,9-nonanediamine (13) 2-methyloctamethylenediamine (2MOD) Manufactured with reference to the production method described in JP-A No. 05-17413 .
(14) Mixture of 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine (TMHD) Aldrich product name C, C, C-1, 6 -Hexamethylenediamine

<(C) Lactam and / or aminocarboxylic acid>
(15) ε-Caprolactam (CPL) Wako Pure Chemical Industries, Ltd. Product name ε-Caprolactam

[(B) Inorganic filler]
(15) Glass fiber (GF) manufactured by Nippon Electric Glass Co., Ltd. ECS03T275H Average fiber diameter (average particle diameter) 10 μmφ (circular shape), cut length 3 mm

[(C) Copper compound and metal halide compound]
(16) Copper iodide (CuI) Wako Pure Chemical Industries, Ltd. Trade name Copper iodide (I)
(17) Potassium iodide (KI) Wako Pure Chemical Industries, Ltd. Product name Potassium iodide [dispersant]
(18) Ethylene bisstearylamide Lion product name Armo wax

[Other ingredients]
(19) Carbon Black Mitsubishi Chemical Co., Ltd. Trade name Mitsubishi Carbon Black # 52

[Calculation of polyamide content]
(A-1) The mol% of the alicyclic dicarboxylic acid is (the number of moles of (a-1) alicyclic dicarboxylic acid added as a raw material monomer / the number of moles of all (a) dicarboxylic acids added as raw material monomers. ) × 100.
(B-1) The mol% of the diamine having a substituent branched from the main chain was added as the raw material monomer (b-1) The number of moles of the diamine having the substituent branched from the main chain / the raw material monomer. All (b) moles of diamine) × 100 were obtained by calculation.
Further, (c) mol% of lactam and / or aminocarboxylic acid is ((c) moles of lactam and / or aminocarboxylic acid added as raw material monomer / all (a) dicarboxylic acid added as raw material monomer. (B) mole number of all diamines + (c) mole number of lactam and / or aminocarboxylic acid) × 100.
In addition, when calculating by the above formula, the denominator and the numerator do not include the number of moles of diamine having a substituent branched from the main chain (b-1) added as an additional component.

[Measuring method]
(1) Melting points Tm1, Tm2 (° C.), heat of fusion ΔH (J / g)
It measured using Diamond-DSC by PERKIN-ELMER according to JIS-K7121. The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample (polyamide) is heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in a nitrogen atmosphere is Tm1. (° C). After maintaining the temperature in the molten state at the highest temperature rise for 2 minutes, the temperature is lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and then similarly raised at a temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when heated was defined as the melting point Tm2 (° C.). The total peak area was defined as the heat of fusion ΔH (J / g). In addition, when there were a plurality of peaks, Tm2 and ΔH were determined after considering that the heat of fusion was 1 J / g or more as a peak. For example, when there are two peaks, melting point 295 ° C., heat of fusion at the melting point = 20 J / g, melting point 325 ° C., heat of fusion at the melting point = 5 J / g, the melting point Tm 2 is 325 ° C. The heat of fusion ΔH was 25 J / g (= 20 J / g + 5 J / g).

(2) Trans isomer ratio 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride and measured by 1H-NMR. When the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid, the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer is The trans isomer ratio of the alicyclic dicarboxylic acid therein was determined.

(3) Glass transition temperature Tg (° C)
It measured using Diamond-DSC by PERKIN-ELMER according to JIS-K7121. Measurement conditions were such that a sample in a molten state obtained by melting a sample (polyamide) with a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the obtained measurement sample, the glass transition temperature Tg was measured by raising the temperature in the range of 30 to 350 ° C. under the temperature rising rate of 20 ° C./min.

(4) Relative viscosity ηr at 25 ° C
It carried out according to JIS-K6920. Specifically, a 1% concentration solution [(polyamide 1 g) / (98% sulfuric acid 100 mL)] was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

(5) Melt shear viscosity ηs (Pa · s)
Under the temperature condition of the melting point + 20 ° C. obtained by the measurement method (1), the fluidity was evaluated by the melt shear viscosity ηs at a shear rate of 1000 sec ⁻¹ . The specific measurement method uses a twin capillary rheometer RH7-2 manufactured by ROSAND, UK. The orifice has a die diameter of 1.0 mm and a die entrance angle of 180 degrees, and the L / D is 16 and 0.25. Two orifices were used.

(6) Tensile strength (MPa) and tensile elongation (%)
Using a dumbbell injection molding test piece (3 mm thickness) for the ASTM tensile test, it was performed according to ASTM D638. Molding test piece is a mold (mold temperature = table 4 to table 7) of a dumbbell test piece (3 mm thickness) for ASTM tensile test (ASTM D638) on an injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.). The glass transition temperature (Tg + 20 ° C.) was attached, and the cylinder temperature = (melting point Tm2 + 10 of polyamide in Table 4 to Table 7) ° C. to (melting point Tm2 + 30 of polyamide in Table 4 to Table 7) ° C. was produced. .

(7) Water absorption rate (%)
A pre-test mass (mass before water absorption) was measured in a dry as mold of a dumbbell injection molded test piece (3 mm thick) for ASTM tensile test. Next, it was immersed in pure water at 80 ° C. for 24 hours. Then, the test piece was taken out from the water, the surface adhering moisture was wiped off, and after standing in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere for 30 minutes, the mass after test (mass after water absorption) was measured. The increment of the mass after water absorption with respect to the mass before water absorption was taken as the amount of water absorption, the ratio of the water absorption amount with respect to the mass before water absorption was determined by the number of trials n = 3, and the average value was made the water absorption rate (%).

(8) Copper concentration, halogen concentration, and molar ratio of halogen and copper (halogen / copper)
The copper concentration was determined by adding sulfuric acid to the sample (polyamide composition), dropping nitric acid while heating to decompose the organic components, measuring the resulting decomposition solution in pure water, and ICP emission analysis (high-frequency plasma emission) Quantitative analysis. As an ICP emission analyzer, Vista-Pro manufactured by SEIKO ELECTRONIC INDUSTRY CO., LTD. Was used.
Taking iodine as an example, the halogen concentration is combusted in a flask in which the sample is replaced with high-purity oxygen, and the generated gas is collected in an absorbing solution. The iodine in the obtained collected solution is 1/100 N. Quantification was performed using potentiometric titration with a silver nitrate solution.
The molar ratio of halogen and copper (halogen / copper) was calculated by converting the molecular weight into a mole using each of the above quantitative values.

(9) High temperature flexural modulus (GPa)
Using a dumbbell injection molding test piece (3 mm thickness) for the ASTM tensile test, it was performed according to ASTM D790. The measurement temperature was 100 ° C. The molding test piece is an injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.), a mold of a dumbbell test piece (3 mm thickness) for ASTM tensile test (ASTM D638) (mold temperature = glass in Tables 4 to 7). A transition temperature Tg + 20 ° C. was attached, and molding was performed at a cylinder temperature = (melting point Tm2 + 10 of polyamide in Tables 4 to 7) ° C. to (melting point Tm2 + 30 of polyamide in Tables 4 to 7) ° C.

(10) Strength half-life (days)
A dumbbell injection molded test piece (3 mm thick) for ASTM tensile test of the above measuring method (6) was treated in a hot air oven at 200 ° C. for a predetermined time, and then the tensile strength was measured according to ASTM-D638. The tensile strength after the heat treatment relative to the tensile strength before the heat treatment was calculated as the tensile strength retention, and the heat treatment time (day) at which the tensile strength retention was 50% was defined as the strength half-life.

(11) Fracture stress (MPa)
A dumbbell injection molded test piece (3 mm thickness) for ASTM tensile test of the above measuring method (6) was used in a 120 ° C. air atmosphere using a hydraulic servo fatigue tester EHF-50-10-3 manufactured by Kashiwamiya Seisakusho Co., Ltd. A tensile load was applied with a sine wave with a frequency of 20 Hz, and the stress (MPa) at which the fracture occurred at 1,000,000 times was determined.

(12) Tensile strength retention after immersion (%)
The dumbbell injection molding test piece (3 mm thickness) for the ASTM tensile test of the above measuring method (6) was immersed in an ethylene glycol 50% aqueous solution at 120 ° C. for 24 hours and 720 hours and left at room temperature. Then, the tensile test was done by the method of the said measuring method (6), and the tensile strength was measured.
The ratio (%) of the tensile strength after immersion for 720 hours to the tensile strength after immersion for 24 hours was determined as the tensile strength retention after immersion.

(13) Surface appearance 60 degree gloss was measured according to JIS-K7150 using the gloss meter (IG320 made from HORIBA) for the center part of the flat plate test piece (130 mm x 130 mm x 3 mm thickness).
The flat plate test piece is an injection molding machine (IS150E manufactured by TOSHIBA MACHINE CO., LTD.), And a flat plate test piece (130 mm × 130 mm × 3 mm thickness) mold (mold temperature = glass transition of polyamide in Tables 4 to 6) (Temperature Tg + 20 ° C.) was attached, and molding was carried out by setting the injection speed to fill the cylinder temperature = melting point Tm2 + 30 ° C. of polyamide in Tables 4 to 6 in 1.0 second.
In addition, in order to carry out with a black flat plate test piece, a blended pellet was prepared by blending 2.5 parts by mass of a black colored master batch pellet of [Production Example 24] described later with respect to 100 parts by mass of the composition. A flat plate test piece was formed using.
For the surface appearance evaluation, the measured gloss values were 70% to 100% ○ (excellent), 50 to 70% Δ (good), and 0 to 50% × (normal).

[Production Example 1]
According to the compounds shown in Table 1 below and the blending amounts, a polyamide polymerization reaction was carried out by a “hot melt polymerization method”.
(A) 896 g (5.20 mol) of CHDA, and (b) 604 g (5.20 mol) of 2MPD were dissolved in 1,500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer. To this homogeneous aqueous solution, 15 g (0.13 mol) of 2MPD was added.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (The liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued, and concentrated until the concentration of the aqueous solution reached about 75% (the liquid temperature in this system was about It was 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). While maintaining the pressure inside the tank at about 30 kg / cm ² , heating was continued until the final temperature (350 ° C. described later) −50 ° C. (here 300 ° C.) was reached while removing water from the system. After the liquid temperature rises to the final temperature (350 ° C. described later) −50 ° C. (here, 300 ° C.), the heating continues while the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 350 ° C. The resin temperature was maintained at about 350 ° C., and the inside of the tank was maintained under a reduced pressure of about 53.3 kPa (400 torr) for 30 minutes by a vacuum apparatus. Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a polyamide.
The results of the above measuring methods (1) to (4) of the obtained polyamide are shown in Table 4 (melting point Tm2, glass transition temperature Tg, trans isomer ratio, and relative viscosity at 25 ° C.).

[Production Examples 2 to 20]
In Production Example 1, as the (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the points and the final amounts of the resin temperatures described in Table 1 or 2 below were used. The polyamide was polymerized by the method described in Production Example 1 except that the temperature was set to the temperature described in Table 4 or 5 below ("Hot melt polymerization method").
The results of the above measuring methods (1) to (4) of the obtained polyamide are shown in Tables 4 and 5 below.

[Comparative Production Example 1]
In Production Example 1, as (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the point and the final temperature of the resin temperature were determined using the compounds and amounts shown in Table 3 below. Except for the temperature set forth in Table 6 below, polyamide was polymerized by the method described in Production Example 1 ("hot melt polymerization method").
In Comparative Production Example 1, since it was solidified in the autoclave during the polymerization, it could not be taken out as a strand. Therefore, after cooling, it was taken out as a lump and pulverized with a pulverizer to a size about pellets. Due to severe foaming during molding, a molded product could not be obtained.

[Comparative Production Examples 2 to 7]
In Production Example 1, as (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the point and the final temperature of the resin temperature were determined using the compounds and amounts shown in Table 3 below. Except for the temperature set forth in Table 6 below, polyamide was polymerized by the method described in Production Example 1 ("hot melt polymerization method"). The results of the above measuring methods (1) to (4) of the obtained polyamide are shown in Table 6 below.

Hereinafter, Production Examples 21 to 23 relate to the production of copper compounds and metal halide compounds.
[Production Example 21]
85.1 parts by mass of KI and 10 parts by mass of ethylene bisstearylamide were mixed to obtain a mixture of KI and ethylenebisstearylamide. 4.9 parts by mass of CuI was mixed well with this mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (1).

[Production Example 22]
80.7 parts by mass of KI and 10 parts by mass of ethylene bisstearylamide were mixed to obtain a mixture of KI and ethylenebisstearylamide. 9.3 parts by mass of CuI was mixed well with this mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (2).

[Production Example 23]
88.0 parts by mass of KI and 10 parts by mass of ethylene bisstearylamide were mixed to obtain a mixture of KI and ethylenebisstearylamide. To this mixture, 2.0 parts by mass of CuI was mixed well and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (3).

[Production Example 24]
Polyamide 66 (Leona 1300, manufactured by Asahi Kasei Chemicals Corporation) 80 parts by mass, 8 parts by mass of ethylene bisstearylamide, and 12 parts by mass of carbon black were mixed, and a twin-screw extruder [TEM 35φL / D = 47. 6. Melting and kneading using polyamide at 280 ° C, screw rotation speed 300rpm], taking out into a strand shape, cooling in a strand bath (water tank), granulating with a cutter to obtain black colored master batch pellets It was.

The following examples and comparative examples relate to polyamide compositions.
[Example 1]
To 100 parts by mass of polyamide of Production Example 1, 6.1 parts by mass of granule (1) produced in Production Example 22 and 55 parts by mass of inorganic filler (GF) were added. TEM35φL / D = 47.6 manufactured by Co., Ltd., and the set temperature is the melting point (Tm2) of the polyamide in Table 4 below + 20 ° C. (specifically, when the polyamide of Production Example 1 is used, 327 + 20 = 347 ° C.) The mixture was melt kneaded using a screw rotation speed of 300 rpm, taken out into a strand, cooled in a strand bath (water tank), and granulated with a cutter to obtain a polyamide composition. The results of the above measuring methods (5) to (13) for the obtained polyamide composition are shown in Table 4 below.

[Examples 2 to 20]
It implemented similarly to Example 1 except having replaced with the polyamide of the manufacture example 1 and having used the polyamide of the manufacture examples 2-20, respectively. The results of the above measuring methods (5) to (13) for the obtained polyamide composition are shown in Tables 4 and 5 below.

[Comparative Example 1]
An attempt was made in the same manner as in Example 1 except that the polyamide in Comparative Production Example 1 was used instead of the polyamide in Production Example 1, but the extruded state was very unstable and the strand-like polyamide composition was used. Could not get.

[Comparative Examples 2 to 7]
It implemented similarly to Example 1 except having replaced with the polyamide of manufacture example 1 and having used the polyamide of comparative manufacture examples 2-7, respectively. The results of the above measuring methods (5) to (13) for the obtained polyamide composition are shown in Table 6 below.

[Example 21]
It implemented like Example 5 except the point which used the granule (1) of manufacture example 21: 3.1 mass part with respect to 100 mass parts of polyamide of manufacture example 5. FIG. Table 7 shows the results of the measurement methods (5) to (12) for the obtained polyamide composition.

[Example 22]
It implemented like Example 5 except the point which used the granule (1) of manufacture example 21: 9.2 mass part with respect to 100 mass parts of polyamide of manufacture example 5. FIG. Table 7 shows the results of the measurement methods (5) to (12) for the obtained polyamide composition.

[Example 23]
It implemented like Example 5 except the point which used the granule (1) of manufacture example 21: 12.2 mass parts with respect to 100 mass parts of polyamide of manufacture example 5. FIG. Table 7 shows the results of the measurement methods (5) to (12) for the obtained polyamide composition.

[Example 24]
It implemented like Example 5 except the point which used the granule (2) of manufacture example 22: 3.2 mass part with respect to 100 mass parts of polyamide of manufacture example 5. FIG. Table 7 shows the results of the measurement methods (5) to (12) for the obtained polyamide composition.

[Example 25]
It implemented similarly to Example 5 except the point which used 15.0 mass parts of granule (3) of manufacture example 23 with respect to 100 mass parts of polyamide of manufacture example 5. FIG. Table 7 shows the results of the measurement methods (5) to (12) for the obtained polyamide composition.

From the results of Tables 4 to 7, from the polyamide compositions of Examples 1 to 25 containing (A) a polyamide obtained by polymerizing a specific (a) dicarboxylic acid and (b) a diamine, and (B) an inorganic filler. The obtained molded product has excellent fluidity, strength, rigidity, toughness and low water absorption, and particularly excellent characteristics in terms of high temperature rigidity, heat aging resistance, vibration fatigue resistance, LLC resistance and surface appearance. It was confirmed that it had.
On the other hand, in Comparative Example 1 containing a polyamide containing less than 50 mol% of 2-methylpentamethylenediamine, the extruded state was unstable, and a polyamide composition could not be obtained.
In addition, the molded articles obtained from the polyamide compositions of Comparative Examples 2 and 3 containing a polyamide obtained by polymerizing less than 50 mol% of an alicyclic dicarboxylic acid are not sufficient in terms of low water absorption, The molded article obtained from the polyamide composition of Example 6 was not sufficient in terms of strength and rigidity.
In addition, as disclosed in Patent Document 1, molded articles obtained from the polyamide compositions of Comparative Examples 4 and 5 containing a polyamide obtained by polymerizing (mainly) terephthalic acid as a dicarboxylic acid have a melt shear viscosity. It was large, the fluidity was too low, and the moldability was not sufficient.
Further, the molded product obtained from the polyamide composition of Comparative Example 7 containing PA66 was inferior in terms of heat resistance and low water absorption.

  INDUSTRIAL APPLICABILITY The present invention has industrial applicability as various automobile parts such as an automobile underhood, an automobile mechanism part, an automobile exterior part, an automobile interior part, and an automobile electrical part.

Claims (18)

(A) (a) a polyamide obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain;
(B) an inorganic filler;
An automobile part comprising a polyamide composition containing   The automobile part according to claim 1, wherein the diamine having a substituent branched from the main chain is 2-methylpentamethylenediamine.   The automobile part according to claim 1 or 2, wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The automobile component according to any one of claims 1 to 3, wherein the (a) dicarboxylic acid containing at least 50 mol% of the alicyclic dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.   The automobile part according to any one of claims 1 to 4, wherein the (A) polyamide is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.   The automobile part according to any one of claims 1 to 5, wherein the polyamide (A) has a melting point of 270 to 350 ° C.   The automobile part according to any one of claims 1 to 6, wherein a trans isomer ratio in a part derived from the alicyclic dicarboxylic acid in the (A) polyamide is 50 to 85%.   The automobile part according to any one of claims 1 to 7, wherein the polyamide composition contains 1 to 200 parts by mass of the inorganic filler (B) with respect to 100 parts by mass of the polyamide (A).   The automobile part according to any one of claims 1 to 8, wherein the polyamide composition further contains (C) a copper compound and a metal halogen compound.   The automobile component according to claim 9, wherein the copper compound is copper acetate and / or copper iodide, and the metal halide is potassium iodide.   The automobile component according to claim 9 or 10, comprising 0.01 to 0.6 parts by mass of the copper compound and 0.05 to 20 parts by mass of the metal halide compound with respect to 100 parts by mass of the polyamide (A). .   The automobile part according to claim 9, wherein a molar ratio of halogen and copper (halogen / copper) is 2/1 to 50/1. The relative 10 ⁶ parts by weight (A) a polyamide, the content of the copper containing the copper compound in such a way that 50 to 2,000 parts by weight, according to any one of claims 9 to 12 Auto parts.   The automobile part according to any one of claims 1 to 13, which is an automobile underhood part.   The automobile part according to claim 1, which is an automobile mechanism part.   The automobile part according to any one of claims 1 to 13, which is an automobile exterior part.   The automobile part according to any one of claims 1 to 13, which is an automobile interior part.   The automobile part according to claim 1, which is an automobile electrical part.