JP5972088B2 - Polyamide resin composition and molded body - Google Patents

Description

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

Polyamide resins have been widely used as various component materials for clothing, industrial materials, automobiles, electrical / electronics, and industrial use because of their excellent molding processability, mechanical properties, and chemical resistance. It has been.
As a technique for improving the properties of polyamide resin, a composition in which a fibrous reinforcing material is kneaded is generally used. Particularly in recent years, in the automobile field, from the viewpoint of weight reduction for improving fuel efficiency, cost reduction, and rationalization of the assembly process, there has been a noticeable movement of replacing automotive parts that have conventionally used metals with glass fiber reinforced polyamide resins. However, in order to replace the parts that have conventionally used metals with plastic, reliability as a material is required more than in conventional applications.

In order to meet such demands, for example, as a material capable of improving the surface appearance and mechanical properties of a molded product, a polyamide made of polyamide 66 / 6I into which an isophthalic acid component is introduced is disclosed (for example, Patent Documents). 1 to 4).
Further, for example, as a material capable of improving impact resistance, a polyamide composed of polyamide 6T / 6I into which a terephthalic acid component and an isophthalic acid component are introduced is disclosed (for example, see Patent Document 5).
Furthermore, for example, a polyamide composition containing an aromatic ring in a molecular constitutional unit is disclosed as a material that can improve salt-caloric resistance and antifreeze resistance (see, for example, Patent Document 6).

JP-A-6-32979 JP-A-6-32980 Japanese Patent Laid-Open No. 7-118522 JP 2000-219808 A JP 2000-191771 A Japanese Patent Application Laid-Open No. 6-100774

  However, polyamides produced by the techniques disclosed in Patent Documents 1 to 4 have a high ratio in which the 6I chain units in polyamide 66 / 6I are copolymerized into blocks in the polyamide chains. Although the surface appearance of the molded product under the molding conditions is improved, the appearance and stability of the molding surface may be deteriorated under severe molding conditions such as high cycle molding conditions.

  Moreover, although the polyamide manufactured by the manufacturing technique disclosed in Patent Document 5 has improved impact resistance, it has a problem that the appearance of the molding surface is deteriorated.

  Further, the polyamide composition disclosed in Patent Document 6 has a problem that the appearance of the molding surface is deteriorated, although the salt-calar resistance and antifreeze resistance are improved.

  Further, materials used in a dynamic environment such as the automobile field are required to have excellent bending vibration fatigue properties as other properties of mechanical properties.

  In addition, in a material that uses various parts in combination, a characteristic that can suppress sink marks and warpage (hereinafter also referred to as “sink / warp characteristics”) may be required from the viewpoint of ease of assembly.

  However, in Patent Documents 1 to 6, a material that has excellent molding surface appearance and simultaneously satisfies bending vibration fatigue characteristics and sink / warp properties has not been studied. Conventionally, a material that satisfies these characteristics simultaneously. Is not yet known.

  Then, in view of the above circumstances, the main object of the present invention is to provide a polyamide resin composition and a molded product that are excellent in molding surface appearance and bending vibration fatigue properties, and also excellent in sink and warpage.

As a result of intensive studies to solve the problems specific to the above-mentioned polyamide 66 / 6I, the present inventors have found that (a) a unit comprising adipic acid and hexamethylenediamine, and (b) isophthalic acid and hexamethylenediamine. In the polyamide including the unit consisting of: and the range of the isophthalic acid component ratio (x) in the total carboxylic acid component in the polyamide, and (EG) = isophthalic acid end group amount / total carboxyl end group amount The value of (Y), {(Y) = [(EG) − (x)] / [1- (x)]}, which is an index in which the 6I chain unit in polyamide 66 / 6I is blocked It has been found that a polyamide resin composition containing a polyamide (A) having a specified numerical range and a fibrous reinforcing material (B) having a number average fiber diameter of 3 to 9 μm can solve the above-mentioned problems. This has led to the formation.
That is, the present invention is as follows.

[1]
(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
A polyamide comprising
(B): a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm;
Containing
In the polyamide (A), the isophthalic acid component ratio (x) in all carboxylic acid components is 0.05 ≦ (x) ≦ 0.5, and (Y) represented by the following formula (1) is A polyamide resin composition satisfying −0.3 ≦ (Y) ≦ 0.8.
(Y) = [(EG)-(x)] / [1- (x)] (1)
(In the formula (1), (EG) represents the ratio of isophthalic acid end groups in all carboxyl end groups contained in the polyamide (A), and is represented by the following formula (2).
(EG) = isophthalic acid end group amount / total carboxyl end group amount (2))
[2]
The polyamide resin composition according to [1], wherein the range of (Y) represented by the formula (1) is 0.05 ≦ (Y) ≦ 0.8.
[3]
The polyamide resin composition according to [1] or [2], wherein the (B) fibrous reinforcing material is glass fiber.
[4]
The polyamide resin composition according to any one of [1] to [3], wherein the (B) fibrous reinforcing material has a weight average fiber length of 100 to 500 μm in the polyamide resin composition.
[5]
(B) A copolymer in which the fibrous reinforcing material comprises a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer The polyamide resin composition according to any one of [1] to [4], which is a fibrous reinforcing material treated with a sizing agent.
[6]
With respect to 100 parts by mass of the (A) polyamide,
The polyamide resin composition according to any one of [1] to [5], comprising 1 to 200 parts by mass of the (B) fibrous reinforcing material.
[7]
(C) Phenol-based heat stabilizer, phosphorus-based heat stabilizer, amine-based heat stabilizer, elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table The polyamide resin composition according to any one of [1] to [6], further comprising one or more heat stabilizers selected from the group consisting of metal salts of the above and alkali metal and alkaline earth metal halides.
[8]
The polyamide resin composition according to [7], wherein the component (C) is a mixture of a copper salt and an alkali metal or alkaline earth metal halide.
[9]
[1] A molded article comprising the polyamide resin composition according to any one of [8].

  According to the present invention, it is possible to provide a polyamide resin composition and a molded product that have excellent molding surface appearance and a good balance between bending vibration fatigue properties and warpage and sinkability.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
A polyamide comprising
(B): a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm;
Containing
In the polyamide, the isophthalic acid component ratio (x) in all carboxylic acid components is 0.05 ≦ (x) ≦ 0.5, and (Y) represented by the following formula (1) is −0. .3 ≦ (Y) ≦ 0.8.
(Y) = [(EG)-(x)] / [1- (x)] (1)
(In the formula (1), (EG) represents the ratio of isophthalic acid end groups in all carboxyl end groups contained in the polyamide (A), and is represented by the following formula (2).
(EG) = isophthalic acid end group amount / total carboxyl end group amount (2))
Hereinafter, the components of the polyamide resin composition of the present embodiment will be described.

((A) Polyamide)
The polyamide constituting the polyamide resin composition of the present embodiment (hereinafter sometimes referred to as “(A) polyamide”, “polyamide (A)”, or simply “polyamide”))
(A) a unit consisting of adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
including.

The isophthalic acid component ratio (x) in all carboxylic acid components in the polyamide (A) is 0.05 ≦ (x) ≦ 0.5, preferably 0.05 ≦ (x) ≦ 0.4. Yes, and more preferably 0.05 ≦ (x) ≦ 0.3.
Here, (A) isophthalic acid component ratio (x) in all carboxylic acid components in the polyamide indicates the ratio of the unit consisting of (b) isophthalic acid and hexamethylenediamine contained in the polyamide.
When the isophthalic acid component ratio (x) is 0.05 or more, the melting point and the solidification temperature of the polyamide are suppressed, and the molded product surface appearance of the polyamide resin composition of the present embodiment becomes stable. Moreover, when the isophthalic acid component ratio (x) is 0.5 or less, a decrease in the crystallinity of the polyamide can be suppressed, and sufficient mechanical strength can be obtained in the molded article of the polyamide resin composition of the present embodiment.

In the (A) polyamide, the range of (Y) represented by the following formula (1) is −0.3 ≦ (Y) ≦ 0.8.
(Y) = [(EG)-(x)] / [1- (x)] (1)
In formula (1), (x) is the ratio of isophthalic acid components in all carboxylic acid components in (A) polyamide, as described above, and consists of (b) isophthalic acid and hexamethylenediamine in polyamide. Indicates the unit ratio.
(EG) indicates the ratio of isophthalic acid end groups in all carboxyl end groups, and is represented by the following formula (2).
(EG) = isophthalic acid end group amount / total carboxyl end group amount (2)

  In the above formula (1), (Y) is an index indicating how much isophthalic acid end groups are present in all carboxyl end groups (hereinafter also referred to as “blocking ratio (Y)”). To do.)

  (A) The ratio of isophthalic acid component (x) in all carboxylic acid components in polyamide and the ratio (EG) of isophthalic acid end groups in all carboxyl end groups contained in (A) polyamide are correlated. There is. That is, the blocking ratio (Y) is such that the 6I chain unit in the polyamide 66 / 6I shifts to the theoretical value (x = EG), that is, the ratio of the 6I chain unit in the polyamide is high. It is also an index showing whether the isophthalic acid end group ratio is high.

  Accordingly, the denominator [1- (x)] of the formula (1) is the ratio of end groups other than the isophthalic acid end groups in all carboxylic acid components in the polyamide (A), and the numerator [1] (EG)-(x)] is the difference between the theoretical isophthalic acid end group ratio (= isophthalic acid component ratio), that is, the actual isophthalic acid end group ratio and the theoretical isophthalic acid end group ratio. It becomes the difference with the ratio. Therefore, (Y), which is an index of the blocking ratio, can be obtained from the equation (1).

In the polyamide (A) constituting the polyamide resin composition of the present embodiment, the blocking ratio (Y) is −0.3 ≦ (Y) ≦ 0.8, preferably 0.05 ≦ (Y) ≦. 0.8, more preferably 0.05 ≦ (Y) ≦ 0.7, and still more preferably 0.1 ≦ (Y) ≦ 0.6.
By setting the isophthalic acid component ratio (x) within the above range and setting the range of (Y) to −0.3 ≦ (Y) ≦ 0.8, the polyamide resin composition of the present embodiment is harsh. The stability of the appearance of the molded product surface under molding conditions is excellent.

The method for determining the isophthalic acid component ratio (x), the amount of isophthalic acid end groups, and the total amount of carboxyl end groups in the polyamide is not particularly limited, but can be determined by a nuclear magnetic resonance method (NMR). Specifically, it can be determined by the method described in Examples described later using ¹ H-NMR.

<Copolymerization components other than adipic acid and isophthalic acid>
The polyamide (A) constituting the polyamide resin composition of the present embodiment includes an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic other than adipic acid and isophthalic acid as long as the purpose of the present embodiment is not impaired. Dicarboxylic acid and diamine having a substituent branched from the main chain other than hexamethylenediamine, aliphatic diamine, aromatic diamine, polycondensable amino acid, lactam, and the like can be used as a copolymerization component.

  The aliphatic dicarboxylic acid is not particularly limited, and examples thereof include malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, 2 , 3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanediate Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

Although it does not specifically limit as said alicyclic dicarboxylic acid, For example, carbon number of alicyclic structures, such as 1, 3- cyclohexane dicarboxylic acid and 1, 3- cyclopentane dicarboxylic acid, is preferable, Include alicyclic dicarboxylic acids having 5 to 10 carbon atoms.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms which are unsubstituted or substituted with various substituents.
Examples of the various substituents include, but are not limited to, halogens such as alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, chloro groups, and bromo groups. Groups, alkyl silyl groups having 3 to 10 carbon atoms, and sulfonic acid groups and groups such as sodium salts thereof.

  The diamine having a substituent branched from the main chain other than the hexamethylene diamine is not particularly limited. For example, 2-methylpentamethylene diamine (also referred to as 2-methyl-1,5-diaminopentane), C3-C20 branched saturated fats such as 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine Group diamine and the like.

  The aliphatic diamine is not particularly limited. For example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene. C2-C20 linear saturated aliphatic diamines, such as diamine and tridecamethylenediamine, etc. are mentioned.

  Although it does not specifically limit as said aromatic diamine, For example, metaxylylenediamine etc. are mentioned.

  The amino acid capable of polycondensation is not particularly limited, and examples thereof include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like.

  The lactam is not particularly limited, and examples thereof include butyl lactam, pivalolactam, caprolactam, capryllactam, enantolactam, undecanolactam, and dodecanolactam.

  Each of the above-described dicarboxylic acid component, diamine component, amino acid component, and lactam component may be used alone or in combination of two or more.

<End sealant>
As a raw material of a polyamide copolymer obtained by polymerizing the polyamide constituting the polyamide resin composition of the present embodiment and other copolymerization components, an end-capping agent may be further added to adjust the molecular weight or improve hot water resistance. it can.
For example, when polymerizing the polyamide used in this embodiment or the above-described polyamide copolymer, the polymerization amount can be controlled by further adding a known end-capping agent.

The end-capping agent is not particularly limited, and examples thereof include acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. .
Of these, monocarboxylic acids and monoamines are preferred.
These end capping agents may be used alone or in combination of two or more.

The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group. For example, 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 aliphatic monocarboxylic acid such as isobutyric acid; cycloaliphatic monocarboxylic acid such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α- And aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
These monocarboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more types.

The monoamine used as the terminal blocking agent is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl And aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine;
These monoamines may be used alone or in combination of two or more.

((A) Polyamide production method)
As a manufacturing method of (A) polyamide which comprises the polyamide resin composition of this embodiment, including the case where it is a polyamide copolymer which has another copolymerization component as mentioned above, in the said all carboxylic acid component The isophthalic acid component ratio (x) is 0.05 ≦ (x) ≦ 0.5, and the range of (Y), which is an index of the blocking ratio in the above formula (1), is −0.3 ≦ (Y) ≦. It is only necessary to obtain a polyamide (or polyamide copolymer) satisfying 0.8, preferably 0.05 ≦ (Y) ≦ 0.8.

  Examples of the method for producing polyamide include heating an aqueous solution of a mixture of adipic acid, isophthalic acid, hexamethylenediamine, and other components as necessary, or a suspension of water, and polymerizing while maintaining the molten state. Method (hot melt polymerization method); Method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hot melt polymerization / solid phase polymerization method); Adipic acid, isophthalic acid Heat an aqueous solution of a mixture of acid, hexamethylenediamine, and other components as necessary, or a suspension of water, and melt the precipitated prepolymer again with an extruder such as a kneader to increase the degree of polymerization. Method (prepolymer / extrusion polymerization method); adipic acid, isophthalic acid, hexamethylenediamine, and other components as necessary, solid salt or Condensates and methods of polymerizing while maintaining the solid state (solid-phase polymerization method).

As a method for controlling the isophthalic acid component ratio (x) in all carboxylic acid components within the above numerical range, adjustment of the amount of raw materials charged and adjustment of polymerization conditions are effective.
In order to control (Y), which is an index of the blocking ratio in the above formula (1), within the above numerical range, it is necessary to control the blocking of the isophthalic acid component. Specifically, in the polymerization system, the pressure is appropriately adjusted while maintaining the molten state, and the mixing temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 170 ° C. or higher. It can be controlled by using a hot melt polymerization method in which the polycondensation reaction proceeds and the final polymerization internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher.

It does not specifically limit as a polymerization form, Either a batch type and a continuous type may be sufficient.
The polymerization apparatus is not particularly limited, and a known apparatus such as an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

As described above, in order for (Y) to be in the range of −0.3 ≦ (Y) ≦ 0.8, a hot melt polymerization method is preferable, and a batch type hot melt polymerization method is more preferable. It is done.
An example of the batch-type hot melt polymerization method will be described below.
Although it does not specifically limit about polymerization temperature conditions, Preferably it is 100 degreeC or more, More preferably, it is 120 degreeC or more, More preferably, it is 170 degreeC or more.
For example, a mixture of adipic acid, isophthalic acid, and hexamethylene diamine, a solid salt or an aqueous solution is stirred at a temperature of 110 to 200 ° C., and steam is gradually removed to about 60 to 90% and concentrated by heating.
Thereafter, heating is continued until the internal pressure becomes about 1.5 to 5.0 MPa (gauge pressure).
Thereafter, while removing water and / or gas components, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure), and when the internal temperature reaches 240 ° C. or higher, more preferably 245 ° C. or higher, The pressure is gradually removed while removing water and / or gas components, and the heat-melting polymerization is carried out by polycondensation at normal pressure or reduced pressure so that the final internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher. Legal methods can be used.
Furthermore, a solid phase polymerization method in which a mixture, a solid salt or a polycondensate of adipic acid, isophthalic acid and hexamethylenediamine is thermally polycondensed at a temperature below the melting point can be used. These methods may be combined as necessary.

When an extrusion reactor such as a kneader is used, the extrusion conditions are preferably as follows.
The degree of vacuum is preferably about 0 to 0.07 MPa.
The extrusion temperature is preferably about 1 to 100 ° C. higher than the melting point obtained by differential scanning calorimetry (DSC) measurement according to JIS-K7121.
The shear rate is preferably about 100 (sec ⁻¹ ) or more, and the average residence time is preferably about 0.1 to 15 minutes.
By setting it as the said extrusion conditions, generation | occurrence | production of problems, such as coloring and high molecular weight being unable to be suppressed, can be suppressed effectively.

In the production of the polyamide (A) constituting the polyamide resin composition of the present embodiment (including a polyamide copolymer, the same shall apply hereinafter), it is preferable to use a predetermined catalyst.
The catalyst is not particularly limited as long as it is a known one used for polyamide. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphorous acid, pyrophosphorous acid, phenylphosphinic acid, phenylphosphonic acid , 2-methoxyphenylphosphonic acid, 2- (2′-pyridyl) ethylphosphonic acid, and metal salts thereof.
The metal of the metal salt is not particularly limited, and examples thereof include metal salts such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony, and ammonium salts. .
Further, phosphate esters such as ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, octadecyl ester, stearyl ester, and phenyl ester can also be used.

((A) Physical properties of polyamide)
The molecular weight of the polyamide (A) constituting the polyamide resin composition of the present embodiment can be determined using a relative viscosity ηr at 25 ° C. as an index.
(A) Relative viscosity ηr at 25 ° C. of polyamide is preferably 1.5 to 7.0 in terms of mechanical properties such as toughness and strength, vibration fatigue properties, sink / warpage, and surface appearance. More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.0.
(A) The relative viscosity ηr at 25 ° C. of polyamide can be measured under the conditions of 98% sulfuric acid concentration of 1% and 25 ° C. according to JIS-K6920 as described in the following examples.

((B) Fibrous reinforcement)
The polyamide resin composition of the present embodiment contains (B) a fibrous reinforcing material (hereinafter also referred to as “component (B)”) having a number average fiber diameter of 3 to 9 μm.
The (B) fibrous reinforcing material used in the present embodiment is not limited to the following, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, and aluminum borate fiber.

  Among these, glass fiber, carbon fiber, potassium titanate fiber, and aluminum borate fiber are preferable from the viewpoint of strength and surface appearance. More preferred are glass fiber and carbon fiber, and still more preferred is glass fiber. The above-mentioned fibrous reinforcing materials may be used alone or in combination of two or more.

  (B) The number average fiber diameter of the fibrous reinforcing material is 3 to 9 μm, preferably 4 to 8 μm, and more preferably 5 to 8 μm. By using the (B) fibrous reinforcing material having a number average fiber diameter within the above range, a polyamide resin composition having excellent bending vibration fatigue properties and excellent sink and warpage properties can be obtained.

In the polyamide resin composition of the present embodiment, the weight average fiber length of the (B) fibrous reinforcing material is preferably 100 to 500 μm, more preferably 120 to 480 μm, and further preferably 150 to 450 μm. preferable. By using the fibrous reinforcing material (B) having a weight average fiber length within the above range, a polyamide resin composition having further excellent bending vibration fatigue characteristics and further excellent sinking and warping properties can be obtained.
Among these, glass fibers and carbon fibers have a number average fiber diameter of 3 to 9 μm and a weight average fiber length of 100 to 100 from the viewpoint of imparting excellent mechanical strength, excellent bending fatigue properties, sink marks and warpage. What is 500 micrometers and whose aspect ratio (L / D) of a weight average fiber length (L) and a number average fiber diameter (D) is 10-100 is used suitably.

  Here, the number average fiber diameter and the weight average fiber length of the (B) fibrous reinforcing material in the present specification are values obtained by the following method. A molded article using the polyamide resin composition of the present embodiment is placed in an electric furnace, and the contained organic matter is incinerated. From the residue after the treatment, 100 or more (B) fibrous reinforcing materials are arbitrarily selected, and observed with a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). (B) The number average fiber diameter is determined by measuring the fiber diameter of the fibrous reinforcing material. In addition, the weight average fiber length is obtained by measuring the fiber length using SEM photographs of the 100 or more (B) fibrous reinforcing materials photographed at a magnification of 1,000 times.

  (B) The fibrous reinforcing material may be surface-treated with a silane coupling agent or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. Examples include aminosilanes, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the group consisting of the above-mentioned components is preferable, and aminosilanes are more preferable.

  In addition, (B) the fibrous reinforcing material further includes a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer as a sizing agent; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary amines thereof And a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer. These may be used individually by 1 type and may be used in combination of 2 or more type.

  (B) The fibrous reinforcing material is a copolymer comprising a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer. It is preferably a fibrous reinforcing material treated with a sizing agent. By using a fibrous reinforcing material treated with such a sizing agent, a polyamide resin composition having even better bending vibration fatigue properties and better sinking and warping properties can be obtained.

In the polyamide resin composition of the present embodiment, the content of the (B) fibrous reinforcing material is preferably 1 to 200 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the polyamide (A) described above. 180 parts by mass, more preferably 1 to 160 parts by mass, and particularly preferably 5 to 150 parts by mass.
(B) By setting the content of the fibrous reinforcing material within the above range, the mechanical strength is improved, and the polyamide resin composition is excellent in the balance of bending vibration fatigue properties, sink / warpage, and surface appearance of the molded product. A thing is obtained.

((C) heat stabilizer)
The polyamide resin composition of the present embodiment preferably further contains (C) a heat stabilizer (hereinafter also referred to as “component (C)”).
Component (C) is a phenol-based heat stabilizer, phosphorus-based heat stabilizer, amine-based heat stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table. One or more heat stabilizers selected from the group consisting of metal salts of group elements and alkali metal and alkaline earth metal halides are preferred.

<Phenolic heat stabilizer>
Although it does not restrict | limit especially as said phenol type heat stabilizer, For example, a hindered phenol compound is mentioned.
Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting 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-hydroxyphenylpropionamide), 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-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
A phenol type heat stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
In particular, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.

  When using a phenol-based heat stabilizer, the blending amount of the phenol-based heat stabilizer in the polyamide resin composition is preferably 0.01 to 1 part by weight, more preferably 100 parts by weight of the polyamide (A). Is 0.1 to 1 part by mass. When the blending amount of the phenol-based heat stabilizer in the polyamide resin composition is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be reduced.

<Phosphorus heat stabilizer>
Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol type phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl 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-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis ( -Methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis (2-t- Butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphos Phyto, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyl diphosphite, Mono, di-mixed nonylphenyl) phosphite, 4,4′-isopropylidenebis ( -T-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di- -T-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) -bis (4,4'-butylidenebis (3-methyl-6-t) -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, -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'-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphite. .
These may be used alone or in combination of two or more.

  Among the phosphorus-based heat stabilizers, among those listed above, pentaerythritol phosphite compounds, tris (2,4-di-t-butylphenyl), from the viewpoint of further improving heat aging resistance and reducing generated gas. ) Phosphite is preferred.

Examples of the pentaerythritol phosphite compound include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di-t-butyl. -4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4 -Methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl- Isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4 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-ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butylcarbitol- Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-nonylphenyl-pentaerythritol Diphosphite, bis (2,6-di-t- Til-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl -2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-cyclohexyl Phenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl-pentaerythritol Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight is mentioned.
These may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-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 is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

(C) When using a phosphorus-based heat stabilizer as the heat stabilizer, the amount of the phosphorus-based heat stabilizer in the polyamide resin composition of the present embodiment is preferably 0 with respect to 100 parts by mass of the (A) polyamide. 0.01 to 1 part by mass, and more preferably 0.1 to 1 part by mass.
When the blending amount of the phosphorus-based heat stabilizer in the polyamide resin composition is within the above range, the heat aging resistance can be further improved and the amount of gas generated can be reduced.

<Amine heat stabilizer>
Examples of the amine heat stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetra Methylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 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, 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) -Tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2 , 6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 -Tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) Lopionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
These may be used alone or in combination of two or more.

  (C) When an amine heat stabilizer is used as the heat stabilizer, the compounding amount of the amine heat stabilizer in the polyamide resin composition of the present embodiment is preferably 0 with respect to 100 parts by mass of (A) polyamide. 0.01 to 1 part by mass, and more preferably 0.1 to 1 part by mass. When the compounding amount of the amine heat stabilizer in the polyamide resin composition is within the above range, the heat aging resistance can be further improved, and the amount of generated gas can be reduced.

<Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table>
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt. .
Examples of the copper salt include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid. Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
These may be used alone or in combination of two or more.

Among the copper salts listed above, one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred, and copper iodide is more preferred. And / or copper acetate.
When such a preferable copper salt is used, a polyamide resin composition having excellent heat aging resistance and capable of suppressing metal corrosion of the screw or cylinder during extrusion (hereinafter also simply referred to as “metal corrosion”) can be obtained.

(C) When using the said copper salt as a heat stabilizer, the compounding quantity of the copper salt in the polyamide resin composition of this embodiment becomes like this. Preferably it is 0.01-0. 2 parts by mass, more preferably 0.02 to 0.15 parts by mass.
When the compounding quantity of the copper salt in the polyamide resin composition is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  Moreover, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably, with respect to the total amount of the polyamide resin composition of the present embodiment. 50-300 ppm.

<Alkali metal halides, alkaline earth metal halides>
Examples of the alkali metal halide and alkaline earth metal halide include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. .
In particular, from the viewpoint of improvement in heat aging resistance and suppression of metal corrosion, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable.

(C) When using the alkali metal halide and / or alkaline earth metal halide as the heat stabilizer, the alkali metal halide and / or alkaline earth metal in the polyamide resin composition of the present embodiment The amount of the halide is preferably 0.05 to 5 parts by mass, more preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the (A) polyamide. When the blending amount of the alkali metal halide and / or alkaline earth metal halide in the polyamide resin composition is within the above range, the heat aging resistance is further improved and copper precipitation and metal corrosion are suppressed. be able to.
The component of the (C) heat stabilizer mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, a mixture of a copper salt and an alkali metal halide and / or an alkaline earth metal halide is preferred.

In the polyamide resin composition of the present embodiment, the mixture of the copper salt and the alkali metal halide and / or the alkaline earth metal halide has a molar ratio of halogen to copper (halogen / copper) of 2/1 to 1. It is preferable to contain so that it may become 40/1. The molar ratio of halogen to copper (halogen / copper) is more preferably 5/1 to 30/1. When the molar ratio of halogen to copper (halogen / copper) is within the above range, the heat aging resistance can be further improved.
When the halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine can be prevented without substantially impairing mechanical properties such as toughness.

You may add the other component for disperse | distributing a copper salt and a metal halide in polyamide to such an extent that the objective of this embodiment is not impaired.
Examples of the other components include higher fatty acids such as lauric acid as lubricants, higher fatty acid metal salts of higher fatty acids and metals such as aluminum, higher fatty acid amides such as ethylenebisstearylamide, and waxes such as polyethylene wax. Is mentioned. Moreover, the organic compound which has at least 1 amide group is also mentioned.

(Degradation inhibitor)
In the polyamide resin composition of the present embodiment, if necessary, the deterioration is suppressed for the purpose of improving thermal deterioration, preventing discoloration during heat, heat aging resistance, and weather resistance, as long as the purpose of the present embodiment is not impaired. An agent (excluding (C) heat stabilizer) may be added.
Although it does not specifically limit as a deterioration inhibitor, For example, phenol type stabilizers, such as a hindered phenol compound; Phosphite type stabilizers; Hindered amine type stabilizers; Triazine type stabilizers; and sulfur type stabilizers etc. are mentioned.
One of these deterioration inhibitors may be used alone, or two or more thereof may be used in combination.

(Formability improver)
If necessary, a moldability improver may be added to the polyamide resin composition of the present embodiment as long as the purpose of the present embodiment is not impaired.
The moldability improver is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

Although it does not specifically limit as said higher fatty acid, For example, a C8-C40 saturated or unsaturated linear chain, such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid Or a branched aliphatic monocarboxylic acid etc. are mentioned.
Among these, stearic acid and montanic acid are preferable.

The higher fatty acid metal salt is a metal salt of the higher fatty acid.
The metal element of the metal salt is not particularly limited, but, for example, Group 1, 2, 3 elements of the periodic table of elements, zinc, aluminum, and the like are preferable, and the first, such as calcium, sodium, potassium, magnesium, etc. , Group 2 elements, aluminum and the like are more preferable.
The higher fatty acid metal salt is not particularly limited, and examples thereof include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, and calcium palmitate.
Among these, a metal salt of montanic acid and a metal salt of stearic acid are preferable.

The higher fatty acid ester is an esterified product of the higher fatty acid and alcohol.
Esters of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms are preferred.
The aliphatic alcohol is not particularly limited, and examples thereof include stearyl alcohol, behenyl alcohol, and lauryl alcohol.
The higher fatty acid ester is not particularly limited, and examples thereof include stearyl stearate and behenyl behenate.

The higher fatty acid amide is an amide compound of the higher fatty acid.
Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearyl amide, N-stearyl erucic amide, and the like.
The higher fatty acid amide is preferably stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucic acid amide, and more preferably ethylene bisstearyl amide and N-stearyl erucic acid amide.

  These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides may be used singly or in combination of two or more.

(Coloring agent)
You may add a coloring agent to the polyamide resin composition of this embodiment in the range which does not impair the objective of this embodiment as needed.
Although it does not specifically limit as a coloring agent, For example, pigments, such as dyes, such as nigrosine, titanium oxide, and carbon black; Aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide, stainless steel, and titanium Metallic pigments such as mica pearl pigments, color graphite, color glass fibers, and color glass flakes.

(Other resins)
If necessary, other resins may be added to the polyamide resin composition of the present embodiment as long as the purpose of the present embodiment is not impaired.
Such a resin is not particularly limited, and examples thereof include a thermoplastic resin and a rubber component described later.

The thermoplastic resin is not particularly limited. For example, polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, and ABS resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate. Other polyamides such as nylon 6, 66, 612 (polyamides other than (A) polyamide used in this embodiment);
Polyether resins such as polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone; condensation resins such as polyphenylene sulfide and polyoxymethylene; acrylic resins such as polyacrylic acid, polyacrylic acid ester, and polymethyl methacrylate; polyethylene, polypropylene Polyolefin resins such as polybutene and ethylene-propylene copolymer; halogen-containing vinyl compound resins such as polyvinyl chloride and polyvinylidene chloride; phenol resins; epoxy resins and the like.
One type of these thermoplastic resins may be used alone, or two or more types may be used in combination.

Examples of the rubber component include, but are not limited to, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and styrene-butadiene block. Polymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene Block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer Polymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene-propylene copolymer ( EPR), ethylene- (1-butene) copolymer, ethylene- (1-hexene) copolymer, ethylene- (1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM), butadiene Acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), core-shell types such as alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core shell rubber (SBR), and siloxane-containing core-shell rubbers such as methyl methacrylate-butyl acrylate siloxane. .
These rubber components may be used alone or in combination of two or more.

(Inorganic filler)
If necessary, an inorganic filler (excluding the component (B)) may be added to the polyamide resin composition of the present embodiment as long as the purpose of the present embodiment is not impaired.
The inorganic filler is not particularly limited as long as it is other than the component (B) described above. For example, glass flakes, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, monohydrogen phosphate Calcium, 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. Of these, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, calcium silicate, sodium aluminosilicate, and magnesium silicate are preferable, and wollastonite, kaolin, mica, and talc are more preferable, and wollastonite and mica. Is more preferable.

[Production method of polyamide resin composition]
The polyamide resin composition of the present embodiment comprises (A) polyamide, (B) fibrous reinforcing material, and (C) thermal stabilizer as necessary, and other inorganic fillers (provided that (B) And a deterioration inhibitor (excluding the component (C)), a moldability improver, various additives such as a colorant, and other resins.
As a blending method, a known extrusion technique can be used.
For example, a method of blending each component by melt-kneading can be mentioned. The melt kneading temperature is preferably about 250 to 350 ° C. as the resin temperature. The melt kneading time is preferably about 1 to 30 minutes.
Moreover, the method of supplying the components constituting the polyamide resin composition to the melt kneader may supply all the components at the same time to the same supply port, or supply the components from different supply ports. Also good.
As a specific melt-kneading method, for example, (A) polyamide, (B) fibrous reinforcing material, and (C) heat stabilizer (for example, copper salt and metal halide) as required are Henschel mixer. Etc., and a method of kneading and supplying them to a melt kneader, or (A) polyamide, if necessary, (C) a heat stabilizer (for example, a copper salt and a metal halide), and a decompressor A method of blending (B) a fibrous reinforcing material from the side feeder after making it into a molten state with a single-screw or twin-screw extruder equipped with

  Moreover, as a manufacturing method of the polyamide resin composition of this embodiment, (C) thermal stabilizer (for example, copper salt and metal halide) is used as needed during the polymerization process of (A) polyamide, for example. A method of adding them individually or in a mixture (hereinafter sometimes abbreviated as “Production Method 1”) or a melt kneader (A) to polyamide, and (C) a heat stabilizer (for example, as necessary) , Copper salts and metal halide compounds) alone or in a mixture (hereinafter, may be abbreviated as “Production Method 2”).

In the manufacturing method of the polyamide resin composition of this embodiment, when adding a copper salt and a metal halogen compound as (C) heat stabilizer, it may be added in a solid state or an aqueous solution. The polyamide polymerization step in production method 1 is any step from the raw material monomer to the completion of polymerization of the polyamide, and may be at any step.
The melt kneader used in production method 2 is not particularly limited, and a known apparatus such as a single kneader or twin screw extruder, a Banbury mixer, a melt kneader such as a mixing roll, or the like can be used. Of these, a twin screw extruder is preferably used.
The temperature of melt kneading is preferably a temperature that is about 1 to 100 ° C. higher than the melting point of (A) polyamide, and more preferably a temperature that is about 10 to 50 ° C. higher.
The shear rate in the melt kneader is preferably about 100 sec ⁻¹ or more, and the average residence time during melt kneading is preferably about 0.5 to 5 minutes.

[Molded body of polyamide resin composition]
A predetermined molded body is obtained by molding the polyamide resin composition of the present embodiment.
It does not specifically limit as a method of obtaining a molded object, A well-known shaping | molding method can be used.
For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, gunshot injection molding, low pressure molding, ultra thin injection molding (ultra high speed injection molding), And molding methods such as in-mold composite molding (insert molding, outsert molding) and the like.

[Use]
The molded body of this embodiment includes the above-described polyamide resin composition. Therefore, the molded body of the present embodiment is excellent in molding surface appearance and bending vibration fatigue characteristics, and is excellent in sink and warpage, and can be used for various applications.
For example, it can be suitably used in the automotive field, electrical / electronic field, machine / industrial field, office equipment field, aerospace field. In particular, it can be suitably used in the automobile field.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

  First, constituent elements of the polyamide resin composition, a method for measuring the properties of the polyamide, and a method for evaluating the properties of the polyamide resin composition are shown below.

〔Measuring method〕
<Quantity of polyamide isophthalic acid component ratio, isophthalic acid end groups, and total carboxyl end groups>
It calculated | required by < ¹ > H-NMR using polyamide.
Bisulfuric acid was used as the solvent.
As an apparatus, “ECA400 type” manufactured by JEOL Ltd. was used.
The repetition time was 12 seconds, and the number of integration was 64.
Calculate the amount of isophthalic acid component, the amount of isophthalic acid end groups, and the amount of other carboxy terminal groups (for example, adipic acid end groups) from the integral value of the characteristic signal of each component, and from these values, isophthalic acid in the total carboxylic acid The component ratio (x), the isophthalic acid end group ratio (EG) in the total carboxyl end groups, and the parameter (Y) in the above formula (1) were further calculated.

<Sulfuric acid relative viscosity ηr>
It carried out according to JIS-K6920.
Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid, and the solution was subjected to a temperature condition of 25 ° C. The sulfuric acid relative viscosity ηr was measured.

<Measurement of bending vibration fatigue characteristics>
Polyamide resin composition pellets produced in examples and comparative examples described later are molded using an injection molding machine (PS-40E: manufactured by Nissei Plastics Co., Ltd.), and the type I test piece described in JIS K7119-1972 (Dimensions: length × width (b) × thickness = 80 mm × 20 mm × 3 mm, R = 40 mm) were prepared. The test piece was used as a fatigue characteristic evaluation test piece. The molding conditions were set such that injection + holding time was 10 seconds, cooling time was 15 seconds, mold temperature was 80 ° C., and molten resin temperature was (A) polyamide Tm 2 (melting point) + 20 ° C.
About the obtained test piece, the frequency | count at the time of the fracture | rupture in 23 degreeC, 20Hz, and the maximum bending stress 100MPa was measured using the repeated vibration fatigue test machine (made by Toyo Seiki Seisakusyo Co., Ltd.) based on JISK7119-1972. .

<Measurement of warpage>
The polyamide resin composition pellets produced in the examples and comparative examples described later are molded using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), and a mold of type D1 is used according to ISO 294-3. A test piece of 60 mm × 60 mm × 1 mm was produced. The molding conditions were set such that injection + holding time was 10 seconds, cooling time was 15 seconds, mold temperature was 80 ° C., and molten resin temperature was (A) polyamide Tm 2 (melting point) + 20 ° C.
The obtained test piece was left for 24 hours in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere. The test piece after standing was placed on a horizontal surface, an arbitrary one of the four corners was fixed on the horizontal surface, and the raised height of the diagonal point was measured as the amount of warpage.

<Measurement of sink marks>
The polyamide resin composition pellets produced in Examples and Comparative Examples described later are molded using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), and a test piece of 125 mm × 12.5 mm × 6.35 mm is obtained. Produced. The molding conditions were set such that injection + holding time was 10 seconds, cooling time was 15 seconds, mold temperature was 80 ° C., and molten resin temperature was (A) polyamide Tm 2 (melting point) + 20 ° C.
The obtained test piece was left for 24 hours in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere. With respect to the test piece after being left, the depths of depressions at three points on the gate side, the central portion and the terminal side were measured using a depth gauge, and the average value was used as a sink.

<Appearance stability during high cycle molding / Evaluation of gloss value>
Polyamide resin composition pellets prepared in Examples and Comparative Examples described later were molded using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), and A-type multipurpose test pieces were prepared according to ISO 3167. The molding conditions are: injection + holding time 15 seconds, cooling time 15 seconds, mold temperature 70 ° C., molten resin temperature (A) polyamide Tm 2 (melting point) + 20 ° C., polyamide resin composition Was molded up to 100 shots to obtain ISO test pieces.
The appearance stability of the obtained molded body (ISO test piece) was determined by the following method by measuring the gloss value using a handy gloss meter “IG320” manufactured by Horiba.
Appearance stability = ((1): Gloss average value of 20-30 shot ISO test piece) − ((2): Gloss average value of 90-100 shot ISO test piece)
It was judged that the smaller the above numerical difference, the better the appearance stability.
In Table 1, “(1) − (2)” indicates a difference in gloss value calculated by the above-described appearance stability formula.

<(B) Weight average fiber length of fibrous reinforcement>
The weight average fiber length of the (B) fibrous reinforcing material in the polyamide resin composition was determined by the following method.
In the above-described high cycle molding, the obtained 50th shot molded body was put in an electric furnace, and the organic matter contained in the molded body was incinerated. From the residue after the treatment, 100 or more (B) fibrous reinforcing materials are arbitrarily selected, and the magnification is 1,000 using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). Taken at double. The weight average fiber length was calculated | required by measuring fiber length using the SEM photograph about the obtained 100 or more (B) fibrous reinforcement.

[(A) Production Example of Polyamide]
<Production Example 1: Production of polyamide (A1)>
1237 g of equimolar salt of adipic acid and hexamethylenediamine, 263 g of equimolar salt of isophthalic acid and hexamethylenediamine, and 0.5 mol% excess of adipic acid with respect to all equimolar salt components are dissolved in 1500 g of distilled water. Thus, an equimolar 50 mass% uniform aqueous solution of the raw material monomer was prepared.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring the aqueous solution at a temperature of 110 to 150 ° C., the water vapor was gradually removed to concentrate to a solution concentration of 70% by mass.
Thereafter, the internal temperature of the autoclave was raised to 220 ° C.
At this time, the pressure in the autoclave was increased to 1.8 MPa.
The autoclave was heated as it was for 1 hour until the internal temperature of the autoclave reached 245 ° C., and water vapor was gradually removed to react for 1 hour while maintaining the pressure in the autoclave at 1.8 MPa.
Next, the pressure inside the autoclave was lowered to 1 MPa over 1 hour, and then the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes.
At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, the inside of the autoclave was pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) was discharged in a strand form. The strand polymer was cooled with water and cut into pellets. This pellet-like polymer was dried at 100 ° C. under a nitrogen atmosphere for 12 hours to obtain polyamide (A1).
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide (A1), isophthalic acid end group ratio (EG) in all carboxyl terminal groups, parameter (Y) represented by the above formula (1), sulfuric acid Properties such as relative viscosity were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 2: Production of polyamide (A2)>
A polyamide (A2) was prepared in the same manner as in Production Example 1, except that the amount of equimolar salt of adipic acid and hexamethylenediamine was changed to 816 g and the amount of equimolar salt of isophthalic acid and hexamethylenediamine was changed to 684 g. )
Polymer properties such as isophthalic acid component ratio (x), isophthalic acid end group ratio (EG), and sulfuric acid relative viscosity of the obtained polyamide (A2) were measured by the method described above. The measurement results are shown in Table 1 below.

<Production Example 3: Production of polyamide (A3)>
The amount of equimolar salt of adipic acid and hexamethylenediamine was changed to 1044 g, the amount of equimolar salt of isophthalic acid and hexamethylenediamine was changed to 456 g, and 0.5 mol relative to the total equimolar salt component A polyamide (A3) was obtained in the same manner as in Production Example 1 except that% excess of adipic acid was not added.
Polymer properties such as isophthalic acid component ratio (x), isophthalic acid end group ratio (EG), and sulfuric acid relative viscosity of the obtained polyamide (A3) were measured by the method described above. The measurement results are shown in Table 1 below.

<Production Example 4: Production of polyamide (A4)>
1455 g of an equimolar salt of adipic acid and hexamethylene diamine and 45 g of an equimolar salt of isophthalic acid and hexamethylene diamine were dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of raw material monomers.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring the aqueous solution at a temperature of 110 to 150 ° C., the water vapor was gradually removed to concentrate to a solution concentration of 70% by mass.
Thereafter, the internal temperature of the autoclave was raised to 220 ° C.
At this time, the autoclave was pressurized to 1.8 MPa.
The autoclave was heated as it was for 1 hour until the internal temperature of the autoclave reached 260 ° C., and water vapor was gradually removed to react for 1 hour while maintaining the pressure in the autoclave at 1.8 MPa.
Next, the pressure inside the autoclave was lowered to 1 MPa over 1 hour, and then the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes.
At this time, the final internal temperature of the polymerization was 290 ° C.
Thereafter, the inside of the autoclave was pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) was discharged in a strand form. The strand polymer was cooled with water and cut into pellets. This pellet polymer was dried at 100 ° C. under a nitrogen atmosphere for 12 hours to obtain polyamide (A4).
Polymer properties such as isophthalic acid component ratio (x), isophthalic acid end group ratio (EG), and sulfuric acid relative viscosity of the obtained polyamide (A4) were measured by the above-described methods. The measurement results are shown in Table 1.

<Production Example 5: Production of polyamide (A5)>
1237 g of equimolar salt of adipic acid and hexamethylenediamine, 263 g of equimolar salt of isophthalic acid and hexamethylenediamine, and 0.5 mol% excess of adipic acid with respect to all equimolar salt components are dissolved in 1500 g of distilled water. Thus, an equimolar 50 mass% uniform aqueous solution of the raw material monomer was prepared.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring the aqueous solution at a temperature of 110 to 150 ° C., the water vapor was gradually removed to concentrate to a solution concentration of 70% by mass.
Thereafter, the internal temperature of the autoclave was raised to 220 ° C.
At this time, the autoclave was pressurized to 1.8 MPa.
The autoclave was heated as it was for 1 hour until the internal temperature of the autoclave reached 260 ° C., and water vapor was gradually removed to react for 1 hour while maintaining the pressure in the autoclave at 1.8 MPa.
Next, the valve in the autoclave was closed, the heater was turned off, and the internal temperature of the autoclave was cooled to room temperature over about 8 hours to obtain a polyamide having a sulfuric acid relative viscosity of 0.9.
After the obtained polyamide was pulverized, it was put into an evaporator having an internal volume of 10 L and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream to obtain polyamide (A5).
Polymer properties such as isophthalic acid component ratio (x), isophthalic acid end group ratio (EG), and sulfuric acid relative viscosity of the obtained polyamide (A5) were measured by the above-described methods. The measurement results are shown in Table 1 below.

<Production Example 6: Production of polyamide (A6)>
The amount of equimolar salt of adipic acid and hexamethylenediamine was changed to 570 g, and the amount of equimolar salt of isophthalic acid and hexamethylenediamine was changed to 930 g. A polyamide (A6) was obtained in the same manner as in Production Example 1, except that a mol% excess of adipic acid was not added.
Polymer properties such as isophthalic acid component ratio (x), isophthalic acid end group ratio (EG) and sulfuric acid relative viscosity of the obtained polyamide (A6) were measured by the above-described methods. The measurement results are shown in Table 1 below.

In the production of the polyamide resin compositions in Examples and Comparative Examples, the following polyamides were used in addition to the polyamide.
Polyamide (A7): Polyamide 66 Sulfuric acid relative viscosity 2.8
Polyamide (A8): Polyamide 66 / 6T (66.6T = 55/45 mass ratio) Sulfuric acid relative viscosity 2.2

[(B) Example of production of fibrous reinforcement]
<Production Example 7: Production of fibrous reinforcing material (B1)>
First, the solid content is 2% by mass of polyurethane resin, 4% by mass of maleic anhydride-butadiene copolymer, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. The following (x-1) to (x-4) were diluted with water to obtain a glass fiber sizing agent.
The obtained glass fiber sizing agent was adhered to glass fibers having a number average fiber diameter of 7 μm. The attachment method was a method in which the sizing agent was attached to the glass fiber by an applicator provided in the middle of winding the melt-proof yarn-proof glass fiber onto a rotating drum. Then, roving of the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying the glass fiber to which this sizing agent was adhered. At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass. The obtained roving was cut to a length of 3 mm to obtain a fibrous reinforcing material (B1) (chopped strand, hereinafter also abbreviated as “(B1)”).

<Production Example 8: Production of fibrous reinforcing material (B2)>
The fibrous reinforcing material (B2) (chopped strand, hereinafter simply referred to as Production Example 7) except that glass fibers having a number average fiber diameter of 5 μm were used instead of the glass fibers having a number average fiber diameter of 7 μm. (Abbreviated as “(B2)”). The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.7% by mass.

<Production Example 9: Production of fibrous reinforcing material (B3)>
First, (x-1), (x-) described later so that the solid content is 6% by mass of polyurethane resin, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. 3) and (x-4) were diluted with water to obtain a glass fiber sizing agent.
A fibrous reinforcing material (B3) (chopped strand, hereinafter simply abbreviated as “(B3)”) was obtained in the same manner as in Production Example 7 except that the obtained glass fiber sizing agent was used. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass.

<Manufacture example 10: manufacture of fibrous reinforcement (B4)>
The fibrous reinforcing material (B4) (chopped strand, hereinafter simply referred to as “(”) except that glass fibers having a number average fiber diameter of 10 μm were used instead of the glass fibers having a number average fiber diameter of 7 μm. B4) ”is also abbreviated). The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.5% by mass.

It shows below about the component which comprises the sizing agent used when manufacturing (B) fibrous reinforcement in manufacture examples 7-10.
(X-1) Polyurethane resin emulsion Product name: Bondic (registered trademark) 1050 (Dainippon Ink Co., Ltd.)
(Aqueous solution with a solid content of 50% by mass)
(X-2) Maleic anhydride copolymer emulsion Product name: Acro Binder (registered trademark) BG-7 (manufactured by Sanyo Chemical Industries, Ltd.)
(Aqueous solution with a solid content of 25% by mass)
(X-3) Aminosilane coupling agent Product name: KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)
γ-Aminopropyltriethoxysilane (x-4) Lubricant Brand name: Carnauba wax (manufactured by Hiroyuki Kato)

[(C) heat stabilizer]
(C1) As a copper salt, copper iodide (CuI) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: copper iodide (I)) was used.
(C2) Potassium iodide (KI) (trade name: potassium iodide manufactured by Wako Pure Chemical Industries, Ltd.) was used as the metal halide.

[Example 1]
Polyamide (A1), fibrous reinforcing material (B1), and heat stabilizer (C1, C2) were blended at a blending ratio shown in Table 1 to obtain a mixture. The mixture was supplied from a feed hopper to a TEM 35 mm twin-screw extruder (set temperature: 290 ° C., screw rotation speed: 300 rpm) manufactured by Toshiba Machine Co., and melt kneading was performed. The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Example 2]
As shown in Table 1, a polyamide resin composition was obtained in the same manner as in the method described in Example 1 except that the addition amount of the fibrous reinforcing material (B1) was changed.
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 3
A polyamide resin composition was obtained in the same manner as described in Example 1 except that the fibrous reinforcing material (B2) was used instead of the fibrous reinforcing material (B1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 4
A polyamide resin composition was obtained in the same manner as described in Example 1 except that the fibrous reinforcing material (B3) was used instead of the fibrous reinforcing material (B1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 5
A polyamide resin composition was obtained in the same manner as described in Example 1 except that polyamide (A2) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 6
A polyamide resin composition was obtained in the same manner as described in Example 1, except that polyamide (A3) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 1]
A polyamide resin composition was obtained in the same manner as in Example 1 except that the fibrous reinforcing material (B4) was used instead of the fibrous reinforcing material (B1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 2]
A polyamide resin composition was obtained in the same manner as described in Example 1 except that polyamide (A4) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 3]
A polyamide resin composition was obtained in the same manner as described in Example 1, except that polyamide (A5) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 4]
A polyamide resin composition was obtained in the same manner as described in Example 1 except that polyamide (A6) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 5]
A polyamide resin composition was obtained in the same manner as described in Example 1 except that polyamide (A7) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 6]
A polyamide resin composition was obtained in the same manner as described in Example 1 except that polyamide (A8) was used instead of polyamide (A1).
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and bending vibration fatigue properties, warpage, sink marks, and appearance stability during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

  As shown in Table 1, the molded articles of the polyamide resin compositions of Examples 1 to 6 are extremely excellent in the balance of bending vibration fatigue properties, warpage / sinking properties, and appearance stability during high cycle molding. Was confirmed.

  The polyamide resin composition of the present invention and a molded article using the same have industrial applicability in the automotive field, electrical / electronic field, mechanical / industrial field, office equipment field, aerospace field, and the like.

Claims (8)

(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
A polyamide comprising
(B): a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm;
Containing
The (B) fibrous reinforcing material is glass fiber,
In the polyamide (A), the isophthalic acid component ratio (x) in all carboxylic acid components is 0.05 ≦ (x) ≦ 0.5, and (Y) represented by the following formula (1) is 0.05 ≦ (Y) ≦ 0.8, a polyamide resin composition.
(Y) = [(EG)-(x)] / [1- (x)] (1)
(In the formula (1), (EG) represents the ratio of isophthalic acid end groups in all carboxyl end groups contained in the polyamide (A), and is represented by the following formula (2).
(EG) = isophthalic acid end group amount / total carboxyl end group amount (2))   The polyamide resin composition according to claim 1, wherein the range of (Y) represented by the formula (1) is 0.1 ≦ (Y) ≦ 0.7. The polyamide resin composition according to claim 1 or 2 , wherein the (B) fibrous reinforcing material has a weight average fiber length of 100 to 500 µm in the polyamide resin composition. (B) A copolymer in which the fibrous reinforcing material comprises a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer The polyamide resin composition according to any one of claims 1 to 3 , which is a fibrous reinforcing material treated with a sizing agent. With respect to 100 parts by mass of the (A) polyamide,
The polyamide resin composition as described in any one of Claims 1-4 containing the said (B) fibrous reinforcement 1-200 mass parts. (C) Phenol-based heat stabilizer, phosphorus-based heat stabilizer, amine-based heat stabilizer, elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table The polyamide resin composition as described in any one of Claims 1-5 which further contains the 1 or more types of heat stabilizer chosen from the group which consists of the metal salt of these, and the halide of an alkali metal and an alkaline-earth metal. The polyamide resin composition according to claim 6 , wherein the component (C) is a mixture of a copper salt and an alkali metal or alkaline earth metal halide. Shaped body comprising a polyamide resin composition according to any one of claims 1-7.