JP2015199873A - Reinforced high molecular weight polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having improved tensile strength, improved tensile elongation, improved Charpy impact as well as improved hydrolysis resistance.SOLUTION: The polyamide resin composition contains 100 pts.mass of a polyamide resin and 10 to 250 pts.mass of (B) reinforcement material and having a difference between a carboxyl group terminal concentration [COOH] and an amino group terminal concentration [NH] ([COOH]-[NH]) in the polyamide resin of -25 to 25 milliequivalent/kg and viscosity number [VN] of 160 mL/g or more.

Description

  The present invention relates to a polyamide resin composition.

  Polyamide resins are known as engineering plastics and are materials for various parts such as general-purpose consumer fields such as packaging and containers, automotive fields, electrical and electronic fields, mechanical and industrial fields, office equipment fields, aviation and space fields. As widely used. In recent years, as a material for these various components, there has been a great demand for substitution from a metal material to a polyamide resin for the purpose of integration and weight reduction. Moreover, the request | requirement which raises toughness, impact property, and durability further as the material of these various components is increasing. As a result, the performance level required for the polyamide resin as a material for the above-mentioned various parts has been further increased.

  Specifically, a resin material having high strength that can be substituted for a metal material and excellent in toughness, impact property, and durability is strongly demanded as a material for the above-described various parts. One way to meet these demands is to increase the molecular weight of the polyamide resin.

  As a method for increasing the molecular weight of a polyamide resin, a method of solid-phase polymerization of a polyamide resin after melt polymerization is known. In order to obtain a desired polyamide resin by the solid phase polymerization method, a large amount of solid phase polymerization time and thermal energy are required. Moreover, in order to ensure the quality of the polyamide resin such as color tone, a process under a nitrogen stream or under reduced pressure is required. Thus, since the solid phase polymerization method is complicated and requires a long time, a simpler and shorter method is required as a method for increasing the molecular weight of the polyamide resin.

  As a method of increasing the molecular weight of a polyamide resin in a short time, a high molecular weight catalyst such as sodium hypophosphite is added to the polyamide resin, and the catalyst is made high molecular weight by melt-kneading under reduced pressure conditions in an extruder. An extrusion method is known (see, for example, Patent Document 1).

  Further, there is also known a catalyst high molecular weight extrusion method in which phosphoric acid is added to a polyamide resin as a high molecular weight catalyst, and melt kneading is performed under reduced pressure using an extruder (see, for example, Patent Document 2). .

JP 2011-26396 A Japanese Patent Laid-Open No. 01-153725

The techniques disclosed in Patent Documents 1 and 2 are techniques for increasing the molecular weight of a polyamide resin in a short time by using an extruder without using solid phase polymerization that requires a long time. However, although the technique disclosed in Patent Document 1 increases the molecular weight of the polyamide resin, there is room for improvement in terms of increasing the molecular weight of the polyamide resin more efficiently.
In the technique disclosed in Patent Document 2, although the effect of increasing the molecular weight of the polyamide resin is high, there is room for improvement in terms of strength and impact of the obtained polyamide resin and further hydrolysis resistance.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyamide resin composition having improved tensile strength, tensile elongation and Charpy impact and improved hydrolysis resistance. It is in.

As a result of intensive studies to solve the above problems, the present inventors contain 100 parts by mass of a polyamide resin and 10 to 250 parts by mass of a reinforcing material (B), and the carboxyl group terminal concentration [COOH] in the polyamide resin A polyamide resin composition having a difference ([COOH] − [NH ₂ ]) from the amino group terminal concentration [NH ₂ ] of −25 to 25 meq / kg and a viscosity number [VN] of 160 mL / g or more. Thus, the present inventors have found that the above problems can be solved and completed the present invention.

That is, the present invention is as follows.
[1]
Containing 100 parts by weight of polyamide resin and 10 to 250 parts by weight of (B) reinforcing material,
The difference ([COOH] − [NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin is −25 to 25 meq / kg,
A polyamide resin composition having a viscosity number [VN] of 160 mL / g or more.
[2]
The difference ([COOH]-[NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin is 0 to 25 meq / kg, according to [1]. Polyamide resin composition.
[3]
The polyamide resin composition according to [1] or [2], wherein the polyamide resin includes a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid.
[4]
The polyamide resin composition according to any one of [1] to [3], wherein the polyamide resin contains 50% by mass or more of a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid.
[5]
The polyamide resin composition according to any one of [1] to [4], wherein the polyamide resin is a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid.
[6]
Furthermore, (C) a phosphoric acid compound is contained,
The polyamide resin composition according to any one of [1] to [5], wherein the phosphorus concentration [P] is 1 to 5000 ppm by mass.
[7]
The polyamide resin composition according to [6], wherein the (C) phosphoric acid compound is at least one selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, and metaphosphoric acid.
[8]
Furthermore, (D) The polyamide resin composition in any one of [1]-[7] containing an amine component.
[9]
The polyamide resin composition according to [8], wherein the (D) amine component is a polyamide resin prepolymer and / or a diamine having an amino group terminal concentration [NH ₂ ] higher than a carboxyl group terminal concentration [COOH].
[10]
The polyamide resin composition according to [8], wherein the amine component (D) is a polyamide resin prepolymer having an amino group terminal concentration [NH ₂ ] higher than a carboxyl group terminal concentration [COOH].
[11]
The polyamide resin composition according to [8], wherein the (D) amine component is a diamine.
[12]
[1] A molded product comprising the polyamide resin composition according to any one of [11].

  According to the present invention, a polyamide resin composition having improved tensile strength, tensile elongation, and Charpy impact and improved hydrolysis resistance can be provided.

FIG. 1 is a schematic view of a twin-screw extruder used in this example.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.
≪Polyamide resin composition≫
The polyamide resin composition of this embodiment is
Containing 100 parts by weight of polyamide resin and 10 to 250 parts by weight of (B) reinforcing material,
The difference ([COOH] − [NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin is −25 to 25 meq / kg,
Viscosity number [VN] is 160 mL / g or more.
Here, the difference ([COOH]-[NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin is the polyamide contained in the polyamide resin composition. It is the difference ([COOH]-[NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the resin.
Hereinafter, each component which comprises the polyamide resin composition of this embodiment is demonstrated.

(Polyamide resin)
The polyamide resin composition of this embodiment contains a polyamide resin.
“Polyamide resin” means a polyamide resin that is a polymer having an amide bond (—NHCO—) in the main chain.
In the present specification, the polyamide resin means not the raw material stage (A) polyamide resin but a polyamide resin contained in the polyamide resin composition unless otherwise specified.
In the present specification, the (A) polyamide resin in the raw material stage used in the method for producing a polyamide resin composition and the polyamide resin contained in the polyamide resin composition can be clearly distinguished by molecular weight. The molecular weight can be evaluated by molecular weight measurement by GPC (gel permeation chromatography), solution viscosity, or the like.
The raw material stage (A) polyamide resin and the polyamide resin contained in the polyamide resin composition have the same characteristics other than the molecular weight, such as the melting point and the peak temperature of the high temperature crystallization temperature. The difference in molecular weight between the raw material stage (A) polyamide resin and the polyamide resin contained in the polyamide resin composition can be analyzed by the GPC and solution viscosity, and the other characteristics are the same. Can also be confirmed by selecting a verification method according to the characteristics.
Examples of the polyamide resin include, but are not limited to, a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, and a self-condensation of an aminocarboxylic acid. Examples thereof include polyamide resins and copolymers obtained by copolymerization of two or more types of units (monomers) constituting these polyamide resins.
As a polyamide resin, only 1 type of the said polyamide may be used independently, and 2 or more types may be used together.

Hereinafter, the raw material of the polyamide resin will be described.
Examples of the diamine include, but are not limited to, aliphatic diamines, alicyclic diamines, and aromatic diamines.

  Examples of the aliphatic diamine include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylene. C2-C20 linear saturated aliphatic diamine such as diamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, and tetradecamethylenediamine; for example, 2-methylpentamethylenediamine (2-methyl-1, 5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylene Branched saturated aliphatic diamines having 3 to 20 carbon atoms such as diamines, and the like. Examples of the branched saturated aliphatic diamine include diamines having substituents branched from the main chain.

  Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclohexane, and the like. Pentanediamine and the like can be mentioned.

  Examples of the aromatic diamine include, but are not limited to, metaxylylenediamine, paraxylylenediamine, metaphenylenediamine, orthophenylenediamine, paraphenylenediamine, and the like.

  Examples of the dicarboxylic acid include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

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

Examples of the alicyclic dicarboxylic acid include, but are not limited to, alicyclics such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Carboxylic acid is mentioned.
The number of carbon atoms in the alicyclic structure of the alicyclic carboxylic acid is not particularly limited, but is preferably 3 to 10 carbon atoms, more preferably from the viewpoint of the balance between water absorption and crystallinity of the obtained polyamide resin. 5-10. Among the alicyclic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of mechanical properties.

  The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include, but are not limited to, for example, 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. And the like.

Examples of the aromatic dicarboxylic acid include, but are not limited to, aromatic dicarboxylic acids having 8 to 20 carbon atoms that are unsubstituted or substituted with a substituent.
Examples of the substituent include, but are not limited to, for example, 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 groups such as halogen groups such as 3 to 10 alkylsilyl groups having 3 to 10 carbon atoms, sulfonic acid groups, and salts thereof such as sodium salts.
Specific examples of the aromatic dicarboxylic acid include, but are not limited to, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Examples include 5-sodium sulfoisophthalic acid.

  The dicarboxylic acid may further include a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid as long as the object of the present embodiment is not impaired. These may be used individually by 1 type and may use 2 or more types together.

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

  Examples of the aminocarboxylic acid include, but are not limited to, compounds such as the above-described lactam ring-opened compounds (ω-aminocarboxylic acid, α, ω-aminocarboxylic acid, and the like).

The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which the ω position is substituted with an amino group from the viewpoint of increasing the crystallinity. Specific examples include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
Among these, 12-aminododecanoic acid is preferable from the viewpoint of low water absorption.

  Examples of the polyamide resin include, but are not limited to, polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), Polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide, hereinafter also referred to as “PA66”), polyamide 610 (polyhexamethylene sebacamide) ), Polyamide 612 (polyhexamethylene dodecamide), polyamide 116 (polyundecamethylene adipamide), polyamide 92 (polynonamethylene oxamide), polyamide TMHT (trimethylhexamethylene terephthalamide), polyamide 6T (poly Oxamethylene terephthalamide), polyamide 2Me-5T (poly 2-methylpentamethylene terephthalamide, Me is a methyl group, the same shall apply hereinafter), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly 2) -Methyl octamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 6C (polyhexamethylenecyclohexanedicarboxamide), polyamide 2Me-5C (poly-2-methylpentamethylenecyclohexanedicarboxamide), polyamide 9C (polynona) Methylenecyclohexanedicarboxamide), 2Me-8C (poly-2-methyloctamethylenecyclohexanedicarboxamide), polyamide PACM12 (polybis (4-aminocyclohexyl) ) Methandecamide), polyamide dimethyl PACM12 (polybis (3-methyl-aminocyclohexyl) methane dodecamide, polyamide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (polyundeca) Methylene terephthalamide), polyamide 12T (polydodecamethylene terephthalamide), polyamide 10C (polydecamethylenecyclohexanedicarboxamide), polyamide 11C (polyundecamethylenecyclohexanedicarboxamide), polyamide 12C (polydodecamethylenecyclohexanedicarboxamide), etc. A polyamide resin is mentioned.

  As an example of the polyamide resin used for this embodiment, it is preferable from a viewpoint of heat resistance, intensity | strength, and a moldability that the polyamide resin obtained by the condensation polymerization of diamine and dicarboxylic acid is included. The polyamide resin used in this embodiment is more preferably a polyamide resin containing 50% by mass or more of a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid, and more preferably a polyamide obtained by condensation polymerization of diamine and dicarboxylic acid. It is a polyamide resin containing 70% by mass or more of a resin, more preferably a polyamide resin containing 90% by mass or more of a polyamide resin obtained by polycondensation of diamine and dicarboxylic acid, and particularly preferably polycondensation of diamine and dicarboxylic acid. The resulting polyamide resin. In the polyamide resin used in the present embodiment, a method for containing a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid is not particularly limited, and examples thereof include copolymerization, alloy (mixing) and the like.

  The polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid is not limited to the following, but examples include polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 2Me-5T (poly-2-methylpentamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly 2) -Methyloctamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 6C (polyhexamethylenecyclohexanedicarboxamide), polyamide 2Me-5C (poly-2-methylpentamethyle) Cyclohexanedicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly-2-methyloctamethylenecyclohexanedicarboxamide), polyamide 10T (polydecamethyleneterephthalamide) and polyamide 10C (polydecamethylenecyclohexanedicarboxamide) ). These polyamide resins are preferable from the viewpoints of toughness, strength, and moldability. From the same viewpoint, the polyamide resin more preferably includes polyamide 66.

  The polyamide resin may be a polyamide copolymer obtained by copolymerizing two or more units (monomers) constituting the various polyamides described above.

  Examples of the polyamide copolymer include, but are not limited to, polyamide 66 / 6I, PA66 / 6I / 6, PA66 / 6T, PA6T / 2Me-5T (Me is a methyl group), PA9T / 2Me. Examples thereof include polyamide copolymers such as -8T, PA6C / 2Me-5C, and PA9C / 2Me-8C.

  Among the polyamide resins described above, the polyamide resin is preferably polyamide 6, polyamide 66, polyamide 610, polyamide 66/6, polyamide 66 / 6I, polyamide 6C / 2Me-5C, polyamide 2Me-5C, and polyamide 6, polyamide 66, polyamide 66/6, and polyamide 66 / 6I are more preferable, and polyamide 66 is still more preferable from the balance of strength / toughness and crystallinity.

  When the monomer of the polyamide resin is polymerized, an end-capping agent can be further added to adjust the molecular weight. The end capping agent is not particularly limited, and a known one can be used.

Examples of the terminal blocking agent include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like.
Among these, monocarboxylic acid and monoamine are preferable from the viewpoint of the thermal stability of the polyamide resin.
These may be used alone or in combination of two or more.

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid , Caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids; benzoic acid, And aromatic monocarboxylic acids such as toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
These may be used alone or in combination of two or more.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylami; Alicyclic monoamines such as cyclohexylamine, dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; etc. Is mentioned.
These may be used alone or in combination of two or more.

Examples of the acid anhydride that can be used as the end-capping agent include, but are not limited to, phthalic anhydride, maleic anhydride, benzoic anhydride, acetic anhydride, hexahydrophthalic anhydride, and the like.
These may be used alone or in combination of two or more.

Examples of the monoisocyanate that can be used as the end-capping agent include, but are not limited to, phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.
These may be used alone or in combination of two or more.

Examples of monoacid halides that can be used as end-capping agents include, but are not limited to, benzoic acid, diphenylmethane carboxylic acid, diphenyl sulfone carboxylic acid, diphenyl sulfoxide carboxylic acid, diphenyl sulfide carboxylic acid, diphenyl ether carboxylic acid. Examples include halogen-substituted monocarboxylic acids of monocarboxylic acids such as acids, benzophenone carboxylic acids, biphenyl carboxylic acids, α-naphthalene carboxylic acids, β-naphthalene carboxylic acids, and anthracene carboxylic acids.
These may be used alone or in combination of two or more.

Monoesters that can be used as end-capping agents include, but are not limited to, for example, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monomontanate, pentaerythritol monopalmitate. , Pentaerythritol monostearate, pentaerythritol monobehenate, pentaerythritol monomontanate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitol Monopalmitate, sorbitol monostearate, sorbitol monobehenate, sorbitol tribehenate, sorbitol monomontanate, sorbi Over distearate montanate and the like.
These may be used alone or in combination of two or more.

Monoalcohols that can be used as end-capping agents include, but are not limited to, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and the like. Nord, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol (over, linear, branched) ), Oleyl alcohol, behenyl alcohol, phenol, cresol (o-, m-, p-isomer), biphenol (o-, m-, p-isomer), 1-naphthol, 2-naphthol, etc. And the like.
These may be used alone or in combination of two or more.

The melting point of the polyamide resin is not particularly limited, but is preferably 200 ° C. or higher and 340 ° C. or lower, more preferably 210 ° C. or higher and 335 ° C. or lower, and further preferably 240 ° C. or higher and 330 ° C. or lower.
By setting the melting point of the polyamide resin to 200 ° C. or higher, the heat resistance of the polyamide resin composition tends to be improved.
By setting the melting point of the polyamide resin to 340 ° C. or lower, thermal decomposition and deterioration during melt processing of the polyamide resin composition tend to be more effectively suppressed.

  The melting point of the polyamide resin can be measured according to JIS-K7121, for example, under a temperature rising rate of 20 ° C./min. As the measuring device, for example, Diamond DSC manufactured by PERKIN-ELMER can be used.

The molecular weight of the raw material (A) polyamide resin and the polyamide resin in the polyamide resin composition can be measured by various methods.
Examples thereof include molecular weight measurement by GPC (gel permeation chromatography) and solution viscosity. Specifically, as the solution viscosity, there are a viscosity number [VN] measured according to ISO 307 (JIS-K6933) and a formic acid relative viscosity [RV] measured according to ASTM-D789. As an example of the measurement according to ISO 307 (JIS-K6933), the measurement can be performed with a polyamide resin concentration of 0.5% by mass in 96% sulfuric acid at 25 ° C.

  For conversion to the different standards, for example, a conversion table described in ISO 307 (JIS-K6933) may be used as appropriate.

  In the present specification, the viscosity number [VN] is used as an index of the molecular weight of the raw material (A) polyamide resin, and the higher the value of VN, the higher the molecular weight. (For the same [VN], [RV] is also shown in parentheses for PA66)

The viscosity number [VN] of the polyamide resin composition of the present embodiment is 160 mL / g (RV (PA66): 58) or more, VN165 mL / g or more and VN350 mL / g or less (RV (PA66): 61 or more and 477 or less). Is preferred. The polyamide resin composition of this embodiment can improve impact resistance by setting the viscosity number [VN] to 160 mL / g or more. Moreover, the polyamide resin composition of this embodiment can ensure melt processability, such as molding, by setting the viscosity number [VN] to 350 mL / g or less. The viscosity number [VN] of the polyamide resin composition of the present embodiment is more preferably 175 mL / g or more and 310 mL / g or less (RV (PA66): 69 or more and 306 or less), and still more preferably 180 mL / g or more. 290 mL / g or less (RV (PA66): 72 to 245), even more preferably 190 mL / g to 270 mL / g (RV (PA66): 81 to 197), particularly preferably 200 mL / G to 250 mL / g (RV (PA66): 90 to 157).
In addition, in this embodiment, the viscosity number [VN] of a polyamide resin composition can be measured by the method as described in the below-mentioned Example.

Examples of a method for obtaining a polyamide resin composition having a viscosity number [VN] in the above range include a method of appropriately adjusting the molecular weight of the raw material (A) polyamide resin.
As a method for adjusting the molecular weight of the raw material (A) polyamide resin, for example, a solid phase polymerization method in which the raw material (A) polyamide resin in a solid state such as pellets is heated to a temperature lower than the melting point to increase the molecular weight, (A) A catalyst high molecular weight extrusion method in which a high molecular weight catalyst is added to a polyamide resin, and the raw material (A) polyamide resin is made high molecular weight by melt extrusion, and the like.
In particular, when the polyamide resin composition is produced by melt kneading by adding the (B) reinforcing material to the raw material (A) polyamide resin, the raw material (A) A catalyst high molecular weight extrusion method capable of simultaneously carrying out (B) kneading of the reinforcing material and high molecular weight of the raw material (A) polyamide resin is preferable to the method of performing high molecular weight because there are few steps.

  In this case, the viscosity number [VN] of the extruded raw material (A) polyamide resin may not be so high. When reducing the load on the extruder motor and increasing the discharge rate to efficiently produce a polyamide resin composition, the viscosity number [VN] of the raw material (A) polyamide resin is 70 mL / g or more and 200 mL / g. The following are preferable, More preferably, they are 90 mL / g or more and 180 mL / g or less, More preferably, they are 100 mL / g or more and 170 mL / g or less, Especially preferably, they are 120 mL / g or more and less than 165 mL / g.

The polymer terminal of the polyamide resin used in the present embodiment is any one of 1) an amino group terminal, 2) a carboxyl group terminal, 3) a terminal end-capping agent, and 4) other terminal.
The polymer terminal of the polyamide resin means a terminal part of a polymer chain of a polymer obtained by polymerizing dicarboxylic acid and diamine (including lactam and / or aminocarboxylic acid, if necessary) by an amide bond.

1) Amino group terminal means that the polymer terminal is an amino group (—NH ₂ ), and the terminal of the polymer chain is derived from a raw material diamine, lactam, or aminocarboxylic acid.
2) The carboxyl group end means that the polymer end is a carboxyl group (—COOH), and the end of the polymer chain is derived from a raw material dicarboxylic acid, diamine, lactam, or aminocarboxylic acid.
3) The end by the end-capping agent means that the end of the polymer is capped by the end-capping agent added at the time of polymerization, and has a structure derived from end-capping agents such as monocarboxylic acid and monoamine. .
4) The other terminal is a polymer terminal not classified in 1) to 4), and examples thereof include a terminal generated by deammonia reaction at the amino group terminal and a terminal generated by decarboxylation reaction at the carboxyl group terminal. It is done.

The quantification of these end groups can be measured, for example, using ¹ H-NMR as described in the following examples. For example, the terminal concentration in the case of an amino group terminal can be calculated based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the terminal amino group.

In the raw material (A) polyamide resin, for example, a carboxyl group terminal and an amino group terminal undergo dehydration polycondensation (amidation reaction) to form an amide bond to increase the molecular weight. This amidation reaction is known to be an equilibrium reaction with a reverse reaction. Therefore, when it is desired to further increase the high molecular weight of the raw material (A) polyamide resin or to maintain the high molecular weight state of the polyamide resin by suppressing the reverse reaction during melt processing such as molding, the polyamide resin It is preferable that the product of the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] is maximized.

There are two polymer ends (for linear polymers) at both ends of the polymer chain. Therefore, the total end group concentration varies depending on the molecular weight of the polymer. That is, when the molecular weight is the same, the total terminal group concentration is constant, and in order to maximize the product of the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ], [COOH ] = [NH ₂ ] ([COOH] − [NH ₂ ] = 0).

By the way, when polymerizing a polyamide resin obtained by condensation polymerization of a diamine such as PA66 and a dicarboxylic acid, an equivalent salt aqueous solution of hexamethylenediamine (diamine) and adipic acid (dicarboxylic acid) is used as a raw material. It is common to polymerize by heating. However, in such a polymerization method, not only water (water of the solvent of the aqueous solution and condensed water at the time of amide bond formation) but also part of the diamine escapes out of the polymerization system due to heating during the polymerization. As the resin, [COOH]-[NH ₂ ]> 30 meq / kg.

Thus, when the polyamide resin is polymerized as it is in the state of [COOH]-[NH ₂ ]> 30 meq / kg, the same number of [COOH] and [NH ₂ ] are consumed. ₂ ] is even less. The amino group terminal in the polyamide resin forms a strong interface by reaction with the surface of the reinforcing material (B) and the surface treatment agent. In order to improve the hydrolysis resistance of the polyamide resin composition, polyamide It is preferable to increase the amino group terminal concentration [NH ₂ ] in the resin so that the amount is balanced with the carboxyl group terminal [COOH] as much as possible.

Therefore, from these two viewpoints, the difference between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin contained in the polyamide resin composition of this embodiment ([COOH] − [NH ₂ ]) is from -25 to 25 meq / kg. In the polyamide resin composition of the present embodiment, the difference ([COOH]-[NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH2] in the polyamide resin is 25 meq / kg or less. And hydrolysis resistance becomes favorable, and since it can suppress generation | occurrence | production of the decomposition gas derived from an amino-group terminal group as it is more than -25 milliequivalent / kg, a moldability improves and a color tone improves.
The difference ([COOH] − [NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin contained in the polyamide resin composition of the present embodiment is preferably -15 to 25 meq / kg, more preferably -5 to 25 meq / kg, more preferably 0 to 25 meq / kg, and even more preferably 1 to 20 meq / kg. Even more preferably, it is 1 to 15 meq / kg, and particularly preferably 5 to 15 meq / kg.

As a method for producing a polyamide resin having such a terminal concentration, for example, a polyamide resin having a general terminal concentration ([COOH]-[NH ₂ ]> 30 meq / kg) is subjected to melt processing such as extrusion. Add an amine component to the resin to increase the amino group terminal concentration of the polyamide resin, or add an excess of the diamine component from the equivalent of dicarboxylic acid and diamine as a monomer raw material for the polyamide resin in anticipation of the above-mentioned escape of diamine The method of manufacturing by using the raw material which carried out and polymerizing from this raw material is mentioned.
In the present embodiment, the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] can be measured by the methods described in Examples described later.

(Production method of (A) polyamide resin as raw material)
The production method of the (A) polyamide resin as a raw material is not particularly limited, and examples thereof include the following various methods.

1) An aqueous solution of dicarboxylic acid and diamine or a suspension of water, or a mixture of dicarboxylic acid and diamine salt and other components such as lactam and / or aminocarboxylic acid (hereinafter, these are abbreviated as “the mixture”) A method in which an aqueous solution or a suspension of water is heated and polymerized while maintaining a molten state (hereinafter, also referred to as “hot melt polymerization method”);
2) A method of heating an aqueous solution or a suspension of water of a dicarboxylic acid and a diamine or a mixture thereof and removing the precipitated prepolymer (“prepolymer method”);
3) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (“hot melt polymerization / solid phase polymerization method”);
4) A method in which an aqueous solution or a suspension of water of dicarboxylic acid and diamine or a mixture thereof is heated, and the precipitated prepolymer is further melted again by an extruder such as a kneader to increase the degree of polymerization (“prepolymer · Extrusion polymerization method ");
5) A method in which an aqueous solution or a suspension of water of dicarboxylic acid and diamine or a mixture thereof is heated, and the precipitated prepolymer is further maintained in a solid state at a temperature below the melting point of polyamide to increase the degree of polymerization (“ Prepolymer / solid phase polymerization method));
6) A method of polymerizing a dicarboxylic acid and a diamine or a mixture thereof while maintaining a solid state (“monomer / solid phase polymerization method”);
7) A method of polymerizing “a salt of dicarboxylic acid and diamine” or a mixture thereof while maintaining a solid state (“salt / solid phase polymerization method”);
8) A method of polymerization using a dicarboxylic acid halide and a diamine equivalent to a dicarboxylic acid (“solution method”).

  In the present embodiment, when (B) a reinforcing material is added to a polyamide resin and a polyamide resin composition is produced by melt kneading, the raw material (A) is made to have a high molecular weight in a separate process such as a solid phase polymerization method. (B) Reinforcement material kneading and raw material (A) high molecular weight of polyamide resin can be carried out simultaneously. Therefore, in this case, from the viewpoint that it is not necessary to deliberately increase the molecular weight of the raw material (A) polyamide resin, among the methods for producing the raw material (A) polyamide resin, there are few steps and thermal melting is easy to obtain a stable molecular weight. A polymerization method and a prepolymer method are preferred.

The polymerization form in the method for producing the (A) polyamide resin as a raw material is not limited to the following, and examples thereof include a batch type and a continuous type.
The polymerization apparatus is not particularly limited, and a known apparatus (for example, an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, etc.) can also be used.

((B) reinforcement)
The polyamide resin composition of the present embodiment contains (B) a reinforcing material.
(B) The reinforcing material is not limited to the following as long as it improves the strength and / or rigidity of the material. For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber , Aluminum borate fiber, flaky glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide , Titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, fluorine Calcium fluoride Morironaito include swellable fluorine mica and apatite.
Among these, from the viewpoint of increasing strength and rigidity, glass fiber, carbon fiber, flaky glass, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotube, graphite, fluorine Calcium fluoride, montmorillonite, swellable fluorinated mica and apatite are preferred.
More preferably, glass fiber, carbon fiber, wollastonite, talc, mica, kaolin and silicon nitride are used. The above-mentioned (B) reinforcing material may be used alone or in combination of two or more.

  From the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition among the above glass fibers and carbon fibers, the number average fiber diameter is 3 to 30 μm, and in the polyamide resin composition, the weight average More preferably, the fiber length is 100 to 750 μm, and the aspect ratio of the weight average fiber length to the number average fiber diameter (value obtained by dividing the weight average fiber length by the number average fiber diameter) is 10 to 100.

  Further, among the above wollastonites, the number average fiber diameter is 3 to 30 μm from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition, and the weight average fiber in the polyamide resin composition It is more preferable that the length is 10 to 500 μm and the aspect ratio is 3 to 100.

  Of the above talc, mica, kaolin, and silicon nitride, those having a number average fiber diameter of 0.1 to 3 μm are more preferable from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition.

  Here, regarding the number average fiber diameter and the weight average fiber length, the polyamide resin composition is put into an electric furnace, the contained organic matter is incinerated, and, for example, 100 or more reinforcing materials are arbitrarily selected from the residue. The number average fiber diameter can be measured by observing with a scanning electron microscope (SEM) and measuring the fiber diameter of these reinforcing materials, and the fiber length is measured using an SEM photograph at a magnification of 1000 times. By doing so, the weight average fiber length can be determined.

The reinforcing material (B) may be subjected to a surface treatment with a silane coupling agent or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Aminosilanes such as dimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
Of these, aminosilanes are preferable.

The glass fiber or carbon fiber may further contain a sizing agent. Examples of the sizing agent include, but are not limited to, for example, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer; , Epoxy compounds, polycarbodiimide compounds, polyurethane resins, acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and their primary, secondary and tertiary copolymers. Examples include salts with secondary amines.
These may be used alone or in combination of two or more.
In particular, from the viewpoint of the mechanical strength of the polyamide resin composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are structural units. A copolymer, an epoxy compound, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are preferably used, and the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer are excluded. A copolymer containing a saturated vinyl monomer as a structural unit, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are more preferable.

Among the copolymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, the carboxylic acid anhydride-containing copolymer Examples of the unsaturated vinyl monomer include, but are not limited to, maleic anhydride, itaconic anhydride and citraconic anhydride, with maleic anhydride being preferred.
On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. The unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer is not limited to the following, for example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, Examples include chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Styrene and butadiene are particularly preferable.

  Among these combinations, selected from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. 1 or more types are more preferable.

  Further, the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight. It is preferably 2,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of a polyamide resin composition, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-1,000,000. In addition, the weight average molecular weight in this specification is a value measured by GPC.

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

  The polycarbodiimide compound can be obtained by condensing a compound containing one or more carbodiimide groups (—N═C═N—).

  The degree of condensation of the polycarbodiimide compound is preferably 1-20, and more preferably 1-10. When the degree of condensation is in the range of 1 to 20, a good aqueous solution or aqueous dispersion is obtained. Furthermore, when the condensation degree is in the range of 1 to 10, a better aqueous solution or aqueous dispersion is obtained.

Moreover, it is preferable that the said polycarbodiimide compound is a polycarbodiimide compound which has a polyol segment partially.
By having a polyol segment, the polycarbodiimide compound is easily water-soluble and can be more suitably used as a sizing agent for glass fibers or carbon fibers.

These polycarbodiimide compounds can be obtained by decarboxylating a diisocyanate compound in the presence of a known carbodiimidization catalyst such as 3-methyl-1-phenyl-3-phospholene-1-oxide.
As the diisocyanate compound, aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, and mixtures thereof can be used. Although not limited to the following, for example, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diene Isocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropyl Such as phenyl isocyanate and 1,3,5-triisopropylbenzene 2,4-diisocyanate. And the polycarbodiimide compound which has two isocyanate groups at the terminal is obtained by carbodiimidizing these diisocyanate compounds. Of these, dicyclohexylmethane carbodiimide can be suitably used from the viewpoint of improving reactivity.

For the polycarbodiimide compound having two isocyanate groups at the terminal, further by a method of carbodiimidizing a monoisocyanate compound or a method of reacting with a polyalkylene glycol monoalkyl ether to produce a urethane bond, etc. A polycarbodiimide compound having one isocyanate group at the terminal is obtained.
Examples of the monoisocyanate compound include, but are not limited to, hexyl isocyanate, phenyl isocyanate, and cyclohexyl isocyanate.
Examples of the polyalkylene glycol monoalkyl ether include, but are not limited to, polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

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

  The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The monomer constituting the copolymer of acrylic acid and other copolymerizable monomer and forming the copolymer with acrylic acid is not limited to the following, but has, for example, a hydroxyl group and / or a carboxyl group Among the monomers, one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid may be mentioned (however, acrylic Except for acid only). In addition, it is preferable that the said other copolymerizable monomer has 1 or more types of ester monomers among the said monomers.

The polymer of acrylic acid (including both homopolymers and copolymers) may be in the form of a salt.
The polymer salt of acrylic acid includes, but is not limited to, primary, secondary or tertiary amine salts. Although not limited to the following, for example, triethylamine salt, triethanolamine salt and glycine salt can be mentioned.
The degree of neutralization is preferably 20 to 90%, preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less are preferable from the viewpoint of improving mechanical properties when a polyamide resin composition is obtained.

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

  In the polyamide resin composition of the present embodiment, the content of the (B) reinforcing material is 10 to 250 parts by mass with respect to 100 parts by mass of the polyamide resin. In the polyamide resin composition of the present embodiment, the effect of improving the strength can be sufficiently achieved by setting the content of the (B) reinforcing material to 10 parts by mass or more with respect to 100 parts by mass of the polyamide resin, and 250 parts by mass or less. By making it, the productivity in extrusion improves. (B) The content of the reinforcing material is preferably 20 to 150 parts by mass, more preferably 25 to 100 parts by mass, and further preferably 30 to 60 parts by mass with respect to 100 parts by mass of the polyamide resin. It is.

(High molecular weight catalyst)
In the polyamide resin composition of this embodiment, although it is an optional component, a high molecular weight catalyst can also be contained. The high molecular weight catalyst is not particularly limited as long as it has a high molecular weight ability, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid and derivatives thereof (esters, metal salts, etc.). (C) Although the phosphoric acid compound will be described later, other detailed examples include phenylphosphinic acid, 2- (2′-pyridyl) ethylphosphonic acid, sodium hypophosphite, and the like.
As the high molecular weight catalyst, a phosphoric acid compound (C) is preferred from the viewpoint of high molecular weight ability and from the viewpoint that no discoloration occurs when copper iodide and potassium iodide, which are heat stabilizers for polyamide resin, are mixed.

((C) Phosphate compound)
In the polyamide resin composition of this embodiment, although it is an optional component, (C) a phosphoric acid compound can also be contained. The (C) phosphoric acid compound, as long as it has a polymerization ability of the polyamide resin (A) of the raw material, for example, orthophosphoric acid with phosphorus oxo acid represented by _{H 3 PO 4, H 4 P} 2 Examples thereof include pyrophosphoric acid (diphosphoric acid) represented by O ₇ , metaphosphoric acid (polyphosphoric acid) represented by (HPO ₃ ) _n , and those phosphoric acid derivatives having a high molecular weight.
The phosphoric acid derivative means one or more H such as H ₃ PO ₄ is an organic substituent (for example, but not limited to, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group) Aliphatic groups such as i-butyl group, t-butyl group, n-pentyl, n-hexyl, n-octyl group, 2-ethylhexyl group, decyl group, lauryl group, tridecyl group, stearyl group, and oleyl group, An aromatic group such as a phenyl group and a biphenyl group.) And phosphoric acid amine salts (including ammonium phosphate salts and phosphoric acid diamine salts) which are salts with bases. . The (C) phosphoric acid compound may be used alone or in combination of two or more.

  (C) As the phosphoric acid compound, the non-substituted orthophosphoric acid, pyrophosphoric acid, and metalin are preferred because the polyamide resin tends to have a higher molecular weight when H in the molecule is not substituted with an organic substituent. Acid is preferred.

  The (C) phosphate compound may be in a solid state or in a liquid (including aqueous solution) state as long as it exhibits a high molecular weight.

  Further, (C) the phosphoric acid compound may be added as it is in the polyamide resin composition, or may be added in a diluted state such as a masterbatch. The master batch is not particularly limited, but may be pellets, granules, or powder, and is preferably diluted with a polyamide resin.

In the polyamide resin composition of this embodiment, when (C) the phosphoric acid compound is contained, the content of the (C) phosphoric acid compound is preferably 0.5 to 1000 mmol with respect to 1 kg of the polyamide resin. The polyamide resin composition of the present embodiment is a catalyst high molecular weight extrusion method in which (C) the phosphoric acid compound is contained in the above range so that the polyamide resin has a high molecular weight during extrusion. The molecular weight is sufficiently increased, and the impact resistance can be further improved. In addition, when content of the said (C) phosphoric acid compound will be less than 0.5 mmol, the high molecular weight of a polyamide resin is not enough, and an impact resistance improvement may become low. On the other hand, when the content of the phosphoric acid compound (C) exceeds 1000 mmol, the polyamide resin composition becomes too high in the catalytic high molecular weight extrusion method, and the load on the extruder becomes too large, resulting in a polyamide resin composition. There is a possibility that the product cannot be produced, or gelation occurs and the physical properties of the polyamide resin composition are lowered. The content of the phosphoric acid compound (C) is preferably 1 to 500 mmol, more preferably 2 to 300 mmol, still more preferably 3 to 100 mmol, and even more with respect to 1 kg of the polyamide resin. Preferably, it is 4-50 mmol, Most preferably, it is 5-20 mmol.
When the polyamide resin composition of the present embodiment contains a phosphoric acid compound (C), the phosphorus concentration [P] is preferably 1 to 5000 ppm by mass, more preferably 50 to 1000 ppm by mass, More preferably, it is 100-500 mass ppm. When the phosphorus concentration [P] is within the above range, the polyamide resin composition of the present embodiment tends to favor the color tone of melt-processed pellets and molded products.
In the present embodiment, the phosphorus concentration [P] can be measured by the method described in Examples described later.

((D) amine component)
In the polyamide resin composition of this embodiment, although it is an optional component, (D) an amine component can also be contained. (D) The amine component is a compound having a monovalent functional group (—NH ₂ , —NHR, —NRR ′) obtained by removing hydrogen from ammonia, a primary amine, or a secondary amine. In order to increase the amino group terminal of the polyamide resin, for example, when the (D) amine component is added at the time of raw material extrusion in the production of the polyamide resin composition, the (D) amine component has two or more —NH _2. Compounds are preferred.

As the compound having an -NH ₂ 2 or more, is not particularly limited, for example, diamines, prepolymers of various polymers with many triamine or amino terminus (oligomer), and the like. Among these, for example, from the viewpoint of compatibility and kneadability at the time of extrusion of the polyamide resin composition raw material, the amine component preferably has a diamine and / or amino group terminal concentration [NH ₂ ] of carboxyl. It is a polyamide resin prepolymer (oligomer) higher than the base end concentration [COOH]. The difference ([NH ₂ ]-[COOH]) between the amino group terminal concentration [NH ₂ ] and the carboxyl group terminal concentration [COOH] in the polyamide resin prepolymer is preferably 10 to 20000 meq / kg, More preferably, it is -10000 meq / kg, More preferably, it is 100-5000 meq / kg, More preferably, it is 300-1000 meq / kg.

  The production method of the polyamide resin prepolymer (oligomer) having many amino group ends is not particularly limited. For example, an excessive amount of diamine is added to an aqueous equivalent salt solution of diamine and dicarboxylic acid, and polymerization is stopped during the polymerization. And a method of obtaining a polyamide resin prepolymer (oligomer) with a lower molecular weight.

  In the polyamide resin composition of the present embodiment, when a diamine is contained, it may be contained as a diamine or a diamine salt with an acid (carbonic acid, phosphoric acid, etc.).

  In the polyamide resin composition of the present embodiment, the (D) amine component may be contained as it is or may be contained in a diluted state such as a masterbatch. (D) The shape of the amine component is not particularly limited, and may be pellets, tablets, or powders.

  When the (D) amine component is contained in the polyamide resin composition of the present embodiment, the content of the (D) amine component is preferably 0.5 to 1000 mmol with respect to 1 kg of the polyamide resin. In the polyamide resin composition of the present embodiment, (D) the amine component is contained in the above range, so that the polyamide resin can have a high molecular weight and the impact resistance can be improved. (D) The content of the amine component is preferably 1 to 500 mmol, more preferably 2 to 300 mmol, still more preferably 3 to 100 mmol, and even more preferably, with respect to 1 kg of the polyamide resin. Is 4 to 50 mmol, particularly preferably 5 to 20 mmol. In addition, when the amine component (D) is a prepolymer (oligomer) or the like, the molecular weight of the prepolymer (oligomer) is measured by GPC, and the obtained number average molecular weight (Mn) is determined as the molecular weight of the (D) amine component. Considering this, the calculation of the content of the (D) amine component is performed.

(Deactivator)
In the polyamide resin composition of this embodiment, a deactivator can also be contained as needed. A deactivator refers to what deactivates the high molecular weight catalyst's high molecular weight ability. Although it does not specifically limit as a deactivator, For example, a metal compound etc. are mentioned.
The metal compound is not particularly limited. For example, lithium halide (lithium iodide, lithium bromide, lithium chloride, lithium fluoride), lithium oxide, lithium hydroxide, lithium carbonate, sodium halide (sodium iodide, Sodium bromide, sodium chloride, sodium fluoride), sodium oxide, sodium hydroxide, sodium carbonate, magnesium halide (magnesium iodide, magnesium bromide, magnesium chloride, magnesium fluoride), magnesium oxide, magnesium hydroxide, carbonic acid Magnesium, potassium halide (potassium iodide, potassium bromide, potassium chloride, potassium fluoride), potassium oxide, potassium hydroxide, potassium carbonate, calcium halide (calcium iodide, calcium bromide, Calcium oxide, calcium fluoride), calcium oxide, calcium hydroxide, calcium carbonate, iron halide (iron iodide, iron bromide, iron chloride, iron fluoride), iron oxide, iron hydroxide, iron carbonate, copper halogen Chloride (copper iodide, copper bromide, copper chloride, copper fluoride), copper oxide, copper hydroxide, copper carbonate, zinc halide (zinc iodide, zinc bromide, zinc chloride, zinc fluoride), zinc oxide Zinc hydroxide, zinc carbonate and the like. The said metal compound may use 1 type and may be used in combination of 2 or more type.

  The metal compound is preferably lithium iodide, lithium bromide, lithium oxide, lithium hydroxide, lithium carbonate, from the viewpoint of reducing corrosion on processing machines such as extruders and molding machines in the production of polyamide resin compositions. Sodium iodide, sodium bromide, sodium oxide, sodium hydroxide, sodium carbonate, magnesium iodide, magnesium bromide, magnesium oxide, magnesium hydroxide, magnesium carbonate, potassium iodide, potassium bromide, potassium oxide, potassium hydroxide , Potassium carbonate, calcium iodide, calcium bromide, calcium oxide, calcium hydroxide, calcium carbonate, iron iodide, iron bromide, iron oxide, iron hydroxide, iron carbonate, copper iodide, copper bromide, copper oxide , Copper hydroxide, copper carbonate, zinc iodide, zinc bromide, zinc oxide, zinc hydroxide, carbonic acid Lead and the like. More preferably, lithium iodide, lithium oxide, lithium carbonate, sodium iodide, sodium oxide, sodium carbonate, magnesium iodide, magnesium oxide, magnesium hydroxide, magnesium carbonate, potassium iodide, potassium oxide, potassium carbonate, iodide Calcium, calcium oxide, calcium hydroxide, calcium carbonate, iron iodide, iron oxide, iron hydroxide, iron carbonate, copper iodide, copper oxide, copper hydroxide, copper carbonate, zinc iodide, zinc oxide, zinc hydroxide And zinc carbonate.

  In the polyamide resin composition of this embodiment, when a quencher is contained, the content of the quencher is preferably 0.5 to 1000 mmol with respect to 1 kg of the polyamide resin. The polyamide resin composition of this embodiment can suppress the gelatinization at the time of thermal residence in manufacture of a polyamide resin composition by containing a quencher in said range. In addition, when content of the said deactivator will be less than 0.5 mmol, suppression of gelatinization at the time of heat retention is not enough. On the other hand, when the content of the deactivator exceeds 1000 mmol, the content of the deactivator is excessive, which may cause a decrease in strength of the polyamide resin composition. Moreover, it can be said that it is preferable that content of a quencher is more than the equivalent of a high molecular weight catalyst from a viewpoint of deactivating the high molecular weight catalyst's high molecular weight capability.

  Moreover, in the polyamide resin composition of the present embodiment, the deactivator may be contained as it is or may be contained in a diluted state such as a masterbatch. The master batch is not particularly limited, but may be pellets, granules, or powder, and is preferably diluted with a polyamide resin component.

(Other components that can be included in the polyamide resin composition)
The polyamide resin composition of this embodiment can contain other components as long as it does not impair the purpose of this embodiment. As other components that can be included in the polyamide resin composition of the present embodiment, other additives used in the polymer or raw material (A) polyamide resin, for example, moldability improver, colorant, flame retardant, Examples include plasticizers, stabilizers, antioxidants, ultraviolet absorbers, crystal nucleating agents, and the like.

  Examples of the other polymer include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS resin, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, (modified) polyphenylene ether, polyphenylene sulfide, Examples include cycloolefin polymer, liquid crystal polyester, polyetherimide, polysulfone, polyethersulfone, polyamideimide, thermoplastic polyimide, polyetherketone, polyetheretherketone, fluororesin, and polybenzimidazole.

  Examples of the moldability improver include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like.

  Examples of the higher fatty acid include, but are not limited to, for example, saturated or unsaturated having 8 to 40 carbon atoms such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid. Saturated, linear or branched aliphatic monocarboxylic acid and the like can be mentioned. Among these, stearic acid and montanic acid are preferable from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposits on the mold during molding.

The higher fatty acid metal salt is a metal salt of a higher fatty acid.
As a metal element which comprises a metal salt, the 1st, 2nd, 3rd group element of an element periodic table, zinc, aluminum, etc. are preferable, and calcium, sodium, potassium, magnesium, etc. are more preferable.
Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. . Among these, the metal salt of montanic acid and the metal salt of stearic acid are preferable from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposits on the mold during molding.

The higher fatty acid ester is an esterified product of higher fatty acid and alcohol.
Among these, from the viewpoints of suppressing gas generation during melt processing and mold deposit suppression to the mold during molding, an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms are used. Esters are preferred.
Here, as the higher fatty acid, those described above can be used.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.
Examples of the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.

The higher fatty acid amide is an amide compound of higher fatty acid.
Examples of the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Examples include acid amides.
Of these, stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucic acid amide are preferable from the viewpoint of suppressing gas generation during melt processing and mold deposits on the mold during molding. Bisstearyl amide and N-stearyl erucamide are more preferred.

These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides may be used alone or in combination of two or more.
When a higher fatty acid metal salt is selected as the moldability improver, the amount of the higher fatty acid metal salt added is not included in the amount of the metal compound as the deactivator component described above.

Examples of the colorant include, but are not limited to, dyes such as nigrosine, pigments such as titanium oxide and carbon black; aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, and oxidation. Metal particles such as iron, stainless steel, and titanium; metallic pigments such as mica pearl pigment, color graphite, color glass fiber, and color glass flake.
When iron oxide or the like is selected as the colorant, the amount of iron oxide added is not included in the amount of the metal compound as the deactivator component described above.

  The flame retardant is preferably a non-halogen flame retardant or a bromine flame retardant from the viewpoint of suppressing gas generation during melt processing or mold deposit on the mold during molding.

  Examples of the non-halogen flame retardant include, but are not limited to, phosphorus flame retardants such as red phosphorus, ammonium phosphate, or ammonium polyphosphate, aluminum hydroxide, magnesium hydroxide, dolomite, hydro Hydrates of metal hydroxides or inorganic metal compounds such as talcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide, zinc stannate, zinc hydroxystannate, and zinc borate , Inorganic compound flame retardants such as boric acid compounds such as zinc metaborate and barium metaborate, melamine, melam, melem, melon (product obtained by deammonation of 3 to 3 molecules of melem above 300 ° C), melamine cyanurate , Melamine phosphate, melamine polyphosphate, succinoguanamine, adipoguanamine Methyl glutarate log guanamine, triazine flame retardant such as melamine resins, silicone resins, silicone oils, silicone flame retardants such as silica.

  The brominated flame retardant is not limited to the following, for example, selected from compounds consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer and brominated crosslinked aromatic polymer. And at least one flame retardant. Flame retardant aids such as antimony trioxide can also be used in combination.

  Examples of the plasticizer include, but are not limited to, aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisurea compounds, polyethylene wax, octyl p-oxybenzoate, and N-butylbenzenesulfonamide. Etc.

The stabilizer may contain a deterioration inhibitor for the purpose of heat deterioration, prevention of discoloration during heat, heat aging resistance, improvement in weather resistance, and the like.
Examples of the deterioration inhibitor include, but are not limited to, for example, copper compounds such as copper acetate and copper iodide, phenolic stabilizers such as hindered phenol compounds; phosphite stabilizers: hindered amines. Stabilizers; triazine stabilizers; sulfur stabilizers and the like.
When copper oxide such as copper oxide or copper iodide is selected as the stabilizer, the amount of copper oxide added is not included in the amount of the metal compound as the deactivator component described above.

  Examples of the antioxidant include, but are not limited to, alkylphenol, alkylene bisphenol, alkylphenol thioether, and the like.

  Examples of the ultraviolet absorber include, but are not limited to, salicylic acid ester, benzotriazole, hydroxybenzophenone, and the like.

  Examples of the crystal nucleating agent include, but are not limited to, boron nitride and talc.

(Manufacturing method of polyamide resin composition)
The method for producing the polyamide resin composition of the present embodiment is not particularly limited. For example, the general molecular weight and terminal raw material (A) polyamide resin ([COOH]-[NH ₂ ]> 30 meq / kg)) by adding high molecular weight catalyst, (D) amine component, and (B) reinforcing material, and performing catalytic high molecular weight extrusion, (B) reinforcing material addition and raw material (A) polyamide Examples of the method include adjusting the terminal groups of the resin and increasing the molecular weight. Also, (B) a reinforcing material is added to a general molecular weight raw material (A) polyamide resin whose amino group terminal concentration is adjusted in an extruder, and then the raw material (A) polyamide resin is added by a solid phase polymerization method or the like. A two-stage production method for increasing the molecular weight can be mentioned.

  In the case of catalyst high molecular weight extrusion, it is preferable to perform a devolatilization (decompression) treatment. The devolatilization (reduced pressure) treatment is preferable for efficiently removing water generated during the high molecular weight reaction (dehydration condensation reaction) of the raw material (A) polyamide resin from the polyamide resin system. By removing water in this way, the equilibrium of the polymerization and depolymerization of the polyamide resin can be further tilted in the polymerization direction, and due to the synergistic effect with the high molecular weight action of the high molecular weight catalyst component, (A ) Higher molecular weight of polyamide resin tends to be further promoted.

  The degree of reduced pressure refers to the difference between the pressure in the devolatilization region and the atmospheric pressure with reference to the atmospheric pressure. For example, the degree of vacuum of 0.02 MPa indicates an absolute pressure of 0.1013-0.02 = 0.0813 MPa when the atmospheric pressure is 0.1013 MPa.

  The degree of reduced pressure during melt kneading is preferably 0.02 MPa or more. By setting the degree of pressure reduction during melt-kneading to 0.02 MPa or more, the water removal rate (removability) tends to be increased. For this reason, there is a tendency that a high molecular weight of the (A) polyamide resin as a sufficient raw material can be realized. Moreover, it exists in the tendency which can be pressure-reduced to the maximum (decompression degree 0.1013MPa) of decompression devices (a vacuum pump etc.). When giving priority to the degree of decompression that is stable for a long period of time, the degree of decompression at the time of melt-kneading is preferably 0.1 MPa or less, more preferably 0.02 MPa or more and 0.1 MPa or less, and still more preferably 0.8. It is 04 MPa or more and 0.097 MPa or less, More preferably, it is 0.05 MPa or more and 0.095 MPa or less, Especially preferably, it is 0.06 MPa or more and 0.093 MPa or less.

  The degree of vacuum can be measured and managed by attaching a vacuum gauge (differential pressure gauge) or vacuum gauge somewhere from the decompression device (vacuum pump, etc.) to the site connected to the devolatilization area of the extruder. it can.

  When measuring the degree of decompression, for example, it is preferable to install a valve or a valved air suction nozzle at any position from a decompression device (such as a vacuum pump) to a site connected to the devolatilization region of the extruder. In this case, the degree of decompression can be adjusted by opening and closing the valve.

  A drain pot for storing drain in the vent gas can be installed between the decompression device (such as a vacuum pump) and the melt-kneading unit. When a vent pot is installed, it is preferable to attach an air suction nozzle to the vent pot.

  When a quenching agent is added to the devolatilization region, it is preferable to undergo at least one devolatilization treatment before the addition. Further, the devolatilization region may or may not be provided after the deactivator is added. It is preferable to provide a devolatilization region even after addition of the deactivator from the viewpoint of removing the gas component of the strand of the extruded molten resin and improving the take-up property of the strand.

  A known apparatus can be used as an apparatus for performing melt kneading. For example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll is preferably used. Among these, a multi-screw extruder equipped with a devolatilization mechanism (vent) device and side feeder equipment is preferable, and a twin-screw extruder is more preferably used.

  In the step of melt kneading with an extruder, the polyamide resin can be made to have a high molecular weight by appropriately setting the kneading conditions such as the resin temperature in extrusion, the degree of vacuum, and the average residence time, and the viscosity number [VN] of the polyamide resin composition Can be adjusted.

The resin temperature of the resin composition at the time of melt kneading is preferably set to the melting point of the raw material (A) polyamide resin to 380 ° C. or less. By making the resin temperature of the resin composition at the time of melt-kneading higher than the melting point of the raw material (A) polyamide resin, the melting of the raw material (A) polyamide resin is sufficient and the load on the extruder motor tends to be reduced. It is in. Moreover, it exists in the tendency which can suppress decomposition | disassembly of polyamide resin itself by making the resin temperature of the resin composition at the time of melt-kneading into 380 degrees C or less.
From the above viewpoint, the resin temperature of the resin composition at the time of melt kneading is more preferably (melting point of the raw material (A) polyamide resin + 5) ° C. or higher and 370 ° C. or lower, more preferably (raw material (A) polyamide). Melting point of resin + 10) ° C. or higher and 360 ° C. or lower, even more preferably (melting point of raw material (A) polyamide resin + 15) ° C. or higher and 355 ° C. or lower, and still more preferably (raw material (A) polyamide resin Melting point + 20) ° C. or higher and 350 ° C. or lower.
For example, when polyamide 66 having a melting point of 260 ° C. is used as a raw material, the resin temperature of the resin composition during melt kneading is preferably 260 ° C. or higher and 380 ° C. or lower. By setting the resin temperature of the resin composition during melt-kneading to 260 ° C. or higher, the polyamide 66 is sufficiently melted and the load on the extruder motor tends to be reduced. Moreover, it exists in the tendency which can suppress decomposition | disassembly of polyamide 66 itself by making the resin temperature of the resin composition at the time of melt-kneading into 380 degrees C or less.
From the above viewpoint, when polyamide 66 having a melting point of 260 ° C. is used as a raw material, the resin temperature of the resin composition during melt kneading is more preferably 265 ° C. or more and 370 ° C. or less, and further preferably 270 ° C. or more and 360 ° C. or less. And more preferably 275 ° C. or higher and 355 ° C. or lower, and further preferably 280 ° C. or higher and 350 ° C. or lower.
Thus, the resin temperature of the resin composition at the time of melt kneading can be appropriately adjusted according to the melting point of the raw material (A) polyamide resin.

  The resin temperature can be measured, for example, by bringing a thermometer such as a thermocouple into direct contact with the molten polyamide resin composition that has come out to the discharge port (spinner) of the extruder. The resin temperature can be adjusted by adjusting the heater temperature of the cylinder of the extruder, or by appropriately adjusting the shear heating value of the resin by changing the number of revolutions and the discharge amount of the extruder.

  The average residence time during melt-kneading is preferably 10 seconds or more and 120 seconds or less. If the average residence time during melt-kneading is 10 seconds or longer, the desired polyamide resin composition of the present embodiment tends to be obtained more efficiently. Further, by setting the average residence time during melt-kneading to 120 seconds or less, the extrusion discharge rate (production rate) tends to increase to some extent. As a result, the productivity of the polyamide resin composition tends to be good. From the above viewpoint, the average residence time during melt-kneading is more preferably 20 seconds or more and 100 seconds or less, still more preferably 25 seconds or more and 90 seconds or less, and still more preferably 30 seconds or more and 80 seconds or less. Yes, and particularly preferably from 35 seconds to 70 seconds.

  The average residence time means the residence time when the residence time in the melt-kneading apparatus is constant, and means the average value of the shortest residence time and the longest residence time when the residence time is not uniform. . Resin that can be distinguished from the raw material (A) polyamide resin used in the present embodiment, such as a resin having a different color from the raw material (A) polyamide resin used in the present embodiment, such as a colorant masterbatch during melt-kneading (hereinafter referred to as the following) X is also abbreviated as X), the discharge start time and discharge end time in the darkest state of X are measured, and the discharge start time and discharge end time are averaged to obtain the average residence time. Can be measured.

  In addition, the said average residence time can be suitably adjusted with the discharge amount (discharge speed) and rotation speed of an extruder.

  The polyamide resin composition obtained by the above production method can efficiently increase the molecular weight of the polyamide resin while ensuring the tensile strength, improve the tensile elongation, and suppress the gelation during heat retention. it can. Therefore, the polyamide resin composition of the present embodiment is a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, foam molding. There is a tendency that good molding can be performed using generally known plastic molding methods such as melt spinning.

≪Molded body≫
The molded product of the present embodiment is a molded product containing the polyamide resin composition. A molded body containing such a polyamide resin composition is excellent in impact resistance and hydrolysis resistance. Therefore, the molded body of this embodiment is expected to be applied to various parts such as automobile parts, electronic / electric parts, industrial machine parts, various gears, and extrusion applications.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited only to these Examples. In addition, the raw material and evaluation method which are used for a present Example are as follows.

[raw materials]
(A) Polyamide resin (produced in the following production example)
PA66-1 (PAN pellets with VN: 141 mL / g, moisture content: 0.08 wt%, [COOH]-[NH ₂ ] = 37 meq / kg).
PA66-2 (VN: 144 mL / g, moisture content: 0.08 mass%, [COOH]-[NH ₂ ] = PA66 pellet with end correction with 13 meq / kg).
PA66-3 (VN: 142mL / g, water content: 0.08 wt%, [COOH] - [NH 2] = - 26 meq / kg and a terminal correcting PA66 pellets went).
PA66-4 (PAN pellets with VN: 141 mL / g, moisture content: 0.08 mass%, [COOH]-[NH ₂ ] = − 33 meq / kg).
PA66-5 (high molecular weight PA66 pellet with VN: 257 mL / g, moisture content: 0.03% by mass, [COOH]-[NH ₂ ] = 35 meq / kg).

(B) Reinforcing material GF (product name: ECS03T275H, manufactured by Nippon Electric Glass, average fiber diameter (average particle diameter): 10 μm (circular shape), cut length: 3 mm glass fiber).

(C) Phosphoric acid compound Phosphoric acid (trade name: phosphoric acid, 85% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.).
PHS (a salt powder of phosphoric acid and hexamethylenediamine produced in the following production example).
SHP (trade name: sodium phosphinate (also known as sodium hypophosphite) manufactured by Wako Pure Chemical Industries, Ltd.).

(D) Amine component NH2-P (number average molecular weight (Mn) produced in the following production example: amino group terminal rich PA prepolymer (oligomer) of 1400 (NH2 prepolymer (oligomer)))

〔Evaluation method〕
(1) Viscosity number <1-1> Viscosity number: VN (mL / g)
The viscosity number was measured according to ISO307 (JIS-K6933) using the pellets of the polyamide resin composition produced in Examples and Comparative Examples described later.
<1-2> Formic acid relative viscosity (RV)
Formic acid relative viscosity (RV) was obtained by comparing the viscosity of a solution obtained by adding a polymer to formic acid and the viscosity of formic acid itself, using pellets of polyamide resin compositions produced in Examples and Comparative Examples described later. . About the concrete measuring method, it shall implement based on ASTM-D789. More specifically, an RV value measured at 25 ° C. using a solution obtained by dissolving polyamide in 8.4% in 90% formic acid (10% water) was adopted.

(2) Measurement of moisture content (% by mass)
Using the pellets of the polyamide resin composition produced in the examples and comparative examples described later, a Karl Fischer moisture meter (coulometric titration method trace moisture measuring device CA-200 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.) is used in a method based on ISO 15512. Using, the moisture content (mass%) was measured.

(3) End group determination [COOH]-[NH ₂ ] (milli equivalent / kg)
The carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin in the polyamide resin composition produced in Examples and Comparative Examples described later are obtained as follows using a JEOL-ESCA500 as a measuring device. It was.
First, from ¹ H-NMR (sulfuric acid-d2 solvent), the amount of each terminal group present in 1 kg of polyamide resin was calculated as follows.
Carboxyl group terminal amount: It was calculated by an integral value of a peak (a ′) of 2.724 ppm related to hydrogen of the methylene group (—CH ₂ —) adjacent to the terminal COOH.
Amino group terminal amount: It was calculated by an integral value of a peak (b ′) near 2.884 ppm related to hydrogen of a methylene group (—CH ₂ —) adjacent to the terminal NH ₂ .
The amount of dicarboxylic acid unit in the polyamide resin main chain was calculated as the integral value of the peak (a) at 2.451 ppm related to hydrogen of the methylene group (—CH ₂ —) adjacent to the amide group.
Amount of diamic acid unit in the polyamide resin main chain: calculated with an integral value of a peak (b) of 3.254 ppm related to hydrogen of a methylene group (—CH ₂ —) adjacent to the amide group.
Next, the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] are calculated from the following formula using the integrated value of the above peak, and the difference between the terminal concentrations ([COOH] − [NH ₂ ]) (Milli equivalent / kg) was obtained by calculation.
Carboxyl group terminal concentration [COOH] (milli equivalent / kg) = (a ′ / 2) / [{(b + b ′) × 114.2 / 4} + {(a + a ′) × 112.1 / 4}]
Amino group terminal concentration [NH ₂ ] (milli equivalent / kg) = ( _b ′ / ₂ ) / [{(b + b ′) × 114.2 / 4} + {(a + a ′) × 112.1 / 4}]

(4) Phosphorus concentration [P] (mass ppm)
The polyamide resin composition 0.5g manufactured by the Example and comparative example which are mentioned later was weighed, 20 ml of concentrated sulfuric acid was added, and it wet-decomposed on the heater. The solution after decomposition was cooled, added with 5 ml of hydrogen peroxide, heated on a heater, and concentrated to a total volume of 2 to 3 ml. The concentrated solution was cooled again and purified water was added to make 500 ml. The obtained aqueous solution is subjected to high-frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by Thermo Jarrel Ash as a measuring device, thereby quantifying the phosphorus concentration [P] at a wavelength of 213.618 (nm). did.

(5) Pellet color tone (b value)
The pellets of the polyamide resin composition produced in Examples and Comparative Examples described later were measured with a color difference meter ND-300A manufactured by Nippon Denshoku Industries Co., Ltd., and the color tone of the pellets was determined based on the b value obtained by the measurement. As the b value is-(negative) and the absolute value is large, the color tone is better without being colored yellow, and when the absolute value is + (positive) and the absolute value is larger, the color is yellow and is not preferable as the color tone. Indicates.

(6) Tensile strength (MPa) and tensile elongation (%)
Small tensile test pieces (type CP13) (3 mm thickness) were prepared from pellets of polyamide resin compositions produced in Examples and Comparative Examples described later, using an injection molding apparatus, in accordance with JIS-K7139. Using a PS40E manufactured by Nissei Plastic Industry Co., Ltd. as an injection molding apparatus, the above-mentioned two-piece mold was attached to the injection molding apparatus. The cylinder temperature was set to the melting point of the polyamide resin + about 15 ° C. (for example, 280 ° C. for PA66), and the mold temperature was set to 80 ° C. Further, the injection molding conditions were injection: 10 seconds, cooling: 7 seconds, and plasticization amount: 30 mm (cushion amount: about 10 mm).
The tensile strength and tensile elongation of the molded body (small tensile test piece (type CP13) (3 mm thickness)) obtained here were measured. Here, the distance between the chucks was 30 mm, and the tensile speed was 50 mm / min (non-strengthened) or 5 mm / min (strengthened). The tensile elongation was calculated by the ratio of the elongation (displacement) at break to the distance between chucks.

(7) Charpy impact strength (kJ / m ² )
A multipurpose test piece (4 mm thickness) was produced from pellets of the polyamide resin composition produced in Examples and Comparative Examples described later using an injection molding machine in accordance with ISO 3167. Using a PS40E manufactured by Nissei Plastic Industry Co., Ltd. as an injection molding apparatus, the above-mentioned two-piece mold was attached to the injection molding apparatus. The cylinder temperature was set to the melting point of the polyamide resin + about 25 ° C. (for example, 290 ° C. for PA66), and the mold temperature was set to 80 ° C. Furthermore, the injection molding conditions were injection: 25 seconds, cooling: 15 seconds, and plasticization amount: 90 mm (cushion amount: about 10 mm).
Using the molded body (multipurpose test piece (4 mm thickness)) obtained here, the Charpy impact strength with a notch was measured according to ISO-179.

(8) Hydrolysis resistance Small tensile test piece prepared in (6) above (type CP13) while heating 50% aqueous solution of antifreeze (Toyota genuine long life coolant) mainly composed of ethylene glycol to 130 ° C (3 mm thickness) was immersed in an autoclave for 500 hours. After the immersion, the tensile strength (MPa) of the small tensile test piece was measured in the same manner as (6) above. The higher the measured value, the better the hydrolysis resistance.

(9) Coloration by mixing with CuI / KI Potassium iodide (KI): 85% by weight, copper iodide (CuI): 5% by weight, calcium montanate: 10% by weight, after stirring, Granules were created. Pellet-like polyamide resin 66 (PA66-1 below): 70% by weight and granulated granules of potassium iodide / copper iodide / calcium montanate: 30% by weight were mixed in a tumbler type blender. The obtained mixture was melt-kneaded by a twin screw extruder to obtain polyamide resin master batch pellets.
The polyamide resin composition pellets produced in Examples and Comparative Examples described later and this master batch pellet were blended at a mass ratio (pellets obtained in each example: master batch pellet) at 98: 2, and obtained. Molding was performed in the same manner as in (6) above using the mixture.
At this time, the presence or absence of purple discoloration (coloring) was confirmed for the molded body.
○: No discoloration to purple was confirmed.
X: Discoloration to purple was confirmed.

[Production of polyamide resin (PA66-1)]
30 kg of a 50% aqueous solution of an equivalent salt of hexamethylenediamine and adipic acid was charged into a 40 L autoclave, kept at 50 ° C. so that the monomer would not precipitate, and stirred well. After sufficiently substituting the inside of the autoclave with nitrogen, the temperature inside the autoclave was raised from about 50 ° C. to about 160 ° C. At this time, in order to maintain the pressure in the autoclave at a gauge pressure of about 0.25 MPa, the aqueous solution was continuously heated while removing water out of the system, and the aqueous solution was concentrated to about 75%. After that, once removal of water is stopped, the temperature in the autoclave is raised to about 220 ° C., and when the pressure in the autoclave reaches about 1.8 MPa, water is again added so as to keep the pressure in the autoclave constant. The aqueous solution continued to be heated while being removed. Then, after the temperature in the autoclave rose to 260 ° C., the pressure in the autoclave was slowly reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) while continuing to heat the aqueous solution and finally applying for about 60 minutes. The pressure in the autoclave was maintained at atmospheric pressure for 30 minutes, and the temperature in the autoclave was finally raised to about 273 ° C. to obtain a polyamide resin (PA66-1). Thereafter, the inside of the autoclave was pressurized with nitrogen, the strand-like polyamide resin (PA66-1) was discharged from the lower nozzle, water-cooled and cut to obtain a pellet-like polyamide resin (PA66-1).
The moisture content in the pellet-like polyamide resin (PA66-1) was 0.08% by mass.
Further, in the obtained polyamide resin (PA66-1), the viscosity number (VN) is 141, the carboxyl group terminal concentration [COOH] is 84 meq / kg, and the amino group terminal concentration [NH ₂ ] is 47. a meq / kg, the difference between the respective ends concentration _{([COOH] - [NH 2} ]) was 37 meq / kg.

[Production of Polyamide Resin (PA66-2) with Terminal Correction]
Pellet-like polyamide resin (PA66- 2) was obtained.
The moisture content in the pellet-like polyamide resin (PA66-2) was 0.08% by mass.
Moreover, in the obtained polyamide resin (PA66-2), the viscosity number (VN) is 144, the carboxyl group terminal concentration [COOH] is 72 meq / kg, and the amino group terminal concentration [NH ₂ ] is 59. The difference in concentration at each end ([COOH]-[NH ₂ ]) was 13 meq / kg.

[Production of Polyamide Resin (PA66-3) with Terminal Correction]
A pellet-like polyamide resin (PA66-) was prepared in the same manner as in the preparation of PA66-1, except that 55.8 g of hexamethylenediamine was added for terminal correction to 30 kg of a 50% aqueous solution of an equivalent salt of hexamethylenediamine and adipic acid. 3) was obtained.
The moisture content in the pellet-like polyamide resin (PA66-3) was 0.08% by mass.
Further, in the obtained polyamide resin (PA66-3), the viscosity number (VN) is 142, the carboxyl group terminal concentration [COOH] is 52 meq / kg, and the amino group terminal concentration [NH ₂ ] is 78. a meq / kg, the difference between the respective ends concentration _{([COOH] - [NH 2} ]) was -26 meq / kg.

[Production of Polyamide Resin (PA66-4) with Terminal Correction]
Pellet-like polyamide resin (PA66- 4) was obtained.
The moisture content in the pellet-like polyamide resin (PA66-4) was 0.08% by mass.
Further, in the obtained polyamide resin (PA66-4), the viscosity number (VN) is 141, the carboxyl group terminal concentration [COOH] is 49 meq / kg, and the amino group terminal concentration [NH ₂ ] is 82. The difference in concentration at each end ([COOH]-[NH ₂ ]) was -33 meq / kg.

[Production of high molecular weight polyamide resin (PA66-5)]
10 kg of the PA66-1 pellets were put into a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen. While the nitrogen was flowing at 1 L / min in the vacuum dryer, the PA66-1 pellets were heated at a temperature of 204 ° C. for 6 hours with stirring. Thereafter, the temperature was lowered while nitrogen was passed through the vacuum dryer, and the pellets were taken out from the vacuum dryer when the temperature reached about 50 ° C. to obtain a high molecular weight polyamide resin (PA66-5).
The moisture content in the pellets of the high molecular weight polyamide resin (PA66-5) was 0.03% by mass.
Further, in the obtained polyamide resin (PA66-5), the viscosity number (VN) is 257, the carboxyl group terminal concentration [COOH] is 53 meq / kg, and the amino group terminal concentration [NH ₂ ] is 18 a meq / kg, the difference between the respective ends concentration _{([COOH] - [NH 2} ]) was 35 meq / kg.

[Production of amino group-terminated rich PA prepolymer (oligomer) (NH2-P)]
30 g of hexamethylene diamine was added to 2000 g of a 50% aqueous solution of an equivalent salt of hexamethylene diamine and adipic acid to obtain a mixed solution. The obtained mixed solution was placed in a 5 L autoclave, kept at 50 ° C. so as not to precipitate the monomer, and stirred well. After sufficiently substituting the inside of the autoclave with nitrogen, the temperature inside the autoclave was raised from about 50 ° C. to about 160 ° C. At this time, in order to maintain the pressure in the autoclave at a gauge pressure of about 0.25 MPa, the mixed solution was continuously heated while removing water out of the system and concentrated to about 75%. Thereafter, removal of water was once stopped, and the temperature in the autoclave was raised to about 220 ° C. Then, when the pressure in the autoclave reached about 1.8 MPa, heating of the mixed solution was stopped, and then the temperature in the autoclave was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 880 g of a prepolymer (oligomer) lump was taken out and pulverized to a pellet size (about 3 to 5 mm). Water was removed from the obtained prepolymer of polyamide resin (PA) by drying. The moisture content in this pulverized product (polyamide resin (PA) prepolymer) was 0.04% by mass.
Moreover, the molecular weight measurement by GPC was performed about the prepolymer of the obtained polyamide resin (PA). In the prepolymer of the obtained polyamide resin (PA), the number average molecular weight (Mn) was 1400, and the weight average molecular weight (Mw) was 2900. In the prepolymer of the obtained polyamide resin (PA), the carboxyl group terminal concentration [COOH] is 460 meq / kg, the amino group terminal concentration [NH ₂ ] is 970 meq / kg, difference in density _{([COOH] - [NH 2} ]) was -510 meq / kg.

[Salt of phosphoric acid and hexamethylenediamine (PHS)]
In a 10 L reaction vessel, 5 L of methanol and 502 g of hexamethylenediamine were added and stirred to obtain a uniform solution. To the solution, 498 g of phosphoric acid was dropped and reacted. Thereafter, the solvent methanol was removed from the solution by filtration, and the residue was taken out. The obtained filtrate was dried and pulverized to obtain a powder (PHS) of a salt of phosphoric acid and hexamethylenediamine (molar ratio 1: 1).

[Comparative Example 1]
As a production apparatus for the polyamide resin composition, a twin-screw extruder (ZSK25 manufactured by COPERION) shown in FIG. 1 was used. The twin-screw extruder has one top supply port (hereinafter abbreviated as top-F) on the first barrel upper surface (top position) from the upstream side of the extruder, and the first downstream supply on the sixth barrel side surface. There are two downstream supply ports, an outlet (hereinafter abbreviated as side1) and a downstream second supply port (hereinafter abbreviated as side2) on the ninth barrel side surface, and a first decompression port ( (Hereinafter abbreviated as “vent1”), a second decompression port (hereinafter abbreviated as “vent2”) on the top surface of the eighth barrel, and a third decompression port (hereinafter abbreviated as “vent3”) on the top surface of the eleventh barrel. It was. In the twin-screw extruder, vent1 and side2 were plugged with plugs and were not used. Further, in the twin-screw extruder, the reverse rotation kneading disk is set such that the seventh and eighth barrels corresponding to vent2 and the tenth, eleventh and twelfth barrels corresponding to vent3 are used as the devolatilization region. It was made possible to seal the front and back of each devolatilization area with a screw incorporating the above.
A blend obtained by adding 0.115 parts by mass of 85% aqueous phosphoric acid to 100 parts by mass of PA66-1 obtained in the above production example, that is, phosphoric acid: 0.098 parts by mass (10 mmol / kg) in advance. PA66-1 pellets: A blend with 100 parts by mass was prepared.
In the twin-screw extruder, the prepared blend of PA66-1 and phosphoric acid is supplied from top-F so that the GF from side1 is 33 parts by mass with respect to 100 parts by mass of PA66-1: 100 parts by mass. Then, melt kneading was performed at a screw rotation speed of 300 rpm, a cylinder temperature of 300 ° C., an extrusion rate of 20 kg / hr, and a degree of vacuum of vent 2 and vent 3 of 0.085 MPa. At this time, the resin temperature near the tip nozzle was 345 ° C., and the average residence time was 55 seconds. Under the above conditions, the polyamide resin composition in a molten state in a strand form was discharged from the tip nozzle, and water cooling and cutting were performed to obtain polyamide resin composition pellets. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 2]
A blend obtained by adding 0.115 parts by mass of 85% aqueous phosphoric acid to 100 parts by mass of PA66-1 obtained in the above production example, that is, phosphoric acid: 0.098 parts by mass (10 mmol / kg) in advance. PA66-1 pellets: Attached to 100 parts by mass, and with respect to PA66-1: 100 parts by mass, the amino group-terminal rich PA prepolymer (oligomer) (NH2-P) obtained in the above production example: 0 A blend was also added with 28 parts by weight (2 mmol / kg) added.
In the twin-screw extruder, instead of top-F, instead of the blend of PA66-1 and phosphoric acid, the blend of PA66-1, the phosphoric acid, and the amino group-terminated rich PA prepolymer (oligomer) prepared above Except having supplied the thing, the pellet of the polyamide resin composition was obtained by the method similar to the comparative example 1. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 1]
A pellet of a polyamide resin composition was obtained in the same manner as in Comparative Example 2, except that the amount of the amino group-terminated rich PA prepolymer (oligomer) (NH2-P) was changed to 0.70 parts by mass (5 mmol / kg). It was. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 2]
A pellet of a polyamide resin composition was obtained in the same manner as in Comparative Example 2 except that the amount of the amino group-terminated rich PA prepolymer (oligomer) (NH2-P) was changed to 1.40 parts by mass (10 mmol / kg). It was. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 3]
A pellet of the polyamide resin composition was obtained in the same manner as in Comparative Example 2, except that the amount of the amino group-terminated rich PA prepolymer (oligomer) (NH2-P) was changed to 2.80 parts by mass (20 mmol / kg). It was. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 4]
PA66-1 obtained in the above Production Example: 100 parts by mass, PHS obtained in the above Production Example: 0.214 parts by mass (10 mmol / kg) was added in advance, and PA66-1 pellets and PHS A blend of was prepared.
In the twin-screw extruder, the same as Comparative Example 1 except that the prepared blend of PA66-1 and PHS was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. Thus, a pellet of the polyamide resin composition was obtained. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 5]
In the twin-screw extruder, the same method as in Comparative Example 1 except that only the PA66-2 obtained in the above Production Example was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. The pellet of the polyamide resin composition was obtained.
Next, 10 kg of the obtained polyamide resin composition pellets were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen. In a vacuum dryer, the polyamide resin composition pellets were heated at 210 ° C. for 2 hours with stirring, while flowing nitrogen at 1 L / min, to carry out solid phase polymerization of the polyamide resin. Thereafter, in a vacuum dryer, the temperature is lowered while flowing nitrogen, and when the temperature reaches about 50 ° C., the pellet is taken out from the vacuum dryer as it is to obtain a polyamide resin composition having a high molecular weight polyamide resin by solid phase polymerization. It was.
About polyamide resin composition in which polyamide resin is made high molecular weight by solid phase polymerization, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength And tensile elongation, Charpy impact strength, hydrolysis resistance, and the presence or absence of coloring due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Example 6]
In the twin-screw extruder, the same method as in Comparative Example 1 except that only the PA66-3 obtained in the above production example was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. The pellet of the polyamide resin composition was obtained. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
Next, 10 kg of the obtained polyamide resin composition pellets were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen. In a vacuum dryer, the polyamide resin composition pellets were heated at 210 ° C. for 2 hours with stirring, while flowing nitrogen at 1 L / min, to carry out solid phase polymerization of the polyamide resin. Thereafter, in a vacuum dryer, the temperature is lowered while flowing nitrogen, and when the temperature reaches about 50 ° C., the pellet is taken out from the vacuum dryer as it is to obtain a polyamide resin composition having a high molecular weight polyamide resin by solid phase polymerization. It was.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 3]
In the twin-screw extruder, the same method as in Comparative Example 1 except that only the PA66-4 obtained in the above production example was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. The pellet of the polyamide resin composition was obtained. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
Next, 10 kg of the obtained polyamide resin composition pellets were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen. In a vacuum dryer, the polyamide resin composition pellets were heated at 210 ° C. for 2 hours with stirring, while flowing nitrogen at 1 L / min, to carry out solid phase polymerization of the polyamide resin. Thereafter, in a vacuum dryer, the temperature is lowered while flowing nitrogen, and when the temperature reaches about 50 ° C., the pellet is taken out from the vacuum dryer as it is to obtain a polyamide resin composition having a high molecular weight polyamide resin by solid phase polymerization. It was.
About polyamide resin composition in which polyamide resin is made high molecular weight by solid phase polymerization, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength And tensile elongation, Charpy impact strength, hydrolysis resistance, and the presence or absence of coloring due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 4]
PA66-1 obtained in the above Production Example: 100 parts by mass of SHP: 0.106 parts by mass (10 mmol / kg) and amino group-terminal rich PA prepolymer (oligomer) obtained in the above Production Example (NH 2 -P): 1.40 parts by mass (10 mmol / kg) was added in advance to prepare a blend of PA66-1 pellets, SHP, and amino group-terminated PA prepolymer (oligomer).
In the twin-screw extruder, instead of the top-F blend of PA66-1 and phosphoric acid, the blend of PA66-1, SHP, and amino group-terminated rich PA prepolymer (oligomer) prepared above A pellet of the polyamide resin composition was obtained in the same manner as in Comparative Example 1 except that was supplied. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 5]
SHP: 0.106 parts by mass (10 mmol / kg) was added in advance to 100 parts by mass of PA66-1 obtained in the above production example to prepare a blend of PA66 pellet-1 and SHP.
In the twin-screw extruder, the same as Comparative Example 1 except that the prepared blend of PA66-1 and SHP was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. Thus, a pellet of the polyamide resin composition was obtained. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 6]
In the twin-screw extruder, the same method as in Comparative Example 1 except that only PA66-1 obtained in the above production example was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. The pellet of the polyamide resin composition was obtained.
Next, 10 kg of the obtained polyamide resin composition pellets were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen. In a vacuum dryer, the polyamide resin composition pellets were heated for 2.5 hours at 210 ° C. with stirring while flowing nitrogen at 1 L / min for solid phase polymerization of the polyamide resin. Thereafter, in a vacuum dryer, the temperature is lowered while flowing nitrogen, and when the temperature reaches about 50 ° C., the pellet is taken out from the vacuum dryer as it is to obtain a polyamide resin composition having a high molecular weight polyamide resin by solid phase polymerization. It was.
About polyamide resin composition in which polyamide resin is made high molecular weight by solid phase polymerization, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength And tensile elongation, Charpy impact strength, hydrolysis resistance, and the presence or absence of coloring due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

[Comparative Example 7]
In the twin-screw extruder, the same method as in Comparative Example 1 except that only the PA66-5 obtained in the above production example was supplied from top-F instead of the blend of PA66-1 and phosphoric acid. The pellet of the polyamide resin composition was obtained. Then, the obtained pellet was dried and the moisture content in a pellet was adjusted.
About the obtained polyamide resin composition, viscosity number (VN), moisture measurement, terminal group determination [COOH]-[NH ₂ ], phosphorus concentration, pellet color tone (b value), tensile strength and tensile elongation, Charpy impact strength , Hydrolysis resistance, and coloration due to mixing with CuI / KI were evaluated. The evaluation results are shown in Table 1.

  According to the present invention, a polyamide resin composition having improved tensile strength, tensile elongation, and Charpy impact and improved hydrolysis resistance can be obtained. The polyamide resin composition of the present invention has industrial applicability in fields such as automobile parts, electronic and electrical parts, industrial machine parts, various gears, and extrusion applications.

Claims (12)

Containing 100 parts by weight of polyamide resin and 10 to 250 parts by weight of (B) reinforcing material,
The difference ([COOH] − [NH ₂ ]) between the carboxyl group terminal concentration [COOH] and the amino group terminal concentration [NH ₂ ] in the polyamide resin is −25 to 25 meq / kg,
A polyamide resin composition having a viscosity number [VN] of 160 mL / g or more. The difference of the carboxyl group end concentration [COOH] and the amino group terminal concentration [NH _2] of the polyamide resin _{([COOH] - [NH 2} ]) is 0 to 25 meq / kg, according to claim 1 Polyamide resin composition.   The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin comprises a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid.   The polyamide resin composition according to any one of claims 1 to 3, wherein the polyamide resin contains 50% by mass or more of a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid.   The polyamide resin composition according to any one of claims 1 to 4, wherein the polyamide resin is a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid. Furthermore, (C) a phosphoric acid compound is contained,
The polyamide resin composition according to any one of claims 1 to 5, wherein the phosphorus concentration [P] is 1 to 5000 ppm by mass.   The polyamide resin composition according to claim 6, wherein the phosphoric acid compound (C) is at least one selected from the group consisting of orthophosphoric acid, pyrophosphoric acid and metaphosphoric acid.   The polyamide resin composition according to any one of claims 1 to 7, further comprising (D) an amine component. The polyamide resin composition according to claim 8, wherein the (D) amine component is a polyamide resin prepolymer and / or a diamine having an amino group terminal concentration [NH ₂ ] higher than a carboxyl group terminal concentration [COOH]. The polyamide resin composition according to claim 8, wherein the amine component (D) is a polyamide resin prepolymer having an amino group terminal concentration [NH ₂ ] higher than a carboxyl group terminal concentration [COOH].   The polyamide resin composition according to claim 8, wherein the (D) amine component is a diamine.   The molded object containing the polyamide resin composition as described in any one of Claims 1-11.