JP5979860B2 - Long fiber reinforced polyamide resin composition pellets and molded products - Google Patents

Description

  The present invention relates to a long fiber reinforced polyamide resin composition pellet 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 the severe molding conditions such as the high cycle molding conditions, the appearance of the molding surface is lowered and the appearance stability is lowered. Have.

  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.

  Conventionally, in order to improve the strength of the polyamide resin, it is known to add a fibrous reinforcing material such as glass fiber, and a fiber reinforced polyamide resin composition obtained by kneading short fibers such as chopped strands with an extruder is provided. is there. On the other hand, as a method for meeting the recent demands for higher mechanical strength and the like, for example, a long fiber reinforced polyamide resin composition obtained by a pultrusion method in which molten polyamide resin is impregnated while drawing continuous reinforcing fibers. Is being considered. However, in such a long fiber reinforced polyamide resin, when the resin component is polyamide 66, the fluidity at the time of extrusion and molding may not be sufficient, and the surface appearance of the molded product may be deteriorated. ing. Such a problem is a problem peculiar to a long fiber reinforced polyamide resin composition, and improvement of molding processability and surface appearance is eagerly desired.

  Therefore, 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, and the long fiber reinforced polyamide resin composition pellets excellent in impact resistance characteristics and The main purpose is to provide molded products.

As a result of intensive studies to solve the above problems, the present inventors have found that (a) a unit composed of adipic acid and hexamethylenediamine, and (b) a unit composed of isophthalic acid and hexamethylenediamine. In the (A) polyamide to be included, the range of the isophthalic acid component ratio (x) in the total carboxylic acid component in the polyamide is specified, and (EG) = isophthalic acid end group amount / total carboxyl end group amount The numerical range of the values 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 long fiber reinforced polyamide resin composition pellets containing the identified polyamide (A) can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention is as follows.

[1]
(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
A polyamide comprising
The isophthalic acid component ratio (x) in the total 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): The weight average fiber length in the long fiber reinforced polyamide resin composition pellets is substantially the same as the length of the long fiber reinforced polyamide resin composition pellets. (B) Fibrous reinforcing material 10
0 to 250 parts by mass;
A long fiber reinforced polyamide resin composition pellet.
[2]
The long fiber reinforced polyamide resin composition pellet according to [1], wherein (Y) represented by the formula (1) satisfies 0.05 ≦ (Y) ≦ 0.8.
[3]
Isophthalic acid component ratio (x) in the total carboxylic acid component, the amount of the isophthalic acid end group,
And the total carboxyl terminal group amount is a value obtained by nuclear magnetic resonance (NMR), the long fiber reinforced polyamide resin composition pellet according to [1] or [2].
[4]
The long fiber reinforced polyamide resin composition pellet according to any one of [1] to [3], wherein the (B) fibrous reinforcing material is a glass fiber having an average fiber diameter of 5 to 20 μm.
[5]
The long fiber reinforced polyamide resin composition pellet according to any one of [1] to [4], wherein the pellet length is 5 to 30 mm.
[6]
A method for producing a long fiber reinforced polyamide resin composition pellet according to any one of [1] to [5],
When polymerizing adipic acid, isophthalic acid, and hexamethylenediamine, the internal pressure was maintained at 1.5 to 5.0 MPa until the internal temperature in the polymerization system reached 240 ° C. or higher, and then the heating was continued. gradually the pressure is removed, so that the final internal temperature reaches or exceeds 250 ° C., obtaining a polyamide by polycondensation under normal pressure or under reduced pressure,
Impregnating polyamide obtained while drawing continuous reinforcing fibers;
A process for producing a long fiber reinforced polyamide resin composition pellet.
[7]
(A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
100 parts by mass of polyamide containing
(B) 100 to 250 parts by mass of a fibrous reinforcing material;
, When performing molding using the long fiber reinforced polyamide resin composition pellets,
(A) 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,
(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))
By using the long fiber reinforced polyamide resin composition pellets in which the weight average fiber length of the (B) fibrous reinforcing material in the long fiber reinforced polyamide resin composition pellets is substantially the same as the length of the pellets,
A method for improving the appearance stability of molded products.
[8]
(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 the total 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) 100 to 250 parts by mass of a fibrous reinforcing material,
(B) A molded article in which the fibrous reinforcing material is dispersed with a weight average fiber length of 1 mm or more.

  According to the present invention, even when molded under severe molding conditions, the long-fiber-reinforced polyamide resin composition pellets have a stable surface appearance, excellent impact resistance, and excellent high-temperature rigidity. And a molded article 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.

[Long fiber reinforced polyamide resin composition pellets]
The long fiber reinforced polyamide resin composition pellets of this embodiment are
(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): The weight average fiber length in the long fiber reinforced polyamide resin composition pellets is substantially the same as the length of the long fiber reinforced polyamide resin composition pellets (hereinafter sometimes simply referred to as pellet length). (B) 100 to 250 parts by mass of a fibrous reinforcing material,
Is contained.

Hereinafter, the components of the long fiber reinforced polyamide resin composition pellets of this embodiment will be described.
((A) Polyamide)
The polyamide contained in the long fiber reinforced polyamide resin composition pellets 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, 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 using the long fiber reinforced polyamide resin composition pellets of this embodiment is stable. It will be something. 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 using the long fiber reinforced polyamide resin composition pellets of the present embodiment. Is obtained.

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 a 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 long fiber reinforced polyamide resin composition pellet 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, still more preferably 0.1 ≦ (Y) ≦ 0.6.
By setting the isophthalic acid component ratio (x) within the above range and the range (Y) within the range of −0.3 ≦ (Y) ≦ 0.8, the surface appearance of the molded product can be stabilized under severe molding conditions. And excellent impact resistance.
(A) Isophthalic acid component ratio (x) in all carboxylic acid components in polyamide, isophthalic acid terminal group amount for calculating isophthalic acid terminal group ratio (EG) in all carboxyl terminal groups, and total carboxyl terminal The method for quantifying the base amount is not particularly limited, but can be determined by nuclear magnetic resonance (NMR). Specifically, it can be determined by ¹ H-NMR.

<Copolymerization components other than adipic acid and isophthalic acid>
The (A) polyamide constituting the long fiber reinforced polyamide resin composition pellets of the present embodiment includes aliphatic dicarboxylic acids and alicyclic dicarboxylic acids other than adipic acid and isophthalic acid as long as the purpose of the present embodiment is not impaired. Diamines having substituents branched from the main chain other than acid, aromatic dicarboxylic acid, and hexamethylenediamine, aliphatic diamines, aromatic diamines, polycondensable amino acids, lactams, and the like can be used as copolymerization components.

  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>
(A) As a raw material of a polyamide copolymer obtained by polymerizing polyamide and other copolymerization components constituting the long fiber reinforced polyamide resin composition pellets of the present embodiment, end-capping for molecular weight adjustment and improvement of hot water resistance An agent can be further added.
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)
The method for producing the polyamide (A) constituting the long fiber reinforced polyamide resin composition pellets of the present embodiment includes all the carboxylic acids including the case of the polyamide copolymer having other copolymerization components as described above. The isophthalic acid component ratio (x) in the acid component is 0.05 ≦ (x) ≦ 0.5, and (Y) which is an index of the blocking ratio in the above formula (1) is −0.3 ≦ (Y ) ≦ 0.8, preferably a polyamide (or polyamide copolymer) satisfying 0.05 ≦ (Y) ≦ 0.8.
(A) As a manufacturing method of polyamide, for example, an aqueous solution of a mixture of adipic acid, isophthalic acid, hexamethylenediamine, and other components as necessary, or a suspension of water was heated to maintain a molten state. Polymerization as it is (hot melt polymerization method); Polyamide obtained by hot melt polymerization method in which the degree of polymerization is increased while maintaining the solid state at a temperature below the melting point (thermal melt polymerization / solid phase polymerization method); Heat the aqueous solution of acid, isophthalic 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 obtain a polymerization degree. (A prepolymer / extrusion polymerization method); adipic acid, isophthalic acid, hexamethylenediamine, and other components as necessary, solid Or polycondensates, polymerization while maintaining a solid state (solid phase polymerization) method for the like.
As a method for controlling the isophthalic acid component ratio (x) in all carboxylic acid components within the above numerical range, adjustment of the amount of raw materials charged and adjustment of polymerization conditions are effective.
In order to control (Y), which is an index of the blocking ratio in the above formula (1), within the above numerical range, it is necessary to control the blocking of the isophthalic acid component. Specifically, in the polymerization system, the pressure is appropriately adjusted while maintaining the molten state, and the mixing temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 170 ° C. or higher. It can be controlled by using a hot melt polymerization method in which the polycondensation reaction proceeds and the final polymerization internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher.

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

As described above, in order for (Y) to be in the range of −0.3 ≦ (Y) ≦ 0.8, it is preferable to prepare a polyamide by a hot melt polymerization method. It is more preferable to prepare polyamide by a 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 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 (A) polyamide (including polyamide copolymer, the same shall apply hereinafter) constituting the long fiber reinforced polyamide resin composition pellets of 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 long fiber reinforced polyamide resin composition pellet 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 is good and the surface appearance is excellent. A molded product is obtained.

((B) Fibrous reinforcement)
The long fiber reinforced polyamide resin composition pellets of the present embodiment include (A) 100 parts by mass of polyamide and (B) fibrous reinforcing material (hereinafter sometimes referred to as fibrous reinforcing material (B)). Contains 100 to 250 parts by weight.
(B) There is no restriction | limiting in particular as a kind of fibrous reinforcement, For example, a glass fiber, carbon fiber, a metal fiber, a high melting | fusing point (high softening point) resin fiber etc. are mentioned.
Among these, glass fiber is preferably used from the viewpoints of processability, moldability, and economy. These fibrous reinforcements may be used alone or in combination of two or more.

The glass fiber is preferably surface-treated from the viewpoint of improving mechanical strength.
Although it does not specifically limit as surface treatment, For example, a coupling agent and a film formation agent can be used.
Although it does not specifically limit as said coupling agent, For example, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

The silane coupling agent is not particularly limited. For example, triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-γ-aminopropyltrimethoxysilane , N-bi Rubenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-hydroimidazolpropyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N N-bis (trimethylsilyl) urea and the like.
Among these, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ethyl Aminosilane such as trimethoxysilane and epoxysilane are preferably used because they are economical and easy to handle.

  The titanium-based coupling agent is not particularly limited. For example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl Bis (ditridecyl phosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisos Alloy distearate acrylic titanate, isopropyl tri (dioctyl phosphate) titanate Isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl, aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

Examples of the film forming agent include, but are not limited to, urethane polymer, acrylic polymer, maleic anhydride and ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1 Copolymers with unsaturated monomers such as 1,3-pentadiene and cyclooctadiene; and polymers such as epoxy polymers, polyester polymers, vinyl acetate polymers and polyether polymers.
Among these, urethane-based polymers, acrylic acid-based polymers, butadiene-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, and mixtures thereof are preferred from the viewpoints of economy and performance.

The method for performing the surface treatment of the glass fiber using the coupling agent and the film forming agent as described above is not particularly limited, and a known method can be used.
For example, a sizing treatment in which an organic solvent solution or suspension of the coupling agent and the film forming agent is applied to the surface as a so-called sizing agent; it is applied using a Henschel mixer, a super mixer, a ready mixer, a V-type blender, or the like. Examples thereof include dry mixing; spraying method by spraying; integral blending method; dry concentrate method.
Moreover, the method (For example, the method of spraying the remaining film forming agent after apply | coating a part of coupling agent and a film forming agent by a sizing process etc.) which combined these methods is also mentioned.
Among these, a sizing treatment, a dry mixing method, a spray method, and a method in which these are combined are preferable from the viewpoint of being economical.

The (B) fibrous reinforcing material contained in the long fiber reinforced polyamide resin composition pellets of this embodiment has a weight average fiber length that is substantially the same as the pellet length.
“The weight average fiber length and the pellet length are substantially the same” means that the weight average fiber length when the weight average fiber length of the (B) fibrous reinforcing material in the pellet is measured as described below is the pellet. It shall be said that it is 0.9 to 1.1 times the length of.
(B) It is preferable that the fibrous reinforcing material is arranged in parallel in the length direction of the long fiber reinforced polyamide resin composition pellet of the present embodiment.

The length of the long fiber reinforced polyamide resin composition pellet of this embodiment is preferably 5 to 30 mm, more preferably 7 to 20 mm, and even more preferably 10 to 15 mm.
If the pellet length is shorter than 5 mm, the strength expression as a long fiber reinforced polyamide resin composition is not sufficient, and if it is longer than 30 mm, classification and bridging with a hopper during molding are likely to occur, and handling properties are deteriorated.

Further, the weight average fiber length of the fibrous reinforcing material in the injection molded product using the long fiber reinforced polyamide resin composition pellets is preferably 1 mm or more, and preferably about 1.5 mm to 5 mm.
If the weight average fiber length of the (B) fibrous reinforcing material dispersed in the molded product is 1 mm or more, the reinforcing effect of the molded product will be exhibited, particularly under the effect of improving rigidity under a high temperature atmosphere or under a constant load. As the amount of deformation with time decreases, the durability until breakage is excellent, and the impact property is remarkably improved.
In addition, the mechanical properties in the direction perpendicular to the flow direction and the anisotropy and warpage of the molding shrinkage ratio in the injection molded product are reduced, which is an advantage in the part design.

(B) The average fiber diameter of the fibrous reinforcing material is preferably 5 to 20 μm, more preferably 10 to 18 μm from the viewpoint of balance between strength development and handleability during extrusion.
(B) The average fiber diameter of the fibrous reinforcing material can be measured by microscopy. For example, the cross section of the glass fiber used is photographed using a microscope, measured by a method of measuring the diameter of the glass fiber cross section, and the average fiber diameter is calculated from the measured value by the following formula (I).
Average fiber diameter = total glass fiber diameter / number of glass fibers (I)

The number average fiber length and weight average fiber length of the (B) fibrous reinforcing material can be measured by microscopy.
For example, a long fiber reinforced polyamide resin composition pellet or a molded product formed using a long fiber reinforced polyamide resin composition pellet is heated at a temperature equal to or higher than the decomposition temperature of the polyamide resin composition. It can measure by the method of taking a photograph using and measuring the length of the glass fiber.
Examples of the method for calculating the number average fiber length and the weight average fiber length from the measurement values obtained by the microscopy include the following formulas (I) and (II).
Number average fiber length = total glass fiber length / number of glass fibers (I)
Weight average fiber length = sum of squares of glass fiber length / total of glass fiber length (II)

The blending ratio of the (B) fibrous reinforcing material in the long fiber reinforced polyamide resin composition pellets of this embodiment is 100 to 250 parts by mass, preferably 100 to 200 parts by mass, with respect to 100 parts by mass of the (A) polyamide. Part, more preferably 150 to 200 parts by weight.
(B) By making the mixture ratio of a fibrous reinforcement into the said range, the outstanding mechanical strength can be obtained and the tendency which impairs extrudability and moldability can be suppressed.

(Degradation inhibitor)
In the long fiber reinforced polyamide resin composition pellets of the present embodiment, if necessary, the deterioration of heat, discoloration during heat, heat aging resistance, and weather resistance can be improved within a range that does not impair the purpose of the present embodiment. A deterioration inhibitor may be added for the purpose.
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 long fiber reinforced polyamide resin composition pellets 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)
If necessary, a colorant may be added to the long fiber reinforced polyamide resin composition pellets of the present embodiment as long as the purpose of the present embodiment is not impaired.
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 long fiber reinforced polyamide resin composition pellets 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 Long Fiber Reinforced Polyamide Resin Composition Pellet]
As a method for producing the long fiber reinforced polyamide resin composition pellets of the present embodiment using the materials described above, a pultrusion method (pulling molding method) is preferably used.
In pultrusion, the resin is basically impregnated while pulling continuous reinforcing fibers. The fiber is impregnated through the impregnation bath containing the molten resin, and the fibers in the crosshead die. A known method such as a method of supplying and impregnating a resin to a crosshead die from an extruder or the like while passing it through to form a strand can be used. When this strand is taken out, it is cooled and solidified, and then pelletized to obtain long fiber reinforced polyamide resin composition pellets.
The polyamide resin composition pellets obtained by such a method are preferably pelletized to a pellet length of 5 to 50 mm.
The (B) fibrous reinforcing material in the polyamide resin composition pellet obtained by the above method is arranged in parallel in the length direction of the pellet, and (B) the weight average fiber length of the fibrous reinforcing material is substantially equal to the pellet. The same length.
As a method for blending the above-described materials, 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 is, for example, mixing (A) polyamide and (B) fibrous reinforcing material, and other materials as necessary, using a Henschel mixer or the like, supplying the mixture to a melt kneader, and kneading. Or a method of blending (B) a fibrous reinforcing material from the side feeder into the molten state (A) in a single-screw or twin-screw extruder equipped with a decompression device, and other materials as required, etc. Is mentioned.

[Molded product using long fiber reinforced polyamide resin composition pellets]
The method for molding the long fiber reinforced polyamide resin composition pellets of the present embodiment to obtain a molded product is not particularly limited, and a known 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 product of the long fiber reinforced polyamide resin composition pellets of this embodiment is particularly resistant to heat because it has excellent surface appearance stability and impact resistance characteristics under severe molding conditions, and also has high temperature rigidity. It can be used for various applications that require high performance.
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.
The amount of isophthalic acid component, the amount of isophthalic acid end groups, and the amount of other carboxyl terminal groups (for example, adipic acid end groups) are calculated from the integral value of the characteristic signal of each component, and from these values, isophthalic acid in all carboxylic acids 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 a long fiber screw having a compression ratio of 1.8, a backflow prevention ring and a screw clearance of 5 mm, and an “FN3000” injection molding machine manufactured by Nissei Resin Co., Ltd.
The injection pressure and injection speed were appropriately adjusted so that the cylinder temperature was 320 ° C. and the filling time was about 1 second, and the mold temperature was appropriately set in the range of 80 to 120 ° C. according to the glass transition temperature of the polyamide resin composition. . Molding was performed up to 100 shots 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 = (Gloss average value of 20-30 shot ISO test piece) − (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.

<Impact characteristics: Charpy impact strength measurement>
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.

<High-temperature rigidity: measurement of bending strength and bending elastic modulus at 23 ° C., 80 ° C., and 120 ° C.>
Using an ISO test piece obtained by the same method as in the appearance stability test, the bending strength and the flexural modulus were measured in an atmosphere of 23 ° C., 80 ° C., and 120 ° C. according to ISO 178. Moreover, the ratio (%) of the bending elastic modulus measured at 120 ° C. with respect to the bending elastic modulus measured at 23 ° C. was defined as the rigidity retention, and it was determined that the higher this value, the better the high-temperature rigidity.
In Tables 1 and 2 below, bending strength is expressed as “strength” and bending elastic modulus is expressed as “elastic modulus”.

<Measurement of weight average fiber length of (B) fibrous reinforcing material in molded product>
The ISO test piece obtained in the high-temperature stiffness evaluation test was placed in a porcelain crucible, and the test piece was burned using an electric muffle furnace (FP-31 manufactured by Yamato Kagaku, set temperature 600 ° C.).
The glass fiber after combustion is transferred onto a slide glass, observed under an optical microscope, and calculated from the following formula (II) from the value obtained by measuring the length of 400 arbitrarily selected glass fibers using an image analyzer. did.
Weight average fiber length = sum of squares of glass fiber length / total of glass fiber length (II)

[(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) Fibrous reinforcement]
(B) The fibrous reinforcing material contained in the polyamide resin composition is shown.
(B1) Glass fiber roving (trade name: ER4301H, manufactured by Chongqing International Composite Material Co., Ltd., average fiber diameter: 17 μm, TEX number: 1200 TEX)
(B2) Glass fiber chopped strand (trade name: T275H, manufactured by Nippon Electric Glass Co., Ltd., average fiber diameter: 10 μm, fiber cut length: 3 mm, cross-sectional shape is circular)

[Example 1]
Polyamide (A1) was supplied from a feed hopper using a twin-screw extruder (Coperion ZSK25), and melt kneaded in the extruder under conditions of a cylinder set temperature: 290 ° C. and a screw rotation speed of 300 rpm.
The melted polyamide resin was supplied to an impregnation die of a long fiber reinforced resin manufacturing apparatus (KOSLFP-212 manufactured by Kobe Steel).
A bundle of three glass fiber rovings (B1) is introduced into this impregnation die, and the bundle of glass fiber rovings (B1) impregnated with the resin melt kneaded material in the die is continuously pulled out from the die nozzle, and one strand The strands were cooled and solidified in a water-cooled bath, and then cut with a pelletizer to obtain long fiber reinforced polyamide resin composition pellets.
The strand take-up speed was 30 m / min, the pellet length of the obtained long fiber reinforced polyamide resin composition was 10 mm, and the glass fiber content of the fibrous reinforcing material in the pellet was 50% by mass. .
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Example 2]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A2) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 3
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A3) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 4
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A4) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 5
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A5) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 6
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A6) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 7
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A7) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 8
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A8) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 9
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A9) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 10
By changing the impregnation die nozzle diameter, the amount of the glass fiber roving (B1) in the polyamide resin composition pellets is set to 60% by mass ((A) 100 parts by mass of polyamide (B) 150 parts by mass of fibrous reinforcing material). A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as described in Example 1 except that.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

Example 11
The length of the polyamide resin composition pellets was changed to 20 mm by changing the take-up speed and the rotation speed of the pelletizer. Other conditions were the same as in the method described in Example 1, and long fiber reinforced polyamide resin composition pellets were obtained.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 1]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A10) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 2]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A11) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 3]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A12) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 4]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A13) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 5]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A14) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 6]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A15) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 7]
A long fiber reinforced polyamide resin composition pellet was obtained in the same manner as in Example 1 except that polyamide (A16) was used.
Using the obtained long fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 8]
Although it implemented similarly to the method described in Example 1 except having used polyamide (A17), the long fiber reinforced polyamide resin composition pellet was not obtained.

[Comparative Example 9]
Using a twin screw extruder (Coperion ZSK25), the polyamide (A1) is fed from the top feed port, and the glass fiber chopped strand (B2) is fed to 50% by mass of the polyamide (A1) from the downstream side feed port. Each was supplied at a ratio of mass%, and melt kneaded in an extruder under conditions of a cylinder setting temperature: 290 ° C. and a screw rotation speed of 300 rpm.
The obtained short glass fiber reinforced polyamide resin composition was shaped into a strand, cooled and solidified in a water-cooled bath, and then pelletized with a pelletizer to obtain short glass fiber reinforced polyamide resin composition pellets.
The length of the obtained pellet was 3 mm, and the weight average fiber length of the glass fiber in the pellet was 0.30 mm.
Using the obtained short glass fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 10]
A glass long fiber reinforced polyamide resin composition pellet was obtained in the same manner as described in Example 1 except that polyamide 66 (trade name: Leona 1200, manufactured by Asahi Kasei Chemicals Corporation) was used as the polyamide.
Using the obtained long glass fiber reinforced polyamide resin composition pellets, a molded product was produced by the method described above, and appearance stability, impact characteristics, and high-temperature rigidity during high cycle molding were evaluated. The evaluation results are shown in Table 1 below.

As shown in Table 1, it was confirmed that the molded articles of the long fiber reinforced polyamide resin compositions of Examples 1 to 11 had extremely excellent appearance stability, impact characteristics, and high temperature rigidity.
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. The molded product of the long fiber reinforced polyamide resin composition of Comparative Examples 1, 2, 6, and 7 that is outside the range of 05 ≦ (x) ≦ 0.5 is greatly reduced in surface appearance stability and impact characteristics. confirmed.
When the short glass fiber was used as in Comparative Example 9, the glass fiber length in the molded product was shortened, so the impact strength and rigidity were low, and the high temperature rigidity was not sufficiently obtained.
Moreover, when the polyamide resin composition containing the normal polyamide 66 was used like the comparative example 10, it was confirmed that the external appearance stability in high cycle molding falls significantly.

  The long fiber reinforced polyamide resin composition pellets of the present invention and molded articles using the same are industrially applicable in the automotive field, electrical / electronic field, mechanical / industrial field, office equipment field, aerospace field, etc. There is.

Claims (8)

(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 the total 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): The weight average fiber length in the long fiber reinforced polyamide resin composition pellets is substantially the same as the length of the long fiber reinforced polyamide resin composition pellets. (B) Fibrous reinforcing material 10
0 to 250 parts by mass;
A long fiber reinforced polyamide resin composition pellet. The long fiber reinforced polyamide resin composition pellets according to claim 1, wherein (Y) represented by the formula (1) satisfies 0.05 ≦ (Y) ≦ 0.8. Isophthalic acid component ratio (x) in the total carboxylic acid component, the amount of the isophthalic acid end group,
The long-fiber reinforced polyamide resin composition pellets according to claim 1 or 2, wherein the total carboxyl end group amount is a value determined by nuclear magnetic resonance (NMR). The long fiber reinforced polyamide resin composition pellet according to any one of claims 1 to 3, wherein the (B) fibrous reinforcing material is a glass fiber having an average fiber diameter of 5 to 20 µm. The long fiber reinforced polyamide resin composition pellet according to any one of claims 1 to 4, wherein the pellet length is 5 to 30 mm. A method for producing a long fiber reinforced polyamide resin composition pellet according to any one of claims 1 to 5,
When polymerizing adipic acid, isophthalic acid, and hexamethylenediamine, the internal pressure was maintained at 1.5 to 5.0 MPa until the internal temperature in the polymerization system reached 240 ° C. or higher, and then the heating was continued. gradually the pressure is removed, so that the final internal temperature reaches or exceeds 250 ° C., obtaining a polyamide by polycondensation under <br/> or under reduced pressure atmospheric pressure,
Impregnating polyamide obtained while drawing continuous reinforcing fibers;
A process for producing a long fiber reinforced polyamide resin composition pellet. (A): (a) a unit comprising adipic acid and hexamethylenediamine;
(B) a unit consisting of isophthalic acid and hexamethylenediamine;
100 parts by mass of polyamide containing
(B) 100 to 250 parts by mass of a fibrous reinforcing material;
, When performing molding using the long fiber reinforced polyamide resin composition pellets,
(A) 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,
(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))
By using the long fiber reinforced polyamide resin composition pellets in which the weight average fiber length of the (B) fibrous reinforcing material in the long fiber reinforced polyamide resin composition pellets is substantially the same as the length of the pellets,
A method for improving the appearance stability of molded products. (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 the total 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) 100 to 250 parts by mass of a fibrous reinforcing material,
(B) A molded article in which the fibrous reinforcing material is dispersed with a weight average fiber length of 1 mm or more.