JP2013122001A - Polyamide resin composition for automobile exterior part and automobile exterior part including the polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automobile exterior part excellent in surface appearance stability and impact resistance.SOLUTION: A polyamide resin composition for an automobile exterior part includes: 100 pts.mass of a polyamide (A) that contains a unit (a) consisting of adipic acid and hexamethylenediamine and a unit (b) consisting of isophthalic acid and hexamethylenediamine, wherein the isophthalic acid component ratio (x) in all carboxylic acid components is 0.05≤ (x) ≤0.5, (Y) shown by formula (1): (Y)=[(EG)-(x)]/[1-(x)] is -0.3≤ (Y) ≤0.8, and wherein in the formula (1), (EG) denotes the isophthalic acid terminal group ratio in all carboxyl end group contained in the polyamide (A) and is shown by the following formula (2): (EG)=(isophthalic acid terminal group amount)/(all carboxyl end group amount); a glass fiber (B); and/or 1-300 pts.mass of an inorganic filler (C).

Description

  The present invention relates to a polyamide resin composition for automobile exterior parts and an automobile exterior part including the polyamide resin composition.

  Since polyamide resins are excellent in molding processability, mechanical properties and chemical resistance, they have been widely used in particular as materials for automobile parts.

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 environment of use is severe in terms of heat and dynamics. Especially in automobile exterior parts such as door mirror sticks, impact characteristics and surface appearance There are many cases in which both sexes 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.
Therefore, in particular, a polyamide resin composition with improved stability of the appearance of the molded product surface during high cycle molding as described above, and further improved impact resistance, and less change in physical properties even under severe molding conditions, and the polyamide There is a demand for automotive exterior parts using a resin composition.

In order to meet such requirements, 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 a molded product (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, the appearance and stability of the molding surface may be deteriorated under severe molding conditions such as high cycle molding conditions.

  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. The fact is that the polyamide resin composition and the automobile exterior parts using the polyamide resin composition with little change in physical properties even when molded below are not yet known.
In addition, it is difficult to maintain the stability of the appearance of the surface of the molded product while maintaining the balance of mechanical properties, which is a characteristic of polyamide. Such a polyamide resin composition and an automobile exterior using the polyamide resin composition are difficult to maintain. Parts are desired.

  Therefore, in the present invention, in view of the above circumstances, even when molded under severe molding conditions, the polyamide resin composition having excellent surface appearance stability and excellent impact resistance characteristics and the polyamide resin composition are used. The main purpose is to provide automobile exterior parts.

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) having a specified numerical range and an automobile exterior part including the polyamide resin composition can solve the above-mentioned problems. This has led to the.
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) <= 0.8 100 mass parts of (A) 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): Glass fiber and / or (C): 1 to 300 parts by mass of an inorganic filler,
A polyamide resin composition for automobile exterior parts.
[2]
The polyamide resin composition for automobile exterior parts according to [1], wherein (Y) represented by the formula (1) is 0.05 ≦ (Y) ≦ 0.8.
[3]
(B) The glass fiber is a polyamide resin composition for automobile exterior parts according to [1] or [2], wherein the number average fiber diameter is 6 μm or more and 20 μm or less.
[4]
Any one of [1] to [3], wherein (C) the inorganic filler is at least one selected from the group consisting of talc, mica, kaolin, silica, wollastonite, aluminum flakes, and aluminum powder. The polyamide resin composition for automobile exterior parts described in 1.
[5]
An automotive exterior part comprising the polyamide resin composition for automotive exterior according to any one of [1] to [4].

  According to the present invention, a polyamide resin composition having a stable surface appearance and excellent impact resistance even when molded under severe molding conditions and an automotive exterior part including the polyamide resin composition are provided. can do.

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 for automobile exterior parts]
The polyamide resin composition for automobile exterior parts of the present embodiment (hereinafter sometimes referred to as the polyamide resin composition used in the present embodiment) is as follows.
(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) <= 0.8 100 mass parts of (A) 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): Glass fiber and / or (C): 1 to 300 parts by mass of an inorganic filler,
Containing.
Hereinafter, the components of the polyamide resin composition used in this embodiment will be described.

((A) Polyamide)
The polyamide constituting the polyamide resin composition used in 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 the solidification temperature of the polyamide are suppressed, and the surface appearance of the molded article, particularly the automobile exterior part of the present embodiment, becomes stable. In addition, 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 a molded article, particularly in the automobile exterior part 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.)

  (A) Correlation between isophthalic acid component ratio (x) in all carboxylic acid components in polyamide and isophthalic acid end group ratio (EG) in all carboxyl terminal groups contained in (A) polyamide That is, the blocking ratio (Y) indicates how much the 6I chain unit in polyamide 66 / 6I shifts to the theoretical value (x = EG), that is, how much of the 6I chain unit in the polyamide The ratio is high, and it is also an index indicating 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. Since this is the difference from the ratio, (Y), which is an index of the blocking ratio, can be obtained from the 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 used in 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 used in the present embodiment is harsh. The surface appearance stability and impact resistance characteristics of the molded product are excellent under various molding conditions.
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 used in the present embodiment includes aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatics other than adipic acid and isophthalic acid as long as the purpose of the present embodiment is not impaired. A dicarboxylic acid having a substituent branched from the main chain other than the aliphatic dicarboxylic acid and hexamethylenediamine, an aliphatic diamine, an aromatic diamine, a polycondensable amino acid, a 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 used in the present embodiment and other copolymerization components, an end-capping agent is further added for molecular weight adjustment and improvement of hot water resistance. Can do.
For example, when polymerizing the polyamide constituting the polyamide resin composition contained in the automobile exterior part of the present embodiment or the above-described polyamide copolymer, the polymerization amount can be increased by further adding a known end-capping agent. Can be controlled.

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 isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids; 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 used for 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 sufficient that a polyamide (or polyamide copolymer) satisfying ≦ 0.8, 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, in order to make (Y) fall within the range of −0.3 ≦ (Y) ≦ 0.8, it is preferable to produce a polyamide by a hot melt polymerization method. More preferably, the polyamide is produced by a legal method.
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 reduced while removing water and / or gas components, and polycondensation is performed at normal pressure or reduced pressure so that the final internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher.
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 (A) polyamide (including polyamide copolymer, the same shall apply hereinafter) constituting the polyamide resin composition used in this embodiment, 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 used in 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 is good and the surface appearance is excellent. Automobile exterior parts can be obtained.

((B): Glass fiber and / or (C): Inorganic filler other than (B))
The polyamide resin composition used in the present embodiment includes (A) 100 parts by mass of polyamide, (B) glass fiber and / or (C) inorganic filler other than (B) (hereinafter referred to as component (B), (It may be described as (C) inorganic filler or component (C).) 1 to 300 parts by mass.
By including the component (B) and / or the component (C), the automobile exterior part of the present embodiment has excellent rigidity.
The (B) glass fiber preferably has a number average fiber diameter of 6 μm to 20 μm, more preferably a number average fiber diameter of 6 μm to 17 μm, and still more preferably 6 μm to 11 μm.
Although it does not specifically limit as said (B) glass fiber, The glass fiber of arbitrary shapes can be used to the thing of a long fiber type, a short fiber type, and a modified cross-section type.
(B) Glass fiber may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the (B) glass fiber include an E glass composition, a C glass composition, an S glass composition, and an alkali-resistant glass composition.
Moreover, (B) Although the tensile strength of glass fiber is arbitrary, it is preferable that it is 290 kg / mm < ² > or more.
Among these, E glass is preferable from the viewpoint of easy availability.

These (B) glass fibers are surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or the like. Preferably, the adhesion amount is 0.01% by mass or more with respect to (B) glass fiber weight (total amount of glass fiber and surface treatment agent).
Furthermore, it can also process with a sizing agent as needed. As the sizing agent, 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 a structural unit, an epoxy compound, Polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary and tertiary amines, and unsaturated vinyl monomers containing carboxylic acid anhydrides And a copolymer containing an unsaturated vinyl monomer excluding 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.
In particular, from the viewpoint of the mechanical strength of automobile exterior parts, carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers as structural units Including copolymers, epoxy compounds and polyurethane resins, and combinations thereof, unsaturated vinyl monomers excluding carboxylic acid anhydride-containing unsaturated vinyl monomers and said carboxylic acid anhydride-containing unsaturated vinyl monomers And a combination of these as a structural unit and a polyurethane resin, and combinations thereof are more preferable.

The inorganic filler (C) is preferably at least one selected from the group consisting of talc, mica, kaolin, silica, wollastonite, aluminum flakes and aluminum powder.
As said (C) inorganic filler, according to the objective, a fibrous, granular, and plate-shaped inorganic filler can be selected.
Examples of the fibrous inorganic filler include inorganic fibrous materials (excluding glass fibers) such as wollastonite, potassium titanate whiskers, silica fibers, boron nitride fibers, and carbon fibers.
The weight average fiber length (L), number average fiber diameter (D), and aspect ratio (L / D) of the fibrous inorganic filler are not particularly limited, but in terms of mechanical properties, the weight average fiber length (L) Is 50 μm or more, the number average fiber diameter (D) is preferably 5 μm or more, and the aspect ratio is preferably 10 or more. Among these, wollastonite having a number average fiber diameter (D) of 3 to 30 μm, a weight average fiber length (L) of 10 to 500 μm, and an aspect ratio of 3 to 100 is preferably used.
Examples of the powdered inorganic filler include kaolin, silica, metal oxides such as titanium oxide, zinc oxide, and alumina, and various metal powders such as aluminum powder.
Examples of the plate-like inorganic filler include various metal foils such as talc, mica, and aluminum flakes.
(C) As the inorganic filler, talc, mica, kaolin, silica, wollastonite, aluminum flakes or aluminum powder are preferable from the viewpoint of the surface appearance and mechanical strength of the automobile exterior part of this embodiment. Lastite is more preferred.

Content of the said (B) glass fiber and / or (C) inorganic filler is 1-300 mass parts with respect to 100 mass parts of (A) polyamide mentioned above, Preferably it is 1-200 mass parts. More preferably, it is 1-180 mass parts, More preferably, it is 5-150 mass parts.
By setting the content of (B) glass fiber and / or (C) inorganic filler to 1 part by mass or more with respect to 100 parts by mass of (A) polyamide, the mechanical strength of the automobile exterior component of this embodiment, etc. In addition, when the content is 300 parts by mass or less, an automotive exterior part having an excellent surface appearance of a molded product can be obtained.

The number average fiber diameter (D) and weight average fiber length (L) of (B) glass fiber and / or (C) inorganic filler described above can be measured by microscopy as follows.
For example, a polyamide resin composition containing pelletized glass fibers is heated above the decomposition temperature of the polyamide resin composition, the remaining glass fibers are photographed using a microscope, and the diameter and length of the glass fibers. Measure.
Examples of the method for calculating the number average fiber diameter (D) and the weight average fiber length (L) from the measurement values obtained by the microscopy include the following formulas (I) and (II).
Number average fiber diameter (D) = total diameter of glass fibers / number of glass fibers (I)
Weight average fiber length (L) = sum of squares of glass fiber length / total length of glass fiber (II)
In addition, the number average fiber diameter (D) and the weight average fiber length (L) are obtained by, for example, putting the polyamide resin composition used in the present embodiment into an electric furnace, incinerating the contained organic matter, and, for example, 100 The number average fiber diameter can be measured by arbitrarily selecting glass fibers of more than one and observing with SEM and measuring the fiber diameter, and the weight average is obtained by measuring the fiber length using an SEM photograph at a magnification of 1000 times. The fiber length can be determined.

(Degradation inhibitor)
The polyamide resin composition used in the present embodiment is deteriorated 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 inhibitor 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 improving agent may be added to the polyamide resin composition used in 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, 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.
The higher fatty acid ester is preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.
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 used for 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 used in 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 for automobile exterior parts]
The polyamide resin composition for automobile exterior parts of the present embodiment includes (A) polyamide, (B): glass fiber and / or (C) inorganic filler, if necessary, deterioration inhibitor, and moldability improver. 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 for supplying the components constituting the polyamide resin composition used in the present embodiment to the melt kneader may supply all the components at the same time to the same supply port, or supply the components differently. You may supply from a mouth.
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.

[Automobile exterior parts]
The automotive exterior component of the present embodiment is formed by using the above-described polyamide resin composition for automotive exterior components of the present embodiment.
It does not specifically limit as a shaping | molding method, 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.

[Applications for automotive exterior parts]
Since the automobile exterior component of the present embodiment is excellent in surface appearance stability and impact resistance characteristics under severe molding conditions, it can be applied to various applications.
For example, it is a part that can be attached to the exterior of an automobile, the outer body of an automobile, or a tire wheel. Specifically, it is a bumper, spoiler, side cover, hood louver, wheel cover, wheel cap, grill apron cover frame, roof rail, roof Examples include automobile components such as legs, door mirror sticks, door mirror covers, door mirror brackets, rain channels, wiper blades, sunroof deflectors, and outdoor handles.

  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.

<Evaluation of appearance stability / gross value during high cycle molding with door mirror stick moldings>
“450MG” manufactured by Mitsubishi Heavy Industries Plastic Technology Co., Ltd. was used as the apparatus.
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 a polyamide resin composition under injection molding conditions of injection 15 seconds and cooling 20 seconds to obtain a door mirror stick molded product. .
The appearance stability of the obtained door mirror stick molded product was determined by the following method by measuring the gloss value at the center of the molded product using a handy gloss meter “IG320” manufactured by Horiba.
Appearance stability = ((1): Gloss average value of 20 to 30 shot door mirror styl compact)-((2): Gloss average value of 90 to 100 shot door mirror styl compact)
It was judged that the smaller the above-mentioned numerical difference, the better the appearance stability of the door mirror stick molded product.
In Tables 1 and 2, “(1)-(2)” indicates a gloss value calculated by the above-described appearance stability formula.

<Impact characteristics by ISO test piece Measurement of Charpy impact strength>
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.
Charpy impact strength was measured according to ISO 179 using the obtained ISO test pieces 20-25 shot ISO test pieces.
The measured value was an average value of n = 6.

[(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: Nippon Electric Glass product name ECS03T275H
(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]
67 parts by mass of polyamide (A1) produced in Production Example 1 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., Ltd.
Furthermore, the glass fiber (B1) was supplied at a ratio of 33 parts by mass to 67 parts by mass of the polyamide from the side feed port, 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.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding by the door mirror stick molded article, and the ISO test piece is used. Impact characteristics were evaluated. The evaluation results are shown in Table 1 below.

[Example 2]
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide (A1) was 50 parts by mass and the glass fiber (B1) was 50 parts by mass.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding by the door mirror stick molded article, and the ISO test piece is used. Impact characteristics were evaluated. The evaluation results are shown in Table 1 below.

Example 3
40 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 (a state where the resin supplied from the top feed port is sufficiently melted), (C): an inorganic filler was supplied according to the types and parts by mass shown in Table 1 below.
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.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding using the door mirror stick molded article, and the ISO test piece is used. Impact characteristics were evaluated. The evaluation results are shown in Table 1 below.

[Examples 4 to 16]
Each polyamide of Production Examples 2 to 9 described above was used.
Furthermore, the supply amount of (B1) glass fiber supplied with respect to polyamide (A), (C): The kind and supply amount of the inorganic filler were changed into the kind and mass part which are shown in Table 1 below.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding by the door mirror stick molded article, and the ISO test piece is used. Impact characteristics 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 polyamide (A12) was used.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding by the door mirror stick molded article, and the ISO test piece is used. Impact characteristics were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Examples 2 to 8]
A polyamide resin composition was obtained in the same manner as in Example 3 except that each polyamide of Production Examples 10 to 16 described above was used.
Further, by using the obtained polyamide resin composition, a door mirror stick molded article and an ISO test piece are manufactured by the method described above, and appearance stability at the time of high cycle molding by the door mirror stick molded article, and the ISO test piece is used. Impact characteristics were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 9]
A polyamide resin composition was obtained in the same manner as in Example 3 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, each of the door mirror stick molded products molded using the polyamide resin compositions prepared in Examples 1 to 16 and the ISO molded pieces have extremely excellent appearance stability and impact characteristics. Was confirmed.
On the other hand, (Y) is out of the range of −0.3 ≦ (Y) ≦ 0.8. A door mirror stick molded article made of the polyamide resin composition of Comparative Examples 1, 4, 5, and 6, and (x) The stability of the surface appearance of the door mirror stick molded article made of the polyamide resin composition of Comparative Examples 2, 3, 7, and 8 outside the range of 0.05 ≦ (x) ≦ 0.5 was greatly reduced. confirmed.
In Comparative Example 9, a molded product could not be obtained.

  Automotive exterior parts molded using the polyamide resin composition for automotive exterior parts of the present invention include bumpers, spoilers, side covers, hood louvers, wheel covers, wheel caps, grill apron cover frames, roof rails, roof legs, door mirror sticks, It has industrial applicability as automotive exterior parts such as door mirror covers, door mirror brackets, rain channels, wiper blades, sunroof deflectors, and outdoor handles.

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 -0.3 <= (Y) <= 0.8 100 mass parts of (A) 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): Glass fiber and / or (C): 1 to 300 parts by mass of an inorganic filler,
A polyamide resin composition for automobile exterior parts.   The polyamide resin composition for automotive exterior parts according to claim 1, wherein (Y) represented by the formula (1) satisfies 0.05 ≦ (Y) ≦ 0.8.   The polyamide resin composition for automotive exterior parts according to claim 1 or 2, wherein the (B) glass fiber has a number average fiber diameter of 6 µm to 20 µm.   The inorganic filler (C) is at least one selected from the group consisting of talc, mica, kaolin, silica, wollastonite, aluminum flakes, and aluminum powder. Polyamide resin composition for automobile exterior parts.   An automotive exterior part comprising the polyamide resin composition for automotive exterior according to any one of claims 1 to 4.