JP2013116963A - Polyamide resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition and a molded article that have excellent stability of surface appearance and impact resistance characteristics and less defective molding.SOLUTION: The polyamide resin composition includes (A) 100 pts.mass of a polyamide which comprises (a) a unit composed of adipic acid and hexamethylenediamine and (b) a unit composed of isophthalic acid and hexamethylenediamine and in which the isophthalic acid component ratio (x) in the total carboxylic acid components is 0.05≤(x)≤0.5, (Y) is -0.3≤(Y)≤0.8, (Y)=[(EG)-(x)]/[1-(x)]...(1), (EG)= isophthalic acid terminal group amount/total carboxy terminal group amount...(2), (B) 1-200 pts.mass of glass fiber and (C) 1-200 pts.mass of an inorganic filler except (B) the glass fiber.

Description

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

  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.

In recent years, a molded body using a polyamide resin may be molded under high cycle molding conditions in which a molding temperature is increased and a mold temperature is lowered in order to improve productivity.
Polyamide resins are widely used in the automotive field. However, in such applications, the usage environment is severe in terms of heat and dynamics. Especially in automobile exterior parts such as door mirrors, impact characteristics and surface appearance In many cases, both are required.

On the other hand, when molding is performed under a high temperature condition, there is a problem that the molded product may not be stably obtained due to degradation of the polyamide resin or a change in fluidity.
Accordingly, there is a demand for a polyamide resin that has improved stability of the molded product surface appearance during high cycle molding as described above, and further improved impact resistance characteristics, and has little change in physical properties even under severe molding conditions.

In order to meet such demands, a polyamide made of polyamide 66 / 6I into which an isophthalic acid component is introduced is disclosed as a material that can improve the surface appearance and mechanical properties of the molded body (for example, Patent Documents 1 to 4). 4).
Further, 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).

JP-A-6-32976 JP-A-6-32980 Japanese Patent Laid-Open No. 7-118522 JP 2000-219808 A JP 2000-191771 A

  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, under severe molding conditions such as the high cycle molding conditions, the appearance and stability of the molding surface are reduced, and further, depending on the molding conditions. However, there is a problem that molding surface defects such as warping occur.

  Further, although the polyamides produced by the techniques disclosed in Patent Documents 1 to 4 have improved mechanical properties such as elastic modulus, as described above, the 6I chain unit in the polyamide 66 / 6I is contained in the polyamide chain. Since the ratio of copolymerized to the block is high, the impact resistance is reduced due to the polymer structure, that is, the structure having a high ratio of 6I chain units copolymerized to the block in the polyamide chain. There is a problem that decreases.

  Furthermore, 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.

As described above, in the polyamide 66 / 6I obtained by the prior art, the ratio of the 6I chain unit in the polyamide 66 / 6I copolymerized to the block is higher than that of an ideal random copolymer. It is difficult to maintain the stability of the molded product surface appearance while maintaining the balance of properties, and to improve the impact resistance properties. It is excellent in the stability of the molded product surface appearance, impact resistance properties, and harsh molding conditions. Even in the case of molding below, the fact is that polyamides with little change in physical properties are not yet known.
In addition, it is difficult to maintain the stability of the appearance of the molded product while maintaining the balance of mechanical properties, which is a characteristic of polyamide, and such a polyamide is desired.

  Accordingly, in the present invention, in view of the above circumstances, even when molded under severe molding conditions, the stability of the surface appearance of the molded product is good, the impact resistance characteristics are excellent, and molding defects (warp generation) are few. The main object is to provide a polyamide resin composition and a molded article.

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 The present inventors have found that a polyamide resin composition containing a polyamide (A) with a specified numerical range can solve the above problems, and have completed the present invention.
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
The isophthalic acid component ratio (x) in all carboxylic acid components in the polyamide is 0.05 ≦ (x) ≦ 0.5,
And (Y) shown by following formula (1) is -0.3 <= (Y) <= 0.8 (A) 100 mass parts of polyamides,
(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))
(B): 1 to 200 parts by mass of glass fiber;
(C): 1 to 200 parts by mass of an inorganic filler other than the (B) glass fiber,
A polyamide resin composition.
[2]
The polyamide resin composition according to [1], wherein (Y) represented by the formula (1) satisfies 0.05 ≦ (Y) ≦ 0.8.
[3]
(C): (B) The inorganic filler other than the glass fiber is at least selected from the group consisting of wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay. The polyamide resin composition according to [1] or [2], which is one kind of inorganic filler.
[4]
Said (C): The polyamide resin composition as described in any one of said [1] thru | or [3] whose average particle diameters of inorganic fillers other than said (B) glass fiber are 0.01-38 micrometers.
[5]
A molded article comprising the polyamide resin composition according to any one of [1] to [4].

  According to the present invention, even when molded under severe molding conditions, the polyamide has a stable surface appearance, excellent impact resistance, and less molding defects (warp generation) due to changes in molding conditions. Resin compositions and molded articles can be provided.

It is a figure showing the relationship between blocking ratio (Y) and the isophthalic-acid component ratio (x) in all the carboxylic acid components in a polyamide.

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
The isophthalic acid component ratio (x) in all carboxylic acid components in the polyamide is 0.05 ≦ (x) ≦ 0.5,
And (Y) shown by following formula (1) is -0.3 <= (Y) <= 0.8 (A) 100 mass parts of polyamides,
(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))
(B): 1 to 200 parts by mass of glass fiber, (C): 1 to 200 parts by mass of inorganic filler other than (B) glass fiber,
Is a polyamide resin composition containing
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) is
(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 solidification temperature of the polyamide are suppressed, and the appearance of the molded product surface 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, (Y) represented by the following formula (1) satisfies −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.)

  There is a correlation between (A) the isophthalic acid component ratio (x) in the total carboxylic acid component in the polyamide and (ISO) the isophthalic acid end group ratio (EG) in all the carboxyl end groups contained in the polyamide. Yes, ie the blocking ratio (Y) is how much the 6I chain unit in polyamide 66 / 6I shifts to the theoretical value (x = EG), ie how much the 6I chain unit in the polyamide is ratio Is also an indicator of whether the isophthalic acid end group ratio is high.

Accordingly, the denominator [1- (x)] in the above formula (1) is the ratio of end groups other than the isophthalic acid end groups in all carboxylic acid components in the (A) polyamide, and the numerator [1 in the above formula (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. Since this is the difference from the ratio, (Y), which is an index of the blocking ratio, can be obtained from the above equation (1).
FIG. 1 is a diagram showing the relationship between the blocking ratio (Y) and the isophthalic acid component ratio (x) of all carboxylic acid components in the polyamide based on Examples and Comparative Examples described later.
An explanation of FIG. 1 is given below.
Horizontal axis: Isophthalic acid component ratio in all carboxylic acids (x)
Vertical axis: Isophthalic acid end group ratio (EG) in all carboxyl end groups
Area surrounded by solid quadrilateral: Area where the area surrounded by the entire two squares is 0.05 ≦ (x) ≦ 0.5 and −0.3 ≦ (Y) ≦ 0.8. 1 is a region where 0.05 ≦ (x) ≦ 0.5 and 0.05 ≦ (Y) ≦ 0.8.
Dotted line: (EG) = (x)
Broken line arrow: shows the relationship between [(EG)-(x)] and [1- (x)].
◇: Polyamide used in examples described later ■: Polyamide used in comparative examples described later

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 (Y) to −0.3 ≦ (Y) ≦ 0.8, the polyamide resin composition of the present embodiment is subjected to severe molding conditions. The surface appearance stability and impact resistance characteristics of the molded product below are excellent, and molding defects due to changes in molding conditions (deterioration of warpage stability due to molding conditions) are small.
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 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.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2,3-diethylglutaric acid. Acid, glutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid And straight chain or branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms such as eicosandioic acid and diglycolic acid.

Examples of the alicyclic dicarboxylic acid include alicyclic structures such as 1,3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid having 3 to 10 carbon atoms, preferably 5 carbon atoms. Alicyclic dicarboxylic acid etc. which are 10-10.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

Examples of the aromatic dicarboxylic acid include unsubstituted or various 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 and substituted with a substituent.
Examples of the various substituents include halogen groups such as an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a chloro group and a bromo group, and 3 carbon atoms. -10 alkylsilyl groups, and sulfonic acid groups and groups such as sodium salts thereof.

  Examples of the diamine having a substituent branched from the main chain other than the hexamethylenediamine include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4. -C3-C20 branched saturated aliphatic diamines such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine It is done.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and trideca diamine. C2-C20 linear saturated aliphatic diamines, such as methylene diamine, etc. are mentioned.

  Examples of the aromatic diamine include metaxylylenediamine.

  Examples of the amino acid capable of polycondensation include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like.

  Examples of the lactam include butyl lactam, pivalolactam, caprolactam, capryl lactam, enantolactam, undecanolactam, dodecanolactam and the like.

  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 polyamide 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 (Y) which is an index of the blocking ratio in the formula (1) is −0.3 ≦ (Y) ≦ 0. It is sufficient that a polyamide (or polyamide copolymer) satisfying 8, preferably 0.05 ≦ (Y) ≦ 0.8 is obtained.
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, (Y) = [(EG) − (x)] / [1- (x)] (Y) is in a range of −0.3 ≦ (Y) ≦ 0.8. In order to achieve this, the hot melt polymerization method is preferably used, and the hot melt polymerization method is more preferably used.
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, solid salt, or aqueous solution of adipic acid, isophthalic acid, and hexamethylenediamine 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 of adipic acid, isophthalic acid and hexamethylenediamine, a solid salt or a polycondensate is thermally polycondensed at a temperature below the melting point can be used. These methods may be combined as necessary.

When using an extrusion type reactor such as a kneader, the degree of pressure reduction 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.
Examples of the metal of the metal salt 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 polyamide (A) constituting the polyamide resin composition of this embodiment preferably has a formic acid solution viscosity (JIS K 6816) of 10 to 30.
When the formic acid solution viscosity is 10 or more, a molded product having practically sufficient mechanical properties can be obtained, and when the formic acid solution viscosity is 30 or less, the fluidity during molding becomes good and the surface appearance is improved. An excellent molded product can be obtained.

((B) Glass fiber)
The polyamide resin composition of the present embodiment includes (A): 100 parts by mass of polyamide and (B): glass fiber (may be described as (B) glass fiber or glass fiber (B)) 1 to 1 described above. 200 parts by mass and (C): inorganic filler other than (B) glass fiber (may be described as (C) inorganic filler other than glass fiber (B), (C) inorganic filler). -200 mass parts. Thereby, the polyamide resin composition of this embodiment has the outstanding rigidity.
(B) The glass fiber may have a round shape or a flat shape in cross section.
(B) When the cross section of the glass fiber is flat, examples of the flat shape include a rectangle, an oval close to a rectangle, an ellipse, and a saddle shape with a narrowed central portion in the longitudinal direction.
The flatness is represented by D2 / D1 when the major axis of the fiber cross section is D2 and the minor axis of the fiber cross section is D1 (in the case of a perfect circle, the oblateness is about 1). . When flat glass fibers are used, the flatness is preferably 1.5 to 10.

From the viewpoint that excellent mechanical strength characteristics can be imparted to the polyamide resin composition, the (B) glass fiber has a number average fiber diameter of 3 to 30 μm, a weight average fiber length of 100 to 750 μm, and a weight average fiber. The aspect ratio (L / D) between the length (L) and the number average fiber diameter (D) is preferably 10 to 100.
In addition, the number average fiber diameter (D) and the weight average fiber length (L) are, for example, putting the polyamide resin composition into an electric furnace, incinerating the contained organic matter, and, for example, 100 or more glass fibers from the residue. The number average fiber diameter (D) can be measured by observing with an SEM and measuring the fiber diameter, and the weight average fiber length by measuring the fiber length using an SEM photograph at a magnification of 1000 times. (L) can be obtained.

The blending amount of the (B) glass fiber is 1 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 20 to 120 parts with respect to 100 parts by weight of the (A) polyamide copolymer. It is a mass part, More preferably, it is 30-100 mass parts, More preferably, it is 40-90 mass parts.
By setting the blending amount of the (B) glass fiber to 1 part by mass or more, the effect of improving the strength of the polyamide resin composition is sufficiently expressed, and by controlling the blending amount to 200 parts by mass or less, extrudability, A polyamide resin composition having excellent moldability and surface appearance is obtained.

<Treatment with surface treatment agent>
The glass fiber (B) may be treated with a surface treatment agent such as a silane coupling agent.
Although it does not restrict | limit especially as a silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyltriethoxysilane, (gamma) -aminopropyltrimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. These may be used alone or in combination of two or more, and aminosilanes are more preferred.

<Treatment with sizing agent>
The (B) glass fiber may be treated with a sizing agent as necessary.
Examples of the sizing agent include a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units, and an epoxy. Resins, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines, carboxylic acid anhydride-containing Examples thereof include a copolymer containing a saturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer. These may be used individually by 1 type and may be used in combination of 2 or more type.
In particular, from the viewpoint of the mechanical strength of the polyamide resin composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are structural units. Copolymer, epoxy resin and polyurethane resin, and combinations thereof are preferably used, and unsaturated vinyl monomer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer containing carboxylic acid anhydride-containing unsaturated vinyl monomer More preferred are copolymers and polyurethane resins containing a polymer as a structural unit, and combinations thereof.

The carboxylic acid anhydride constituting the copolymer comprising the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units. The contained unsaturated vinyl monomer is not particularly limited, and examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.
On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. The unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer is not limited to the following, but examples thereof include styrene, α-methylstyrene, ethylene, propylene, and butadiene. , Isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. In particular, styrene and butadiene are preferable. Among these combinations, selected from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. It is more preferable that it is 1 type or more.
In addition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight of 2 1,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of the polyamide resin composition of this embodiment, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-1,000,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  Examples of the epoxy resin include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide undecene oxide, dodecene. Aliphatic epoxy compounds such as oxide, pentadecene oxide and eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1, 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohex Alicyclic epoxy compounds such as oxides and epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil And epoxidized linseed oil.

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

The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
The polyacrylic acid may be in a salt form. Examples of the salt of polyacrylic acid include primary, secondary and tertiary amines. For example, triethylamine, triethanolamine, glycine and the like can be mentioned. The degree of neutralization is preferably 20 to 90% and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and from the viewpoint of reducing amine odor. It is more preferable. The weight average molecular weight of the polyacrylic acid salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. (B) 3,000 or more is preferable from the viewpoint of improving the convergence of the glass fiber, and 50,000 or less is preferable from the viewpoint of improving strength and rigidity.

The monomer that forms a copolymer of the acrylic acid and other copolymerizable monomers is not limited to the following examples. For example, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid And at least one selected from monomers having a hydroxyl group and / or a carboxyl group, such as itaconic acid, citraconic acid and mesaconic acid (except for acrylic acid only).
In addition, it is preferable to have 1 or more types of ester type monomers among the monomers mentioned above.
The copolymer of acrylic acid and other copolymerizable monomer may be in the form of a salt. Salts of copolymers of acrylic acid and other copolymerizable monomers are not limited to the following examples, but include primary, secondary, and tertiary amines. For example, triethylamine, triethanolamine and glycine can be mentioned. The degree of neutralization is preferably 20 to 90%, preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.
The weight average molecular weight of the salt of the copolymer of acrylic acid and other copolymerizable monomer is not particularly limited, but is preferably in the range of 3,000 to 50,000.
(B) 3,000 or more is preferable from the viewpoint of improving the convergence of the glass fiber, and 50,000 or less is preferable from the viewpoint of improving strength and rigidity.

The treatment with the sizing agent can be carried out by applying the glass fiber to the glass fiber using a known method such as a roller-type applicator and drying the fiber strand in a known glass fiber production process.
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. Such a sizing agent preferably imparts (adds) 0.2 to 3% by mass or more, more preferably 0.3 to 2% by mass (added) as a solid content with respect to 100% by mass of the glass fiber. . (B) From the viewpoint of maintaining the bundling of the glass fiber, it is preferable that the addition amount of the bundling agent is 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition, it is preferably 3% by mass or less. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

((C): (B) inorganic filler other than glass fiber)
(C): (B) The compounding quantity of inorganic fillers other than glass fiber is 1-200 mass parts with respect to 100 mass parts of (A) polyamide copolymers mentioned above, Preferably it is 2-150 mass parts. Yes, more preferably 3 to 120 parts by mass, still more preferably 5 to 100 parts by mass, and even more preferably 10 to 80 parts by mass.
(C): (B) By making the compounding quantity of inorganic fillers other than glass fiber 1 mass part or more, the rigidity improvement effect of a polyamide resin composition will express, and the compounding quantity shall be 200 mass parts or less. Thus, a polyamide resin composition having excellent extrudability and moldability can be obtained.

(C): (B) The inorganic filler other than the glass fiber is not particularly limited. For example, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc , Kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silica Calcium oxide, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swelling fluorine Mother and apatite, and the like.
In particular, from the viewpoint of strength, rigidity, surface appearance of the polyamide resin composition of the present embodiment, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay are preferable, More preferred are wollastonite, kaolin, mica and talc, still more preferred are wollastonite and mica, and even more preferred is wollastonite.
(C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(C): (B) The average particle diameter of the inorganic filler other than glass fibers is preferably 0.01 to 38 μm, preferably 0.03 to 30 μm, from the viewpoint of the toughness and surface appearance of the polyamide resin composition of the present embodiment. Is more preferable, 0.05 to 25 μm is more preferable, 0.1 to 20 μm is still more preferable, and 0.15 to 15 μm is still more preferable. By setting the average particle size to 38 μm or less, a polyamide resin composition excellent in toughness and surface appearance can be obtained, and by setting it to 0.01 μm or more, further 0.1 μm or more, cost and powder handling are possible. The balance between surface and physical properties will be good.
In addition, among inorganic fillers, those having a needle-like shape such as wollastonite have an average fiber diameter as an average particle diameter. Furthermore, when the 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 needle-shaped one, the appearance of the molded product and the viewpoint of wear of metallic parts such as injection molding machines Therefore, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.
As a specific method for measuring the average particle diameter, using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F), (C): (B) an inorganic filler image other than glass fiber. Images are taken at a magnification of 1000 to 50000, the particle size is measured from 500 inorganic fillers arbitrarily selected, and an average value is calculated. (C) When the inorganic filler is needle-shaped and the cross section is a circle, the needle diameter is the particle diameter, and when the cross-section is not a circle, the maximum length of the needle-shaped body is the needle diameter. And this is regarded as the particle size.

<Treatment with surface treatment agent>
(C): (B) The inorganic filler other than the glass fiber may be subjected to a surface treatment with a silane coupling agent or the like.
The silane coupling agent is not limited to the following examples. For example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-amino Examples include aminosilanes such as propylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. In particular, aminosilanes are more preferable.
A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The surface treatment agent may be previously treated on the surface of the (C) inorganic filler, or may be added when (A) polyamide, (B) glass fiber, and (C) inorganic filler are mixed. The amount of the surface treatment agent is preferably in the range of 0.05 parts by mass to 1.5 parts by mass with respect to 100 parts by mass of the (C) inorganic filler.

(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 may be added.
Although it does not specifically limit as a deterioration inhibitor, For example, Copper compounds, such as copper acetate and copper iodide; Phenol stabilizers, such as a hindered phenol compound; A phosphite stabilizer, A hindered amine stabilizer; A triazine stabilizer And sulfur stabilizers.
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.
Although it does not specifically limit as a moldability improving agent, A higher fatty acid, a higher fatty acid metal salt, a higher fatty acid ester, a higher fatty acid amide, etc. are mentioned.

Examples of the higher fatty acids include stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid, which are saturated or unsaturated, linear or branched fatty acids having 8 to 40 carbon atoms. Group monocarboxylic acid and the like.
Among these, stearic acid and montanic acid are preferable.

The higher fatty acid metal salt is a metal salt of the higher fatty acid.
As the metal element of the metal salt, group 1, 2, 3 elements of the periodic table, zinc, aluminum, etc. are preferable, group 1, 2, elements such as calcium, sodium, potassium, and magnesium, and aluminum Etc. are more preferable.
Examples of the higher fatty acid metal salt include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like.
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.
Examples of the aliphatic alcohol include stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Examples of higher fatty acid esters 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.

Examples of the thermoplastic resin include polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, and ABS resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6,66. , 612, etc. (polyamides other than the polyamide of this embodiment); Polycarbonate resins such as polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone; Condensation resins such as polyphenylene sulfide and polyoxymethylene; Polyacrylic acid , Acrylic resins such as polyacrylic acid ester and polymethyl methacrylate; polyolefin resins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer ; Polyvinyl chloride, halogen-containing vinyl compound resin 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 natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and styrene-butadiene block copolymer (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 (SEPS), Tylene-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), Al Le acrylate - butadiene - acrylonitrile - styrene core-shell rubbers (AABS), butadiene - styrene - core shell rubber (SBR), methyl methacrylate - include core-shell type, etc. such as a siloxane-containing core-shell rubber, including butyl acrylate siloxane.
These rubber components may be used alone or in combination of two or more.

[Production method of polyamide resin composition]
The polyamide resin composition of the present embodiment comprises (A) polyamide, (B) glass fiber, (C) inorganic filler other than glass fiber (B), a deterioration inhibitor, and a moldability improver as necessary. It can be produced by blending a colorant and other resins.
As a blending method, a known extrusion technique can be used.
For example, 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.
Specifically, the mixing method includes, for example, a method in which polyamide and an inorganic filler are mixed using a Henschel mixer or the like, supplied to a melt kneader, kneaded, or a single-screw or twin-screw extrusion equipped with a decompression device. Examples include a method of blending an inorganic filler from a side feeder into a polyamide melted by a machine.

[Molded product of polyamide resin composition]
A predetermined molded product is obtained by molding the polyamide resin composition of the present embodiment.
It does not specifically limit as a method of obtaining a molded article, 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 article of the polyamide resin composition of the present embodiment is excellent in stability of the surface appearance of the molded article under severe molding conditions, impact resistance characteristics, and less dependent on molding conditions on moldability such as warpage, It can be used for various purposes.
For example, it can be suitably used in the automotive field, electrical / electronic field, machine / industrial field, office equipment field, aerospace 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 polyamide, methods for measuring physical properties, and methods for evaluating properties 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.

<Viscosity of formic acid solution>
Polyamide was dissolved in formic acid and measured according to JIS K6810.

<Appearance stability during high cycle molding / Evaluation of gloss value>
The apparatus used was “FN3000” manufactured by Nissei Resin Co., Ltd.
The cylinder temperature was set to 320 ° C., the mold temperature was set to 70 ° C., and molding was performed up to 100 shots using the polyamide resin composition under injection molding conditions of 17 seconds for injection and 20 seconds for cooling to obtain ISO test pieces.
The appearance stability of the obtained molded product (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 Tables 1 and 2, “(1)-(2)” indicates a gloss value calculated by the above-described appearance stability formula.

<Measurement of impact properties Charpy impact strength>
Charpy impact strength was measured according to ISO 179 using 20 to 25 shot ISO test pieces obtained in the appearance stability test.
The measured value was an average value of n = 6.

<Shaping of molded products>
For evaluation of the warpage of the molded product, a molded product produced as follows was used.
The molded product was produced using an injection molding machine.
As the injection molding machine, “PS40E” manufactured by Nissei Resin Co., Ltd. was used.
120 × 80 × 3mm test with cylinder temperature set at 290 ° C, mold temperature set at 70 ° C, fixed with cooling for 20 seconds, and changing injection time (condition 1 = 2 seconds, condition 2 = 8 seconds) I got a piece.
For the measurement of the warp, the test piece was placed on a horizontal surface, the side on the gate side was fixed to a horizontal surface, and the lifting height of the end surface on the opposite side (flow end side) was measured as the amount of warp.
A smaller warp stability value indicates less molding dependency.
Sleigh stability = [War amount of condition 2 (injection time 8 seconds)]-[War amount of condition 1 (injection time 2 seconds)]
In Tables 1 and 2, “Condition 1 (mm)” means the amount of warping when the test piece prepared in Condition 1 is used, and “Condition 2 (mm)” means in Condition 2 It means the amount of warping when the prepared test piece is used.

[(A) 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 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 245 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure 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 is pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) is discharged as a strand, cooled with water, cut into pellets, dried at 100 ° C. in a nitrogen atmosphere for 12 hours, and polyamide Got.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 2: Production of polyamide (A2)>
1132 g of an equimolar salt of adipic acid and hexamethylenediamine and 368 g of an equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, a polyamide was obtained by the same method as in Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 3: Production of polyamide (A3)>
1044 g of equimolar salt of adipic acid and hexamethylenediamine and 456 g of equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, a polyamide was obtained by the same method as in Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 4: Production of polyamide (A4)>
816 g of equimolar salt of adipic acid and hexamethylenediamine and 684 g of equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, a polyamide was obtained by the same method as in Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 5: Production of polyamide (A5)>
1237 g of equimolar salt of adipic acid and hexamethylenediamine and 263 g of equimolar salt of isophthalic acid and hexamethylenediamine were used. No 0.5 mol% excess of adipic acid was added relative to all equimolar salt components.
Under other conditions, polyamide was obtained by the method of Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 6: Production of polyamide (A6)>
1044 g of equimolar salt of adipic acid and hexamethylenediamine and 456 g of equimolar salt of isophthalic acid and hexamethylenediamine were used. No 0.5 mol% excess of adipic acid was added relative to all equimolar salt components.
Under other conditions, polyamide was obtained by the method of Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 7: Production of polyamide (A7)>
1114 g of equimolar salt of adipic acid and hexamethylene diamine, 386 g of equimolar salt of isophthalic acid and hexamethylene diamine, 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 245 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure 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 400 torr for 10 minutes with a vacuum apparatus.
At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, the inside of the autoclave is pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) is discharged as a strand, cooled with water, cut into pellets, dried at 100 ° C. in a nitrogen atmosphere for 12 hours, and polyamide Got.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 8: Production of polyamide (A8)>
1114 g of equimolar salt of adipic acid and hexamethylene diamine, 368 g of equimolar salt of isophthalic acid and hexamethylene diamine, 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 245 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure 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 20 minutes.
At this time, the final internal temperature of the polymerization was 270 ° C.
Thereafter, the inside of the autoclave is pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) is discharged as a strand, cooled with water, cut into pellets, dried at 100 ° C. in a nitrogen atmosphere for 12 hours, and polyamide Got.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 9: Production of polyamide (A9)>
Distilled 1109 g of equimolar salt of adipic acid and hexamethylene diamine, 368 g of equimolar salt of isophthalic acid and hexamethylene diamine, 5 g of ε caprolactam, and 0.5 mol% excess of adipic acid with respect to all equimolar salt components It was dissolved in 1500 g of water, and 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 245 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure 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 is pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) is discharged as a strand, cooled with water, cut into pellets, dried at 100 ° C. in a nitrogen atmosphere for 12 hours, and polyamide Got.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 1 below.

<Production Example 10: Production of polyamide (A10)>
1500 g of equimolar salt of adipic acid and hexamethylenediamine, 0.5 mol% excess adipic acid with respect to all equimolar salt components is dissolved in 1500 g of distilled water, and an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer is prepared. did.
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 for 1 hour until the internal temperature of the autoclave reached 260 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure 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 is pressurized with nitrogen, and the polymer obtained from the lower nozzle (nozzle) is discharged as a strand, cooled with water, cut into pellets, dried at 100 ° C. in a nitrogen atmosphere for 12 hours, and polyamide Got.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 11: Production of polyamide (A11)>
1455 g of an equimolar salt of adipic acid and hexamethylenediamine and 45 g of an equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, a polyamide was obtained by the same method as in Production Example 10.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 12: Production of polyamide (A12)>
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 for 1 hour until the internal temperature of the autoclave reached 260 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa.
Next, the valve 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 formic acid solution viscosity of 7.
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.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 13: Production of polyamide (A13)>
816 g of equimolar salt of adipic acid and hexamethylenediamine and 684 g of equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, polyamide was obtained by the same method as in Production Example 12.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 14: Production of polyamide (A14)>
1220 g of equimolar salt of adipic acid and hexamethylene diamine, 280 g of equimolar salt of isophthalic acid and hexamethylene diamine, 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 for 2 hours as it was until the internal temperature of the autoclave reached 260 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa.
Next, the pressure in the autoclave was lowered to 1 MPa over 1 hour, then the valve 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 polyamide. After pulverizing the obtained polyamide, it was dried at 100 ° C. under a nitrogen atmosphere for 12 hours to obtain a polyamide.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 15: Production of polyamide (A15)>
570 g of an equimolar salt of adipic acid and hexamethylenediamine and 930 g of an equimolar salt of isophthalic acid and hexamethylenediamine were used.
Under other conditions, a polyamide was obtained by the same method as in Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 16: Production of polyamide (A16)>
570 g of an equimolar salt of adipic acid and hexamethylenediamine and 930 g of an equimolar salt of isophthalic acid and hexamethylenediamine were used.
No 0.5 mol% excess of adipic acid was added relative to all equimolar salt components.
Under other conditions, a polyamide was obtained by the same method as in Production Example 1.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

<Production Example 17: Production of polyamide (A17)>
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 for 1 hour until the internal temperature of the autoclave reached 260 ° C., and the reaction was carried out for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa.
Next, the valve 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 formic acid solution viscosity of 7.
Isophthalic acid component ratio (x) in all carboxylic acids of the obtained polyamide, isophthalic acid end group ratio (EG) in all carboxyl end groups, parameter (Y) represented by the above formula (1), formic acid solution viscosity, etc. The polymer properties were measured and calculated by the method described above. These are shown in Table 2 below.

[(B): Glass fiber]
(B1) Glass fiber Product name: ECS03T275H manufactured by Nippon Electric Glass
Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm
[(C): (B) inorganic filler other than glass fiber]
(C1) Wollastonite Made by NYCO Product name NYAD400
Average fiber diameter (average particle diameter) 7.0 μm Average fiber length 35 μm
(C2) Wollastonite Product made by NYCO Brand name NYAD5000
Average fiber diameter (average particle diameter) 2.2 μm Average fiber length 7.2 μm
(C3) Mica Yamaguchi Mica Industrial Co., Ltd. Product name A-21
Average particle size 22μm
(C4) Talc Fuji Talc Kogyo Co., Ltd. Product name PKP-80
Average particle size 14μm
(C5) Kaolin Hayashi Kasei Co., Ltd. Product name TRANSLINK 445 Average particle size 1.5 μm

[Example 1]
100 parts by mass of the polyamide (A1) produced in Production Example 1 was supplied from a top feed port to a TEM 35 mm twin screw extruder (set temperature: 290 ° C., screw rotation speed 300 rpm) manufactured by Toshiba Machine Co., Ltd.
Further, two side feed ports are provided, and from the side feed port 1 on the upstream side of the extruder (the state where the resin supplied from the top feed port is sufficiently melted), (B): glass fibers are shown in Table 1 below. Supplied according to type and part by mass.
From the side feed port 2 on the downstream side of the extruder (the resin supplied from the top feed port is sufficiently melted), the types and masses of inorganic fillers other than the above (C) :( B) are shown in Table 1 below. Supplied according to part.
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 appearance stability, impact characteristics, and warpage of the molded product were evaluated during high cycle molding. The evaluation results are shown in Table 1 below.

[Examples 2-14, Comparative Examples 1-7]
Instead of the polyamide (A1) of Production Example 1, the polyamides of Production Examples 2 to 13 described above were used.
Furthermore, Table 1 and Table 2 below show the supply amount of (B1) glass fiber supplied to 100 parts by mass of polyamide (A), and the types and supply amounts of inorganic fillers other than (C) :( B). It changed into the kind and mass part to show.
Moreover, using the obtained polyamide resin composition, a molded product was produced by the method described above, and appearance stability, impact characteristics, and warpage of the molded product were evaluated during high cycle molding. The evaluation results are shown in Tables 1 and 2 below.

[Comparative Example 8]
A polyamide resin composition was obtained in the same manner as in Example 1 except that polyamide (A17) was used.
However, since the melt viscosity is low, the extrusion processability is poor and a molded product cannot be obtained.

As shown in Table 1, it was confirmed that the molded articles of the polyamide resin compositions of Examples 1 to 14 all had extremely excellent appearance stability, impact characteristics, and warp stability.
On the other hand, the molded product of the polyamide resin composition of Comparative Examples 3, 4, 5, and 8 in which (Y) is outside the range of −0.3 ≦ (Y) ≦ 0.8, and (x) is 0.00. It was confirmed that the stability of the surface appearance and warpage stability of the molded products of the polyamide resin compositions of Comparative Examples 1, 2, 6, and 7 outside the range of 05 ≦ (x) ≦ 0.5 were greatly reduced. It was.

  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 (5)

(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
A polyamide comprising
The isophthalic acid component ratio (x) in all carboxylic acid components in the polyamide is 0.05 ≦ (x) ≦ 0.5,
And (Y) shown by following formula (1) is polyamide 100 mass part whose -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))
(B): 1 to 200 parts by mass of glass fiber;
(C): 1 to 200 parts by mass of an inorganic filler other than the (B) glass fiber,
A polyamide resin composition.   The polyamide resin composition according to claim 1, wherein (Y) represented by the formula (1) satisfies 0.05 ≦ (Y) ≦ 0.8.   (C): (B) The inorganic filler other than the glass fiber is at least selected from the group consisting of wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay. The polyamide resin composition according to claim 1, which is a kind of inorganic filler.   The polyamide resin composition according to any one of claims 1 to 3, wherein an average particle diameter of the inorganic filler other than (C): (B) glass fiber is 0.01 to 38 µm.   The molded article containing the polyamide resin composition as described in any one of Claims 1 thru | or 4.