JP6505530B2 - Polyamide resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a polyamide resin composition and a method for producing the same.

Polyamide resins are known as engineering plastics, and materials for various parts such as general-purpose consumption fields such as packaging and containers, automotive fields, electric and electronic fields, machinery and industrial fields, office equipment fields, and aerospace and space fields As widely used.
In recent years, with regard to these various parts, there has been a great increase in demand for replacing metal materials with polyamide resins for the purpose of integral molding, weight reduction, and the like.
In addition, there is an increasing demand for further enhancing the toughness, impact resistance and durability.
As a result, the performance levels required for polyamide resins are becoming even higher.

Specifically, there is a strong demand for a polyamide resin material which has high strength which can be substituted for metal materials and which is excellent in toughness, impact resistance and durability.
Increasing the molecular weight of polyamide resin is one of the methods to meet these demands.

As a method of increasing the molecular weight of the polyamide resin, a method of solid-phase polymerizing a polyamide resin after melt polymerization is known.
On the other hand, in order to obtain a desired high molecular weight polyamide resin by solid phase polymerization, a large amount of solid phase polymerization time and heat energy are required. Moreover, in order to ensure the quality of the polyamide resin such as color tone, a process under nitrogen flow or under reduced pressure is required. As described above, since the solid phase polymerization method is complicated in process and requires a long time, a method of obtaining a polyamide having a high molecular weight in a simpler and shorter time is required.

  As a method of polymerizing polyamide resin in a short time, adding a polymerizing catalyst such as sodium hypophosphite to the polyamide resin and polymerizing the catalyst by melt kneading under conditions of reduced pressure with an extruder Methods of extrusion are known (see, for example, Patent Document 1).

JP, 2011-26396, A

  However, although the technology disclosed in Patent Document 1 can achieve high molecular weight formation of polyamide resin to some extent by sodium hypophosphite catalyst, further high molecular weight formation is required while maintaining characteristics sufficient for practical use. And in the case where it is desired to reduce the amount of catalyst, there is a problem that it can not be sufficiently addressed. Therefore, there is a demand for a catalyst having a further high molecular weight formation ability.

  Then, in this invention, it aims at providing the high molecular weight polyamide resin composition which is excellent in the plasticity at the time of injection molding, maintaining high Charpy impact strength.

As a result of intensive studies to solve the problems of the prior art described above, the present inventors added (B) triaryl phosphite as a phosphorus element at a predetermined content to 100 parts by mass of (A) polyamide resin. It is a polyamide resin composition formed by melting and kneading, and the above-mentioned problems can be solved by setting the viscosity number (VN) of the polyamide resin component in the polyamide resin composition to a predetermined value or more. The present invention has been completed.
That is, the present invention is as follows.

[1]
(A) A polyamide resin composition obtained by adding and melting 0.0062 to 0.31 parts by mass of triaryl phosphite as a phosphorus element with respect to 100 parts by mass of a polyamide resin,
(B) triaryl phosphite is triphenyl phosphite,
The viscosity number (VN) of the polyamide resin component in the polyamide resin composition is 160 mL / g
The polyamide resin composition which is the above.
[2]
Further, (C) a carboxylic acid compound was added in an amount of 0.
The polyamide resin composition as described in said [1] which adds a 0.5-0.3 mass part.
[3]
The polyamide resin composition according to the above [2], wherein the (C) carboxylic acid compound is a metal salt of a monocarboxylic acid having 10 or more carbon atoms.
[4]
The polyamide resin composition according to any one of the above [1] to [3], wherein the polyamide resin component in the polyamide resin composition comprises a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid.
[5]
[1] to [4], wherein the polyamide resin component in the polyamide resin composition contains 50% by mass or more of a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid
The polyamide resin composition as described in any one of the above.
[6]
The polyamide resin composition according to any one of the above [1] to [5], wherein the polyamide resin component in the polyamide resin composition is a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid.
[7]
The polyamide resin composition according to any one of the above [4] to [6], wherein the diamine and dicarboxylic acid are linear aliphatic diamine and linear aliphatic dicarboxylic acid having no branched structure or cyclic structure, respectively. object.
[8]
The ratio of the total number N (ar) of aryl groups of the triaryl phosphite (B) to the total number N (al) of alkyl substituents on the aryl group: N (al) / N (ar) is 0 , The polyamide resin composition as described in any one of 1] to [7].
[9]
With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition, (D
The polyamide resin composition according to any one of the above [1] to [8] , which further comprises 10 to 250 parts by mass of a reinforcing material.
[10]
With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is preferably 0.0062 to 0. 0 as a phosphorus element.
The polyamide resin composition according to any one of the above [1] to [9] , which is 31 parts by mass.
[11]
With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is 0.0093-0.
The polyamide resin composition according to any one of the above [1] to [10] , which is contained in 15 parts by mass.
[12]
With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is 0.012 to 0.0 as a phosphorus element
The polyamide resin composition according to any one of the above [1] to [11] , which is contained in 93 parts by mass.
[13]
It is a manufacturing method of the polyamide resin composition as described in any one of said [1] thru | or [12] ,
(A) A polyamide having a step of adding triphenyl phosphite as a triaryl phosphite (B) as triaryl phosphite to a mass of 100 parts by mass of the polyamide resin (0.0062 to 0.31 parts by mass as a phosphorus element) and melt-kneading Method for producing a resin composition.
[14]
The manufacturing method of the polyamide resin composition as described in said [13] whose viscosity number of said (A) polyamide resin is less than 160 mL / g.
[15]
The ratio N (al) / N (ar) of the total number N (ar) of aryl groups of the triaryl phosphite (B) to the total number N (al) of alkyl substituents on the aryl group is 0 , The manufacturing method of the polyamide resin composition as described in said [13] or [14] .

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular weight polyamide resin composition which is excellent in the plasticity at the time of injection molding can be provided, maintaining high Charpy impact strength.

Hereinafter, modes for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail.
The following present embodiment is an example for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist of the present invention.

[Polyamide resin composition]
In the polyamide resin composition of the present embodiment, 0.0062 to 0.31 parts by mass of (B) triaryl phosphite as a phosphorus element is added to 100 parts by mass of (A) polyamide resin, and melt-kneaded The viscosity number (VN) of the polyamide resin component in the polyamide resin composition is 160 mL / g or more.

((A) Polyamide resin)
In the present embodiment, the "polyamide resin" means a polyamide resin which is a polymer having an amide bond (-NHCO-) in the main chain.
Examples of the polyamide resin include, but are not limited to, polyamide resins obtained by condensation polymerization of diamine and dicarboxylic acid, polyamide resins obtained by ring-opening polymerization of lactam, self-condensation of aminocarboxylic acid The polyamide resin and the copolymer obtained by the copolymerization of two or more types of monomers which comprise these polyamide resin are mentioned.
One of these polyamide resins may be used alone, or two or more thereof may be used in combination.

  Hereinafter, the raw material of a polyamide resin is demonstrated.

  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, for example. Straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as diamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine and the like; for example, 2-methylpentamethylenediamine (2-methyl-1, 2-, 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. As this branched saturated aliphatic diamine, the diamine which has the substituent branched from the principal chain is mentioned.

  The above-mentioned alicyclic diamine (also described as alicyclic diamine) is not limited to the following, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclo A pentane diamine etc. are mentioned.

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

  Among the above diamines, in particular, one having no branched structure or ring structure which causes steric hindrance in the polymerization condensation reaction in the vicinity of the amino group which is a reactive functional group can achieve higher molecular weight, and thus a linear saturated aliphatic Diamines are preferred.

  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, and 2,2- Diethyl succinic acid, 2,3-diethyl glutaric acid, glutaric acid, 2,2- dimethyl glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane 2 Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acids, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosane diacid, diglycolic acid and the like.

The above-mentioned alicyclic dicarboxylic acid is not limited to the following, but, for example, an alicyclic group such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and the like Carboxylic acid is mentioned.
The carbon number of the alicyclic structure of the alicyclic carboxylic acid is not particularly limited, but is preferably 3 to 10, more preferably 5 to 10, from the viewpoint of the balance between the water absorbability and the degree of crystallization of the resulting polyamide resin. It is.
From the viewpoint of mechanical properties, 1,4-cyclohexanedicarboxylic acid is preferred as the alicyclic dicarboxylic acid.

  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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like And alkyl groups of the following.

Although it does not limit as said aromatic dicarboxylic acid below, For example, C8-C20 aromatic dicarboxylic acid etc. which are unsubstituted or substituted by the substituent are mentioned.
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 the like, and groups which are halogen salts such as C.sub.10-C.sub.10 alkylsilyl groups, sulfonic acid groups, and salts thereof such as sodium salts.
Examples of aromatic dicarboxylic acids include, but are not limited to, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium Sulfoisophthalic acid and the like can be mentioned.

  The dicarboxylic acid may contain 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. One of these may be used alone, or two or more may be used in combination.

  Among the above-mentioned dicarboxylic acids, in particular, one having no branched structure or ring structure which causes steric hindrance in the polymerization condensation reaction in the vicinity of the carboxyl group which is a reactive functional group can achieve higher molecular weight, Family dicarboxylic acids are preferred.

  Examples of the lactam include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, 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 in which the above-described lactam is ring-opened (ω-aminocarboxylic acid, α, ω-aminocarboxylic acid, etc.), and the like.

The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms, which is substituted at the ω-position with an amino group, from the viewpoint of increasing the degree of crystallinity of the polyamide resin. Examples of aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 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 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), polyamide 12 (poly dodecane amide), for example. , Polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene) Methylene dodecamide), polyamide 116 (polyundecamethylene adipamide), polyamide 92 (polynona methylene oxamide), polyamide TMHT (polytrimethylhexamethylene terephthalamide), polyamide 6T (polyhexamethylene terephamide) Luamide), polyamide 2 Me-5 T (poly 2-methylpentamethylene terephthalamide), polyamide 9 T (poly nona methylene terephthalamide), 2 Me-8 T (poly 2-methyl octamethylene terephthalamide), polyamide 6 I (polyhexamethylene isophthalamide) ), Polyamide 6C (polyhexamethylenecyclohexanedicarboxamide), polyamide 2Me-5C (poly 2-methylpentamethylenecyclohexanedicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly 2-methyloctamethylene) Cyclohexanedicarboxamide), polyamide PACM 12 (polybis (4-aminocyclohexyl) methan dodecamide), polyamide dimethyl PACM 12 (polyvinyl diamide) (3-Methyl-aminocyclohexyl) methandodecamide, polyamide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (polyundecamethylene terephthalamide), polyamide 12T (polydodeca) Examples thereof include polyamide resins such as methylene terephthalamide), polyamide 10C (polydecamethylene cyclohexane dicarboxamide), polyamide 11 C (polyundecamethylene cyclohexane dicarboxamide), and polyamide 12 C (polydodecamethylene cyclohexane dicarboxamide).

  In the polyamide resin composition of the present embodiment, the polyamide resin component in the polyamide resin composition contains a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid according to a method such as copolymerization or alloy (mixture). It is preferable from the viewpoint of heat resistance, strength and moldability to contain. More preferably, the polyamide resin component in the polyamide resin composition contains 50% by mass or more, more preferably 70% by mass or more of polyamide obtained by condensation polymerization of diamine and dicarboxylic acid. More preferably, it contains 90 mass% or more, More preferably, it contains 100 mass%.

The polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid is not limited to, for example, 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) -Methyl octamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 6C (polyhexamethylene cyclohexane dicarboxamide), polyamide 2Me-5C (poly 2-methylpentamethylene) Hexanehexanedicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly 2-methyloctamethylenecyclohexanedicarboxamide), polyamide 10T (polydecamethylene terephthalamide) and polyamide 10C (polydecamethylenecyclohexanediamide) Carboxamide) and the like.
These polyamide resins are preferable from the viewpoint of toughness, strength and moldability. From the same viewpoint, the (A) polyamide resin in the polyamide resin composition of the present embodiment more preferably contains polyamide 66.

  As described above, the polyamide resin may be a polyamide copolymer obtained by copolymerizing two or more types of units constituting the various polyamide resins.

  Examples of the polyamide copolymer include, but are not limited to, polyamide 66 / 6I, polyamide 66 / 6I / 6, polyamide 66 / 6T, polyamide 6T / 2Me-5T, polyamide 9T / 2Me-8T, for example. And copolymers of polyamide 6C / 2Me-5C, polyamide 9C / 2Me-8C, and the like.

  Among them, polyamide 66, polyamide 610, polyamide 66/6, polyamide 66/6 I, polyamide 6C / 2Me-5C, polyamide 2Me-5C are preferable, and polyamide 66, from the viewpoint of balance of strength, toughness and crystallinity. The polyamide 66/6 and the polyamide 66 / 6I are more preferable, and the polyamide 66 is more preferable.

When polymerizing the above-described polyamide resin monomer, an end capping agent can be further added for molecular weight control.
The end capping agent is not particularly limited, and any known end capping agent may be used.

Examples of the end capping agent include, but are not limited to, for example, acid anhydrides such as monocarboxylic acid, monoamine and phthalic anhydride, monoisocyanate, mono acid halide, monoesters, monoalcohols Etc.
Among these, monocarboxylic acids and monoamines are preferable from the viewpoint of the thermal stability of the polyamide resin.
One of these may be used alone, or two or more may be used in combination.

As a monocarboxylic acid which can be used as the end capping agent, any one having reactivity with an amino group may be used, and it is not limited to the following. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid Aliphatic monocarboxylic acids such as caproic acid, caprylic acid, lauric acid, tridecylic acid, myristyl acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, Toluic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylic acid, methyl naphthalene carboxylic acid, and aromatic monocarboxylic acids such as phenylacetic acid; and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.

The monoamine that can be used as the end capping agent may be any one having reactivity with a carboxyl group, and is not limited to the following, for example, methylamine, ethylamine, propylamine, butylamine, hexylamine, Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine It can be mentioned.
These may be used singly 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.
One of these may be used alone, or two or more may be used in combination.

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

Examples of mono acid 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 Acids, benzophenone carboxylic acids, biphenyl carboxylic acids, α-naphthalene carboxylic acids, β-naphthalene carboxylic acids, halides of mono acids such as anthracene carboxylic acids can be mentioned.
One of these may be used alone, or two or more may be used in combination.

Examples of monoesters that can be used as the end capping agent include, but are not limited to, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monomontanate, pentaerythritol monopalmitate, for example. , 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, Sorbite Over distearate montanate and the like.
One of these may be used alone, or two or more may be used in combination.

Examples of 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, tetradec, for example. Nole, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol (above, linear, branched ), Oleyl alcohol, behenyl alcohol, phenol, cresol (o-, m-, p-body), biphenol (o-, m-, p-body), 1-naphthol, 2-naphthol, etc. And the like.
One of these may be used alone, or two or more may be used in combination.

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

  The melting point of the (A) polyamide resin can be measured according to JIS-K7121. As a measuring device, for example, Diamond DSC or the like manufactured by PERKIN-ELMER can be used.

The peak temperature of the low temperature crystallization temperature measured by differential scanning calorimetry (DSC) of the polyamide resin (A) used for the polyamide resin composition of the present embodiment is not particularly limited, but is preferably 215 ° C. or more.
(A) By setting the peak temperature of the temperature-fall crystallization temperature of the polyamide resin to 215 ° C. or higher, the moldability tends to be further improved.
In addition, differential scanning calorimetry (DSC) can be performed on the conditions of a temperature increase rate of 20 degrees C / min. According to JIS-K7121.

The molecular weight of the raw material (A) polyamide resin in the polyamide resin of this embodiment and the polyamide resin component in a polyamide resin composition can be measured by various methods.
For example, molecular weight measurement by GPC (gel permeation chromatography), solution viscosity and the like can be mentioned.
Specifically, as the solution viscosity, there are a viscosity number (VN) measured in accordance with ISO 307 (JIS-K6933) and a formic acid relative viscosity (RV) measured in accordance with ASTM-D789.
As measurement according to ISO 307 (JIS-K6933), for example, it can be measured with a 0.5% by mass solution of polyamide resin in sulfuric acid of 96% concentration at 25 ° C.

  Moreover, about conversion to said different specification, the conversion table etc. which are described in ISO307 (JIS-K6933 etc. may be used suitably, for example.

  In the present specification, the viscosity number (VN) measured in accordance with the above-mentioned ISO 307 (JIS-K6933) is used as an index of the molecular weight of the polyamide resin, and it is evaluated that the higher the value of VN, the higher the molecular weight.

The viscosity number [VN] of the polyamide resin component in the polyamide resin composition in the present embodiment is
160 mL / g or more, preferably 180 mL / g or more and 340 mL / g or less, more preferably 200 mL / g or more and 325 mL / g or less, still more preferably 220 mL / g or more and 295 mL / g or less, and further more Preferably it is 235 mL / g or more and 265 mL / g or less.
When the [VN] is 160 mL / g or more, impact resistance can be improved, and by making the VN 325 or less, moldability can be improved.
The viscosity number of the polyamide resin component in the polyamide resin composition can be determined by measuring the solution viscosity of the polyamide resin composition.

In order to set the viscosity number [VN] of the polyamide resin component in the polyamide resin composition to the above range, for example, a method of appropriately adjusting the molecular weight of the raw material (A) polyamide resin may be mentioned.
As a method of 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 A catalyst of high molecular weight is added to the (A) polyamide resin of (A), and a catalyst high molecular weight extrusion method or the like which causes the raw material (A) polyamide resin to be high molecular weight by melt extrusion can be mentioned.
In particular, when an additive such as (D) reinforcing material is added to the raw material (A) polyamide resin and the polyamide resin composition is produced by melt-kneading, the raw material (A A catalyst high molecular weight extrusion method which can simultaneously carry out the mixing of additives and the high molecular weight formation of the raw material (A) polyamide resin is required in fewer steps and requires more processes than the method of increasing the molecular weight of polyamide resin It is preferable because the time is short. Moreover, since it is excellent in plasticization also at the time of melt processing, such as shaping | molding, it is preferable.

In addition, if necessary, the raw material (A) polyamide resin can be polymerized in an extruder to produce a polyamide resin composition.
In this case, the viscosity number [VN] of the (A) polyamide resin of the extrusion raw material may not be so high.
When it is desired to reduce the load on the extruder motor and increase the discharge amount to efficiently produce a polyamide resin composition, the viscosity number [VN] of the raw material (A) polyamide resin is 60 mL / g or more and 180 mL / g The following is preferable, More preferably, they are 80 mL / g or more and 170 mL / g or less, More preferably, they are 100 mL / g or more and 165 mL / g or less, Still more preferably, they are 120 mL / g or more and less than 160 mL / g.

In the case of producing a polyamide resin composition by polymerizing the raw material (A) polyamide resin in the extruder to produce a polyamide resin composition, one or more vacuum vents are used for the purpose of removing water vapor generated along with the polymerization of polyamide resin. It is preferable to use a twin-screw extruder which has, and more preferably, a twin-screw extruder having two or more vacuum vents.
The degree of vacuum in the vacuum vent is preferably 0.04 MPa or less, more preferably 0.03 MPa or less, still more preferably 0.02 MPa or less, and still more preferably 0.015 MPa or less. Preferably it is 0.01 MPa or less.

((A) Method for producing polyamide resin)
It does not specifically limit as a manufacturing method of (A) polyamide resin as a raw material in the polyamide resin composition of this embodiment, For example, various methods are employable as described below.

1) Aqueous solutions or suspensions of dicarboxylic acids and diamines, or mixtures of dicarboxylic acids and diamine salts with other components such as lactams and / or amino carboxylic acids (hereinafter referred to as "the mixtures thereof" A method of heating a suspension of an aqueous solution or water of some cases) and polymerizing the solution while maintaining the molten state (hereinafter, also referred to as a “hot melt polymerization method”);
2) A method of heating a suspension of an aqueous solution or water of a dicarboxylic acid and a diamine or a mixture thereof, and removing the precipitated prepolymer ("prepolymer method");
3) A method of raising 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 of heating a suspension of an aqueous solution or water of a dicarboxylic acid and a diamine or a mixture thereof and further melting the precipitated prepolymer again with an extruder such as a kneader to raise its polymerization degree ("prepolymer Extrusion polymerization method));
5) A method of heating a suspension of an aqueous solution or water of a dicarboxylic acid and a diamine or a mixture thereof and maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide to increase its polymerization degree (" Prepolymer / solid phase polymerization method);
6) A method of polymerizing dicarboxylic acid and 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) Method of polymerization using dicarboxylic acid halide and diamine equivalent to dicarboxylic acid ("solution method").

  In the method for producing the (A) polyamide resin as the above-mentioned raw material, a heat melting polymerization method or a prepolymer method is preferable from the viewpoint of easy production of stable molecular weight with few steps.

The polymerization form in the method for producing the (A) polyamide resin is not particularly limited, and may be, for example, a batch system or a continuous system.
The polymerization apparatus is not particularly limited, and a known apparatus (for example, an autoclave-type reactor, a tumbler-type reactor, or an extruder-type reactor such as a kneader) can also be used.

((B) Triaryl phosphite)
The polyamide resin composition of the present embodiment contains (B) triaryl phosphite (hereinafter, may be simply referred to as “component (B)” or “(B)”).
The triaryl phosphite (B) is not particularly limited, but a compound represented by the following general formula (1) can be used.

(In the formula (1), Ar ₁ , Ar ₂ and Ar ₃ each represent an aryl group.
The aryl groups Ar ₁ , Ar ₂ and Ar ₃ in the formula (1) may be identical to or different from each other. )

The carbon number of Ar ₁ , Ar ₂ and Ar ₃ is preferably 6 to 30, and more preferably 6 to 10.
Examples of the aryl group include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenanthrene ring, fluorene ring, pyrene ring, perylene ring, tetracene ring, pentaphen ring, pentacene ring, rubicene ring, etc. And aryl groups derived from
The aryl group may have a substituent. The substituent of the aryl group is not limited to the following, and examples thereof include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 5 carbon atoms. 20 (preferably 1 to 10, more preferably 1 to 5) alkoxy groups and the like can be mentioned.
The alkyl group may be linear or branched, and the carbon number thereof is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10.
The alkyl group is not limited to, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group , Neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, An octadecyl group, a nonadecyl group, an icosyl group etc. are mentioned.
The alkyl group may have a substituent. As a substituent of an alkyl group, a halogen atom and a C1-C20 (preferably 1-10, More preferably 1-5) alkoxy group is mentioned, for example.

Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aryl group which may have a substituent, preferably a phenyl group which may have a substituent, and more preferably 1 to 10 carbon atoms It is a phenyl group which may have at least one chosen from the group which consists of an alkyl group of 1. and a C1-C10 alkoxy group.
The number of substituents which the phenyl group has is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or still more preferably 0.

  (B) The triaryl phosphite is preferably triphenyl phosphite from the viewpoint that the molecular weight can be increased by a smaller amount and gas generation at the time of molding is small.

  The above (B) triaryl phosphite may be used in the solid state or in the liquid (including aqueous solution) state.

  In addition, (B) triaryl phosphite may be added as it is in the production process of the polyamide resin composition, or may be added in a diluted state such as a master batch. The masterbatch is not particularly limited, but may be pellets, granules or powders, and is preferably diluted with a polyamide resin.

In the polyamide resin composition of the present embodiment, it is also possible to sufficiently achieve high molecular weight by the step of increasing the molecular weight of the raw material (A) polyamide resin in the extruder.
In this case, Ar ₁ , Ar ₂ and Ar ₃ in the triaryl phosphite (B) are selected from the viewpoint of high reactivity for polymerizing the raw material (A) polyamide resin in the extruder. Preferably each independently a phenyl group which may have a substituent, more preferably at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms It is a phenyl group which may be possessed.
The number of substituents of the phenyl group is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and still more preferably 0.

When melt-kneading the polyamide resin composition of the present embodiment, 0.0062 to 0.31 parts by mass of (B) triaryl phosphite as a phosphorus element is added to 100 parts by mass of (A) polyamide resin It is obtained by melt-kneading.
The addition amount (parts by mass) of the component (B) as a phosphorus element can be calculated by (the amount of addition of the component (B) × atomic weight of the phosphorus element) / molecular weight of the component (B).
By adding 0.0062 to 0.31 parts by mass of (B) triaryl phosphite as a phosphorus element to (A) 100 parts by mass of the polyamide resin, separation at the time of molding of the polyamide resin composition of the present embodiment There is a tendency for the moldability and the color tone to be improved.
In addition, the mold releasability at the time of shaping | molding of a polyamide resin composition, a color tone, etc. by adding 0.0062 mass part or more of (B) triaryl phosphite as phosphorus element with respect to 100 mass parts of (A) polyamide resin. Will be better.
On the other hand, by adding 0.31 parts by mass or less of (B) triaryl phosphite as a phosphorus element to 100 parts by mass of the polyamide resin, gas is generated during melt processing such as extrusion or molding of the polyamide resin composition. Etc., and melt processability tends to be good.
From the same viewpoint as above, when melt-kneading the polyamide resin composition of the present embodiment, (B) triaryl phosphite as a phosphorus element with respect to 100 parts by mass of (A) polyamide resin is 0.0062 to 0. It is preferable to add 25 parts by mass, more preferably 0.0077 to 0.22 parts by mass, still more preferably 0.0093 to 0.15 parts by mass, and still more preferably 0.011 to 0. It is 12 parts by mass, and more preferably 0.012 to 0.093 parts by mass.

In the polyamide resin composition of the present embodiment, the phosphorus compound derived from the (B) triaryl phosphite is used as the phosphorus element at 0.0062 to 100 parts by mass of the polyamide resin component in the polyamide resin composition. The content is preferably 0.31 parts by mass, preferably 0.0093 to 0.15 parts by mass, and more preferably 0.012 to 0.093 parts by mass.
With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition, when the phosphorus compound derived from (B) triaryl phosphite is 0.0062 parts by mass or more as the phosphorus element concentration, the color tone at the time of molding is lowered. Can be suppressed, and when the amount is 0.31 parts by mass or less, gelling at the time of retention in the molding machine can be suppressed.
The phosphorus element concentration derived from the phosphorus compound derived from (B) triaryl phosphite in the polyamide resin composition is controlled by adjusting the addition amount of (B) triaryl phosphite to (A) polyamide resin can do.

The concentration (parts by mass) as the phosphorus element of the phosphorus compound derived from (B) triaryl phosphite relative to 100 parts by mass of the polyamide resin component in the polyamide resin composition can be measured by various methods.
For example, high frequency inductively coupled plasma (ICP) emission analysis and the like can be mentioned.
Specifically, the phosphorus atom concentration (% by mass) in the polyamide resin composition is determined by ICP analysis, while the ash content in the polyamide resin composition is measured, for example, based on the definition of ISO3451-4, and from the polyamide resin composition The phosphorus element amount (parts by mass) relative to 100 parts by mass of the polyamide resin component in the polyamide resin composition can be determined by calculating the amount of the polyamide resin from which the ash content has been subtracted.

In the triaryl phosphite (B) used for the polyamide resin composition of the present embodiment, the ratio of the total number of aryl groups N (ar) to the total number N of alky substituents on the aryl groups N (al) = N ( Preferably, al) / N (ar) is 2 or less.
More preferably, it is 1 or less, more preferably 0.
When the N (al) / N (ar) is 2 or less, higher molecular weight can be achieved, and Charpy impact strength can be improved.
In order to control N (al) / N (ar) to 2 or less, a suitable (B) component may be selected.

((C) Carboxylic acid compound)
The polyamide resin composition of the present embodiment is obtained by further adding (C) a carboxylic acid compound in an amount of 0.05 to 0.3 (parts by mass) with respect to 100 parts by mass of (A) a polyamide resin, and melt-kneading It is preferred that More preferably, it is 0.02-0.2 mass part, More preferably, it is 0.03-0.1 mass part.
Examples of the carboxylic acid compound (C) include, but are not limited to, monocarboxylic acids having 10 or more carbon atoms, metal salts of monocarboxylic acids having 10 or more carbon atoms, and monocarboxylic acids having 10 or more carbon atoms. Ester compounds and amide compounds of monocarboxylic acids having 10 or more carbon atoms.

Examples of the monocarboxylic acid having 10 or more carbon atoms include, but are not limited to, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid. And 40 saturated or unsaturated, linear or branched aliphatic monocarboxylic acids and the like.
Among these, stearic acid and montanic acid are preferable from the viewpoint of suppression of gas generation at the time of melt processing and suppression of mold deposition on a mold at the time of molding processing.

The metal element of the metal salt of a monocarboxylic acid having 10 or more carbon atoms is preferably a first, second or third element of the Periodic Table of the Elements, zinc, aluminum or the like, and calcium, sodium, potassium, magnesium, etc. Is more preferred.
The metal salt of a monocarboxylic acid having 10 or more carbon atoms is not limited to, for example, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, palmitin Acid calcium etc. are mentioned. Among these, metal salts of montanic acid and metal salts of stearic acid are preferable from the viewpoint of suppression of gas generation during melt processing and suppression of mold deposition on a mold during molding processing.

As the ester compound of a monocarboxylic acid having 10 or more carbon atoms, an aliphatic carboxylic acid having 10 to 40 carbon atoms, carbon, from the viewpoint of suppression of gas generation during melt processing and suppression of mold deposit on a mold during molding processing Esters with several 10 to 40 aliphatic alcohols 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 higher fatty acid esters include, but are not limited to, stearyl stearate, behenyl behenyl and the like.

Examples of the amides of monocarboxylic acids having 10 or more carbon atoms include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bis stearylamide, ethylene bis oleyl amide, N- Stearyl stearylamide, N-stearyl erucic acid amide, etc. are mentioned.
Among these, stearic acid amide, erucic acid amide, ethylene bis stearylamide, and N-stearyl erucic acid amide are preferable from the viewpoints of gas generation suppression at the time of melt processing and mold deposit suppression at the time of molding processing, ethylene More preferred are bis stearylamide and N-stearyl erucic acid amide.

  These monocarboxylic acids having 10 or more carbon atoms, metal salts of monocarboxylic acids having 10 or more carbon atoms, ester compounds of monocarboxylic acids having 10 or more carbon atoms, and amide compounds of monocarboxylic acids having 10 or more carbon atoms are each 1 The species may be used alone, or two or more species may be used in combination.

Among the above-mentioned carboxylic acid compounds, metal salts of montanic acid and metal salts of stearic acid are particularly preferable from the viewpoint of suppression of gas generation during melt processing and suppression of mold deposition on a mold during molding processing.
By adding 0.05 parts by mass or more of (C) a carboxylic acid compound to 100 parts by mass of (A) polyamide resin, it is possible to improve the releasability at the time of molding processing, and the addition amount is 0.3 parts by mass By setting it as the following, generation | occurrence | production of the decomposition gas at the time of a shaping | molding process can be suppressed.

((D) Reinforcement)
The polyamide resin composition of the present embodiment may contain (D) a reinforcing material.
The reinforcing material (D) may be any one as long as it improves the strength and / or rigidity of the polyamide resin composition, and is not limited to the following.
(D) As a reinforcing material, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, Zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, Acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluoromica and apatite can be mentioned.
Among them, glass fibers, carbon fibers, glass flakes, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotubes, graphite, fluoride, among them from the viewpoint of increasing strength and rigidity Calcium, montmorillonite, swellable fluoromica and apatite are preferred.
More preferably, glass fibers, carbon fibers, wollastonite, talc, mica, kaolin and silicon nitride.
The above-described reinforcing materials may be used alone or in combination of two or more.

  Among the glass fibers and carbon fibers, 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 length in the polyamide resin composition Is 100 to 750 μm, and the aspect ratio of weight average fiber length to number average fiber diameter (value obtained by dividing weight average fiber length by number average fiber diameter) is more preferably 10 to 100.

  Further, among the wollastonite, the number average fiber diameter is 3 to 30 μm, and the weight average fiber length in the polyamide resin composition can be provided from the viewpoint of being able to impart excellent mechanical properties to the polyamide resin composition. Is more preferably 10 to 500 μm, and the aspect ratio is 3 to 100.

  Further, among the 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 of being able to impart excellent mechanical properties to the polyamide resin composition.

  Here, with respect to the number average fiber diameter and the weight average fiber length in the present specification, the polyamide resin composition is put in an electric furnace, the contained organic matter is incinerated, and, for example, 100 or more reinforcing materials from the residue. The number average fiber diameter can be measured by arbitrarily selecting and observing with SEM and measuring the fiber diameter of these reinforcing materials, and measuring the fiber length using a SEM photograph at a magnification of 1000 times The weight average fiber length can be determined by

The above-mentioned (D) reinforcing material may be surface-treated with a silane coupling agent or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Aminosilanes such as dimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxy silanes; vinyl silanes.
Among them, aminosilanes are preferred.

In addition, with regard to the above glass fibers and carbon fibers, as a bundling agent, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the above-mentioned carboxylic acid anhydride-containing unsaturated vinyl monomer , An epoxy compound, a polycarbodiimide compound, a polyurethane resin, a homopolymer of acrylic acid, a copolymer of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary of these. It may also contain a salt with a secondary amine.
These may be used alone or in combination of two or more.
Among them, from the viewpoint of mechanical strength of the polyamide resin composition, a constituent unit of a carboxylic acid anhydride containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the above carboxylic acid containing unsaturated vinyl monomer. Copolymers, epoxy compounds, polycarbodiimide compounds, polyurethane resins, and combinations thereof are preferable, and carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated monomers other than the above-mentioned carboxylic anhydride-containing unsaturated vinyl monomers are preferred. A copolymer containing a saturated vinyl monomer as a constitutional unit, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are more preferable.

Among the copolymers containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and a unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer as a constituent unit, the above-mentioned carboxylic acid anhydride-containing Examples of unsaturated vinyl monomers 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. Examples of unsaturated vinyl monomers other than the above-mentioned carboxylic acid anhydride-containing unsaturated vinyl monomers include, but are not limited to, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, etc. Chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate can be mentioned. In particular, styrene and butadiene are preferred.

  Among these combinations, 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 are selected. It is more preferable that it is 1 or more types.

  Further, the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer as a constituent unit has a weight average molecular weight It is preferable that it is 2,000 or more. In addition, from the viewpoint of improving the flowability of the polyamide resin composition, it is more preferably 2,000 to 1,000,000, and still more preferably 2,000 to 1,000,000. The weight average molecular weight can be 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, for example. 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, vinylcyclo Alicyclic epoxy compounds such as xene 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 is 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 to 20, and more preferably 1 to 10. When the degree of condensation of the polycarbodiimide compound is in the range of 1 to 20, an aqueous solution or an aqueous dispersion of a good bundling material is obtained. Furthermore, when the degree of condensation is in the range of 1 to 10, better aqueous solutions or aqueous dispersions are obtained.

Moreover, it is preferable that the said polycarbodiimide compound is a polycarbodiimide compound which has a polyol segment partially.
By having the polyol segment, the polycarbodiimide compound is easily solubilized in water, and can be more suitably used as a glass fiber or carbon fiber bundling agent.

These polycarbodiimide compounds are obtained by decarboxylation reaction of a diisocyanate compound in the presence of a known carbodiimidization catalyst such as 3-methyl-1-phenyl-3-phospholene-1-oxide.
As diisocyanate compounds, it is possible to use aromatic diisocyanates, aliphatic diisocyanates and cycloaliphatic diisocyanates, and mixtures thereof.
Examples of the diisocyanate compound include, but are not limited to, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1 2,4-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 diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethyl xylylene diisocyanate Aneto, like 2,6-diisopropylphenyl isocyanate and 1,3,5-triisopropylbenzene 2,4-diisocyanate. And the polycarbodiimide compound which has two isocyanate groups at the terminal is obtained by carrying out the carbodiimide formation of these diisocyanate type compounds. Among these, dicyclohexylmethane carbodiimide is preferably usable from the viewpoint of improving the reactivity.

Furthermore, the method of forming an equimolar amount of a monoisocyanate compound with respect to a polycarbodiimide compound having two isocyanate groups at the end, or equimolar amount reaction with a polyalkylene glycol monoalkyl ether to generate a urethane bond, etc. A polycarbodiimide compound having one isocyanate group at the end is obtained.
Examples of the monoisocyanate compound include, but are not limited to, hexyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate and the like.
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, and, for example, m-xylylene diisocyanate (XDI), 4,4'-methylene bis (cyclohexyl isocyanate) Those synthesized from isocyanates such as (HMDI) and isophorone diisocyanate (IPDI) and diols of polyester type and polyether type can be suitably used.

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

  The monomer forming the copolymer of the acrylic acid and the other copolymerizable monomer, which forms the copolymer with the acrylic acid, is not limited to the following, for example, has 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, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid can be mentioned (however, acrylics) Except for acid only). In addition, it is preferable that the said other copolymerizable monomer has 1 or more types of ester-type monomers among the said monomers.

Polymers of acrylic acid (including both homopolymers and copolymers) may be in the form of a salt.
Polymeric salts of acrylic acid include, but are not limited to, primary, secondary and tertiary amine salts. Examples of salts of polymers of acrylic acid include, but are not limited to, triethylamine salts, triethanolamine salts and glycine salts, for example.
The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60%, from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (silane coupling agent etc.) and reducing amine odor. Is more preferred.

  The weight average molecular weight of the polymer of acrylic acid which forms a salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. It is preferably 3,000 or more from the viewpoint of the improvement of the bundling ability of glass fibers and carbon fibers, and is preferably 50,000 or less from the viewpoint of the mechanical characteristics improvement when it is made into a polyamide resin composition.

A glass fiber or carbon fiber containing a bundling agent is a fiber produced by applying the bundling agent described above to glass fiber or carbon fiber using a known method such as a roller applicator in a known production process of glass fiber or carbon fiber It is obtained by producing a strand, drying it and reacting continuously.
The fiber strand may be used as a roving as it is as glass fiber or carbon fiber, or may be used as a chopped glass strand after obtaining a cutting process.
The bundling agent is preferably added (added) as a solid fraction of 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, per 100% by mass of the glass fiber or carbon fiber Added. From the viewpoint of maintaining the convergence of the glass fiber and the carbon fiber, it is preferable that the addition amount of the bundling agent is 0.2% by mass or more as a solid fraction with respect to 100% by mass of the glass fiber or the carbon fiber. On the other hand, it is preferable that it is 3 mass% or less from a viewpoint of the heat stability improvement of a polyamide resin composition. Also, the drying of the strand may be performed after the cutting step, or the strand may be cut after drying.

The content of the (D) reinforcing material in the polyamide resin composition of the present embodiment is not particularly limited because it is an optional component, but when it is added, it is based on 100 parts by mass of the (A) polyamide resin. Preferably, it is 10 to 250 parts by mass of the reinforcing material (D).
By making the content of the reinforcing material (D) 10 parts by mass or more with respect to 100 parts by mass of (A), the strength improvement effect can be sufficiently exhibited, and by making the amount 250 parts by mass or less, the production in the extrusion process Improves the quality. More preferably, it is 20 to 150 parts by mass, still more preferably 25 to 100 parts by mass, and still more preferably 30 to 60 parts by mass.

(Other components which may be contained in the polyamide resin composition)
In the polyamide resin composition of the present embodiment, the above-described (A) polyamide resin, (B) triaryl phosphite, (C) carboxylic acid compound within the range not impairing the purpose of the present embodiment, as necessary. And (D) can contain components other than a reinforcement.
As other components that may be contained in the polyamide resin composition of the present embodiment, other polymers other than polyamide resin, and conventional additives used for polyamide resin, such as colorants, flame retardants, plasticizers, stabilizers And those used as antioxidants, ultraviolet light absorbers, crystal nucleating agents and the like.

  Examples of the other polymer include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, (modified) polyphenylene ether, polyphenylene sulfide, Examples thereof include cycloolefin polymers, liquid crystal polyesters, polyetherimides, polysulfones, polyethersulfones, polyamideimides, thermoplastic polyimides, polyether ketones, polyether ether ketones, fluorine resins, polybenzimidazoles and the like.

  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, oxidized Metal particles such as iron, stainless steel and titanium; pearl pigments made of mica; metallic pigments such as colored graphite, colored glass fibers, colored glass flakes and the like.

  As the flame retardant, non-halogen flame retardants and brominated flame retardants are preferable from the viewpoint of suppression of gas generation at the time of melt processing and suppression of mold deposits on the mold at the time of molding.

  Non-halogen flame retardants include, but are not limited to, for example, phosphorus flame retardants such as red phosphorus, ammonium phosphate or ammonium polyphosphate; aluminum hydroxide, magnesium hydroxide, dolomite, hydrotal Hydrates of metal hydroxides or inorganic metal compounds such as calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide, zinc stannate, zinc hydroxystannate, zinc borate, Inorganic compound flame retardants such as boric acid compounds such as zinc metaborate and barium metaborate; melamine, melam, melem, melon (product of deammoniaation from 3 molecules of melem to 3 molecules at 300 ° C. or higher), melamine cyanurate, Melamine phosphate, melamine polyphosphate, succinoguanamine, adipoguanamine, Ruguru catalog guanamine, triazine flame retardant such as melamine resin; and silicone resins least one flame retardant selected from silicone-based flame retardants such as silicone oil, silica.

  Examples of the brominated flame retardants include, but are not limited to, compounds composed of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol epoxy polymer and brominated cross-linked aromatic polymer. There is at least one flame retardant selected. In addition, a flame retardant auxiliary 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-hydroxybenzoate, N-butylbenzenesulfonamide Etc.

  The stabilizer may contain a deterioration inhibitor for the purpose of preventing thermal deterioration, discoloration during heat, improvement in heat aging resistance, weather resistance, and the like. Examples of the deterioration inhibitor include, but are not limited to, phenol stabilizers such as copper compounds such as copper acetate and copper iodide and hindered phenol compounds; phosphite stabilizers: hindered amine stabilizers Agents; triazine stabilizers; sulfur stabilizers and the like.

  Examples of the antioxidant include, but are not limited to, alkylphenols, alkylene bisphenols, alkylphenol thioethers and the like.

  Examples of the UV 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.

[Method of producing polyamide resin composition]
The polyamide resin composition of the present embodiment is melt-kneaded with (B) 0.0062 to 0.31 parts by mass of triaryl phosphite as a phosphorus element with respect to 100 parts by mass of (A) polyamide resin. Obtained by
In addition, a method may be applied in which polymerization is performed from the state in which the component (B) is added to the component (A) precursor in the stage of the polyamide monomer aqueous solution.

In the polyamide resin composition of the present embodiment, the viscosity number (VN) of the polyamide resin component in the polyamide resin composition is 160 mL / g or more, and thus the viscosity of the polyamide resin in the polyamide resin composition In order to make the number [VN] be 160 mL / g or more, the following method can be adopted.
That is, although it is not limited to the following, (1) Polyamide resin component of VN 160 mL / g or more which has been made high molecular weight beforehand by solid phase polymerization etc. is melt-kneaded using (B) component and an extruder with raw material. A method of obtaining a polyamide resin composition containing a target polyamide resin of 160 mL / g or more of VN; (2) (A) polyamide resin component of less than 160 mL / g of VN (for example, general molecular weight of about 140 mL / g of VN) Method of obtaining a polyamide resin composition containing, as a raw material, a component (B) and a polyamide resin composition aimed at the same time as melt kneading with an extruder at the same time as melt kneading, to obtain a target polyamide resin of VN 160 mL / g or more; For example, (A) polyamide resin component of general molecular weight of about RV 140 mL / g) is melt-kneaded using (B) component and an extruder with the raw material Once a polyamide resin composition containing a polyamide resin of less than 160 mL / g of VN is obtained, a polyamide resin composition containing a target polyamide resin of which the molecular weight is increased in a later step such as solid phase polymerization The method etc. of obtaining a thing can be mentioned.

From the viewpoint of the number of processes and the color tone of the polyamide resin composition, a method of causing the (B) component and the (B) component to melt and knead simultaneously with the (A) polyamide resin component as a raw material simultaneously with the (2) VN 160 mL / g It is preferable to adopt
At this time, as VN of the raw material (A) polyamide resin component, it is easy to obtain, extrudability in melt-kneading (from the viewpoint of ease of cutting of the strand after kneading and load on the extruder motor (torque) VN 60 mL / g or more and VN 160 mL / g or more tends to make it easier to cut the strand after kneading of the extruder more stably, and by making it less than 160 mL VN, Since the load of the zone for melting the polyamide resin on the upstream side in the extruder tends to be reduced, the discharge amount (production amount) tends to be able to be increased From the same viewpoint as above, more preferably VN 80 mL / g More than VN155mL / g, more preferably more than VN100mL / g and more than VN150mL / g, and still more preferably It is less than VN120mL / g or more VN145mL / g.

  Moreover, when manufacturing the polyamide resin composition of this embodiment by the method of polymerizing from the state which added the (B) component with respect to the precursor of the (A) polyamide resin component of the stage of the polyamide monomer aqueous solution, a polyamide resin In order to increase the viscosity number [VN] of the polyamide resin component in the composition to 160 mL or more, the polymerization is completed by the operation of increasing the molecular weight, such as reducing pressure treatment or extending the process time, Alternatively, after completion of the polymerization in a low molecular weight state of less than 160 mL / g of VN, the polymerization may be separately performed by solid phase polymerization or the like.

  In the embodiment, (C) a carboxylic acid compound may be mixed together with (A) a polyamide resin and (B) a triaryl phosphite, and may be melt-kneaded in an extruder, or (A) a polyamide resin and (A) (C) A carboxylic acid compound may be used by sprinkling pellets of a polyamide resin composition obtained by melt-kneading B) triaryl phosphite. When using (C) a carboxylic acid compound, an oily component such as polyethylene glycol may be used as an adhesion agent. From the viewpoint of improving the plasticity at the time of molding, (C) carboxylic acid compound is added to pellets of a polyamide resin composition obtained by melt-kneading (A) polyamide resin and (B) triaryl phosphite. It is preferable to use it as a mask.

A well-known apparatus can be used as an apparatus which performs melt-kneading.
For example, melt kneaders such as single-screw or twin-screw extruders, Banbury mixers, mixing rolls and the like are preferably used.
Among them, a multi-screw extruder equipped with a degassing mechanism (vent) device and a side feeder equipment is preferable, and a twin-screw extruder is more preferably used.

  Above all, in the method of polymerizing a polymer resin raw material having a general molecular weight of about VN 140 mL / g at the time of melt-kneading, polymerizing it by utilizing the polymerizing action of the component (B) it can.

  In the process of melt-kneading with an extruder, the viscosity number [VN] of the polyamide resin in the polyamide resin composition is 160 mL / mL by appropriately setting the kneading conditions such as the resin temperature in the extrusion, the degree of pressure reduction, and the average residence time. The molecular weight can be increased by adjusting to g or more.

In the case of polyamide 66 having a melting point of 260 ° C., for example, the resin temperature at the time of melt-kneading is preferably 260 ° C. or more and 400 ° C. or less.
By setting the resin temperature at the time of melt-kneading to 260 ° C. or higher, the polyamide resin tends to be melted sufficiently and the load on the extruder motor can be reduced.
In addition, by setting the resin temperature at the time of melt-kneading to 400 ° C. or less, decomposition of the polyamide resin itself tends to be suppressed.
From the viewpoint described above, more preferably 265 ° C. or more and 380 ° C. or less, still more preferably 270 ° C. or more and 370 ° C. or less, still more preferably 275 ° C. or more and 365 ° C. or less, still more preferably 280 ° C. or more It is less than ° C.
Even when using other polyamide resin, it can be suitably adjusted according to the melting point.

The resin temperature can be measured, for example, by bringing a molten polyamide resin composition coming out to the discharge port (spinning port) of an extruder into direct contact with a thermometer such as a thermocouple.
The resin temperature can be controlled by adjusting the heater temperature of the cylinder of the extruder, and appropriately adjusting the shear heating value of the resin by changing the number of rotations of the extruder and the discharge amount.

  The pressure reduction degree refers to the atmospheric pressure, and means the difference between the pressure in the volatilization region and the atmospheric pressure. For example, the reduced pressure degree 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 volatilization region is a region connected to a pressure reducing device in the melt-kneading device and having a pressure reduction degree equivalent to that of the pressure reducing device, and is a region in which the device wall, the stirring device, and the filled resin etc. .

  The reduced pressure treatment is preferable in order to efficiently remove water generated in the polymerization reaction (dehydration condensation reaction) of the polyamide resin from the polyamide system. Thus, by removing water, the equilibrium reaction of polymerization / depolymerization of the polyamide resin can be further inclined in the polymerization direction, and the synergetic effect with the high molecular weight action of the component (B) makes it possible to increase the strength of the polyamide resin. Molecular weight tends to be further promoted.

As a pressure reduction degree at the time of melt-kneading, 0.02 MPa or more is preferable. By setting the degree of pressure reduction to 0.02 MPa or more, the removal rate (removal capacity) of water tends to be enhanced. Therefore, it tends to be able to realize sufficient high molecular weight formation.
Further, the pressure can be reduced to the maximum (pressure reduction degree 0.1013 MPa) of the pressure reducing device (vacuum pump etc.).
When priority is given to the pressure reduction that has been stable for a long time, the pressure reduction is preferably 0.1 MPa or less. The pressure is preferably 0.02 MPa or more and 0.1 MPa or less, more preferably 0.04 MPa or more and 0.097 MPa or less, still more preferably 0.05 MPa or more and 0.095 MPa or less, and still more preferably 0. 06 MPa or more and 0.093 MPa or less.

  The degree of pressure reduction may be measured and managed by attaching a pressure gauge (differential pressure gauge), a vacuum gauge, etc. anywhere from the pressure reducing device (vacuum pump etc.) to the part connected to the volatilization area of the extruder. it can.

  When measuring the degree of pressure reduction, for example, it is preferable to install a valve or a valve-equipped air suction nozzle at any position from a pressure reducing device (vacuum pump or the like) to a portion connected to the volatilization region of the extruder. In this case, the degree of pressure reduction can be adjusted by opening and closing the valve.

  In addition, a drain pot for storing drain in the vent gas can be installed between the pressure reducing device (vacuum pump or the like) and the melting and kneading unit. When the vent pot is installed, it is preferable to attach an air suction nozzle to the vent pot.

The average residence time at the time of melt-kneading is preferably 10 seconds or more and 120 seconds or less.
If the average residence time is 10 seconds or more, it tends to be easy to control the polyamide resin in the polyamide resin composition to a desired physical property.
In addition, by setting the time to 120 seconds or less, the extrusion discharge rate (production rate) tends to increase to some extent. As a result, the productivity also tends to be good.
From the above viewpoint, the average residence time at the time of melt-kneading is more preferably 20 seconds to 100 seconds, still more preferably 25 seconds to 90 seconds, and still more preferably 30 seconds to 80 seconds. More preferably, it is 35 seconds or more and 70 seconds or less.

The average residence time at the time of melt-kneading means the residence time when the residence time in the melt-kneading apparatus is constant, and when the residence time is nonuniform, the average of the shortest residence time and the longest residence time Means a value.
A resin etc. (abbreviated as X hereinafter) that can be distinguished from the polyamide resin of the present embodiment, such as a colorant master batch during melt-kneading, a resin having a color different from that of the polyamide resin, etc. The average residence time can be measured by measuring the discharge start time and the discharge end time of X, and averaging the discharge start time and the discharge end time.

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

In the method for producing a polyamide resin composition of the present embodiment, the ratio of the total number N of aryl groups in the triaryl phosphite (B) to the total number N of alky substituents on the aryl group: It is preferable that N (al) / N (ar) be 2 or less.
More preferably, it is 1 or less, more preferably 0.
When the N (al) / N (ar) is 2 or less, higher molecular weight can be achieved, and Charpy impact strength can be improved.
In order to control N (al) / N (ar) to 2 or less, a suitable (B) component may be selected.

With regard to (A) polyamide resin and (B) triaryl phosphite used in the method for producing a polyamide resin composition of the present embodiment, any of those described in the item of [polyamide resin composition] described above may be used. it can.
In particular, with respect to (B) triaryl phosphite, triphenyl phosphite is preferable from the viewpoint of achieving high molecular weight with a smaller amount and reducing gas generation at the time of molding.

[Molded body]
By using the polyamide resin composition of the present embodiment, it is possible to obtain a polyamide molded article having excellent tensile elongation, Charpy impact and good moldability.
For the molded body, the polyamide resin composition of the present embodiment is used and 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, melt spinning, etc., by generally known plastic molding methods.

  The molded article of the polyamide resin composition of the present embodiment is excellent in moldability and physical properties, and excellent in color tone, surface appearance, heat discoloration, weather resistance, heat aging resistance, light resistance, chemical resistance and the like. Therefore, application to various parts such as automobile parts, electronic and electric parts, industrial machine parts, various gears, and extrusion applications is expected.

Hereinafter, the present embodiment will be specifically described by citing specific examples and comparative examples, but the present embodiment is not limited to only the following examples.
In addition, the evaluation method applied by the Example and the comparative example is as follows.

〔raw materials〕
((A) Polyamide)
PA66 The following [Production of Polyamide (PA66)] Viscosity number [VN]: 141 mL / g, PA66 pellet having a moisture content of 0.08 mass% PA9C The following [Production of Polyamide (PA 9 C)] Viscosity PA9C pellet ((B) triaryl phosphite) which is the number [VN]: 114 mL / g and moisture content 0.02 mass%
Triphenyl phosphite (TPP) manufactured by Wako Pure Chemical Industries, Ltd. trade name Triphenyl phosphite tris tris (2,4-di-t-butylphenyl) phosphite manufactured by BASF Japan Ltd. trade name IRGAFOS 168
Tris (nonylphenyl) phosphite (TNP) manufactured by Sigma-Aldrich Co. Trade name Tris (nonylphenyl) phosphite
((C) Carboxylic acid compound)
Calcium Stearate NIPPON SHOKAI CO., LTD. Trade name calcium stearate adipic acid Wako Pure Chemical Industries Ltd. trade name Adipic acid ((D) other phosphorus compounds)
Sodium hypophosphite sodium made by Taihei Kagaku Sangyo Co., Ltd. Sodium hypophosphite sodium hypophosphite made by Wako Pure Chemical Industries, Ltd. trade name calcium hypophosphite sodium sodium phenylphosphonate manufactured by Wako Pure Chemical Industries, Ltd. trade name Phosphorus Acid disodium dihydrate

〔Characteristic〕
(1) Viscosity number <1-1> Viscosity number: VN (mL / g)
The viscosity number of the polyamide resin component in a polyamide resin composition was measured according to ISO307 (JIS-K6933) using the pellet of the polyamide resin composition manufactured by the example and comparative example which are mentioned below.
More specifically, the measurement was carried out at a polyamide resin concentration of 0.5% by mass in 96% sulfuric acid at 25 ° C.
In addition, when a reinforcing material such as GF is contained, the percentage of ash in the polyamide resin composition is measured in advance, for example, based on the definition of ISO 3451-4, and the percentage of polyamide resin is used to reduce the percentage of polyamide resin. The amount of polyamide resin was calculated from the resin composition.
<1-2> Formic acid relative viscosity (RV)
Formic acid relative viscosity (RV) of the polyamide resin component in the polyamide resin composition using the pellets of the polyamide resin composition manufactured in Examples and Comparative Examples described later, and the viscosity of the solution obtained by adding the polyamide resin composition to formic acid It was determined by comparing the viscosity of formic acid itself.
About a specific measuring method, it shall carry out based on ASTM-D 789.
More specifically, an RV value measured at 25 ° C. was adopted using a solution of 8.4 mass% polyamide resin dissolved in 90 mass% formic acid (10 mass% water).
In addition, when a reinforcing material such as GF is contained, the percentage of ash in the polyamide resin composition is measured in advance, for example, based on the definition of ISO 3451-4, and the percentage of polyamide resin is used to reduce the percentage of polyamide resin. The amount of polyamide resin was calculated from the resin composition.

(2) Measurement of moisture content (mass%)
Using the pellets of the above (A) polyamide resin, using a Karl Fischer moisture meter (a coulometric titration type trace water content measuring device CA-200 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to the method according to ISO 15512 Mass% was measured.

(3) Amount of phosphorus element derived from triaryl phosphite with respect to 100 parts by mass of polyamide resin component in polyamide resin composition (part by mass)
The amount of phosphorus element is (A) the addition amount (parts by mass) of (B) triaryl phosphite added to 100 parts by mass of polyamide resin, (B) molecular weight of (B) triaryl phosphite, and (B) phosphorous It can be calculated from the weight of elemental phosphorus in one molecule of triaryl phosphate.

(4) (B) Ratio of the total number N (ar) of aryl groups of triaryl phosphite to the total number N (al) of alkyl substituents on the aryl group: N (al) / N (ar)
(B) The aryl group of triaryl phosphite is a functional group derived from an aromatic hydrocarbon directly bonded to each of the three oxygen atoms bonded to a phosphorus atom, and may be monocyclic or polycyclic Good.
N (ar) is an aromatic hydrocarbon directly bonded to each of three oxygen atoms bonded to a phosphorus atom in a predetermined amount of (B) triaryl phosphite added to 100 parts by mass of a polyamide resin Total number of functional groups derived.
The alkyl substituent on the aryl group is a generic name of sp3 hybrid carbon substituents present on the aromatic ring of the aryl group of (B) triaryl phosphite.
N (al) is a predetermined amount of (B) triaryl phosphite added to 100 parts by mass of the polyamide resin based on the number of alkyl substituents on the aryl group per one molecule of (B) triaryl phosphite It calculated by multiplying the number of molecules.

(5) Charpy impact strength (kJ / m ² )
Examples and Comparative Examples Multi-purpose test pieces (4 mm thick) were produced from the pellets of the polyamide resin composition obtained, using an injection molding machine, in accordance with ISO 3167.
A mold for taking the above-mentioned two test pieces was attached using PS40E manufactured by Nisshin Plastic Industry Co., Ltd. as an injection molding apparatus.
The cylinder temperature was set to the melting point of the polyamide resin + about 25 ° C., and in the case of PA 66, it was set to 290 ° C. and the mold temperature 80 ° C.
Furthermore, a dumbbell-shaped molded body was obtained from pellets of the polyamide resin composition under injection molding conditions of injection 25 seconds, cooling 15 seconds, plasticization amount 90 mm (cushion amount about 10 mm), screw rotation speed 200 rpm.
Notched Charpy impact strength was measured according to ISO-179 using the obtained molded body.

(6) Plasticization time stability The plasticization at the time of 50 shot molding of ISO 3167 multi-purpose test pieces (4 mm thick) performed by molding in the same manner as molding the test pieces for evaluation of Charpy impact strength in (4) above. Time was measured. The plasticization time stability (standard deviation) was determined by the following equation.

Ai = 50 shots plasticization time X 1 = 50 shots arithmetic average n = number of shots (50 shots)
It was judged that the smaller the above-mentioned standard deviation, the better the plasticization time stability.

(7) Releasability The releasability at the time of shaping | molding a test piece for evaluation of the Charpy impact strength of said (4) was evaluated.
Evaluation criteria for releasability were as follows.
The molding cycle time: injection 25 seconds, cooling 15 seconds, molding at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C.
○: The mold was released without any problem. (Level capable of fully automatic molding)
Fair: There were times when the mold was released without problems and when the mold was not released. (Semi-automatically moldable level)
X: Almost no mold release, and a hand was required to take out a molded article.

(8) Gas generation during molding When molding a test piece for evaluation of Charpy impact strength in the above (4), spouting of resin due to gasification from a cylinder nozzle (Hana Taare) as evaluation of gas generation during molding Evaluated by the criteria of
Evaluation criteria of gas generation at the time of molding 噴出: There was almost no ejection of resin due to gasification from a cylinder nozzle during molding.
:: A small amount of resin was ejected by gasification from the cylinder nozzle during molding. Automatic molding is possible.
Δ: Ejection of resin by gasification from the cylinder nozzle during molding was a little more, but it could be molded automatically.
X: A large amount of resin was ejected from the cylinder nozzle during molding due to gasification, and sometimes manual labor was required to remove the resin.

[Production of Polyamide Resin (PA 66)]
30 kg of a 50% by mass aqueous solution of hexamethylenediamine and an equivalent salt of adipic acid were charged in a 40 L autoclave, kept at 50 ° C. so as not to precipitate a monomer, and stirred well.
After thoroughly purging the autoclave with nitrogen, the temperature was raised from about 50 ° C to about 160 ° C. At this time, heating was continued while removing water out of the system in order to keep the pressure in the tank at about 0.25 MPa as gauge pressure, and was concentrated to about 75% by mass.
Then, once the removal of water was stopped, the temperature was raised to about 220 ° C., and when the pressure was about 1.8 MPa, heating was continued while removing water so as to keep the pressure constant again.
Then, after the temperature rose to 260 ° C., the pressure was slowly reduced to atmospheric pressure (gauge pressure: 0 MPa) while continuing heating for about 60 minutes.
The temperature was maintained at atmospheric pressure for 30 minutes, and the temperature was finally raised to about 273 ° C.
Then, nitrogen pressure was applied to form a strand from the lower nozzle, followed by water cooling and cutting to discharge in the form of pellets to obtain a polyamide resin (PA66).
The moisture content of the polyamide resin pellets was 0.08% by mass. Moreover, VN was 143 mL / g.

[Production of Polyamide Resin (PA9C)]
7.82 kg of 1,4-cyclohexanedicarboxylic acid and 7.19 kg of 1,9-nonanediamine were dissolved in 15 kg of distilled water to prepare an equimolar 50% by mass homogeneous aqueous solution of the raw material monomer.
The obtained aqueous solution was charged into an autoclave having an inner volume of 40 L, kept warm until the solution temperature (internal temperature) reached 50 ° C., and stirred well. After purging the inside of the autoclave with nitrogen, the temperature was raised from about 50 ° C to about 160 ° C. At this time, heating was continued while removing water out of the system in order to keep the pressure in the tank at about 0.25 MPa as gauge pressure, and was concentrated to about 75% by mass.
After that, the removal of water was once stopped and heating was continued until the pressure in the tank reached about 3.0 MPa. Heating was continued until the temperature reached 290 ° C. while water was removed out of the system to maintain the pressure in the tank at 3.0 MPa. While the heating was further continued, the pressure in the tank was reduced from 3.0 MPa to atmospheric pressure (gauge pressure is 0 MPa) over 60 minutes.
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was 320 ° C. The resin temperature was maintained at 320 ° C., and the inside of the tank was maintained for 10 minutes under a reduced pressure of 1.33 × 10 4 Pa (100 torr) by a vacuum device.
Then, it was pressurized with nitrogen and made into a strand from the lower spinning nozzle (nozzle), water cooled and cut, and discharged in the form of pellets to obtain a polyamide.
The resulting polyamide was dried in a stream of nitrogen and the moisture content was adjusted to be less than about 0.2% by weight.
The polyamide resin pellet had a VN of 114 mL / g.

Comparative Example 1
100 parts by mass of polyamide 66 (polyamide 66 polymerized as described above, relative viscosity (RV) 48 of formic acid at 25 ° C., moisture content 0.08 mass%, also abbreviated as “PA 66” in this example) 0.03 parts by mass of triphenyl acid and 0.05 parts by mass of calcium stearate were blended, and melt kneading was performed using a twin-screw extruder (ZSK25 manufactured by COPERION).
(B) The addition amount of triphenyl phosphite as the phosphorus element is 0.03 (mass part) × 30.97 (atomic weight of phosphorus element) /310.29 (molecular weight of triphenyl phosphite) = 0. It is 00 229 ≒ 0.003 (parts by mass).
At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 300 ° C., and the resin temperature in the vicinity of the tip nozzle was 312 ° C.
The extrusion rate was 20 kg / hr and the average residence time was 45 seconds.
Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa.
The polyamide resin was discharged in a strand form from the tip nozzle, and water cooling and cutting were performed to obtain pellets.
The VN and RV of the obtained polyamide resin composition pellet, the plasticization time stability at the time of molding the pellet, releasability, gas generation, and Charpy impact strength of the molded product were evaluated.
The evaluation results are shown in Table 1.

Comparative Example 2
The amount of triphenyl phosphite was changed to 0.05 parts by mass. The other conditions were the same as in Comparative Example 1, and pellets and molded articles of the polyamide resin composition of Comparative Example 2 were obtained.
The evaluation results are shown in Table 1.

[Examples 1 to 10]
The amount of triphenyl phosphite described in Table 1 was changed.
The other conditions were the same as in Comparative Example 1 to obtain pellets and molded articles of Examples 1 to 10.
The evaluation results are shown in Tables 1 and 2.

[Example 11]
Pellets and molded articles of the polyamide resin composition of Example 11 were obtained in the same manner as in Comparative Example 1 except that the amount of triphenyl phosphite was 1.5 parts by mass, and the other conditions were the same.
The evaluation results are shown in Table 2.

[Reference Example 12]
Instead of triphenyl phosphite, 0.63 parts by mass of tris (2,4-di-t-butylphenyl) phosphite was blended. The other conditions were the same as in Comparative Example 1 to obtain pellets and molded articles of the polyamide resin composition of Reference Example 12 .
The evaluation results are shown in Table 2.

Reference Example 13
The amount of tris (2,4-di-t-butylphenyl) phosphite added and the amount of calcium stearate added were as shown in Table 2. The other conditions were the same as in Reference Example 12 to obtain pellets and a molded article of the polyamide resin composition of Reference Example 13 .
The evaluation results are shown in Table 2.

[Reference Example 14]
Tris (phosphorus acid) instead of tris (2,4-di-t-butylphenyl) phosphite
Pellets and a molded body of the polyamide resin composition of Reference Example 14 were obtained in the same manner as in Reference Example 13 except that 0.69 parts by mass of nonylphenyl was blended. The evaluation results are shown in Table 2.

Comparative Example 3
1.0 part by mass of triphenyl phosphite and 0.05 parts by mass of adipic acid are added to 100 parts by mass of PA66 manufactured in the above-mentioned preparation example, and 0.5 parts by mass of calcium hypophosphite is further added to obtain biaxial Melt-kneading was performed using an extruder (ZSK25 manufactured by COPERION).
At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 300 ° C., and the resin temperature in the vicinity of the tip nozzle was 310 ° C.
The extrusion rate was 20 kg / hr and the average residence time was 45 seconds.
Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa.
The polyamide resin composition was discharged in a strand form from the tip nozzle, and water cooling and cutting were performed to obtain pellets of the polyamide resin composition.
The VN and VR of the pellet of the obtained polyamide resin composition, the plasticization time stability at the time of molding the pellet, releasability, gas generation, and Charpy impact strength of the molded body were evaluated.
The evaluation results are shown in Table 2.

Comparative Example 4
0.1 parts by mass of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by mass of calcium stearate are mixed with 100 parts by mass of PA66 prepared in the above preparation example, and a twin-screw extruder (COPERION) Melt-kneading was performed using a company-made ZSK 25). At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 300 ° C., and the resin temperature near the tip nozzle was 311 ° C. The extrusion rate was 20 kg / hr and the average residence time was 45 seconds. Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa. The polyamide resin was discharged in a strand form from the tip nozzle, and water cooling and cutting were performed to obtain pellets. The VN of the obtained pellet, the plasticization time stability at the time of shaping the pellet, and the Charpy impact strength of the shaped body were evaluated.
The evaluation results are shown in Table 2.

Comparative Example 5
0.05 parts by mass of calcium stearate and 0.11 parts by mass of sodium hypophosphite are mixed with 100 parts by mass of PA66 prepared in the above production example, and melt kneading is performed using a twin-screw extruder (ZSK25 manufactured by COPERION) went. At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 300 ° C., and the resin temperature in the vicinity of the tip nozzle was 313 ° C. The extrusion rate was 20 kg / hr and the average residence time was 45 seconds. Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa. The polyamide resin was discharged in a strand form from the tip nozzle, and water cooling and cutting were performed to obtain pellets. The VN of the obtained pellet, the plasticization time stability at the time of shaping the pellet, and the Charpy impact strength of the shaped body were evaluated.
The evaluation results are shown in Table 2.

Comparative Example 6
0.05 parts by mass of calcium stearate and 0.2 parts by mass of sodium phenylphosphonate are mixed with 100 parts by mass of PA66 prepared in the above preparation example, and melt kneading is performed using a twin-screw extruder (ZSK25 manufactured by COPERION) The
At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 300 ° C., and the resin temperature in the vicinity of the tip nozzle was 312 ° C.
The extrusion rate was 20 kg / hr and the average residence time was 45 seconds.
Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa.
The polyamide resin composition was discharged in the form of a strand from the tip nozzle, and water cooling and cutting were performed to obtain pellets.
The VN and VR of the pellet of the obtained polyamide resin composition, the plasticization time stability at the time of molding the pellet, releasability, gas generation, and Charpy impact strength of the molded body were evaluated.
The evaluation results are shown in Table 2.

[Example 15]
0.31 parts by mass of triphenyl phosphite and 0.05 parts by mass of calcium stearate are added to 100 parts by mass of PA9C prepared in the above preparation example, and melt-kneaded using a twin-screw extruder (ZSK25 manufactured by COPERION) Did.
At this time, the screw rotation speed was 300 rpm, the cylinder temperature was 320 ° C., and the resin temperature in the vicinity of the tip nozzle was 334 ° C.
The extrusion rate was 20 kg / hr and the average residence time was 45 seconds.
Under the above conditions, extrusion was performed at a reduced pressure of 0.085 MPa.
The polyamide resin composition was discharged in the form of a strand from the tip nozzle, and water cooling and cutting were performed to obtain pellets.
The VN and VR of the pellet of the obtained polyamide resin composition, the plasticization time stability at the time of molding the pellet, releasability, gas generation, and Charpy impact strength of the molded body were evaluated.
The evaluation results are shown in Table 2.

  The polyamide resin composition of the present invention has industrial applicability in the fields of automobile parts, electronic and electrical parts, industrial machine parts, various gears, extrusion applications and the like.

Claims (15)

(A) A polyamide resin composition obtained by adding and melting 0.0062 to 0.31 parts by mass of triaryl phosphite as a phosphorus element with respect to 100 parts by mass of a polyamide resin,
(B) triaryl phosphite is triphenyl phosphite,
The viscosity number (VN) of the polyamide resin component in the polyamide resin composition is 160 mL / g
The polyamide resin composition which is the above. Further, (C) a carboxylic acid compound was added in an amount of 0. 1 to 100 parts by mass of the (A) polyamide resin.
The polyamide resin composition of Claim 1 which adds a 0.5-0.3 mass part. The polyamide resin composition according to claim 2, wherein the (C) carboxylic acid compound is a metal salt of a monocarboxylic acid having 10 or more carbon atoms. The polyamide resin composition according to any one of claims 1 to 3, wherein the polyamide resin component in the polyamide resin composition 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 4, wherein the polyamide resin component in the polyamide resin composition contains 50% by mass or more of 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 5, wherein the polyamide resin component in the polyamide resin composition is a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid. The polyamide resin composition according to any one of claims 4 to 6, wherein the diamine and the dicarboxylic acid are respectively a linear aliphatic diamine and a linear aliphatic dicarboxylic acid having no branched structure or cyclic structure. The ratio of the total number N (ar) of aryl groups of the triaryl phosphite (B) to the total number N (al) of alkyl substituents on the aryl group: N (al) / N (ar) is 0. The polyamide resin composition according to any one of 1 to 7. With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition, (D
The polyamide resin composition according to any one of claims 1 to 8 , further comprising 10 to 250 parts by mass of a reinforcing material. With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is preferably 0.0062 to 0. 0 as a phosphorus element.
The polyamide resin composition according to any one of claims 1 to 9 , which is 31 parts by mass. With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is 0.0093-0.
The polyamide resin composition according to any one of claims 1 to 10 , which is contained in an amount of 15 parts by mass. With respect to 100 parts by mass of the polyamide resin component in the polyamide resin composition,
B) The phosphorus compound derived from triaryl phosphite is 0.012 to 0.0 as a phosphorus element
The polyamide resin composition according to any one of claims 1 to 11 , which is contained in 93 parts by mass. A method of producing a polyamide resin composition according to any one of claims 1 to 12 , wherein
(A) A polyamide having a step of adding triphenyl phosphite as a triaryl phosphite (B) as triaryl phosphite to a mass of 100 parts by mass of the polyamide resin (0.0062 to 0.31 parts by mass as a phosphorus element) and melt kneading Method for producing a resin composition. The manufacturing method of the polyamide resin composition of Claim 13 whose viscosity number of said (A) polyamide resin is less than 160 mL / g. The ratio N (al) / N (ar) of the total number N (ar) of aryl groups of the triaryl phosphite (B) to the total number N (al) of alkyl substituents on the aryl group is 0 , The manufacturing method of the polyamide resin composition of Claim 13 or 14 .