JP2014231603A - Polyamide resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having excellent strength, releasability, whiteness, heat-resistant re-flowing property, and fogging property.SOLUTION: A polyamide resin composition comprises (A) polyamide comprising (a) a unit composed of dicarboxylic acid comprising alicyclic dicarboxylic acid and (b) a unit composed of diamine comprising aliphatic diamine, and (B) low-molecular weight olefinic resin.

Description

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

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

In the automobile industry, as a measure for the environment, a reduction in body weight is required in order to reduce exhaust gas. In order to meet these requirements, polyamide materials are often used as metal substitutes as exterior materials and interior materials for automobiles. For this reason, required properties such as heat resistance, strength, and appearance for polyamide materials are being used. The level is further improved. In particular, since the temperature in the engine room is on the rise, there is an increasing demand for higher heat resistance for polyamide materials.
In addition, in the electrical and electronic industries such as home appliances, a polyamide material having high heat resistance that can withstand the rise in melting point of solder is required to cope with lead-free surface mount (SMT) solder.

On the other hand, 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 problems related to the heat resistance 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., even if an attempt is made to obtain a molded product by melt molding, the polyamide undergoes severe thermal decomposition, making it difficult to obtain a molded product having sufficient characteristics.

In order to solve the problems related to the thermal decomposition of PA6T as described above, PA6T is composed of aliphatic polyamides such as PA6 and PA66, and amorphous aromatic polyamides composed of isophthalic acid and hexamethylenediamine (hereinafter referred to as “PA6I”). A high melting point semi-aromatic polyamide (hereinafter referred to as “PA6T”) containing terephthalic acid and hexamethylenediamine, which are copolymerized as a main component and having a melting point lowered to about 220 to 340 ° C. In some cases, it is abbreviated as “copolymer”.
As the PA6T copolymer, 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”).

In addition 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 fat. An alicyclic polyamide composed of a cyclic dicarboxylic acid and an aliphatic diamine has been proposed.
For example, Patent Documents 2 and 3 disclose semi-fats of an alicyclic polyamide (hereinafter sometimes abbreviated as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide. A cyclic polyamide (hereinafter sometimes abbreviated as “PA6C copolymer”) is disclosed.
Patent Document 2 discloses that semi-alicyclic polyamide electrical and electronic members containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit have improved solder heat resistance. Discloses that semi-alicyclic polyamide automobile parts are excellent in fluidity and toughness.

In Patent Document 4, a polyamide composed of a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has 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 lower to produce a prepolymer, the prepolymer is solid-phase polymerized at 230 ° C., and melting point 311 A process for producing polyamides at 0C is disclosed.
Further, 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.

  Patent Document 6 discloses a composition in which titanium oxide is highly blended with polyamide using 1,4-cyclohexanedicarboxylic acid as a raw material.

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 International Publication No. 2012/101997 Pamphlet

However, although the PA6T copolymer certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low fluidity from the viewpoint of moldability and surface appearance characteristics of the molded product. Insufficient and further inferior toughness and light resistance. Therefore, appearance characteristics are required as in exterior parts, and when used for applications such as exposure to sunlight, improvement of those characteristics is required.
Further, PA6T copolymer has a large specific gravity, and improvement in lightness is also desired.

Specifically, PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of conventional PA6T copolymer, but fluidity, moldability, toughness, appearance of molded product surface, In terms of light resistance, the improvement level is insufficient.
In addition, the PA 46 has good heat resistance and moldability, but has a high water absorption rate, and there is a problem that a dimensional change due to water absorption and a decrease in mechanical properties are remarkably large. There are cases where the demand cannot be met.

Furthermore, the PA6C copolymers 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 are also insufficiently improved in terms of toughness, strength, and fluidity.

  Furthermore, the polyamide disclosed in Patent Document 6 does not improve the mold release performance, and there is still room for improvement from this viewpoint.

As described above, all of the conventionally proposed polyamides have points to be improved in terms of characteristics, and in order to satisfy the demand for higher heat resistance especially in the automobile industry and the electrical and electronic industries in the future. It is necessary to further improve characteristics such as thermal stability, thermal durability, and fogging properties.
In addition, the conventionally proposed polyamides have not yet obtained sufficient characteristics with respect to releasability and heat resistance under the strictest precision molding conditions currently required.

  In view of the above-described problems of the prior art, an object of the present invention is to provide a polyamide resin composition excellent in strength, releasability, whiteness, heat reflow resistance, and fogging property, and a molded product thereof.

As a result of intensive studies to solve the above problems, the present inventors have obtained a unit comprising an alicyclic dicarboxylic acid, a polyamide containing a unit comprising an aliphatic diamine, and a specific low molecular weight olefin resin. The present inventors have found that the polyamide resin composition contained can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention is as follows.

[1]
(A) (a) a unit consisting of a dicarboxylic acid containing an alicyclic dicarboxylic acid, and (b) a unit consisting of a diamine containing an aliphatic diamine,
And a polyamide containing
(B) a low molecular weight olefin resin;
A polyamide resin composition.
[2]
The polyamide resin composition according to [1], wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.
[3]
The polyamide resin composition according to [1] or [2], wherein (B) the low molecular weight olefin resin is at least one selected from the group consisting of low molecular weight polyethylene, modified low molecular weight polyethylene, and low molecular weight polypropylene. .
[4]
The (B) low molecular weight olefin resin is
The polyamide resin composition according to any one of [1] to [3], which is a modified low molecular weight polyethylene having an acid value of 20 mgKOH / g or less and / or an unmodified low molecular weight polyethylene.
[5]
The polyamide resin composition according to any one of [1] to [4], wherein the number average molecular weight of the (B) low molecular weight olefin resin is 2000 to 8000.
[6]
The polyamide resin composition according to any one of [1] to [5], containing 0.075 to 5 parts by mass of the low molecular weight olefin resin (B) with respect to 100 parts by mass of the polyamide resin composition. object.
[7]
The polyamide resin composition according to any one of [1] to [6], which is obtained by a method of blending the (B) low molecular weight olefin resin from a side feeder of an extruder.
[8]
The polyamide resin composition according to any one of [1] to [7], wherein (b) the aliphatic diamine is 2-methylpentamethylenediamine.
[9]
The polyamide resin composition according to any one of [1] to [7], wherein (b) the aliphatic diamine is decamethylenediamine.
[10]
(A) The polyamide is polymerized by adding an end-capping agent,
The (A) polyamide has a terminal blocking ratio of 10% or more by the terminal blocking agent.
The polyamide resin composition according to any one of [1] to [9].
[11]
The polyamide resin composition according to any one of [1] to [10], wherein (A) the polyamide is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.
[12]
[1] to [11], further comprising at least one component selected from the group consisting of inorganic fillers, nucleating agents, lubricants, stabilizers, titanium oxide, and polymers other than the (A) polyamide. ] The polyamide resin composition as described in any one of.
[13]
A molded article comprising the polyamide resin composition according to any one of [1] to [12].
[14]
The molded article according to [13], which is any one selected from the group consisting of automobile parts, electronic parts, home appliance parts, OA equipment parts, and portable equipment parts.
[15]
The molded product according to [14], which is an LED reflector.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition excellent in intensity | strength, mold release property, whiteness, heat-resistant reflow property, and fogging property can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A) (a) a unit consisting of a dicarboxylic acid containing an alicyclic dicarboxylic acid, and (b) a unit consisting of a diamine containing an aliphatic diamine,
And a polyamide containing
(B) a low molecular weight olefin resin;
Is a polyamide resin composition containing

((A) Polyamide)
The polyamide (A) used in the polyamide resin composition of the present embodiment is a polyamide having units consisting of the following (a) and (b).
(A) A dicarboxylic acid containing an alicyclic dicarboxylic acid (hereinafter sometimes referred to simply as (a) dicarboxylic acid).
(B) A diamine containing an aliphatic diamine (hereinafter sometimes simply referred to as (b) diamine).
That is, (A) polyamide is a polyamide obtained by polymerizing (a) a dicarboxylic acid containing an alicyclic dicarboxylic acid and (b) a diamine containing an aliphatic diamine.

  (A) In the polyamide, the proportion of the units consisting of the above (a) and (b) is from 80 to 100 mol in 100 mol% of all the structural units of polyamide from the viewpoint of heat resistance, fluidity, toughness, rigidity and the like. %, More preferably 90 to 100 mol%, and even more preferably 100 mol%.

  (A) In the polyamide, the structural unit other than the units consisting of the above (a) and (b) is not particularly limited, and examples thereof include a unit consisting of (c) described later.

  In the polyamide resin composition of the present embodiment, the polyamide contained therein means a polymer having an amide (—NHCO—) bond in the main chain.

  Hereinafter, the components (a) and (b) will be described in detail.

<(A) Dicarboxylic acid containing alicyclic dicarboxylic acid>
The (a) dicarboxylic acid used in the polyamide resin composition of the present embodiment includes (a-1) an alicyclic dicarboxylic acid.

(A-1) The alicyclic dicarboxylic acid (also referred to as alicyclic dicarboxylic acid) is not limited to the following, but, for example, an alicyclic ring having 3 to 10 carbon atoms in the alicyclic structure. An aliphatic dicarboxylic acid, preferably an alicyclic dicarboxylic acid having 5 to 10 carbon atoms in the alicyclic structure.
Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. Can be mentioned.

(A-1) The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent include, but are not limited to, for example, a carbon number of 1 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. -4 alkyl groups and the like.

(A-1) The alicyclic dicarboxylic acid is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, low water absorption, rigidity and the like of the polyamide.
(A-1) One type of alicyclic dicarboxylic acid may be used alone, or two or more types may be used in combination.

(A-1) Alicyclic dicarboxylic acids have trans and cis geometric isomers.
As the raw material monomer (a-1), the alicyclic dicarboxylic acid may be used in either a trans form or a cis form, or may be used as a mixture of various ratios of the trans form and the cis form.

  (A-1) The alicyclic dicarboxylic acid has the characteristics that it is isomerized at a high temperature to have a constant ratio, and that the cis isomer has higher water solubility in the equivalent salt with the diamine than the trans isomer. From this, the trans isomer / cis isomer ratio (molar ratio) of (a-1) alicyclic dicarboxylic acid as a raw material monomer used in this embodiment is preferably 50/50 to 0/100, more preferably. Is 40/60 to 10/90, more preferably 35/65 to 15/85.

  (A-1) 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).

The (a) dicarboxylic acid used in the polyamide resin composition of the present embodiment may include (a-2) a dicarboxylic acid other than (a-1).
(A-2) The dicarboxylic acid other than (a-1) is not particularly limited, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2- Diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedi Examples thereof include straight-chain or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

  Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5 -An aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with various substituents such as sodium sulfoisophthalic acid.

  Examples of the various substituents include, but are not limited to, 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, and a chloro group. And a halogen group such as a bromo group, a silyl group having 1 to 6 carbon atoms, a sulfonic acid group and a salt thereof (such as a sodium salt), and the like.

  (A-2) As the dicarboxylic acid other than (a-1), it is preferable to use an aliphatic dicarboxylic acid from the viewpoints of heat resistance, fluidity, toughness, low water absorption, rigidity, and the like of the polyamide. Preferably, an aliphatic dicarboxylic acid having 6 or more carbon atoms is used.

  Among them, (a-2) As the dicarboxylic acid other than (a-1), an aliphatic dicarboxylic acid having 10 or more carbon atoms is preferable from the viewpoint of heat resistance and low water absorption of polyamide. 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. Among these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide.

  (A-2) Only one type of dicarboxylic acid other than (a-1) may be used alone, or two or more types may be used in combination.

  (A) As a dicarboxylic acid component, you may further contain trivalent or more polyvalent carboxylic acid, such as trimellitic acid, trimesic acid, and pyromellitic acid, in the range which does not impair the objective of this embodiment. Only one type of polyvalent carboxylic acid may be used alone, or two or more types may be used in combination.

  The ratio (mol%) of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is preferably 50 to 100 mol%, more preferably 70 to 100%, based on the total number of moles of dicarboxylic acid. It is 100 mol%, More preferably, it is 100 mol%. (A) When the ratio of (a-1) alicyclic dicarboxylic acid in dicarboxylic acid is 50 mol% or more, a polyamide having excellent heat resistance, fluidity, toughness, low water absorption, rigidity and the like is obtained. It is done.

  (A) The proportion (mol%) of the dicarboxylic acid other than (a-2) (a-1) in the dicarboxylic acid is preferably 0 to 50 mol%, and preferably 0 to 40 mol%. More preferred.

  When (a) the dicarboxylic acid component contains (a-2) an aliphatic dicarboxylic acid having 10 or more carbon atoms, (a-1) the alicyclic dicarboxylic acid is 50 to 99.9 mol% and (a- 2) The aliphatic dicarboxylic acid having 10 or more carbon atoms is preferably 0.1 to 50 mol%, (a-1) the alicyclic dicarboxylic acid is 60 to 95 mol%, and (a-2) 10 carbon atoms. More preferably, the aliphatic dicarboxylic acid is 5 to 40 mol%, (a-1) the alicyclic dicarboxylic acid is 80 to 95 mol%, and (a-2) the aliphatic dicarboxylic acid has 10 or more carbon atoms. Is more preferably 5 to 20 mol%.

  In the polyamide resin composition of the present embodiment, (a) the 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. Is mentioned.

<(B) Diamine Containing Aliphatic Diamine>
(A) (b) Diamine which comprises polyamide contains aliphatic diamine.
Examples of diamines other than aliphatic diamines include, but are not limited to, alicyclic diamines and aromatic diamines.
(B) The diamine preferably includes (b-1) a diamine having a substituent branched from the main chain as the aliphatic diamine. By using (b) diamine containing (b-1) a diamine having a substituent branched from the main chain, the polyamide resin composition of the present embodiment can simultaneously satisfy fluidity, toughness, rigidity, and the like.

  Examples of the substituent branched from the main chain include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. C1-C4 alkyl groups etc. are mentioned.

  The diamine having a substituent branched from the main chain (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane) is used. 2) 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, etc. And branched saturated aliphatic diamines.

  The diamine having a substituent branched from the main chain (b-1) is preferably 2-methylpentamethylenediamine or 2-methyloctamethylenediamine from the viewpoints of heat resistance and rigidity. The (b-1) diamine having a substituent branched from the main chain may be used alone or in combination of two or more.

  The diamine other than (b-2) (b-2) (b-1) of (b) diamine used in the polyamide resin composition of the present embodiment is not limited to the following. For example, aliphatic diamine (however, , (B-1) is excluded), alicyclic diamines, and aromatic diamines.

  Examples of the aliphatic diamine (excluding (b-1) above) are not limited to the following, but include, for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene. Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine. Among these, decamethylenediamine is preferable from the viewpoints of heat resistance, low water absorption, strength, and rigidity.

  Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclohexane. And cyclopentanediamine.

  The aromatic diamine may be a diamine containing an aromatic, and is not limited to the following, and examples thereof include metaxylylenediamine.

  (B-2) The diamine other than (b-1) is preferably an aliphatic diamine (however, excluding (b-1) above, from the viewpoint of heat resistance, low water absorption, strength and rigidity of the polyamide. ) And alicyclic diamines, more preferably nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, more preferably decamethylene diamine and dodecamethylene diamine, and even more preferably. Decamethylenediamine. (B-2) Diamines other than (b-1) may be used alone or in combination of two or more.

  (B) The diamine component may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine as long as the object of the present embodiment is not impaired. Only one kind of the polyvalent aliphatic amine may be used alone, or two or more kinds may be used in combination.

  (B) From the viewpoint of strength and toughness, the proportion of the aliphatic diamine in the diamine is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and 80 to 100 mol%. More preferably.

(B) The proportion (mol%) of the diamine having a substituent branched from the main chain (b-1) in the diamine is not limited to the following, but is preferably 50 to 100 mol%. More preferably, it is 60-100 mol%, More preferably, it is 85-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is 100 mol%.
(B) When the ratio of the diamine having a substituent branched from the main chain (b-1) in the diamine is at least 50 mol%, a polyamide having excellent fluidity, toughness, and rigidity can be obtained.

  (B) Ratio (mol%) of diamine other than (b-2) (b-1) in diamine is preferably 0 to 50 mol%, more preferably 0 to 40 mol%. .

  (A) When manufacturing polyamide, it is preferable that the addition amount of (a) dicarboxylic acid and the addition amount of (b) diamine are the same molar amount vicinity. 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 preferable that it is 0.9-1.2, More preferably, it is 0.95-1.1, More preferably, it is 0.98-1.05.

<(C) Lactam and / or aminocarboxylic acid>
The polyamide (A) contained in the polyamide resin composition of the present embodiment may further contain a unit consisting of (c) lactam and / or aminocarboxylic acid from the viewpoint of polyamide toughness.
In addition, the (c) lactam and / or aminocarboxylic acid used in this embodiment means a lactam and / or aminocarboxylic acid that can be condensed (condensed).

  (A) when the polyamide is a polyamide obtained by polymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the (c) lactam and / or aminocarboxylic acid From the viewpoint of toughness, it is preferable to use a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms, and it is more preferable to use a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms.

  Examples of the lactam include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like. Among these, ε-caprolactam, laurolactam and the like are preferable from the viewpoint of toughness of polyamide, and ε-caprolactam is more preferable as the lactam.

Examples of the aminocarboxylic acid include, but are not limited to, ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which the lactam is ring-opened.
From the viewpoint of thermal stability, the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted at the ω position with an amino group. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.

  The (c) lactam and / or aminocarboxylic acid may be used alone or in combination of two or more.

(A) When producing polyamide, the ratio (mol%) of the (c) lactam and / or aminocarboxylic acid is the same as the (a) dicarboxylic acid, (b) diamine and (c) lactam and / or aminocarboxylic acid. From the viewpoints of heat resistance and strength, 0 to 20 mol% is preferable, 0 to 15 mol% is more preferable, and 0 to 10 mol% is preferable. Further preferred.
(D) The content (mol%) of the unit consisting of lactam and / or aminocarboxylic acid is not particularly limited, but is preferably 0 mol% with respect to 100 mol% of units consisting of all monomers constituting the copolymerized polyamide. It is 20 mol% or less, more preferably 0 mol% or more and 18 mol% or less.
(D) When the unit consisting of lactam and / or aminocarboxylic acid is contained, the content of the unit consisting of (d) is preferably 0.5 mol% or more, for example. (D) Copolymer having excellent heat resistance, low water absorption, strength, releasability, etc. by adjusting the content of units consisting of lactam and / or aminocarboxylic acid in the range of 0 mol% to 18 mol%. It can be a polyamide.

<End sealant>
The polyamide of the present embodiment is known for controlling the molecular weight when polymerized using the above-mentioned (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid as necessary. An end capping agent may be used, and (A) polyamide may have a residue of the end capping agent at the molecular end.
Examples of the end capping agent include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride; monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint of thermal stability, monocarboxylic acids and monoamines are preferable.
As the terminal blocking agent, only one type may be used alone, or two or more types may be used in combination.

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 And aromatic monocarboxylic acids such as acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
As monocarboxylic acid, only 1 type may be used independently and 2 or more types may be used in combination.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatics such as aniline, toluidine, diphenylamine, and naphthylamine Monoamines; and cyclic amines such as pyrrolidine, piperidine, 3-methylpiperidine; and the like.
Monoamines may be used alone or in combination of two or more.
(A) As for polyamide, the terminal group of the molecular chain may be sealed with the terminal blocker mentioned above.
The ratio of the end groups of the molecular chain being sealed with the end-capping agent (end-capping rate) is 10 from the viewpoints of fluidity, releasability and heat discoloration of the polyamide resin composition of the present embodiment. % Or more, more preferably 20% or more, further preferably 30% or more, still more preferably 40% or more, and most preferably 50% or more.
The terminal blocking rate of the molecular chain of the polyamide can be measured by the method described in Examples described later.

<(A) Polymer terminal of polyamide>
The polymer terminal of (A) polyamide used for the polyamide resin composition of this embodiment can be classified and defined as follows.
That is, 1) amino terminal, 2) carboxylic acid terminal, 3) cyclic amino terminal, 4) terminal by sealing agent, and 5) other terminal.

1) The amino terminal is an amino group (—NH ₂ group) bonded to the polymer terminal, and is derived from the raw material diamine.

  2) The carboxylic acid terminal is a carboxyl group (—COOH group) bonded to the polymer terminal and is derived from the raw material dicarboxylic acid.

3) The cyclic amino terminus is a cyclic amino group (group represented by the following formula 1) bonded to the polymer terminus.
In the following formula 1, R represents a substituent bonded to the carbon constituting the piperidine ring.
Examples of R include, but are not limited to, a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group. Further, for example, even when piperidine cyclized by a deammonia reaction of a diamine having a pentamethylenediamine skeleton as a raw material is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. The structure of the cyclic amino terminal may be taken when a monomer having a pentamethylenediamine skeleton is included.

4) The terminal by a sealing agent is formed when a sealing agent is added at the time of superposition | polymerization.
Examples of the sealant include carboxylic acid or amine. The polymer terminal is sealed with the sealing agent.

  5) The other terminal is a polymer terminal not classified in the above 1) to 4), and examples include a terminal generated by deammonia reaction at the amino terminal and a terminal generated by decarboxylation from a carboxylic acid terminal.

  In the polyamide resin composition of this embodiment, in (A) the polyamide, the amount of the 3) cyclic amino terminal is preferably 30 μ equivalent / g or more and 65 μ equivalent / g or less, and 30 μ equivalent / g or more and 60 μ or less. It is more preferable that it is equivalent / g or less, and it is further more preferable that it is 35 microequivalent / g or more and 55 microequivalent / g or less. When the amount of the cyclic amino terminal is in the above range, (A) the toughness, hydrolysis resistance, and processability of the polyamide can be improved.

3) The amount of the cyclic amino terminus can be measured using 1H-NMR.
For example, it can be calculated based on the integral ratio of hydrogen bonded to the carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to the carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

  3) The cyclic amino terminus is generated by a dehydration reaction between a cyclic amine and a carboxylic acid terminus, or a deammonia reaction at the amino terminus in a polymer molecule.

The 3) cyclic amino terminal can also be generated by adding a cyclic amine as a terminal blocking agent, and a diamine having a pentamethylenediamine skeleton, which is a polyamide raw material, is deammoniated to cyclize and react in the reaction system. Can also be generated.
In the present embodiment, the 3) cyclic amino terminal is preferably derived from a raw material diamine.
Adding a cyclic amine as an end-capping agent at the initial stage of polymerization results in the end of the low molecular weight carboxylic acid being capped at the initial stage of polymerization. It becomes difficult to obtain.
In contrast, when a cyclic amine is generated during the reaction, the end of the carboxylic acid is capped with the cyclic amine at a later stage of polymerization, so that a high molecular weight polymer of polyamide is easily obtained.

  3) The cyclic amine that forms the cyclic amino terminus is generated as a by-product during the polymerization reaction of the polyamide. In this cyclic amine formation reaction, the higher the reaction temperature, the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the (A) polyamide used in the present embodiment constant, it is preferable to promote the generation of cyclic amine. Therefore, the reaction temperature for the polymerization of (A) polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.

  As a method for adjusting these cyclic amino ends to a certain amount, there is a method of controlling by appropriately adjusting the polymerization temperature, the time of 300 ° C. or more during the polymerization step, the addition amount of amine forming a cyclic structure, and the like. Can be mentioned.

  In the polyamide (A) used in the polyamide resin composition of the present embodiment, 1) the amount of the amino terminal is preferably 20 to 100 μequivalent / g, and more preferably 25 to 70 μequivalent / g. 1) When the amount of the amino terminal is in the above range, (A) the hydrolysis resistance and heat retention stability of the polyamide can be improved.

((A) Polyamide production method)
The method for producing the polyamide (A) contained in the polyamide resin composition of the present embodiment is not particularly limited, and (a) a dicarboxylic acid containing an alicyclic dicarboxylic acid and (b) an aliphatic diamine. The method of including the process of superposing | polymerizing with the diamine containing is mentioned.
The polyamide (A) contained in the polyamide resin composition of the present embodiment is preferably a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.
(A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

The method for producing (A) polyamide contained in the polyamide resin composition of the present embodiment is not particularly limited, and examples thereof include the methods exemplified 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 suspension of water of a dicarboxylic acid / diamine 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 “prepolymer”). -It may be abbreviated as "extrusion polymerization method").
4) A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the degree of polymerization is increased while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide And may be abbreviated as “prepolymer / solid phase polymerization method”.
5) A method in which the dicarboxylic acid / diamine salt or a mixture thereof is polymerized in one step while maintaining the solid state (hereinafter, sometimes abbreviated as “one-step solid phase polymerization method”).
6) A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter sometimes abbreviated as “solution method”).

(A) As a manufacturing method of polyamide, the above 1) hot melt polymerization method, 2) hot melt polymerization / solid phase polymerization method, 3) prepolymer / extrusion polymerization method, 4) prepolymer / solid phase polymerization method, And 5) a single-stage solid-phase polymerization method is preferred, more preferably the 4) prepolymer / solid-phase polymerization method and 5) a single-stage solid-phase polymerization method.
(A) In the method for producing polyamide, it is preferable to carry out a solid phase polymerization method from the viewpoint of improving the molecular weight of the polyamide, and the method for carrying out the solid phase polymerization method to improve the molecular weight of the polyamide is Rather than improving the molecular weight by the melt polymerization method, it is preferable from the viewpoint that the cyclic amino terminal amount of the polyamide can be controlled to a predetermined amount.

(A) In the production process of polyamide, when performing polymerization, it is preferable to add an additive during the polymerization.
As an additive at the time of superposition | polymerization, (b) diamine which is a raw material of (A) polyamide is mentioned. In this case, (b) diamine means (b) diamine which is further added separately from (b) diamine used in the production of an equimolar amount of dicarboxylic acid / diamine salt, and (b) diamine as the additive Is preferably 0.1 to 10 mol%, more preferably 0.5 to 5.0 mol%, still more preferably 1. (b) when the diamine is 100 mol%. It is 5-4.5 mol%, More preferably, it is 2.6-4.0 mol%.
(B) By making the addition amount of a diamine into the said range, said 3) cyclic amino terminal amount mentioned above and said 1) amino terminal amount can be controlled to a desired numerical value range.

(A) As an additive at the time of superposition | polymerization of polyamide, organic acids, such as formic acid and an acetic acid other than the said diamine, etc. are mentioned.
By adding formic acid or the like, the amount of the cyclic amino terminus at the polymer end tends to decrease, which is effective as a method for controlling the amount of the cyclic amino terminus to the target value.

(A) The polymerization form in the polyamide production process may be either batch or continuous.
Further, the reactor used by a method other than the solid phase polymerization method is not limited to the following, for example, an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, etc. These can be used to carry out various polymerization reactions.

(A) The solid-phase polymerization method as a method for producing polyamide uses, for example, a tumbler reactor, a vibratory dryer reactor, a Nauter mixer reactor, a stirring reactor, and the like. It can be carried out.
Specifically, (A) polyamide pellets, flakes, or powder is placed in the reactor to polymerize the polyamide. At this time, it may be performed under a stream of inert gas such as nitrogen, argon, and helium or under reduced pressure, and the inert gas is supplied from the lower part of the reactor while pulling the internal gas to the reduced pressure at the upper part of the reactor. Alternatively, (A) The molecular weight of the polyamide can be improved by heating at a temperature below the melting point of the polyamide.
The reaction temperature of the solid phase polymerization is preferably 100 to 350 ° C, more preferably 120 to 300 ° C, and further preferably 150 to 270 ° C.
After the polymerization, the heating is stopped, and the reaction temperature is preferably lowered from 0 to 100 ° C., more preferably from room temperature to 60 ° C., and then (A) polyamide can be taken out from the reactor.

(A) In the polyamide production process, in any of the above-mentioned “prepolymer / solid phase polymerization method”, “one-stage solid phase polymerization method”, and “solution method”, It is preferable to polymerize (a) dicarboxylic acid and (b) diamine (including (c) lactam and / or aminocarboxylic acid, if necessary). In addition, when manufacturing a prepolymer, in the manufacturing process of the said prepolymer, you may carry out by the reaction temperature more than melting | fusing point of (A) polyamide, and may obtain a prepolymer by quenching after that.
In the polymerization step, the maximum ultimate pressure is preferably 10 kg / cm ² or more, more preferably 12 kg / cm ² or more. Thereby, escape of (b) diamine can be suppressed and the target (A) polyamide can be made high molecular weight.
Furthermore, it is preferable that the final temperature of the polymerization be (A) the melting point of the polyamide or lower. Thereby, the effect which suppresses the production | generation of a cyclic amine compound is acquired.
(A) In the production process of polyamide, the amount of cyclic amino terminal can be easily achieved by using the above-mentioned “hot melt polymerization / solid phase polymerization method”, “prepolymer / solid phase polymerization method” and “one-stage solid phase polymerization method”. (A) polyamide having a high melting point that can be increased in molecular weight and has excellent heat resistance, heat stability, heat-resistant color tone stability, heat reflow resistance, and fogging properties.

  (A) In the production process of polyamide, in order to control the molecular weight when polymerizing using (a) dicarboxylic acid and (b) diamine, and (c) lactam and / or aminocarboxylic acid as necessary The above-described known end capping agent may be further added to carry out the polymerization.

((A) Properties of polyamide)
<Sulfuric acid relative viscosity>
Regarding the molecular weight of the polyamide (A) used in the polyamide resin composition of the present embodiment, the sulfuric acid relative viscosity ηr at 25 ° C. can be used as an index.
The polyamide (A) used in this embodiment preferably has a sulfuric acid relative viscosity ηr of 25% at a concentration of 1% in 98% sulfuric acid measured according to JIS-K6920 from the viewpoint of mechanical properties such as toughness and rigidity, and moldability. Is 1.5 to 7.0, more preferably 1.7 to 6.0, and even more preferably 1.9 to 5.5.
The sulfuric acid relative viscosity ηr at 25 ° C. can be measured by the method described in the following examples.

<Melting point Tm2>
(A) The melting point Tm2 of the polyamide is preferably 270 to 350 ° C. from the viewpoint of heat resistance and suppressing thermal decomposition in the melting step. (A) Melting | fusing point Tm2 of polyamide 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 of the (A) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, still more 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. Further, by setting the melting point Tm2 of the polyamide (A) to 350 ° C. or lower, it is possible to suppress the thermal decomposition of the polyamide in the melt processing such as extrusion and molding.

<Heat of fusion ΔH>
The heat of fusion ΔH of the polyamide (A) used in the present embodiment is preferably 10 J / g or more, more preferably 14 J / g or more, further preferably 18 J / g or more, from the viewpoint of heat resistance. More preferably, it is 20 J / g or more.

  The (A) polyamide melting point Tm2 and heat of fusion ΔH used in the polyamide resin composition of the present embodiment can be measured in accordance with JIS-K7121.

  Although it does not specifically limit as a measuring apparatus of melting | fusing point Tm2 and heat of fusion (DELTA) H, For example, Diamond-DSC by PERKIN-ELMER company etc. are mentioned.

<Glass transition temperature Tg>
It is preferable that the glass transition temperature Tg of (A) polyamide used for the polyamide resin composition of this embodiment is 90-170 degreeC.
(A) The glass transition temperature of the polyamide is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, even more preferably 115 ° C. or higher, and still more preferably. 120 ° C. or higher.
Moreover, the glass transition temperature of (A) polyamide 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 good external appearance can be obtained by setting the glass transition temperature of (A) polyamide to 170 ° C. or lower.

  The glass transition temperature can be measured according to JIS-K7121.

  Although it does not specifically limit as a measuring apparatus of a glass transition temperature, For example, Diamond-DSC by PERKIN-ELMER company etc. are mentioned.

((B) Low molecular weight olefin resin)
The polyamide resin composition of this embodiment contains (A) polyamide mentioned above and (B) low molecular weight olefin resin.
The low molecular weight olefin-based resin means “an olefin-based resin having a number average molecular weight of 500 to 35000, preferably 2000 to 8000, and more preferably 3000 to 8000.
By using a low molecular weight olefin resin in the above numerical range, good characteristics can be obtained in strength, releasability, whiteness, heat reflow resistance, and fogging property.
The content of the (B) low molecular weight olefin resin in the polyamide resin composition of the present embodiment is not particularly limited, but preferably 0 when the total mass of the polyamide resin composition is 100 parts by mass. 0.05 to 5 parts by mass, more preferably 0.075 to 5 parts by mass, still more preferably 0.3 to 3 parts by mass, and still more preferably 0.5 to 2.5 parts by mass.

  A polyamide resin composition having excellent strength, releasability, whiteness, heat reflow resistance, and fogging properties when the content of (B) the low molecular weight olefin resin in the polyamide resin composition of the present embodiment is within the above range. A thing is obtained.

(B) The low molecular weight olefin resin is preferably an unmodified low molecular weight olefin. Thereby, the polyamide resin composition excellent in releasability, whiteness, and heat reflow property is obtained.
(B) The low molecular weight olefin-based resin is not limited to the following, but includes ethylene, a homopolymer of an α-olefin having 3 to 12 carbon atoms, or other monomers copolymerizable therewith. The copolymer of is mentioned as a preferable thing.
Examples of the α-olefin having 3 to 12 carbon atoms include, but are not limited to, polypropylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl. Examples include -1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene.
Examples of the copolymer with the other monomer include acrylonitrile-styrene copolymer grafted polypropylene, acrylonitrile-styrene copolymer grafted polyethylene, styrene polymer grafted polypropylene, and styrene polymer grafted polyethylene.
(B) The low molecular weight olefin-based resin includes at least one compound, may be a mixture, and includes a modified body of each compound.

  (B) The low molecular weight olefin-based resin is preferably a polyethylene, a homopolymer of an α-olefin having 3 to 8 carbon atoms, from the viewpoints of releasability, whiteness, and heat reflowability. It is more preferable that

(B) When polyethylene is used as the low molecular weight olefin resin, the polyethylene preferably has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 1000 to 10,000, more preferably 2000 to 2000. It is 8000, More preferably, it is 3000-8000.
When the Mn of polyethylene is within the above range, a polyamide resin composition having excellent strength, releasability, heat reflow resistance, and fogging properties can be obtained.

(B) When polyethylene is used as the low molecular weight olefin-based resin, the polyethylene preferably has a melting point measured by a differential scanning calorimeter (DSC) of 90 ° C to 130 ° C, more preferably 100 ° C to 120 ° C, and still more preferably. 105 ° C to 115 ° C.
The polyethylene may be an unmodified low molecular weight polyethylene, a modified low molecular weight polyethylene containing a polar terminal and / or a side chain, or both of them.
The modified low molecular weight polyethylene is a product obtained by partially oxidizing a low molecular weight polyethylene with an oxidizing agent or the like, and examples thereof include those having a carboxylic acid group at the terminal or having branched side chains. The degree of oxidation can be controlled by the reaction.
The modified low molecular weight polyethylene preferably has an acid value as an index of modification amount of 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and even more preferably 10 mgKOH. / G to 20 mgKOH / g.
When the acid value of the modified low molecular weight polyethylene is within the above range, a polyamide resin composition excellent in releasability, heat reflow resistance, and fogging properties can be obtained.
Specifically, the modified low molecular weight polyethylene has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of preferably 1000 to 10,000, more preferably 1000 to 8000, and still more preferably 2000 to 8000. It is.
When the Mn of the modified low molecular weight polyethylene is within the above range, a polyamide resin composition having excellent strength, releasability, heat reflow resistance, and fogging properties can be obtained.
The modified low molecular weight polyethylene preferably has a melting point measured by a differential scanning calorimeter (DSC) of 90 ° C to 130 ° C, more preferably 100 ° C to 120 ° C, and particularly preferably 100 ° C to 110 ° C.

For both unmodified and modified low molecular weight polyethylene, there are two types of polyethylene for the polymerization process.
One is linear polyethylene (HDPE) polymerized under low pressure using a Ziegler catalyst, and the other is branched polyethylene (LDPE) polymerized under high pressure using a radical catalyst.
The unmodified low molecular weight polyethylene may be a low molecular weight polyethylene obtained by a thermal decomposition method. From the viewpoint of releasability and heat reflow resistance, branched polyethylene (LDPE) polymerized under high pressure using a radical catalyst is preferable.
In the case of using a modified low molecular weight polyethylene, a linear polyethylene (HDPE) polymerized under a low pressure using a Ziegler catalyst is preferably partially oxidized. A polyamide containing a unit composed of a dicarboxylic acid containing an alicyclic dicarboxylic acid and a unit consisting of a diamine containing an aliphatic diamine has a specific structure. By combining the molecular weight polyethylene, it is excellent in releasability, heat reflow resistance, and fogging property, and further, plasticization time stability is dramatically increased, and stable mass production becomes possible.

  (B) When polypropylene is used as the low molecular weight olefin resin, the polypropylene preferably has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 1000 to 20000, more preferably 2000 to 2000. It is 10,000, More preferably, it is 2000-8000. When the Mn of the low molecular weight polyethylene is within the above range, a polyamide resin composition having excellent strength, releasability, whiteness, heat reflow resistance and fogging properties can be obtained.

  (B) When polypropylene is used as the low molecular weight olefin resin, the polypropylene preferably has a melting point measured by a differential scanning calorimeter (DSC) of 130 ° C to 160 ° C, more preferably 140 ° C to 160 ° C, and even more preferably. Is above 140 ° C. to 150 ° C.

The polypropylene may be a modified low molecular weight polypropylene containing polar ends and / or side chains.
The modified low molecular weight polypropylene is obtained by partially oxidizing a low molecular weight polypropylene with an oxidizing agent or the like, and examples thereof include those having a carboxylic acid group at the terminal or having branched side chains. The degree of oxidation can be controlled by the reaction.
Specifically, the modified low molecular weight polypropylene preferably has a number average molecular weight (Mn) measured by GPC of preferably 10,000 to 30,000, more preferably 12,000 to 27,000, and even more preferably 15,000 to 25,000.
When the Mn of the modified low molecular weight polypropylene is within the above range, a polyamide resin composition excellent in strength, releasability, heat reflow resistance and fogging properties can be obtained.
The modified low molecular weight polypropylene preferably has a melting point measured by a differential scanning calorimeter (DSC) of 120 ° C. to 150 ° C., more preferably 125 ° C. to 140 ° C.

(B) The low molecular weight olefin resin is preferably at least one selected from the group consisting of low molecular weight polyethylene, modified low molecular weight polyethylene, and low molecular weight polypropylene from the viewpoints of releasability, heat reflow property, and fogging property. Of these, low molecular weight polyethylene and low molecular weight polypropylene are more preferable.
These (B) low molecular weight olefin resins may be used alone or in combination of two or more.
These (B) low molecular weight olefin-based resins are preferably introduced at the time of compounding in the production process of the polyamide resin composition, and more preferably introduced from the side feeder of the extruder. (B) By introducing a low molecular weight olefin resin from the side feeder, a polyamide resin composition having excellent heat reflow properties and fogging properties can be obtained.

  The polyamide resin composition of the present embodiment is composed of the above-described (A) polyamide, (B) low molecular weight olefin resin, inorganic filler, nucleating agent, lubricant, stabilizer, and polymer other than polyamide described later. You may further contain 1 or more types of components chosen from the group which consists of.

(Inorganic filler)
The polyamide resin composition of the present embodiment may further contain an inorganic filler from the viewpoint of mechanical properties such as strength and rigidity.
By containing an inorganic filler, the polyamide resin composition has excellent heat resistance, thermal stability, heat resistant color tone stability, heat reflow resistance, and fogging properties, and does not impair the properties of polyamide having a high melting point. In addition, while satisfying heat resistance, thermal stability, heat-resistant color tone stability, heat-resistant reflow property, fogging property, etc., it is particularly excellent in strength and moldability.

Examples of the inorganic filler include, but are not limited to, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, flaky glass, talc, kaolin, mica, hydro Talsite, 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 nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, and apatite And the like.
Among these, the inorganic filler is at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate, and clay. It is preferable from the viewpoints of mechanical strength, appearance, whiteness and the like.

The glass fiber or carbon fiber may have a perfect circular shape or a flat shape in cross section.
Examples of the 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.
The flatness ratio is expressed by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section. In the case of a perfect circle, the flatness is about 1.

  Glass fibers and carbon fibers preferably have a number average fiber diameter of 3 to 30 μm and a weight average fiber length of 100 to 750 μm from the viewpoint that excellent mechanical strength characteristics can be imparted to the polyamide resin composition. The aspect ratio (L / D) between the weight average fiber length L and the number average fiber diameter D is preferably 10 to 100.

  Further, the glass fiber or carbon fiber preferably has a flatness ratio of 1.5 or more, more preferably, from the viewpoints of reduction of warpage of the plate-shaped molded product, heat resistance, toughness, low water absorption, and heat aging resistance. Is from 1.5 to 10.0, more preferably from 2.5 to 10.0, and even more preferably from 3.1 to 6.0. Glass fibers and carbon fibers whose flatness is within the above range are less likely to be crushed during mixing, molding, and other treatments as well as mixing with other components, and easily achieve a desired effect.

  The thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is not particularly limited, but the minor axis D1 of the fiber cross section is 0.5 to 25 μm, and the major axis D2 of the fiber cross section is 1. It is preferable that it is 25-250 micrometers. When the short diameter D1 and long diameter D2 of the glass fiber or carbon fiber are within the above range, the fiber is easily spun and the strength of the molded article of the polyamide resin composition is improved by increasing the contact area with the polyamide. Tend to.

  The short diameter D1 of the cross section of the fiber is preferably 3 μm or more from the viewpoint of low warpage. Furthermore, it is preferable that the minor axis D1 of the cross section of the fiber is 3 μm or more and the flatness of the fiber is larger than 3.

The above-described glass fiber or carbon fiber having a flatness ratio of 1.5 or more is produced by a method described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. be able to.
In particular, in an orifice plate having a large number of orifices on the bottom surface, an orifice plate that surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes. A glass fiber having a flatness ratio of 1.5 or more produced using a nozzle chip for deformed cross-section glass fiber spinning provided with a plurality of convex edges extending downward from the front end of the outer peripheral portion is preferable.
These fibrous inorganic fillers such as glass fibers and carbon fibers described above may be used as fiber strands as rovings, or may be used as chopped glass strands after a cutting step is obtained.

  Here, the number average fiber diameter and the weight average fiber length in this specification are, for example, that the polyamide resin composition is placed in an electric furnace, the organic matter contained in the polyamide resin composition is incinerated, and from the residue, for example, arbitrary More than 100 glass fibers or carbon fibers selected in the above are observed with a scanning electron microscope (SEM), and the number average fiber diameter is obtained by measuring the fiber diameter of these glass fibers or carbon fibers, and the magnification There is a method of obtaining the weight average fiber length by measuring the fiber length using an SEM photograph at 1000 times.

  Further, the minor axis D1 and the major axis D2 of the cross section of the fiber in this specification can also be measured in the same manner as the method for measuring the number average fiber diameter and the weight average fiber length.

  The glass fiber or carbon fiber may be subjected to a surface treatment with a silane coupling agent or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Aminosilanes such as dimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; An epoxy compound, a polyurethane resin, a homopolymer of acrylic acid, a copolymer of acrylic acid and other copolymerizable monomers; and their primary, secondary, and tertiary amines And a copolymer containing an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer. These may be used alone or in combination of two or more.

  Among them, from the viewpoint of the mechanical strength of the polyamide resin composition of the present embodiment, the sizing agent includes carboxylic acid anhydride-containing unsaturated vinyl monomers and carboxylic acid anhydride-containing unsaturated vinyl monomers. A copolymer containing a saturated vinyl monomer as a constitutional unit, an epoxy compound and a polyurethane resin, and a combination thereof are preferable. The unsaturated vinyl monomer containing a carboxylic acid anhydride and the unsaturated vinyl monomer containing the carboxylic acid anhydride are preferable. A copolymer and a polyurethane resin containing an unsaturated vinyl monomer excluding a monomer as a constituent unit, and a combination thereof are more preferable.

Glass fiber or carbon fiber is a fiber strand produced by applying a known sizing agent to a glass fiber or carbon fiber using a known method such as a roller-type applicator in a known glass fiber or carbon fiber production process. Can be obtained by continuous reaction by drying.
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 gives (adds) a solid content of 0.2 to 3% by mass, more preferably 0.3 to 2% by mass (added) to 100% by mass of glass fiber or carbon fiber. Added.
From the viewpoint of maintaining the bundling of the glass fiber or carbon fiber, 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 fiber or carbon fiber.
On the other hand, the addition amount of the sizing agent is preferably 3% by mass or less from the viewpoint of improving the thermal stability of the polyamide resin composition. The strand may be dried after the cutting step, or may be cut after the strand is dried.

  Examples of inorganic fillers other than glass fibers and carbon fibers include wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, titanic acid, from the viewpoint of strength, rigidity and surface appearance of the polyamide resin composition of the present embodiment. Potassium, aluminum borate, and clay are preferable, more preferably wollastonite, kaolin, mica, and talc, more preferably wollastonite and mica, and still more preferably wollastonite.

The average particle diameter of inorganic fillers other than glass fibers and carbon fibers is preferably 0.01 to 38 μm, more preferably 0.03 to 30 μm, in terms of toughness and surface appearance of the polyamide resin composition of the present embodiment, 0.05-25 micrometers is further more preferable, 0.1-20 micrometers is still more preferable, 0.15-15 micrometers is still more preferable.
By setting the average particle size of the inorganic filler other than the glass fiber and the carbon fiber to 38 μm or less, a polyamide resin composition having excellent toughness and surface appearance can be obtained. Further, by making the average particle size 0.1 μm or more, the balance between cost and powder handling surface and physical properties is excellent.
In addition, the said average particle diameter can be measured by SEM, for example.

  Among inorganic fillers, the number average fiber diameter is the average particle diameter for an inorganic filler having a needle-like shape such as wollastonite. Furthermore, in the case of an inorganic filler whose cross section is not a circle, the maximum value of the length is taken as the fiber diameter.

  Regarding the aspect ratio (L / D) between the weight average fiber length L and the number average fiber diameter D of the inorganic filler having a needle shape, from the viewpoint of the appearance of the molded product and the wear of metallic parts such as injection molding machines. 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is still more preferable.

The inorganic filler other than glass fiber and carbon fiber used in the polyamide resin composition of the present embodiment is a surface with a normal surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent. You may use what processed.
The silane coupling agent is not limited to the following, but, for example, an epoxy silane coupling agent is preferable. As the silane coupling agent, a mixture of polyalkoxysiloxane and epoxysilane coupling agent and / or a reaction product of polyalkoxysiloxane and epoxysilane coupling agent can also be preferably used. Such a surface treating agent can be added to the surface of the inorganic filler in advance, or (A) it may be added when the polyamide and the inorganic filler are mixed. Moreover, the preferable addition amount of a surface treating agent is the range of 0.05 mass%-1.5 mass% with respect to an inorganic filler.

In the polyamide resin composition of the present embodiment, the titanium oxide used as the inorganic filler described above is not limited to the following. For example, titanium oxide (TiO), dititanium trioxide (Ti ₂ O _3). ) And titanium dioxide (TiO ₂ ). Among these, titanium dioxide is preferable from the viewpoint of light resistance.

  The crystal structure of titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance of the polyamide resin composition.

  The number average particle diameter of titanium oxide is preferably 0.1 to 0.8 μm, more preferably 0.15 to 0.4 μm, and still more preferably, from the viewpoint of toughness and extrusion processability of the polyamide resin composition. Is 0.15 to 0.3 μm.

  The number average particle diameter of titanium oxide can be measured by electron micrograph. For example, the polyamide resin composition is put in an electric furnace, the organic matter contained in the polyamide resin composition is incinerated, and for example, 100 or more arbitrarily selected titanium oxides are observed with an electron microscope from the residue, By measuring these particle sizes, it is possible to determine the number average particle size of titanium oxide.

  Titanium oxide may be obtained, for example, by a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed or by a so-called chlorine method in which titanium halide is vapor-phase oxidized. From the viewpoint of properties, the sulfuric acid method is preferred.

  The surface of the titanium oxide particles is preferably coated. More preferably, the surface of the titanium oxide particles is first coated with an inorganic coating and then with an organic coating applied over the inorganic coating. The titanium oxide particles may be coated using any method known in the art. The inorganic coating preferably contains a metal oxide. The organic coating preferably includes one or more of carboxylic acids, polyols, alkanolamines and / or organosilicon compounds. Above all, from the viewpoint of light resistance and extrusion processability of the polyamide resin composition, the surface of the titanium oxide particles is more preferably coated with polyols and organosilicon compounds, and is generated during processing of the polyamide resin composition. From the viewpoint of reducing gas, it is more preferable to coat using an organosilicon compound.

  Note that one type of titanium oxide may be used, or two or more types may be used in combination.

  The content of titanium oxide in the polyamide resin composition of the present embodiment is preferably 20 to 50% by mass and more preferably 100% by mass with respect to 100% by mass of the polyamide resin composition from the viewpoint of whiteness of the polyamide resin composition. Is 25-50 mass%, More preferably, it is 30-50 mass%.

  The content of the inorganic filler in the polyamide resin composition of the present embodiment is preferably 0 to 50% by mass, more preferably 20 to 50% by mass with respect to 100% by mass of the polyamide resin composition, More preferably, it is 30-50 mass%. When the content of the inorganic filler is within the above range, the strength, rigidity and toughness of the polyamide resin composition can be maintained in a well-balanced manner.

(Nucleating agent)
The nucleating agent means that the addition increases the crystallization peak temperature of the polyamide resin composition, reduces the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak, or obtains molded product balls. It means a substance capable of obtaining the effect of refining crystals or making the size uniform.
Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
Only one type of nucleating agent may be used alone, or two or more types may be used in combination.
The nucleating agent is preferably talc or boron nitride from the viewpoint of the nucleating agent effect.
Moreover, since a nucleating agent effect is high, the nucleating agent whose number average particle diameter is 0.01-10 micrometers is preferable.
The number average particle size of the nucleating agent is determined by dissolving the molded article in a solvent in which polyamide such as formic acid is soluble, and arbitrarily selecting, for example, 100 or more nucleating agents from the obtained insoluble components, It can be determined by observing and measuring with an optical microscope or a scanning electron microscope.
In the polyamide resin composition of the present embodiment, the content of the nucleating agent is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0 part per 100 parts by mass of the (A) polyamide. 0.5 parts by mass, and more preferably 0.001 to 0.09 parts by mass.
By making the content of the nucleating agent 0.001 part by mass or more with respect to 100 parts by mass of the (A) polyamide, the heat resistance of the polyamide resin composition is improved, and the content of the nucleating agent is reduced. By setting the content to 1 part by mass or less with respect to 100 parts by mass of polyamide, a polyamide resin composition having excellent toughness can be obtained.

(lubricant)
Examples of the lubricant include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.
One type of lubricant may be used alone, or two or more types may be used in combination.
Examples of higher fatty acids include, for example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and saturated or unsaturated, linear or branched aliphatic having 8 to 40 carbon atoms Examples thereof include monocarboxylic acids, and stearic acid and montanic acid are preferred.
As the higher fatty acid, one kind may be used, or two or more kinds may be used in combination.
The higher fatty acid metal salt is a metal salt of the higher fatty acid.
The metal element constituting the higher fatty acid metal salt is preferably a group 1, 2, 3 element of the periodic table, zinc, aluminum or the like, more preferably first, such as calcium, sodium, potassium, magnesium or the like. Examples include Group 2 elements, aluminum, and the like.
Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. A metal salt of montanic acid and a metal salt of stearic acid are preferred.
A higher fatty acid metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
The higher fatty acid ester is an esterified product of the higher fatty acid and alcohol. An ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Examples of the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.
As a higher fatty acid ester, one type may be used alone, or two or more types may be used in combination.
The higher fatty acid amide is an amide compound of the higher fatty acid.
Examples of the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Examples include amides.
The higher fatty acid amide is preferably stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucamide, and more preferably ethylene bisstearyl amide and N-stearyl erucamide.
Only one type of higher fatty acid amide may be used alone, or two or more types may be used in combination.
The lubricant is preferably a higher fatty acid metal salt or a higher fatty acid amide, more preferably a higher fatty acid metal salt, from the viewpoint of improving moldability.
The content of the lubricant in the polyamide resin composition of the present embodiment is preferably 0.001 to 1 part by weight, more preferably 0.03 to 0.5 part by weight with respect to 100 parts by weight of the polyamide. Part.
When the content of the lubricant is within the above range, the polyamide resin composition having excellent releasability and plasticization time stability and excellent toughness can be obtained, and the molecular chain is broken. The extreme molecular weight reduction of the polyamide can be prevented.

(Stabilizer)
Examples of the stabilizer include, but are not limited to, phosphorus compounds, phenolic antioxidants and / or amine antioxidants, amine light stabilizers, and organic phosphorus antioxidants.

<Phosphorus compounds>
The polyamide resin composition of the present embodiment may contain a phosphorus compound from the viewpoint of thermal stability.
Examples of phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) phosphoric acid, Examples thereof include phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof. An inorganic phosphorus type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following. Examples thereof include phosphoric acid, pyrophosphoric acid, and metalin. Examples thereof include acids, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, and diphosphorous acid.

  The metal salts of 2) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following, but include, for example, phosphorus of 1) above. Mention may be made of salts of the compounds with Group 1 and 2 of the periodic table, manganese, zinc and aluminum.

More preferable phosphorus compounds are one selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts and intermolecular condensates of these metal salts. That's it. A more preferable phosphorus compound is a metal salt composed of a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal selected from Groups 1 and 2 of the periodic table, manganese, zinc and aluminum. Or an intramolecular condensate of these metal salts or an intermolecular condensate of these metal salts.
An even more preferable phosphorus compound is a metal salt composed of a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid and a metal selected from Groups 1 and 2 of the periodic table. Examples of such metal salts include, but are not limited to, for example, monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, Examples thereof include sodium pyrophosphate, sodium metaphosphate, calcium metaphosphate, sodium hypophosphite, calcium hypophosphite, and the like, and anhydrous salts and hydrates thereof. Among these, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable, and calcium hypophosphite and magnesium hypophosphite are more preferable.

  The content of the phosphorus compound in the polyamide resin composition of the present embodiment is preferably 0.5 to 7% by mass, more preferably 1.1 to 7% by mass with respect to 100% by mass of the polyamide resin composition. %, More preferably 1.1 to 4% by mass. When the content of the phosphorus compound is within the above range, the polyamide resin composition can further improve heat discoloration resistance and light discoloration resistance.

  The phosphorus element concentration in the polyamide resin composition of the present embodiment is preferably 1400 to 20000 ppm relative to (A) polyamide, more preferably from the viewpoint of heat discoloration resistance and light discoloration resistance of the polyamide resin composition. Is 2000 to 20000 ppm, more preferably 3000 to 20000 ppm.

Furthermore, the ratio of the metal element concentration to the phosphorus element in the polyamide resin composition (metal element concentration / phosphorus element concentration) is 0.3 to 0.8. It is preferable from a viewpoint of property, More preferably, it is 0.3 to 0.7%.
The metal element is a metal in the phosphorus compound. For example, when sodium hypophosphite, a phosphorus compound, is added, the above (metal element concentration / phosphorus element concentration) is sodium concentration / phosphorus element concentration.

<Phenolic antioxidant and / or amine antioxidant>
The polyamide resin composition of the present embodiment may contain a phenol-based antioxidant and / or an amine-based antioxidant from the viewpoint of thermal stability.

  Examples of phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

  Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-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, , 5-Di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. In this embodiment, only one type of phenolic antioxidant may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of improving heat aging resistance, the phenolic antioxidant is preferably N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4- Hydroxyphenylpropionamide)].

The content of the phenolic antioxidant in the polyamide resin composition of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide resin composition. %, And more preferably 0.1 to 1% by mass. When the content of the phenolic antioxidant is within the above range, the polyamide resin composition can further improve the heat aging resistance and further reduce the amount of generated gas.

  Examples of amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl-α-naphthylamine, 4,4-bis (α, α-dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-pheny Aromatic amines such as Njiamin like. In this specification, the amine-based antioxidant, refers to an aromatic amine compound.

  The content of the amine-based antioxidant in the polyamide resin composition of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide resin composition. %, And more preferably 0.1 to 1% by mass. When the content of the amine-based antioxidant is within the above range, the polyamide resin composition can further improve the heat aging resistance and further reduce the amount of generated gas.

<Amine-based light stabilizer>
The polyamide resin composition of the present embodiment may further contain an amine light stabilizer from the viewpoint of light stability.

  Examples of the amine light stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 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-tetramethyl Peridine, 4- (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-tetramethyl) -4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pen) Methyl-4-piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6) , 6-Tetramethyl-4-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetra Methyl-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, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- ( N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5 -Triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Piperidyl) Butylamine polycondensate Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl ) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetra Methyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4 − [3- (3,5- -T-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl Examples include condensates of -4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. Only one amine light stabilizer may be used alone, or two or more amine stabilizers may be used in combination.

  The amine light stabilizer is preferably a low molecular weight type having a molecular weight of less than 2,000 from the viewpoint of further improving the light stability of the polyamide resin composition. More preferably, the molecular weight of the amine light stabilizer is less than 1,000.

  In addition, the amine light stabilizers are NH type (indicating that hydrogen is bonded to the amino group), NR type (indicating that the alkyl group is bonded to the amino group), NOR type. There are types such as (indicating that an alkoxy group is bonded to an amino group). Among them, the NH type is preferable from the viewpoint of further improving the light stability of the polyamide resin composition.

  As the amine light stabilizer, from the viewpoint of improving light stability, 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-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4- Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred, and bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate is more preferred, and N, N′-bis-2,2,6,6-tetramethyl-4- Piperidinyl-1,3-benzenedicarboxamide is more preferred.

  The content of the amine light stabilizer in the polyamide resin composition of the present embodiment is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the polyamide resin composition. %, And more preferably 0.1 to 2% by mass. When the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide resin composition can be further improved, and the amount of generated gas can be further reduced.

The polyamide resin composition of the present embodiment may contain an organic phosphorus antioxidant from the viewpoint of thermal stability.
<Organic phosphorus antioxidant>
Examples of the organic phosphorus antioxidants include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, tris Decyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butyryl Den-bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis (2-t-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxy) Phenyl) butanediphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyldi Phosphite, Tris (mono, dimixed nonylphenyl) phosphite, 9,10-di-hydride -9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropyl Ridendiphenyl 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-t-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3- Stearoyloxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2 -Methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphos Phyto, and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.

  In the polyamide resin composition of the present embodiment, only one organic phosphorus antioxidant may be used alone, or two or more organic phosphorus antioxidants may be used in combination.

Among the organophosphorus antioxidants listed above, from the viewpoint of further improving the heat aging resistance of the polyamide resin composition and reducing the generated gas, pentaerythritol phosphite compound, tris (2,4-di-t -Butylphenyl) phosphite is preferred, and pentaerythritol phosphite compound is more preferred.
Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, -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- Tyl-4-methylphenyl-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-ethylcellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl- Butylcarbitol pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonyl Phenyl-pentaerythritol diphosphite, 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-cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl-pentae Rithritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite Examples include phosphites and bis (2,4-dicumylphenyl) pentaerythritol diphosphites.
A pentaerythritol type phosphite compound may be used alone or in combination of two or more.

  Among the pentaerythritol phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphos is preferred from the viewpoint of further improving the heat aging resistance and reducing the generated gas. Phyto, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4 -Dicumylphenyl) pentaerythritol diphosphite is preferred.

  The content of the organic phosphorus antioxidant in the polyamide resin composition of the present embodiment is preferably 0 to 2% by mass, more preferably 0.01 to 2% with respect to 100% by mass of the polyamide resin composition. It is a mass part, More preferably, it is 0.1-2 mass%. When the content of the organophosphorus antioxidant is within the above range, the heat resistance discoloration and extrusion processability can be further improved in the polyamide resin composition, and the amount of generated gas can be further reduced.

((A) Polymer other than polyamide)
Examples of the polymer other than polyamide include, but are not limited to, for example, (A) polyamide other than polyamide, polyester, liquid crystal polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenol resin, epoxy resin, and the like. Can be mentioned.
(A) Polyamides other than polyamide are not limited to the following. For example, polyamide 66, polyamide 56, polyamide 46, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I, polyamide 6, polyamide 11, polyamide 12, polyamide MXD6 and the like, and homopolymers or copolymers thereof.
Examples of the polyester include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.
(A) As for content of polymers other than polyamide, 1-200 mass parts is preferable with respect to 100 mass parts of polyamide, More preferably, it is 5-100 mass parts, More preferably, it is 5-50 mass parts. By setting the content of polymers other than polyamide in the polyamide resin composition of the present embodiment within the above range, a polyamide resin composition having excellent heat resistance and releasability can be obtained.

(Other ingredients)
In addition to the above-described components, the polyamide resin composition of the present embodiment may further include other predetermined components as necessary within a range that does not impair the effects of the present embodiment.

Examples of other components include, but are not limited to, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, fluorescent whitening agents, and plasticizing agents. Agents, copper compounds, alkali metal halide compounds, antioxidants, ultraviolet absorbers, antistatic agents, fluidity improvers, reinforcing agents, spreading agents, rubbers, reinforcing agents, and other polymers.
Here, since the above-mentioned other components are greatly different in properties, there are various suitable contents for each component that hardly impair the effects of the present embodiment. A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of polyamide resin composition]
The production method of the polyamide resin composition of the present embodiment includes the (A) polyamide, (B) low molecular weight olefin resin, and, if necessary, the above-mentioned inorganic filler, nucleating agent, lubricant, stabilizer. (A) It will not specifically limit if it is a method of mixing polymers other than a polyamide, and another component.
As a method for mixing the constituent materials of the polyamide resin composition, for example, a method of mixing using a Henschel mixer or the like, supplying to a melt kneader and kneading, or a melted state using a single or twin screw extruder (A) polyamide And (B) The method of mix | blending an inorganic filler and another component from a side feeder with a polyolefin-type compound, etc. are mentioned.
The method of supplying the components constituting the polyamide resin composition to the melt kneader may supply all the components ((A) polyamide and (B) polyolefin compound, etc.) to the same supply port at once. The constituent 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 0.5 to 5 minutes.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The 25 ° C. sulfuric acid relative viscosity ηr, the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide resin composition of this embodiment can be measured by the same method as that for the polyamide. Moreover, the polyamide resin composition which is excellent in heat resistance, a moldability, and chemical resistance can be obtained because the measured value in a polyamide resin composition exists in the range similar to a preferable range as a measured value of the said polyamide.

[Molded product of polyamide resin composition]
The molded article of the polyamide resin composition of the present embodiment includes the polyamide resin composition of the present embodiment.
The molded product of this embodiment is a known molding method using the polyamide resin composition of this embodiment, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, It can be produced using hollow molding, multilayer molding, melt spinning and the like.

A molded article containing the polyamide resin composition of the present embodiment is excellent in strength, heat resistance, thermal stability, heat resistant color tone stability, whiteness, heat reflow resistance, fogging properties, and molding processability.
Therefore, the polyamide resin composition of the present embodiment is suitably used as various parts materials for automobiles, electronics, household appliances, OA equipment or portable equipment, industrial materials, etc., and extrusion applications. Can do.

Although it does not specifically limit as an object for motor vehicles, For example, it uses for an intake system component, a cooling system component, a fuel system component, an interior component, an exterior component, an electrical component, etc.
Examples of the automobile intake system parts include, but are not limited to, an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body. It is done.
Examples of the automobile cooling system parts include, but are not limited to, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.
Examples of the automobile fuel system parts include, but are not limited to, a fuel delivery pipe and a gasoline tank case.
Examples of the interior parts include, but are not limited to, an instrument panel, a console box, a glove box, a steering wheel, and a trim.
Examples of the exterior component include, but are not limited to, a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
Examples of the electrical components include, but are not limited to, connectors, wire harness connectors, motor components, lamp sockets, sensor on-vehicle switches, and combination switches.
For electrical and electronic use, although not limited to the following, for example, for connectors, LED reflectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, motor end caps, etc. Used.
Although it is not limited to the following for industrial materials, For example, it is used for a gear, a cam, an insulation block, a valve, a power tool part, an agricultural tool part, an engine cover, etc.
Although it is not limited to the following for daily use and household goods, for example, it is used for buttons, food containers, office furniture, and the like.
Although it is not limited to the following as an extrusion use, For example, it is used for a film, a sheet | seat, a filament, a tube, a rod, a hollow molded article, etc.

  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〕
((A) Polyamide)
The polyamide (A) used in the examples and comparative examples was produced using the following (a) and (b) as appropriate.

<(A) Dicarboxylic acid>
(A-1) 1,4-cyclohexanedicarboxylic acid (CHDA) (manufactured by Eastman Chemical Co., Ltd., trade name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75))
(A-2) Terephthalic acid (TPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
<(B) Diamine>
(B-1) 2-methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry)
(B-2) 1,9-nonamethylenediamine (C9DA) (manufactured by Aldrich)
(B-3) 2-Methyloctamethylenediamine (2MC9DA) (produced with reference to the production method described in JP-A No. 05-17413)
(B-4) 1,10-diaminodecane (C10DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
<(C) End sealant>
Benzoic acid (Wako Pure Chemical Industries)

((B) Low molecular weight olefin resin)
(B-1) Polyethylene wax (low density, non-oxidizing type) Sun wax 165-P Sanyo Chemical Industries, Ltd. (number average molecular weight: 5000)
(B-2) Polyethylene wax Sun wax (low density, non-oxidizing type) 171-P manufactured by Sanyo Chemical Industries, Ltd. (number average molecular weight: 1500)
(B-3) Oxidized polyethylene sun wax (low density, oxidized type, acid value: 20 mgKOH / g) E-250P manufactured by Sanyo Chemical Industries, Ltd. (number average molecular weight: 2000)
(B-4) Polypropylene wax Biscol 660-P manufactured by Sanyo Chemical Industries, Ltd. (number average molecular weight is 3000)
(B-5) Polyethylene wax Sun wax LEL-400P (EX) (high density, oxidized type, acid value: 1 mg KOH / g) manufactured by Sanyo Chemical Industries, Ltd. (number average molecular weight is 4000)
(B-6) Polyethylene wax Licowax PE190 (high density, non-oxidizing type) manufactured by Clariant (weight average molecular weight: 5500)
(B-7) Polyethylene wax Licowax PE191 (high density, oxidized type, acid value: 17 mg KOH / g) manufactured by Clariant Co., Ltd. (weight average molecular weight: 2000)

(Higher fatty acid metal salt)
Calcium stearate (trade name: calcium stearate manufactured by Wako Pure Chemical Industries)

(Phenolic antioxidant)
Phenol-based antioxidant (trade name: IRGANOX (registered trademark) 1098, manufactured by BASF)

(Inorganic filler)
Wollastonite (number average fiber diameter 8μm)
The number average fiber diameter of the inorganic filler is obtained by placing the polyamide resin composition in an electric furnace, incinerating the organic matter contained in the polyamide resin composition, and selecting 100 or more glass fibers arbitrarily selected from the residue, The number average fiber diameter was determined by observing with SEM and measuring the fiber diameter of these glass fibers.

(Crystal nucleating agent)
Talc Product name: Microace L-1 (Nihon Talc)

(Titanium oxide)
TiO ₂ (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei (registered trademark) CR-63, number average particle size: 0.21 μm, coating: alumina, silica and siloxane compound)
In this example, the number average particle size of titanium oxide was measured by electron micrograph as follows.
The polyamide resin composition is put in an electric furnace, the organic matter contained in the polyamide resin composition is incinerated, and 100 or more titanium oxides arbitrarily selected from the residue are observed with an electron microscope, and these particles By measuring the diameter, the number average particle diameter of titanium oxide was determined.

[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.

[Measurement method of characteristics]
(1) Sulfuric acid relative viscosity ηr at 25 ° C.
The sulfuric acid relative viscosity ηr at 25 ° C. was measured according to JIS-K6810.
Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid, and the resulting solution was used at a temperature of 25 ° C. The sulfuric acid relative viscosity ηr was measured under the conditions.

(2) Melting points Tm1, Tm2 (° C.)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER.
The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample 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 was lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and the same at the temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when the temperature was raised to the melting point was Tm2 (° C.), and the total peak area was the heat of fusion ΔH (J / g).
In addition, as Tm2, when there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks. For example, as Tm2, when two peaks of melting point 295 ° C., ΔH = 20 J / g and melting point 325 ° C., ΔH = 5 J / g exist, the melting point is 325 ° C. and ΔH is 25 J / g.

(3) Glass transition temperature The glass transition temperature of the polyamide obtained by the Example and the comparative example was measured as follows using Diamond-DSC by PERKIN-ELMER according to JIS-K7121.
First, the sample was melted on a hot stage (EP80 manufactured by Mettler). The obtained sample in the molten state was quenched with liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature Tg was measured by raising the temperature in the range of 30 to 350 ° C. under the condition of a temperature elevation rate of 20 ° C./min.

(4) End sealing rate (%)
(A) The number average molecular weight (Mn) of the polyamide was measured by GPC, and the total number of molecular chain end groups was calculated using the relational expression: total number of molecular chain end groups (eq / g) = 2 / Mn.
The number of carboxyl group ends of the polyamide by titration (eq / g) [polyamide benzyl alcohol solution titrated with 0.1N sodium hydroxide] and the number of amino group ends (eq / g) [polyamide phenol solution 0.1N Titration with hydrochloric acid] was measured, and the end-capping rate was determined by the following formula (1).
Terminal sealing rate (%) = [(A−B) ÷ A] × 100 (1)
In the formula (1), A represents the total number of molecular chain end groups (this is usually equal to twice the number of polyamide molecules), and B represents the total number of carboxyl group terminals and amino group terminals.
The number average molecular weight (Mn) of the polyamide was determined by gel permeation chromatography (GPC).
The apparatus is HLC-8020 manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved, and the column is Tosoh ( Two TSKgel-GM HHR-H and one G1000 HHR manufactured by the same company were used.
The solvent flow rate was 0.6 mL / min, and the sample concentration was 1 to 3 (mg sample) / 1 (mL solvent).
Based on the obtained elution curve, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polymethyl methacrylate (PMMA).

(5) Trans isomerization rate The trans isomerization rate in the part derived from the alicyclic dicarboxylic acid of the polyamide obtained by the Example and the comparative example was calculated | required as follows.
30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and ¹ H-NMR was measured using the resulting solution. In the case of 1,4-cyclohexanedicarboxylic acid, from the ratio of the peak area of 1.98 ppm derived from the trans isomer to the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer in ¹ H-NMR measurement. The trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid of the copolymerized polyamide was determined.

(6) Tensile strength Multi-purpose specimen A type according to ISO3167, using pellets of polyamide resin compositions obtained in Examples and Comparative Examples, using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.) The molded piece was molded.
Specific molding conditions were injection + holding time 25 seconds, cooling time 15 seconds, mold temperature 80 ° C., and molten resin temperature set to the high temperature melting peak temperature (T _pm-1 ) + 20 ° C. of polyamide. .
Using the obtained multi-purpose test piece A-shaped molded piece, in accordance with ISO 527, a tensile test was performed at 23 ° C. and a tensile speed of 50 mm / min, and a tensile yield stress was measured to obtain a tensile strength.

(7) Evaluation of releasability: measurement of protruding stress As an injection molding machine, “SE50D” manufactured by Nissei Resin Co., Ltd. was used.
When forming an ISO test piece (3 mm thick) by fixing with an injection time of 2 seconds, a holding pressure time of 10 seconds, and cooling for 20 seconds, and changing the mold temperature (condition 1 = 90 ° C., condition 2 = 50 ° C.) The releasability of was evaluated. The evaluation of releasability was measured as the protruding stress when the molded part was taken out from the mold.
The parts were assumed to have a connector shape with an outer diameter of 16 mm and a thickness of 1 mm.
A pressure sensor was placed behind the ejector pin (diameter 2 mm).
The signal was expanded by an amplifier and recorded on a personal computer by an A / D (analog / digital) board.

(8) Fogging property Both ends of the multipurpose test piece (A type) obtained by the method of (6) above were cut to produce a rectangular solid shaped piece having a thickness of 4 mm, a width of 10 mm and a length of 50 mm.
Two obtained molded pieces were put into a glass bottle having an outer diameter of 25 mm and a height of 70 mm, and an internal volume of 50 cm ³ , and a glass plate was placed on the upper part of the glass bottle and covered.
The glass bottle containing the molded piece was placed in a hot air oven set at 220 ° C. and allowed to stand for about 20 hours.
Then, it cooled to room temperature, taken out the glass plate, and evaluated by the following reference | standard.
(Double-circle): A deposit is not seen.
○: A very small amount of deposit is observed.
X: Obvious deposits are observed.

(9) Heat-resistant reflow property Pellets of the polyamide resin compositions produced in the examples and comparative examples were molded using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), and were 60 mm long x 60 mm wide x thick. A molded piece having a thickness of 0.5 mm was produced.
During the molding, the injection + holding time was set to 10 seconds, the cooling time was set to 15 seconds, the mold temperature was set to 120 ° C., and the molten resin temperature was set to the melting point Tm2 + 20 ° C. of (A) polyamide.
The obtained molded piece was heated in a hot air reflow furnace to check the occurrence of blisters, the shape change, and the degree of discoloration of the test piece, and evaluated according to the following criteria.
<Blister outbreak status>
A: Blister does not occur.
○: Very few blisters are generated.
X: Blister occurs.
<Shape change>
A: No deformation of the test piece.
○: There is very little deformation of the test piece.
X: There is deformation of the test piece.
<Degree of discoloration>
(Double-circle): The slight discoloration of a test piece is recognized.
○: Slight discoloration of the test piece is observed.
X: Clear discoloration of a test piece is recognized.
The hot-air reflow furnace used at this time was a lead-free solder compatible reflow furnace (UNI-6116H, manufactured by Nippon Antom Co., Ltd.). Set to ° C.
The conveyor belt speed in the reflow furnace was set to 0.3 m / min. Under this condition, the temperature profile in the furnace was confirmed. The heat exposure time at 140 ° C. to 200 ° C. was 90 seconds, the heat exposure time at 220 ° C. or higher was 48 seconds, and the heat exposure time at 260 ° C. or higher was 11 seconds. There was a maximum temperature of 265 ° C.

(10) Initial reflectance (%)
The molded piece obtained by the method (9) was irradiated with light having a wavelength of 450 nm, and the reflectance of the light was measured with a Hitachi spectrophotometer (U-3310) to obtain the initial reflectance.

(11) Evaluation of plasticization time stability The pellets of the polyamide resin compositions obtained in the examples and comparative examples were in accordance with ISO 3167 using an injection molding machine [PS-40E: manufactured by Nissei Plastics Co., Ltd.]. Then, it was molded into a multi-purpose test piece A-shaped molded piece. Specific molding conditions are: injection + pressure holding time 25 seconds, cooling time 15 seconds, mold temperature 120 ° C, molten resin temperature set to polyamide polyamide melting point Tm2 + 20 ° C, molding up to 1000 shots, ISO test piece Got.
In each shot of the injection molding, the time until the polyamide composition pellets were plasticized (hereinafter also referred to as “plasticization time”) was measured. Based on the measured value, the plasticization time stability (standard deviation) was determined by the following formula.

Plasticization time for each of Ai = 1000 shots X1 = arithmetic average of plasticization time for 1000 shots It was determined that the smaller the standard deviation (σ), the better the plasticization time stability.

[(A) Production of polyamide]
(Production Example 1)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass water mixture of the raw material monomers.
The obtained water mixture and 21 g (0.18 mol) of 2MC5DA, which is an additive at the time of melt polymerization, were charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L.
Next, it heated until the liquid temperature (internal temperature) in an autoclave became 50 degreeC.
Thereafter, the inside of the autoclave was purged with nitrogen.
Until the pressure in the autoclave tank (hereinafter also referred to simply as “inside the tank”) reaches about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). Heating was continued (at this time the liquid temperature was up to about 145 ° C).
While maintaining the pressure in the tank at about 2.5 kg / cm ² , heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution in the tank was about 85% by mass.
Next, removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² .
While maintaining the pressure in the tank at about 30 kg / cm ² , the water was removed from the system, and heating was continued until the temperature reached 50 ° C. (about 295 ° C.) lower than the final temperature (about 345 ° C.).
While further heating, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 60 minutes.
The heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 345 ° C.
While maintaining the resin temperature in the tank, the inside of the tank was maintained for 10 minutes under a reduced pressure of 100 torr with a vacuum apparatus.
Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle).
Furthermore, the strand-like product was cooled with water and cut to obtain pellets of polyamide (polyamide pellets).

10 kg of the obtained polyamide pellets were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The polyamide pellets were heated at 240 ° C. for 6 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer.
Thereafter, the temperature in the vacuum dryer is lowered to about 50 ° C. while circulating nitrogen, and the polyamide pellets are taken out from the vacuum dryer in the form of pellets, and polyamide (hereinafter also abbreviated as “PA-1”) is removed. Obtained.
The obtained polyamide (PA-1) was dried in a nitrogen stream and the moisture content was adjusted to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
Polyamide (PA-1) has a cyclic amino terminal end-capping rate of 35%, a melting point Tm2 of 327 ° C., a glass transition temperature Tg of 150 ° C., a trans isomer ratio of 71%, and a sulfuric acid relative to 25 ° C. The viscosity was 3.1.

(Production Example 2)
CHDA 782 g (4.54 mol), C9DA 575 g (3.63 mol), and 2MC8DA 144 g (0.91 mol) were dissolved in distilled water 1500 g to prepare an aqueous mixture of 50 mol% by mass of the raw material monomer.
The obtained water mixture and 11 g (0.07 mol) of C9DA, which is an additive at the time of melt polymerization, were charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L.
Next, it heated until the liquid temperature (internal temperature) in an autoclave became 50 degreeC. Thereafter, the inside of the autoclave was purged with nitrogen.
Until the pressure in the autoclave tank (hereinafter also referred to simply as “inside the tank”) reaches about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). Heating was continued (at this time the liquid temperature was up to about 145 ° C).
Heating was continued while removing water out of the system in order to keep the pressure in the tank at about 2.5 kg / cm ^2, and the solution was concentrated until the concentration of the aqueous solution in the tank was about 75% by mass.
The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² .
While maintaining the pressure in the tank at about 30 Kg / cm ² , heating was continued until the temperature reached 50 ° C. (about 290 ° C.) lower than the final temperature (about 340 ° C.) while removing water from the system.
While further heating, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 90 minutes.
The heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C.
While maintaining the resin temperature in the tank, the inside of the tank was maintained for 30 minutes under a reduced pressure of 400 torr with a vacuum apparatus.
Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle).
Further, the strand-like product was cooled with water and cut to obtain a pellet-like polyamide (hereinafter also abbreviated as “PA-2”).
The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
Polyamide (PA-2) had an end-capping rate of 0%, a melting point Tm2 of 316 ° C., a glass transition temperature Tg of 119 ° C., a trans isomer ratio of 70%, and a sulfuric acid relative viscosity at 25 ° C. of 2.4. .

(Production Example 3)
CHDA 750 g (4.35 mol) was used as the raw material dicarboxylic acid, C10DA 750 g (4.35 mol) was used as the raw material diamine, C10DA 15 g (0.09 mol) was used as an additive during melt polymerization, and the resin temperature ( Polymerization was carried out in the same manner as described in Production Example 2 except that the final temperature of the liquid temperature was 355 ° C. to obtain polyamide (hereinafter also abbreviated as “PA-3”).
The obtained polyamide (PA-3) was dried in a nitrogen stream and the moisture content was adjusted to be less than about 0.2% by mass, and then each property of the polyamide was measured based on the measurement method.
Polyamide (PA-3) had an end-capping rate of 0%, a melting point Tm2 of 334 ° C., a glass transition temperature Tg of 121 ° C., a trans isomer ratio of 70%, and a sulfuric acid relative viscosity at 25 ° C. of 2.3. .

(Production Example 4)
CHDA 750 g (4.35 mol) was used as a raw material dicarboxylic acid, C10DA 750 g (4.35 mol) was used as a raw material diamine, C10DA 15 g (0.09 mol), benzoic acid 10 g (0 mol) were used as additives during melt polymerization. 0.08 mol), and polymerization was carried out in the same manner as described in Production Example 2 except that the final temperature of the resin temperature (liquid temperature) was 355 ° C., and polyamide (hereinafter referred to as “PA-4”) was used. Also abbreviated).
The obtained polyamide (PA-4) was dried in a nitrogen stream and the moisture content was adjusted to less than about 0.2% by mass, and then each property of the polyamide was measured based on the measurement method.
Polyamide (PA-4) had an end-capping rate of 45%, a melting point Tm2 of 334 ° C., a glass transition temperature Tg of 121 ° C., a trans isomer ratio of 70%, and a relative viscosity of sulfuric acid at 25 ° C. of 2.0. .

(Production Example 5)
10 kg of the polyamide (PA-4) pellets obtained in Production Example 4 were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The polyamide pellets were heated at 220 ° C. for 6 hours while stirring with nitrogen flowing at 1 L / min in the vacuum dryer.
Thereafter, the temperature in the vacuum dryer is lowered to about 50 ° C. while circulating nitrogen, and the polyamide pellets are taken out from the vacuum dryer in the form of pellets, and polyamide (hereinafter also abbreviated as “PA-5”) is removed. Obtained.
The obtained polyamide (PA-5) was dried in a nitrogen stream and the moisture content was adjusted to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.
Polyamide (PA-5) had an end-capping rate of 85%, a melting point Tm2 of 327 ° C., a glass transition temperature Tg of 121 ° C., a trans isomer ratio of 71%, and a sulfuric acid relative viscosity at 25 ° C. of 2.8. .

(Production Example 6)
Polyamide 9T (hereinafter also abbreviated as “PA-6”) was produced according to the method described in Example 1 of JP-A-7-228689.
At that time, terephthalic acid was used as the starting dicarboxylic acid, and 1,9-nonamethylenediamine and 2-methyloctamethylenediamine [1,9-nonamethylenediamine: 2-methyloctamethylenediamine = 80: 20 (molar ratio)], benzoic acid was used.
Specifically, the above raw materials, distilled water and the like were put into a 20 liter autoclave to obtain a water mixture. Next, the inside of the autoclave was replaced with nitrogen. Thereafter, the water mixture in the autoclave was stirred at 100 ° C. for 30 minutes.
Next, the internal temperature of the autoclave was raised to 210 ° C. over 2 hours. At that time, the autoclave was pressurized to 22 kg / cm ² .
After the reaction was continued for 1 hour, the internal temperature of the autoclave was raised to 230 ° C. Thereafter, the internal temperature of the autoclave was kept constant at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and maintaining the pressure in the autoclave at 22 kg / cm ² .
Next, the pressure in the autoclave was lowered to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer.
The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. The pulverized prepolymer was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide (PA-6).
Each characteristic of this polyamide (PA-6) was measured based on the said measuring method. As a result of the measurement, polyamide (PA-6) had a terminal blocking ratio of 77%, a melting point Tm2 of 298 ° C., a glass transition temperature Tg of 122 ° C., and a sulfuric acid relative viscosity of 25 ° C. of 2.6.

[Production of polyamide resin composition]
(Examples 1-14 and Comparative Examples 1-4)
A polyamide resin composition was produced using the polyamides obtained in Production Examples 1 to 6 and the raw materials described above in the types and proportions shown in Table 1 below.

  The polyamides obtained in Production Examples 1 to 6 were dried in a nitrogen stream and adjusted to a moisture content of about 0.2% by mass, and then used as a raw material for the polyamide resin composition.

As an apparatus for producing a polyamide resin composition, a twin screw extruder (ZSK-26MC: manufactured by Coperion (Germany)) was used.
The twin-screw extruder had an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the eighth barrel. In the twin-screw extruder, L / D (extruder cylinder length / extruder cylinder diameter) was 48, and the number of barrels was 12.
In the twin-screw extruder, the temperature from the upstream supply port to the die is set to the melting point Tm2 + 20 ° C. of each (A) polyamide (PA-1 to PA-6) produced in Production Examples 1 to 6, and the screw The rotation speed was set to 250 rpm and the discharge rate was set to 25 kg / h.

After the dry blending of (A) polyamide, (B) low molecular weight polyolefin resin, higher fatty acid metal salt, and phenolic antioxidant so as to have the types and ratios shown in Table 1 below, the above twin screw extruder From the upstream supply port.
Next, wollastonite was supplied from the downstream supply port of the twin-screw extruder at the types and ratios shown in Table 1 below.
The raw materials supplied as described above were melt-kneaded with the twin-screw extruder to produce polyamide resin composition pellets.
The obtained pellets of the polyamide resin composition were dried in a nitrogen stream, and the water content in the polyamide resin composition was adjusted to 500 ppm or less.
Various evaluations were performed as described above using the polyamide resin composition after the moisture content was adjusted. The evaluation results are shown in Table 1 below.

  From the results of Table 1, it was confirmed that the polyamide resin compositions of Examples 1 to 14 were excellent in strength, releasability, heat reflow property, and fogging property, and had a good balance of these properties.

(Examples 15 to 25 and Comparative Examples 5 to 8)
After the dry blending of (A) polyamide, (B) low molecular weight polyolefin resin, higher fatty acid metal salt, talc, phenolic antioxidant so as to have the types and ratios described in Table 2 below, the biaxial It supplied from the upstream supply port of the extruder.
Next, titanium oxide was supplied from the downstream first supply port of the twin-screw extruder at the types and ratios shown in Table 2 below.
Furthermore, the inorganic filler was supplied from the downstream second supply port of the twin-screw extruder at the types and ratios shown in Table 2 below.
The raw material supplied as described above was melt-kneaded with the twin-screw extruder to produce polyamide resin composition pellets.
The obtained pellets of the polyamide resin composition were dried in a nitrogen stream, and the water content in the polyamide resin composition was adjusted to 500 ppm or less.
Various evaluations were performed as described above using the polyamide resin composition after the moisture content was adjusted.
The evaluation results are shown in Table 2 below.

(Example 26)
(A) Polyamide, talc, and phenolic antioxidant were dry-blended so as to have the types and ratios shown in Table 2, and then supplied from the upstream supply port of the twin-screw extruder.
Next, titanium oxide was supplied from the downstream first supply port of the twin-screw extruder at the types and ratios shown in Table 2 below.
Furthermore, (B) low molecular weight polyolefin resin and an inorganic filler were supplied from the downstream second supply port of the twin-screw extruder in the types and proportions shown in Table 2 below.
The raw material supplied as described above was melt-kneaded with the twin-screw extruder to produce polyamide resin composition pellets.
The obtained pellets of the polyamide resin composition were dried in a nitrogen stream, and the water content in the polyamide resin composition was adjusted to 500 ppm or less.
Various evaluations were performed as described above using the polyamide resin composition after the moisture content was adjusted.
The evaluation results are shown in Table 2 below.

  From the results in Table 2, it was confirmed that the polyamide resin compositions of Examples 15 to 24 were excellent in releasability, whiteness, heat reflow resistance, and fogging properties, and had a good balance of these properties.

  The polyamide resin composition of the present invention has industrial applicability as a molding material for various parts such as automobiles, electric and electronic, industrial materials, daily products and household products.

Claims (15)

(A) (a) a unit consisting of a dicarboxylic acid containing an alicyclic dicarboxylic acid, and (b) a unit consisting of a diamine containing an aliphatic diamine,
And a polyamide containing
(B) a low molecular weight olefin resin;
A polyamide resin composition.   The polyamide resin composition according to claim 1, wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide resin composition according to claim 1 or 2, wherein the (B) low molecular weight olefin resin is at least one selected from the group consisting of low molecular weight polyethylene, modified low molecular weight polyethylene, and low molecular weight polypropylene. The (B) low molecular weight olefin resin is
The polyamide resin composition according to any one of claims 1 to 3, which is a modified low molecular weight polyethylene having an acid value of 20 mgKOH / g or less and / or an unmodified low molecular weight polyethylene.   The polyamide resin composition according to any one of claims 1 to 4, wherein the number average molecular weight of the (B) low molecular weight olefin resin is 2000 to 8000.   The polyamide resin composition according to any one of claims 1 to 5, comprising 0.075 to 5 parts by mass of the low molecular weight olefin resin (B) with respect to 100 parts by mass of the polyamide resin composition.   The polyamide resin composition as described in any one of Claims 1 thru | or 6 obtained by the method of mix | blending the said (B) low molecular-weight olefin resin from the side feeder of an extruder.   The polyamide resin composition according to any one of claims 1 to 7, wherein the (b) aliphatic diamine is 2-methylpentamethylenediamine.   The polyamide resin composition according to any one of claims 1 to 7, wherein the (b) aliphatic diamine is decamethylenediamine. (A) The polyamide is polymerized by adding an end-capping agent,
The (A) polyamide has a terminal blocking ratio of 10% or more by the terminal blocking agent.
The polyamide resin composition according to any one of claims 1 to 9.   The polyamide resin composition according to any one of claims 1 to 10, wherein the (A) polyamide is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.   The inorganic filler, nucleating agent, lubricant, stabilizer, titanium oxide, and (A) one or more components selected from the group consisting of polymers other than polyamide, further comprising any one of claims 1 to 11 The polyamide resin composition according to claim 1.   A molded article comprising the polyamide resin composition according to any one of claims 1 to 12.   The molded article according to claim 13, which is any one selected from the group consisting of automobile parts, electronic parts, household electrical appliance parts, OA equipment parts, and portable equipment parts.   The molded article according to claim 14, which is an LED reflector.