JP2020033412A - Resin composition and molded article - Google Patents

Abstract

To provide a resin composition which contains MXD6 polyamide and a flame retardant, and has good rigidity when being heated and surface appearance, flame retardance and impact resistance when being formed into a molded article.SOLUTION: A resin composition contains (A) aliphatic polyamide, (B) MXD6 polyamide, (C) an amorphous resin having a glass transition temperature of 80°C or higher and 250°C or lower obtained when raising a temperature at 20°C/min in differential scanning calorimetry according to JIS-K7121, (D1) a flame retardant and (D2) a flame retardant assistant; and has tanδ peak temperature of 90°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a molded product.

Polyamides represented by polycaproamide (hereinafter, also referred to as "polyamide 6" or "PA6") and polyhexamethylene adipamide (hereinafter, also referred to as "polyamide 66" or "PA66") have molding processability, Because of their excellent mechanical properties and chemical resistance, they are widely used as various component materials for automobiles, electric and electronic devices, industrial materials, industrial materials, daily products and household products.
In recent years, not only the balance between rigidity and impact resistance, but also required properties such as flame retardancy, heat resistance, gas permeability resistance, oil resistance, etc. have become strict. For example, amide (hereinafter, also referred to as “polyamide MXD6” or “MXD6 polyamide”), polymethaxylylene terephthalamide (hereinafter, also referred to as “polyamide MXDT”), and the like have come to be used. Among them, the MXD6 polyamide has excellent properties in terms of mechanical properties such as rigidity and gas permeation resistance.

However, polyamide MXD6 has a further problem in terms of impact resistance, and there is a demand for an improvement in impact resistance, particularly when a flame retardant is contained.
As an impact modifier for engineering plastics, a technique of adding an elastomer is already known. For example, Patent Literature 1 discloses a technique of adding an acid-modified polyolefin elastomer polymerized using a metallocene catalyst in order to improve the impact resistance of polyamide MXD6, and Patent Literature 2 discloses hydrogenation. A technique for adding styrene butadiene rubber is disclosed.

JP-A-11-021446 JP 2005-126630 A

According to the techniques described in Patent Literatures 1 and 2, the impact resistance of MXD6 polyamide is improved, but there is a problem that, for example, excellent mechanical properties of MXD6 polyamide cannot be maintained.
As described above, there is a method for improving the rigidity, the low-temperature impact resistance, the flame retardancy, the gas permeability, the heat resistance and the like of the polyamide containing an aromatic ring, particularly the polyamide MXD6 containing a flame retardant, at present. do not do.

  The present invention has been made in view of the above circumstances, and includes MXD6 polyamide and a flame retardant, and has excellent heat stiffness, and excellent surface appearance, flame retardancy, and impact resistance when molded. Provided are a resin composition and a molded article obtained by molding the resin composition.

  The present inventors have intensively studied to achieve the above object, and as a result, MXD6, aliphatic polyamide, and amorphous glass having a glass transition temperature measured by differential scanning calorimetry according to JIS-K7121 in a specific range. A resin composition containing a water-soluble resin and a flame retardant has been found to have excellent rigidity when heated, and a good balance of surface appearance, flame retardancy and impact resistance when formed into a molded product, and complete the present invention. Reached.

That is, the present invention includes the following aspects.
The temperature of the resin composition according to the first embodiment of the present invention is raised at a rate of 20 ° C./min in (A) aliphatic polyamide, (B) MXD6 polyamide, and (C) differential scanning calorimetry according to JIS-K7121. A glass transition temperature of 80 ° C. or higher and 250 ° C. or lower, (D1) a flame retardant, and (D2) a flame retardant auxiliary, and a tan δ peak temperature of 90 ° C. or higher. is there.
The (A) aliphatic polyamide may include an aliphatic polyamide containing a dicarboxylic acid unit and a diamine unit.
The (A) aliphatic polyamide may include polyamide 66.
The content of the (A) aliphatic polyamide may be more than 0% by mass and 50% by mass or less based on the total mass of the polyamide in the resin composition.
The content of the (B) MXD6 polyamide may be 50% by mass or more and less than 100% by mass with respect to the total mass of the polyamide in the resin composition.
The weight average molecular weight Mw of the resin composition may be 10,000 or more and 60,000 or less.
The content of the amorphous resin (C) may be 0.1% by mass or more and 30% by mass or less based on the total mass of the resin composition.
The amorphous resin (C) may not contain polyamide.
The amorphous resin (C) may be at least one selected from the group consisting of a polystyrene resin, an acrylic resin, and a polyether resin.
The amorphous resin (C) may be at least one selected from the group consisting of polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polyphenylene ether and polycarbonate. .
The flame retardant (D1) is a brominated polystyrene, and the content of the brominated polystyrene is 2% by mass or more and 7% by mass or less based on the total mass of the resin composition, and the (D2) The flame retardant aid may be Sb ₂ O ₃ , and the content of Sb ₂ O ₃ may be 0.1% by mass or more and 4% by mass or less based on the total mass of the resin composition.
The resin composition according to the first aspect further contains (E) a white pigment, and the content of the (E) white pigment is 0.5% by mass or more with respect to the total mass of the resin composition. It may be not more than mass%.
The (E) white pigment may be at least one selected from the group consisting of zinc sulfide, zinc oxide and titanium oxide.
The resin composition according to the first aspect further contains (F) an ultraviolet absorber, and the content of the (F) ultraviolet absorber is 0.1% by mass based on the total mass of the resin composition. It may be not less than 5% by mass.
The (F) ultraviolet absorber may be at least one selected from the group consisting of benzotriazole and triazine-based ultraviolet absorbers.
The resin composition according to the first embodiment may further contain (G) a polymer containing α, β unsaturated dicarboxylic anhydride units.
The polymer (G) containing α, β unsaturated dicarboxylic anhydride units may be maleic anhydride-modified polyphenylene ether.
The resin composition according to the first aspect may further contain (H) a filler.
The (H) filler may be glass fiber, and the content of the glass fiber may be 40% by mass or more and 60% by mass or less based on the total mass of the resin composition.

  The molded article according to the second aspect of the present invention is obtained by molding the resin composition according to the first aspect, and has a surface gloss value of 50 or more.

  According to the resin composition of the above aspect, there is provided a resin composition containing an MXD6 polyamide and a flame retardant, and having good heat stiffness, and good surface appearance, flame retardancy, and impact resistance when molded. be able to. The molded article of the above embodiment is obtained by molding the resin composition, and has good surface appearance, flame retardancy and impact resistance.

  Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification 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 invention.

  In addition, in this specification, "polyamide" means a polymer having an amide (-NHCO-) group in the main chain.

≪Resin composition≫
The resin composition of the present embodiment contains the following components (A) to (D2), and has a tan δ peak temperature of 90 ° C. or higher.
(A) an aliphatic polyamide;
(B) MXD6 polyamide;
(C) In a differential scanning calorimetry according to JIS-K7121, an amorphous resin having a glass transition temperature of 80 ° C. or more and 250 ° C. or less when heated at a rate of 20 ° C./min (hereinafter referred to as “(C) non-crystalline resin Abbreviated as "crystalline resin");
(D1) a flame retardant;
(D2) Flame retardant aid

  According to the resin composition of the present embodiment, by having the above-described configuration, a resin composition having good rigidity at heat, and good surface appearance, flame retardancy and impact resistance when formed into a molded product is provided. be able to.

  The molecular weight, molecular weight distribution, and tan δ peak temperature of the resin composition of the present embodiment can be configured as follows, and specifically, can be measured by a method described in Examples described later.

<Weight average molecular weight (Mw) of resin composition>
As an index of the molecular weight of the resin composition, a weight average molecular weight (Mw) can be used.
The weight average molecular weight (Mw) of the resin composition is preferably from 10,000 to 60,000, more preferably from 17,000 to 60,000, still more preferably from 20,000 to 60,000, even more preferably from 30,000 to 55,000, particularly preferably from 35,000 to 55,000. It is preferably 35,000 or more and 50,000 or less.

  When the weight average molecular weight (Mw) of the resin composition is in the above range, a resin composition excellent in mechanical properties, particularly, water rigidity, rigidity under heat, fluidity, and the like can be obtained. In addition, a molded article obtained from a resin composition containing a component represented by a filler has more excellent surface appearance.

  As a method for controlling the weight average molecular weight (Mw) of the resin composition within the above range, for example, the weight average molecular weight (Mw) of (A) aliphatic polyamide, (B) MXD6 polyamide and (C) amorphous resin Is used in the range described below.

  The weight average molecular weight (Mw) can be measured using gel permeation chromatography (GPC), as described in Examples below.

<Molecular weight distribution of resin composition>
The molecular weight distribution of the resin composition of the present embodiment uses the weight average molecular weight (Mw) / number average molecular weight (Mn) as an index.
The weight average molecular weight (Mw) / number average molecular weight (Mn) of the resin composition of the present embodiment is preferably 2.4 or less, more preferably 1.0 or more and 2.4 or less, and 1.7 or more and 2.3 or less. Is more preferably 1.8 to 2.2, still more preferably 1.9 to 2.1.

  When the weight average molecular weight (Mw) / number average molecular weight (Mn) is in the above range, a resin composition having more excellent fluidity and the like tends to be obtained. Further, molded articles obtained from a resin composition containing a component represented by a filler tend to be more excellent in surface appearance.

As a method for controlling the weight average molecular weight (Mw) / number average molecular weight (Mn) of the resin composition within the above range, (B) weight average molecular weight (Mw (B)) of MXD6 polyamide / number average molecular weight (Mn ( And B)) in a range described below.
When an aromatic compound unit is contained in the molecular structure of the resin composition, the molecular weight distribution (Mw / Mn) tends to increase with increasing the molecular weight. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional molecular structure. Therefore, by controlling Mw / Mn within the above range, the progress of three-dimensional structuring of molecules during high-temperature processing can be suppressed, and a resin composition having better fluidity and the like can be obtained. In addition, the surface appearance of a molded product obtained from a resin composition containing a component represented by a filler becomes more excellent.

  The weight average molecular weight (Mw) / number average molecular weight (Mn) of the resin composition can be calculated using the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained using GPC.

<Tan δ peak temperature of resin composition>
The lower limit of the tan δ peak temperature of the resin composition is 90 ° C., preferably 105 ° C., more preferably 110 ° C., and even more preferably 115 ° C. On the other hand, the upper limit of the tan δ peak temperature of the resin composition is preferably 150 ° C., more preferably 140 ° C., and even more preferably 135 ° C.
That is, the tan δ peak temperature of the resin composition is 90 ° C. or higher, preferably 105 ° C. to 150 ° C., more preferably 110 ° C. to 140 ° C., and even more preferably 115 ° C. to 135 ° C.

  When the tan δ peak temperature of the resin composition is equal to or higher than the lower limit value, the resin composition tends to be more excellent in water absorption rigidity and rigidity when heated. On the other hand, when the tan δ peak temperature of the resin composition is equal to or lower than the upper limit, a molded article obtained from the resin composition containing a component represented by the filler tends to have a more excellent surface appearance. is there.

  As a method for controlling the tan δ peak temperature of the resin composition within the above range, for example, the content of (A) the aliphatic polyamide, (B) the MXD6 polyamide and (C) the amorphous resin is controlled to the range described later. Method and the like.

  Hereinafter, details of each component of the resin composition of the present embodiment will be described.

<(A) Aliphatic polyamide>
The structural unit of the aliphatic polyamide (A) contained in the resin composition of the present embodiment preferably satisfies at least one of the following conditions (1) and (2).
(1) It contains at least one kind of (Aa) aliphatic dicarboxylic acid unit and at least one kind of (Ab) aliphatic diamine unit.
(2) (Ac) It contains at least one structural unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit.
The resin composition of the present embodiment can contain, as (A) an aliphatic polyamide, one or more polyamides satisfying at least one of the above conditions (1) and (2).

[(A-a) aliphatic dicarboxylic acid unit]
(Aa) Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include a linear or branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms.
Examples of the linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , Sebacic acid, dodecandioic acid, tetradecandioic acid, hexadecandioic acid, octadecandioic acid, eicosantioic acid, diglycolic acid and the like.
Examples of the branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, Examples thereof include 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid.
These aliphatic dicarboxylic acids constituting the (Aa) aliphatic dicarboxylic acid unit may be used alone or in combination of two or more.
Above all, the heat resistance, fluidity, toughness, low water absorption, and rigidity of the resin composition tend to be more excellent. Therefore, as the aliphatic dicarboxylic acid constituting the (A-a) aliphatic dicarboxylic acid unit, A straight-chain saturated aliphatic dicarboxylic acid having 6 or more carbon atoms is preferred.

Specific examples of preferred straight-chain saturated aliphatic dicarboxylic acids having 6 or more carbon atoms include, for example, adipic acid, sebacic acid, dodecandioic acid, tetradecandioic acid, hexadecandioic acid, octadecandioic acid, eicosanedioic acid, and the like. Can be
Above all, as the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms, adipic acid, sebacic acid or dodecane diacid is preferable from the viewpoint of heat resistance of the resin composition and the like.

  In addition, the aliphatic polyamide (A) may further include a unit derived from a trivalent or higher polycarboxylic acid, if necessary, as long as the effect of the resin composition of the present embodiment is not impaired. Examples of the trivalent or higher polycarboxylic acid include trimellitic acid, trimesic acid, and pyromellitic acid. These trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[(A-b) Aliphatic diamine unit]
As the aliphatic diamine constituting the (Ab) aliphatic diamine unit, for example, a linear saturated aliphatic diamine having 2 to 20 carbon atoms or a branched saturated aliphatic diamine having 3 to 20 carbon atoms Diamines and the like can be mentioned.
Examples of the linear saturated aliphatic diamine having 2 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and octaamine. Examples include methylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine.
Examples of the branched saturated aliphatic diamine having 3 to 20 carbon atoms include, but are not limited to, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane). 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), 2,4-dimethyl Octamethylene diamine and the like can be mentioned.
As the aliphatic diamine constituting the (A-b) aliphatic diamine unit, only one type may be used alone, or two or more types may be used in combination.
Above all, the number of carbon atoms of the aliphatic diamine constituting the (A-b) aliphatic diamine unit is preferably from 6 to 12, more preferably from 6 to 10. (Ab) When the carbon number of the aliphatic diamine constituting the aliphatic diamine unit is not less than the lower limit, the heat resistance of the obtained molded product is more excellent. On the other hand, when the number of carbon atoms is equal to or less than the above upper limit, the obtained molded article is more excellent in crystallinity and releasability.

Specific examples of preferred linear or branched saturated aliphatic diamines having 6 to 12 carbon atoms include, for example, hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine and the like. No.
Among them, hexamethylenediamine or 2-methylpentamethylenediamine is preferred as the linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms. By including such an (A-b) aliphatic diamine unit, a molded product obtained from the resin composition is more excellent in heat resistance, rigidity, and the like.

  In addition, the aliphatic polyamide (A) may further include a unit derived from a trivalent or higher polyvalent aliphatic amine, if necessary, as long as the effect of the resin composition of the present embodiment is not impaired. Examples of the trivalent or higher polyvalent aliphatic amine include bishexamethylene triamine.

[(Ac) at least one structural unit selected from the group consisting of lactam units and aminocarboxylic acid units]
(A) The aliphatic polyamide may contain at least one structural unit selected from the group consisting of (A-c) a lactam unit and an aminocarboxylic acid unit. By including such a unit, a polyamide having excellent toughness tends to be obtained.
Here, the “lactam unit” and the “aminocarboxylic acid unit” refer to a lactam and an aminocarboxylic acid which are polycondensed.

Examples of the lactam constituting the lactam unit include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, capryloractam, enantholactam, undecanolactam, laurolactam (dodecanolactam), and the like. Can be
Among them, the lactam constituting the lactam unit is preferably ε-caprolactam or laurolactam, and more preferably ε-caprolactam. By including such a lactam, the toughness of a molded article obtained from the resin composition tends to be more excellent.

Examples of the aminocarboxylic acid constituting the aminocarboxylic acid unit include, but are not limited to, ω-aminocarboxylic acids and α, ω-amino acids which are compounds in which a lactam is opened.
As the aminocarboxylic acid constituting the aminocarboxylic acid unit, a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms and substituted at the ω-position with an amino group is preferable. Such aminocarboxylic acids are not limited to the following, but include, for example, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. In addition, examples of the aminocarboxylic acid include para-aminomethylbenzoic acid.

  Lactam and aminocarboxylic acid constituting at least one kind of structural unit selected from the group consisting of these (Ac) lactam units and aminocarboxylic acid units may be used alone or in combination of two or more. May be used in combination.

  Among them, as the (A) aliphatic polyamide contained in the resin composition of the present embodiment, a polyamide containing a dicarboxylic acid unit and a diamine unit is preferable from the viewpoint of mechanical properties, heat resistance, moldability and toughness, and polyamide 66 (PA66) is more preferred. PA66 is considered to be a material suitable for automotive parts because of its excellent mechanical properties, heat resistance, moldability and toughness.

  The content of the aliphatic polyamide (A) in the resin composition of the present embodiment can be, for example, more than 0% by mass and 50% by mass or less based on the total mass of the polyamide in the resin composition. % By mass to 45% by mass, for example, 5% by mass to 40% by mass, for example, 7% by mass to 35% by mass, for example, 10% by mass to 30% by mass. % Or less.

<(B) MXD6 polyamide>
The MXD6 polyamide (B) contained in the resin composition of the present embodiment is a crystalline polyamide obtained by polymerizing a diamine containing meta-xylylenediamine (MXDA) and a dicarboxylic acid containing adipic acid. A polyamide containing a diamine unit containing a diamine unit and a dicarboxylic acid unit containing an adipic acid unit.

  (B) The MXD6 polyamide preferably contains 20 mol% or more and 80 mol% or less of an aromatic constitutional unit, and preferably 30 mol% or more and 70 mol% or less of an aromatic constitutional unit based on all constitutional units of the (B) MXD6 polyamide. More preferably, it contains a structural unit, and even more preferably, it contains 40 to 60% by mole of an aromatic structural unit. Here, the “aromatic structural unit” means an aromatic diamine unit and an aromatic dicarboxylic acid unit.

  (B) MXD6 polyamide is (B) a dicarboxylic acid unit containing 50 mol% or more of adipic acid units and 50 mol% or more of metaxylylenediamine unit with respect to all dicarboxylic acid units of MXD6 polyamide. (Bb) diamine unit.

  At this time, the total content of the adipic acid unit and the metaxylylenediamine unit in the (B) MXD6 polyamide is preferably 50 mol% or more, and more preferably 80 mol%, based on all the structural units of the (B) MXD6 polyamide. It is more preferably at least 100 mol%, more preferably at least 90 mol% and at most 100 mol%, particularly preferably at least 100 mol%.

  In addition, the ratio of the predetermined monomer unit which comprises (B) MXD6 polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) etc.

  (B) MXD6 polyamide contained in the resin composition of the present embodiment is a material suitable for automobile parts because it has excellent heat resistance, moldability and flame retardancy.

The content of (B) MXD6 polyamide in the resin composition of the present embodiment can be, for example, 50% by mass or more and less than 100% by mass with respect to the total mass of polyamide in the resin composition, and is, for example, 55% by mass. % To 98% by mass, for example, 58% to 95% by mass, for example, 60% to 92% by mass, for example, 62% to 90% by mass. It can be:
(B) By setting the content of the MXD6 polyamide in the above range, the mechanical properties of a molded product obtained from the resin composition are more excellent. In addition, by including a component represented by a filler, the surface appearance of a molded article obtained from the resin composition becomes more excellent.

<(A) Method for producing aliphatic polyamide and (B) MXD6 polyamide>
When producing the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) contained in the resin composition of the present embodiment, the amount of the dicarboxylic acid added and the amount of the diamine added are around the same molar amount. Is preferred. The molar amount of the entire diamine is preferably 0.9 or more and 1.2 or less with respect to the molar amount of the entire dicarboxylic acid of 1, taking into consideration the amount of the diamine escaping out of the reaction system during the polymerization reaction. , 0.95 or more and 1.1 or less, more preferably 0.98 or more and 1.05 or less.

The method for producing the polyamide is not limited to the following, but includes, for example, the following polymerization step (1) or (2).
(1) A step of polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.
(2) a step of polymerizing at least one member selected from the group consisting of a lactam constituting a lactam unit and an aminocarboxylic acid constituting an aminocarboxylic acid unit to obtain a polymer;

  The method for producing a polyamide preferably further includes, after the polymerization step, a step of increasing the degree of polymerization of the polyamide. Further, if necessary, a sealing step of sealing the terminal of the obtained polymer with a terminal blocking agent may be included after the polymerization step and the raising step.

Specific methods for producing polyamide include, for example, various methods as exemplified in the following 1) to 4).
1) One or more aqueous solutions or aqueous suspensions selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams, and aminocarboxylic acids are heated and polymerized while maintaining a molten state (Hereinafter, may be referred to as “hot melt polymerization method”).
2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature equal to or lower than the melting point (hereinafter, may be referred to as "hot melt polymerization / solid state polymerization method").
3) A method of polymerizing one or more selected from the group consisting of a dicarboxylic acid-diamine salt, a mixture of a dicarboxylic acid and a diamine, a lactam, and an aminocarboxylic acid while maintaining a solid state (hereinafter, referred to as “solid phase weight”). Legally ").
4) A method of polymerizing using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (hereinafter, may be referred to as a "solution method").

Above all, as a specific method for producing a polyamide, a production method including a hot melt polymerization method is preferable. Further, when producing a polyamide by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to manufacture the polyamide under polymerization conditions suitable for the polyamide. Examples of the polymerization conditions include the following conditions and the like. First, the polymerization pressure in the hot melt polymerization method is controlled to 14 kg / cm ² or more and 25 kg / cm ² or less (gauge pressure), and heating is continued. Next, the pressure is reduced while applying pressure for 30 minutes or more until the pressure in the tank becomes atmospheric pressure (gauge pressure is 0 kg / cm ² ).

In the method for producing a polyamide, the polymerization form is not particularly limited, and may be a batch type or a continuous type.
The polymerization apparatus used for producing the polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include an autoclave reactor, a tumbler reactor, and an extruder reactor (such as a kneader).

Hereinafter, a method for producing a polyamide by a batch-type hot-melt polymerization method will be specifically described as a method for producing the polyamide, but the method for producing the polyamide is not limited thereto.
First, a raw material component of a polyamide (a combination of a dicarboxylic acid and a diamine and, if necessary, at least one selected from the group consisting of a lactam and an aminocarboxylic acid) is contained in an amount of about 40% by mass or more and 60% by mass or less. Prepare an aqueous solution. Next, the aqueous solution is concentrated to about 65% to 90% by mass in a concentration tank operated at a temperature of 110 ° C to 180 ° C and a pressure of about 0.035 MPa to 0.6 MPa (gauge pressure). To obtain a concentrated solution.
Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave becomes about 1.2 MPa or more and 2.2 MPa or less (gauge pressure).
Next, in the autoclave, the pressure is maintained at about 1.2 MPa to 2.2 MPa (gauge pressure) while removing at least one of water and gas components. Next, when the temperature reaches about 220 ° C. to 260 ° C., the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). By reducing the pressure in the autoclave to the atmospheric pressure and then reducing the pressure as necessary, water by-produced can be effectively removed.
Next, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as strands. The extruded strand is cooled and cut to obtain polyamide pellets.

<Polyamide terminal of polyamide>
The polymer terminals of the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) contained in the resin composition of the present embodiment are not particularly limited, but are classified and defined as 1) to 4) below. Can be.
That is, 1) amino terminal, 2) carboxy terminal, 3) terminal by sealant, 4) other terminal.
1) The amino terminal is a polymer terminal having an amino group (—NH ₂ group) and is derived from a diamine unit.
2) The carboxy terminal is a polymer terminal having a carboxy group (—COOH group) and is derived from dicarboxylic acid.
3) The terminal by the sealant is a terminal formed when the sealant is added at the time of polymerization. Examples of the sealing agent include terminal sealing agents described below.
4) The other terminal is a polymer terminal that is not classified in the above 1) to 3). Specific examples of the other terminal include a terminal generated by a deammonification reaction of an amino terminal and a terminal generated by a decarboxylation reaction from a carboxy terminal.

[Terminal blocking agent]
The ends of the polyamide may be end-capped with a known end-capping agent.
Such a terminal blocking agent can also be added as a molecular weight regulator when producing a polyamide from the dicarboxylic acid and the diamine.
Further, a polyamide composition containing a polyamide whose terminal is blocked by a terminal blocking agent tends to be more excellent in heat resistance, fluidity, toughness, low water absorption and rigidity.

Examples of the terminal blocking agent include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Examples of the acid anhydride include phthalic anhydride.
Above all, a monocarboxylic acid or a monoamine is preferable as the terminal blocking agent. When the terminal of the polyamide is blocked with the terminal blocking agent, the polyamide composition tends to be more excellent in thermal stability.
One type of terminal blocking agent may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the terminal blocking agent may be any one having reactivity with an amino group that may be present at the terminal of the polyamide, and is not limited to the following. Examples include acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. Examples of the aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylic acid. No. Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid. Examples of the aromatic monocarboxylic acid include benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and the like.
Monocarboxylic acids may be used alone or in combination of two or more.

The monoamine that can be used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group that may be present at the terminal of the polyamide, and examples thereof include, but are not limited to, aliphatic monoamine and alicyclic ring. Group monoamines and aromatic monoamines. Examples of the aliphatic monoamino include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine and the like. Examples of the alicyclic monoamine include cyclohexylamine, dicyclohexylamine, and the like. Examples of the aromatic monoamine include aniline, toluidine, diphenylamine, naphthylamine and the like.
Monoamines may be used alone or in combination of two or more.

<Characteristics of polyamide>
[(A) Characteristics of aliphatic polyamide]
(A) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the aliphatic polyamide can have the following constitution, and can be specifically measured by the following method.

((A) Weight average molecular weight Mw (A) of aliphatic polyamide)
(A) As an index of the molecular weight of the aliphatic polyamide, a weight average molecular weight can be used. (A) The weight average molecular weight (Mw (A)) of the aliphatic polyamide is preferably from 10,000 to 50,000, more preferably from 15,000 to 45,000, further preferably from 20,000 to 40,000, and particularly preferably from 25,000 to 35,000.
When the Mw (A) is in the above range, a resin composition which can simultaneously satisfy mechanical properties, particularly, water absorption stiffness, stiffness at heat, fluidity, and the like tends to be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.
The weight average molecular weight (Mw (A)) of the aliphatic polyamide (A) can be measured using GPC.

((A) Molecular weight distribution of aliphatic polyamide)
The molecular weight distribution of (A) the aliphatic polyamide is represented by (A) weight average molecular weight of the aliphatic polyamide (Mw (A)) / (A) number average molecular weight of the aliphatic polyamide (Mn (A)).
Mw (A) / Mn (A) is preferably 1.0 or more, more preferably 1.8 or more and 2.2 or less, and still more preferably 1.9 or more and 2.1 or less.
When Mw (A) / Mn (A) is in the above range, a resin composition having excellent fluidity and the like can be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.

As a method of controlling Mw (A) / Mn (A) within the above range, for example, a method shown in the following 1) or 2) can be mentioned.
1) A method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during hot melt polymerization of polyamide.
2) In addition to the above method 1), a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions.

  Note that Mw (A) / Mn (A) can be calculated using Mw (A) and Mn (A) obtained using GPC.

((A) Melting point Tm2 of aliphatic polyamide)
(A) The lower limit of the melting point Tm2 of the aliphatic polyamide is preferably 220 ° C, more preferably 230 ° C, and still more preferably 240 ° C. On the other hand, the upper limit of the melting point Tm2 of the aliphatic polyamide (A) is preferably 300 ° C, more preferably 290 ° C, further preferably 280 ° C, and particularly preferably 270 ° C.
That is, the melting point Tm2 of the aliphatic polyamide (A) is preferably from 220 ° C to 300 ° C, more preferably from 230 ° C to 290 ° C, further preferably from 240 ° C to 280 ° C, particularly preferably from 240 ° C to 270 ° C. preferable.
(A) When the melting point Tm2 of the aliphatic polyamide is equal to or more than the above lower limit, the molded article obtained from the resin composition tends to have higher rigidity at heat and the like. On the other hand, when the melting point Tm2 of the aliphatic polyamide (A) is equal to or less than the above upper limit, thermal decomposition of the resin composition in melt processing such as extrusion and molding tends to be further suppressed.

((A) Enthalpy of crystallization ΔH of aliphatic polyamide)
(A) The lower limit of the crystallization enthalpy ΔH of the aliphatic polyamide is preferably 30 J / g, more preferably 40 J / g, and still more preferably 50 J / g, from the viewpoint of mechanical properties, in particular, water absorption rigidity and rigidity at the time of heating. 60 J / g is particularly preferred. On the other hand, the upper limit of the crystallization enthalpy ΔH of the aliphatic polyamide (A) is not particularly limited, and the higher the higher, the better.
(A) As an apparatus for measuring the melting point Tm2 and crystallization enthalpy ΔH of the aliphatic polyamide, for example, Diamond-DSC manufactured by PERKIN-ELMER and the like can be mentioned.

((A) Tan δ peak temperature of aliphatic polyamide)
(A) The tan δ peak temperature of the aliphatic polyamide is preferably 40 ° C or higher, more preferably 50 ° C or higher and 110 ° C or lower, still more preferably 60 ° C or higher and 100 ° C or lower, particularly preferably 70 ° C or higher and 95 ° C or lower, and 80 ° C. The temperature is more preferably at least 90 ° C.
(A) When the tan δ peak temperature of the aliphatic polyamide is equal to or higher than the lower limit, the molded article obtained from the composition tends to have more excellent water absorption rigidity and thermal rigidity.
(A) The tan δ peak temperature of the aliphatic polyamide can be measured using a viscoelasticity measurement analyzer or the like (manufactured by Rheology: DVE-V4).

[(B) Characteristics of MXD6 polyamide]
(B) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, tan δ peak temperature, amino terminal amount, and carboxy terminal amount of the MXD6 polyamide can be configured as follows, and specifically, can be measured by the following method. it can.

((B) Weight average molecular weight Mw (B) of MXD6 polyamide)
As an index of the molecular weight of (B) MXD6 polyamide, the weight average molecular weight (Mw (B)) of (B) MXD6 polyamide can be used.
(B) The weight average molecular weight (Mw (B)) of the MXD6 polyamide is preferably from 10,000 to 70,000, more preferably from 15,000 to 70,000, further preferably from 15,000 to 65,000, particularly preferably from 20,000 to 65,000, and more preferably from 3,000 to 65,000. 60000 or less is most preferred.
(B) When the weight average molecular weight (Mw (B)) of the MXD6 polyamide is in the above range, a resin composition having excellent mechanical properties, particularly excellent water absorption stiffness, hot stiffness, fluidity, and the like can be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.
The weight average molecular weight (Mw (B)) of (B) MXD6 polyamide can be measured by using GPC.

((B) Molecular weight distribution of MXD6 polyamide)
The molecular weight distribution of (B) MXD6 polyamide is represented by the weight average molecular weight (Mw (B)) of (B) MXD6 polyamide / number average molecular weight (Mn (B)) of (B) MXD6 polyamide.
Mw (B) / Mn (B) is preferably 2.4 or less, more preferably 1.0 or more and 2.4 or less, still more preferably 1.7 or more and 2.4 or less, and 1.8 or more and 2.3 or less. Still more preferably, 1.9 or more and 2.2 or less are particularly preferable, and 1.9 or more and 2.1 or less are most preferable.
When Mw (B) / Mn (B) is in the above range, a resin composition having more excellent fluidity and the like can be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.

As a method for controlling Mw (B) / Mn (B) within the above range, for example, the following methods 1) and 2) can be mentioned.
1) A method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during hot melt polymerization of polyamide.
2) A method in which polymerization conditions such as heating conditions and reduced pressure conditions are controlled in addition to the above method 1) to complete the polycondensation reaction at a temperature as low as possible and in a short time.

  When the aromatic compound unit is contained in the molecular structure of the polyamide, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional molecular structure. Therefore, by controlling Mw (B) / Mn (B) within the above range, the progress of three-dimensional structuring of molecules during high-temperature processing can be suppressed, and a resin composition having better fluidity and the like can be obtained. In addition, the surface appearance of a molded product obtained from a resin composition containing a component represented by a filler becomes more excellent.

  The measurement of Mw (B) / Mn (B) can be calculated using Mw (B) and Mn (B) obtained using GPC.

((B) Crystallization enthalpy ΔH of MXD6 polyamide)
(B) The crystallization enthalpy ΔH of the MXD6 polyamide is preferably 15 J / g or more and 70 J / g or less, more preferably 25 J / g or more and 60 J / g or less, and more preferably 30 J / g from the viewpoint of mechanical properties, particularly water absorption stiffness and stiffness when heated. / G or more and 50 J / g or less are particularly preferable.
(B) As an apparatus for measuring the crystallization enthalpy ΔH of the MXD6 polyamide, for example, Diamond-DSC manufactured by PERKIN-ELMER and the like can be mentioned.

((B) Tan δ peak temperature of MXD6 polyamide)
(B) The tan δ peak temperature of the MXD6 polyamide is preferably 70 ° C or higher, more preferably 100 ° C or higher and 160 ° C or lower, further preferably 110 ° C or higher and 150 ° C or lower, particularly preferably 120 ° C or higher and 145 ° C or lower, and 130 ° C or higher. 140 ° C. or lower is most preferred.
(B) When the tan δ peak temperature of the MXD6 polyamide is equal to or higher than the above lower limit, a resin composition having excellent water absorption rigidity and hot rigidity tends to be obtained. In addition, when the tan δ peak temperature of the resin composition is equal to or lower than the above upper limit, the surface appearance of a molded product obtained from the resin composition containing a component represented by the filler becomes more excellent.
(B) The tan δ peak temperature of the MXD6 polyamide can be measured using, for example, a viscoelasticity measurement analyzer (manufactured by Rheology: DVE-V4).

((B) Amount of amino terminal of MXD6 polyamide)
The amino terminal amount of (B) MXD6 polyamide is preferably 5 μg or more and 100 μg or less, more preferably 10 μg or more and 90 μg or less, further preferably 20 μg or more and 80 μg or less, particularly preferably 30 μg or more and 70 μg or less, based on 1 g of (B) MXD6 polyamide. It is most preferably 40 μg or more and 60 μg or less.
(B) When the amount of amino terminal of the MXD6 polyamide is in the above range, a resin composition which is more excellent in discoloration to heat and light can be obtained.
The amino terminal amount can be measured by neutralization titration.

((B) Carboxy terminal amount of MXD6 polyamide)
(B) The carboxy terminal amount of the MXD6 polyamide is preferably from 5 μg to 200 μg, more preferably from 10 μg to 150 μg, more preferably from 20 μg to 130 μg, and particularly preferably from 30 μg to 100 μg, based on 1 g of the (D) MXD6 polyamide. It is most preferably 40 μg or more and 80 μg or less.
(B) When the carboxy terminal amount of the MXD6 polyamide is in the above range, a resin composition having more excellent fluidity and the like can be obtained. In addition, the surface appearance of a molded product obtained from a resin composition containing a component represented by a filler becomes more excellent.
The carboxy terminal amount can be measured by neutralization titration.

[Total amount of amino terminal amount and carboxy terminal amount of polyamide]
The total amount of the amino terminal amount and the carboxy terminal amount of the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) is preferably from 10 μg to 350 μg, more preferably from 20 μg to 300 μg, based on 1 g of the polyamide, It is more preferably from 20 μg to 200 μg, particularly preferably from 30 μg to 150 μg, and most preferably from 50 μg to 120 μg.
When the total amount of the amino terminal amount and the carboxy terminal amount of the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) is within the above range, a resin composition having more excellent fluidity and the like can be obtained. In addition, the surface appearance of a molded product obtained from a resin composition containing a component represented by a filler becomes more excellent.
The total amount of the amino terminal and the carboxy terminal of the polyamide can be calculated using the amount of the amino terminal and the amount of the carboxy terminal obtained by neutralization titration.

<(C) Amorphous resin>
(C) The amorphous resin contained in the resin composition of the present embodiment has a glass transition temperature of 80 ° C. or higher when heated at a rate of 20 ° C./min in differential scanning calorimetry according to JIS-K7121. There is no particular limitation as long as the temperature is 250 ° C. or lower.
One kind of these (C) amorphous resins may be used alone, or two or more kinds may be used in combination.

(C) Examples of the amorphous resin include an amorphous polyamide resin, a polystyrene resin, an acrylic resin, a polyether resin, and the like.
Examples of the amorphous polyamide resin include PA6I, PA6I / 6T, PAMACMI, PA12 / MACMI, PAMACM12, PAPACM12, and PATMHAT.
Examples of the polystyrene resin include atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, acrylonitrile-styrene copolymer (hereinafter sometimes abbreviated as “AS”) resin, and acrylonitrile-butadiene-styrene copolymer. And a resin (hereinafter sometimes abbreviated as “ABS”).
Examples of the polyether-based resin include polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone.
Examples of the acrylic resin include polyacrylic acid, polyacrylate, polymethyl methacrylate (polymethyl methacrylate), and the like.
Among them, (C) the amorphous resin preferably does not contain a polyamide resin, more preferably a polystyrene resin, an acrylic resin or a polyether resin, and atactic polystyrene, an AS resin, an ABS resin, and polymethyl methacrylate. , Polyphenylene ether or polycarbonate is more preferable, and atactic polystyrene, AS resin, ABS resin, polycarbonate or polymethyl methacrylate is particularly preferable.

((C) Weight average molecular weight Mw of amorphous resin (B))
As the index of the molecular weight of the (C) amorphous resin, the weight average molecular weight (Mw (C)) of the (C) amorphous resin can be used.
(C) The weight average molecular weight (Mw (C)) of the amorphous resin is preferably 10,000 or more and 1,000,000 or less, more preferably 15,000 or more and 700,000 or less, further preferably 20,000 or more and 600,000 or less, and particularly preferably 25,000 or more and 500,000 or less. Most preferably, it is 30,000 or more and 400,000 or less.
(C) When the weight average molecular weight (Mw (C)) of the amorphous resin is within the above range, a resin composition having excellent mechanical properties, particularly excellent water absorption stiffness, stiffness when heated, fluidity, and the like can be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.
The weight average molecular weight (Mw (C)) of the amorphous resin (C) can be measured using GPC.

((C) Glass transition temperature of amorphous resin)
(C) In the differential scanning calorimetry of the amorphous resin according to JIS-K7121, the glass transition temperature obtained when the temperature is raised at 20 ° C./min is 80 ° C. or more and 250 ° C. or less, and 85 ° C. or more. 250 ° C or lower is preferable, 85 ° C or higher and 220 ° C or lower is more preferable, 85 ° C or higher and 200 ° C or lower is further preferable, and 90 to 180 ° C or lower is further preferable.
(C) When the glass transition temperature of the amorphous resin is in the above range, a resin composition excellent in mechanical properties, particularly, rigidity at heat, impact resistance, fluidity, and the like can be obtained. Further, a molded article obtained from a resin composition containing a component represented by a filler has a more excellent surface appearance.

((C) Crystalline enthalpy of amorphous resin ΔH)
(C) The crystallization enthalpy ΔH of the amorphous resin is preferably 0 J / g or more and 15 J / g or less, more preferably 0 J / g or more and 10 J / g or less, from the viewpoint of mechanical properties, particularly, the water absorption rigidity and the rigidity when heated. , 0 J / g or more and 5 J / g or less.
(C) Examples of an apparatus for measuring the glass transition temperature and ΔH of an amorphous resin include Diamond-DSC manufactured by PERKIN-ELMER.

<(D1) Flame retardant>
The flame retardant (D1) contained in the resin composition of the present embodiment is not particularly limited as long as it contains a halogen element. (D1) Examples of the flame retardant include a chlorine-based flame retardant and a bromine-based flame retardant.
One of these (D1) flame retardants may be used alone, or two or more thereof may be used in combination.

  Examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (Dechlorane Plus 25 (registered trademark) manufactured by Oxydental Chemical), and hetic anhydride. Can be

  Examples of the brominated flame retardant include hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A (TBBA), bis (tribromophenoxy) ethane, and bis (pentabromo). Phenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (bistetrabromophthal) imide (EBTBPI), ethylenebispentabromodiphenyl, tris (tri) (Bromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobi Phenol S (DBP-TBBS), brominated polyphenylene ether (including poly (di) bromophenylene ether, etc.) (BrPPE), brominated polystyrene (including polydibromostyrene, polytribromostyrene, cross-linked brominated polystyrene, etc.) ( BrPS), brominated cross-linked aromatic polymer, brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP) , Polybromotrimethylphenylindane (PBPI), tris (dibromopropyl) -isocyanurate (TDBPIC) and the like.

  Among them, the (D1) flame retardant is used from the viewpoint of suppressing the amount of corrosive gas generated during melt processing such as extrusion or molding, and further from the viewpoint of manifestation of flame retardancy and mechanical properties such as toughness and rigidity. , Brominated polyphenylene ether (including poly (di) bromophenylene ether, etc.) or brominated polystyrene (including polydibromostyrene, polytribromostyrene, cross-linked brominated polystyrene, etc.) is preferred, and brominated polystyrene is more preferred. .

The method for producing the brominated polystyrene is not particularly limited, and examples thereof include the following methods 1) and 2).
1) A method of producing a polystyrene by polymerizing a styrene monomer and then brominating a benzene ring of the polystyrene.
2) A method of producing by polymerization of a brominated styrene monomer (bromostyrene, dibromostyrene, tribromostyrene, etc.).

The bromine content in the brominated polystyrene is preferably from 55% by mass to 75% by mass.
By setting the bromine content to the above lower limit or more, the bromine amount required for flame retardancy can be satisfied with a small amount of brominated polystyrene. Further, a resin composition excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and flame retardancy can be obtained without impairing the properties of the polyamide copolymer.
On the other hand, when the bromine content is equal to or less than the above upper limit, thermal decomposition can be more effectively suppressed during melt processing such as extrusion or molding, and gas generation and the like can be more effectively suppressed. In addition, a resin composition having better heat discoloration resistance can be obtained.

<(D2) Flame retardant aid>
The resin composition of this embodiment can be made into a resin composition having more excellent flame retardancy by containing (D2) a flame retardant aid.

The (D2) flame retardant aid contained in the resin composition of the present embodiment is not particularly limited, and examples thereof include antimony oxides, tin oxides, iron oxides, other metal oxides, and metal water. Examples include oxides, metal powders, metal carbonates, metal borates, and silicone.
Examples of antimony oxides include diantimony trioxide (Sb ₂ O ₃ ), diantimony tetroxide, diantimony pentoxide, and sodium antimonate.
Examples of tin oxides include tin monoxide, tin dioxide, and the like.
Examples of the iron oxides include ferric oxide and gamma iron oxide.
Other metal oxides include, for example, zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina), aluminum oxide (boehmite), silicon oxide (silica), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, Examples include cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.
Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide and the like.
Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten.
Examples of the metal carbonate include zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate and the like.
Examples of the metal borate include magnesium borate, calcium borate, aluminum borate and the like.
One type of these (D2) flame retardant aids may be used alone, or two or more types may be used in combination.

Among them, as the (D2) flame retardant aid contained in the resin composition of the present embodiment, antimony oxides, tin oxides, iron oxides, metal hydroxides, zinc oxide, Alternatively, zinc borate is preferable, antimony oxides, magnesium hydroxide, or zinc borate is more preferable, antimony oxides or magnesium hydroxide is further preferable, and diantimony trioxide (Sb ₂ O ₃ ) or magnesium hydroxide is used. Is particularly preferred.

From the viewpoint of enhancing the flame retardant effect, the average particle size of the flame retardant aid (D2) is preferably 0.01 μm or more and 10 μm or less.
The average particle size can be measured using a laser diffraction scattering particle size distribution analyzer or a precision particle size distribution analyzer.

<(E) White pigment>
The resin composition of the present embodiment may further contain a white pigment in addition to the components (A) to (D2).
Examples of the white pigment include, but are not particularly limited to, zinc sulfide, zinc oxide, titanium oxide, barium sulfate, calcium carbonate, aluminum oxide, lead carbonate, lead hydroxide, and silicon dioxide. Among them, at least one white pigment selected from the group consisting of zinc sulfide (ZnS), zinc oxide (ZnO), and titanium oxide is selected depending on mechanical properties such as toughness, strength and rigidity, and the balance between flame retardancy and coloring. preferable.

<(F) UV absorber>
The resin composition of the present embodiment may further contain (F) an ultraviolet absorber in addition to the components (A) to (D2).
The ultraviolet absorber is not particularly limited, for example, benzotriazole ultraviolet absorber, triazine ultraviolet absorber, benzophenone ultraviolet absorber, cyanoacrylate ultraviolet absorber, salicylate ultraviolet absorber, oxalinite ultraviolet absorber And the like.
Among them, in the resin composition, toughness, strength, and mechanical properties such as rigidity, and balance with flame retardancy, at least one selected from the group consisting of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. UV absorbers are preferred.

<(G) Polymer Containing α, β Unsaturated Dicarboxylic Anhydride Unit>
The resin composition of this embodiment may further contain (G) a polymer containing an α, β unsaturated dicarboxylic anhydride unit in addition to the components (A) to (D2). (G) By containing a polymer containing α, β unsaturated dicarboxylic anhydride units, a resin composition having more excellent mechanical properties such as toughness and rigidity can be obtained.

Examples of the polymer containing (G) an α, β unsaturated dicarboxylic anhydride unit contained in the resin composition of the present embodiment include, for example, a polymer containing an α, β unsaturated dicarboxylic anhydride as a copolymer component, Polymers modified with α, β unsaturated dicarboxylic anhydrides are exemplified.
Examples of the α, β unsaturated dicarboxylic anhydride include a compound represented by the following general formula (I) (hereinafter sometimes referred to as “compound (I)”).

In the general formula (I), R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ and R ¹² may be the same or different. Above all, it is preferable that R ¹¹ and R ¹² are the same because of easy production.
Examples of the alkyl group having 1 to 3 carbon atoms in R ¹¹ and R ¹² include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Above all, as R ¹¹ and R ¹² , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

  Preferred compounds (I) (α, β unsaturated dicarboxylic anhydride) include, for example, maleic anhydride, methyl maleic anhydride and the like. Among them, maleic anhydride is preferable as the compound (I) (α, β unsaturated dicarboxylic anhydride).

[Copolymer of aromatic vinyl compound and α, β unsaturated dicarboxylic anhydride]
As a polymer containing an α, β unsaturated dicarboxylic anhydride as a copolymer component, an aromatic vinyl compound and an α, β unsaturated compound can be used from the viewpoint of the efficiency of improving flame retardancy (expressed with a small amount of addition). Copolymers with dicarboxylic anhydrides are preferred.
As the aromatic vinyl compound used for producing the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic anhydride, for example, a compound represented by the following general formula (2) (hereinafter, “compound ( II) ").

In the general formula (II), R ²¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. R ²² is a substituent on a benzene ring. R ²² is an alkyl group having 1 to 3 carbon atoms. n21 is an integer of 0 or more and 5 or less. When n21 is 0, the benzene ring is unsubstituted.

As the alkyl group having 1 to 3 carbon atoms for R ²¹ and R ^22, the same as those exemplified for the above compound (I) can be mentioned.
Among them, R ²¹ is preferably a hydrogen atom or a methyl group. R ²² is preferably a methyl group.

n21 represents the number of ^{R 22} is a substituent of the benzene ring. n21 is preferably an integer of 0 or more and 1 or less, and more preferably 0.

  Preferred compounds (II) (aromatic vinyl compounds) include, for example, styrene, α-methylstyrene, p-methylstyrene and the like. Among them, styrene is preferable as the compound (II) (aromatic vinyl compound).

  (G) When the polymer containing an α, β unsaturated dicarboxylic anhydride unit contains an aromatic vinyl compound unit, the aromatic vinyl compound unit has an affinity for (D1) a flame retardant (eg, brominated polystyrene). Also, the α, β unsaturated dicarboxylic anhydride unit has an affinity or reaction with (B) MXD6 polyamide. It is thought that this helps the (D1) flame retardant to disperse in the polyamide matrix and allows the flame retardant to be finely dispersed.

The ratio of the aromatic vinyl compound unit and the α, β unsaturated dicarboxylic anhydride unit in the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic acid anhydride is difficult to obtain in the resin composition. From the viewpoints of flammability, fluidity, thermal decomposition resistance, etc., the aromatic vinyl compound unit accounts for 50% by mass based on all constituent units of the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic anhydride. It is preferable that the content of α, β unsaturated dicarboxylic anhydride units is 1% by mass to 50% by mass.
The ratio of the α, β unsaturated dicarboxylic anhydride unit in the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic anhydride is determined by the ratio of the aromatic vinyl compound to the α, β unsaturated dicarboxylic anhydride. The content is more preferably 5% by mass or more and 20% by mass or less, and further preferably 8% by mass or more and 15% by mass or less, based on all constituent units of the copolymer with the product.
When the ratio of the α, β unsaturated dicarboxylic anhydride unit in the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic anhydride is equal to or more than the lower limit, mechanical properties such as toughness and rigidity are obtained. In addition, a resin composition having more excellent flame retardancy can be obtained. On the other hand, when the ratio of the α, β unsaturated dicarboxylic anhydride units is not more than the above upper limit, the deterioration of the resin composition due to the α, β unsaturated dicarboxylic anhydride can be more effectively prevented.

[Polymer modified with α, β unsaturated dicarboxylic anhydride]
Examples of the polymer modified with α, β unsaturated dicarboxylic anhydride include polyphenylene ether and polypropylene modified with α, β unsaturated dicarboxylic anhydride. Among them, maleic anhydride-modified polyphenylene ether is preferred as the polymer modified with α, β unsaturated dicarboxylic anhydride.

  The content of the polymer modified with the α, β unsaturated dicarboxylic anhydride is preferably 0.05% by mass or more and 5% by mass or less based on the total mass of the resin composition.

<(H) filler>
The resin composition of the present embodiment may further contain a filler (H) in addition to the components (A) to (D2). (H) By containing a filler, a resin composition having more excellent mechanical properties such as toughness and rigidity can be obtained.

The (H) filler contained in the resin composition of the present embodiment is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, and glass. Flake, talc, kaolin, mica, hydrotalcite, zinc carbonate, calcium monohydrogen phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black Furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, apatite, and the like.
One type of these (H) fillers may be used alone, or two or more types may be used in combination.
Among them, (H) fillers include glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium monohydrogen phosphate, wollastonite, carbon nanotube, graphite, and fluoride from the viewpoint of rigidity and strength. Calcium, montmorillonite, swellable fluoromica, or apatite are preferred. As the filler (H), glass fiber or carbon fiber is more preferable, and glass fiber is more preferable.

(H) When the filler is glass fiber or carbon fiber, the number average fiber diameter (d) is preferably 3 μm or more and 30 μm or less. The weight average fiber length (l) is preferably 100 μm or more and 750 μm or less. The aspect ratio ((l) / (d)) of the weight average fiber length (l) to the number average fiber diameter (d) is preferably 3 or more and 100 or less. By using the glass fiber or the carbon fiber having the above configuration, higher characteristics can be exhibited.
When the filler (H) is glass fiber, the number average fiber diameter (d) is 3 μm or more and 30 μm or less, the weight average fiber length (l) is 103 μm or more and 500 μm or less, and the aspect ratio (( 1) / (d)) is more preferably 3 or more and 100 or less.

(H) The number average fiber diameter and the weight average fiber length of the filler can be measured using the following method.
First, a molded article of the resin composition is dissolved in a solvent in which polyamide is soluble, such as formic acid. Next, for example, 100 or more fillers are arbitrarily selected from the obtained insoluble components. Next, the filler can be determined by observing the filler with an optical microscope, a scanning electron microscope, or the like.

<Contents of (C) to (H) in resin composition>
[(C) Content of amorphous resin]
The content of the amorphous resin (C) in the resin composition of the present embodiment is preferably from 0.1% by mass to 30% by mass, and more preferably from 1% by mass to 20% by mass, based on the total mass of the resin composition. %, More preferably 2% by mass or more and 15% by mass or less, even more preferably 3% by mass or more and 10% by mass or less.
By setting the content of (C) the amorphous resin to the above lower limit or more, a resin composition having excellent rigidity and impact resistance can be obtained. On the other hand, when the content of the amorphous resin (excluding polyamide) is not more than the above lower limit, decomposition gas is generated at the time of melt-kneading, flowability at the time of molding is reduced, and contamination of the molding die is caused. It is possible to more effectively suppress the adhesion of the conductive substance. Further, a decrease in mechanical properties such as toughness and rigidity and appearance of a molded product can be more effectively suppressed.

[(D1) Flame retardant content]
The content of the flame retardant (D1) in the resin composition of the present embodiment is preferably from 0.1% by mass to 30% by mass, and more preferably from 1% by mass to 15% by mass, based on the total mass of the resin composition. Is more preferable, and 2 to 7% by mass is further preferable.
By setting the content of (D1) the flame retardant to the lower limit or more, a resin composition having more excellent flame retardancy can be obtained. On the other hand, when the content of the flame retardant (D1) is equal to or less than the above lower limit, generation of decomposition gas at the time of melt-kneading, reduction of fluidity at the time of molding, and adhesion of contaminants to the molding die are more effective. Can be suppressed. Further, a decrease in mechanical properties such as toughness and rigidity and appearance of a molded product can be more effectively suppressed.

[(D2) Content of flame retardant aid]
The content of (D2) the flame retardant aid in the resin composition of the present embodiment is preferably from 0.1% by mass to 10% by mass, and more preferably from 0.1% by mass to 4% by mass, based on the total mass of the resin composition. % Is more preferred.
By setting the content of the (D2) flame-retardant auxiliary to the lower limit or more, a resin composition having more excellent flame retardancy can be obtained. (D2) By controlling the content of the flame retardant auxiliary to the above upper limit or less, the viscosity during melt processing can be controlled to an appropriate range, the torque during extrusion increases, and the moldability during molding decreases. In addition, it is possible to more effectively suppress the deterioration of the appearance of the molded product. Further, a resin composition having more excellent toughness and the like can be obtained without impairing the properties of polyamide having excellent mechanical properties such as toughness and rigidity.

[Type and content of (D1) flame retardant and (D2) flame retardant auxiliary]
As a particularly preferred combination of the (D1) flame retardant and the (D2) flame retardant aid contained in the resin composition of the present embodiment, (D1) the flame retardant is a brominated polystyrene, and the content of the brominated polystyrene is 2% by mass or more and 7% by mass or less based on the total mass of the composition, and (D2) the flame retardant aid is diantimony trioxide (Sb ₂ O ₃ ), and diantimony trioxide (Sb ₂ The content of O ₃ ) is 0.1% by mass or more and 4% by mass or less based on the total mass of the resin composition.

[(E) Content of pigment]
In the case of containing the (E) white pigment, the content of the (E) white pigment in the resin composition of the present embodiment is 0.1% by mass or more and 5% by mass or less based on the total mass of the resin composition. Is preferable, and 0.5 mass% or more and 5 mass% or less are more preferable.
(E) When the content of the white pigment is in the above range, the color tone and mechanical properties (particularly, mechanical strength) tend to be more favorable.

[(F) Content of ultraviolet absorber]
In the case of containing the (F) ultraviolet absorber, the content of the (F) ultraviolet absorber in the resin composition of the present embodiment is from 0.1% by mass to 5% by mass relative to the total mass of the resin composition. % Or less, more preferably 0.1% by mass or more and 3% by mass or less, further preferably 0.1% by mass or more and 2.5% by mass or less, particularly preferably 0.2% by mass or more and 2.0% by mass or less. .
In particular, (F) the ultraviolet absorber is at least one selected from the group consisting of benzotriazole-based and triazine-based ultraviolet absorbers, and the content of (F) the ultraviolet absorber is based on the total mass of the resin composition. When the content is within the above range, a resin composition excellent in weather discoloration resistance and mechanical properties (particularly mechanical strength) can be obtained.

[(G) Content of polymer containing α, β unsaturated dicarboxylic anhydride units]
(G) When the polymer containing the α, β unsaturated dicarboxylic anhydride unit in the resin composition of the present embodiment when the polymer containing the α, β unsaturated dicarboxylic anhydride unit is contained, The content is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 20% by mass, and more preferably from 1% by mass to 15% by mass, based on the total mass of the resin composition. More preferably, the content is 1% by mass or more and 10% by mass or less.
(G) When the content of the polymer containing an α, β unsaturated dicarboxylic anhydride unit is at least the above lower limit, the fine dispersion effect of (D1) the flame retardant in the resin composition by compatibilization can be more improved. Can be enhanced. Further, there is a tendency that a resin composition which is more excellent in the effect of improving flame retardancy and strength can be obtained. On the other hand, when the content of the polymer containing (G) an α, β unsaturated dicarboxylic anhydride unit is not more than the above upper limit, the polyamide properties such as mechanical properties (particularly, toughness and rigidity) are not impaired. There is a tendency that a resin composition which is more excellent in strength, strength and the like can be obtained.

[(H) Content of filler]
In the case of containing the (H) filler, the content of the (H) filler in the resin composition of the present embodiment is preferably from 1% by mass to 80% by mass with respect to the total mass of the resin composition. The content is more preferably from 10% by mass to 70% by mass, further preferably from 30% by mass to 70% by mass, particularly preferably from 30% by mass to 60% by mass, and most preferably from 40% by mass to 60% by mass.
(H) When the content of the filler is not less than the lower limit, mechanical properties such as strength and rigidity of the resin composition tend to be further improved. On the other hand, when the content of the filler (H) is equal to or less than the upper limit, a resin composition having more excellent moldability tends to be obtained.
In particular, when the filler (H) is glass fiber and the content of the filler (H) is in the above range with respect to the total mass of the resin composition, the strength and rigidity of the resin composition are improved. Tends to be further improved.

<(J) Other additives>
In the resin composition of the present embodiment, in addition to the components (A) to (D2), (J) is commonly used for polyamide as long as the effect of the resin composition of the present embodiment is not impaired. Other additives may be included. (J) Other additives include, for example, (J1) a moldability improver (hereinafter also referred to as “lubricant”), (J2) a deterioration inhibitor, (J3) a nucleating agent, (J4) a heat stabilizer, (J5) Other resins and the like.
Since the content of (J) and other additives in the resin composition of the present embodiment varies depending on the type thereof, the use of the resin composition, and the like, it is within a range that does not impair the effects of the resin composition of the present embodiment. It is not particularly limited.

[(J1) Formability improver]
The (J1) moldability improver that can be included in the resin composition of the present embodiment is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

(Higher fatty acids)
Examples of the higher fatty acids include linear or branched, saturated or unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms.
Examples of the linear saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, and montanic acid.
Examples of the branched saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include isopalmitic acid and isostearic acid.
Examples of the linear unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include oleic acid and erucic acid.
Examples of the branched unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include isooleic acid.
Among them, stearic acid or montanic acid is preferable as the higher fatty acid.

(Metal salts of higher fatty acids)
The higher fatty acid metal salt is a metal salt of a higher fatty acid.
Examples of the metal element of the metal salt include a Group 1 element, a Group 2 element and a Group 3 element of the periodic table of the elements, zinc, and aluminum.
Examples of Group 1 elements of the periodic table include sodium, potassium, and the like.
Examples of the Group 2 element of the periodic table include calcium, magnesium, and the like.
Examples of Group 3 elements of the periodic table include scandium, yttrium, and the like.
Among them, a Group 1 element, a Group 2 element, or aluminum of the periodic table of the elements is preferable, and sodium, potassium, calcium, magnesium, or aluminum is more preferable.

Specific examples of the higher fatty acid metal salt include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like.
Among them, as the higher fatty acid metal salt, a metal salt of montanic acid or a metal salt of stearic acid is preferable.

(Higher fatty acid ester)
The higher fatty acid ester is an esterified product of a higher fatty acid and an alcohol.
As the higher fatty acid ester, an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
Examples of the aliphatic alcohol having 8 to 40 carbon atoms include stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Specific examples of higher fatty acid esters include stearyl stearate and behenyl behenate.

(Higher fatty acid amide)
The higher fatty acid amide is an amide compound of a higher fatty acid.
Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearylamide, ethylenebisoleylamide, N-stearylstearic acid amide, N-stearylerucic acid amide and the like.

  Each of these higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.

[(J2) Deterioration inhibitor]
The (J2) deterioration inhibitor that can be included in the resin composition of the present embodiment is used for the purpose of preventing thermal deterioration, discoloration during heating, and improving heat aging resistance.
(J2) The deterioration inhibitor is not particularly limited, but examples thereof include a copper compound, a phenol-based stabilizer, a phosphite-based stabilizer, a hindered amine-based stabilizer, a triazine-based stabilizer, a benzotriazole-based stabilizer, and a benzophenone-based stabilizer. , Cyanoacrylate-based stabilizers, salicylate-based stabilizers, sulfur-based stabilizers and the like.
Examples of the copper compound include copper acetate, copper iodide and the like.
Examples of the phenol stabilizer include a hindered phenol compound.
One of these (J2) deterioration inhibitors may be used alone, or two or more thereof may be used in combination.

[(J3) Nucleating agent]
(J3) The nucleating agent means a substance capable of obtaining at least one of the following effects (1) to (3) by addition.
(1) The effect of increasing the crystallization peak temperature of the resin composition.
(2) The effect of reducing the difference between the extrapolation start temperature and extrapolation end temperature of the crystallization peak.
(3) The effect of making the spherulite of the obtained molded product finer or uniform in size.

The nucleating agent (J3) that can be included in the resin composition of the present embodiment is not limited to the following, but, for example, talc, boron nitride, mica, kaolin, silicon nitride, carbon black, potassium titanate And molybdenum disulfide.
As the nucleating agent (J3), only one type may be used alone, or two or more types may be used in combination.
Above all, talc or boron nitride is preferable as the nucleating agent (J3) from the viewpoint of the nucleating agent effect.

In addition, since the effect of the nucleating agent is high, the number average particle size of (J3) the nucleating agent is preferably from 0.01 μm to 10 μm.
The number average particle size of the nucleating agent can be measured using the following method. First, the molded article is dissolved in a solvent in which polyamide such as formic acid is soluble. Next, for example, 100 or more nucleating agents are arbitrarily selected from the obtained insoluble components. Then, it can be determined by observing with an optical microscope, a scanning electron microscope or the like, and measuring the particle size.

The content of the nucleating agent in the resin composition of the present embodiment is 0.001 to 1 part by mass based on 100 parts by mass of the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide). Preferably, it is 0.001 part by mass or more and 0.5 part by mass or less, more preferably 0.001 part by mass or more and 0.09 part by mass or less.
By setting the content of the nucleating agent to 100 parts by mass or more of the polyamide and the lower limit or more, the heat resistance of the resin composition tends to be further improved. By setting the content to 100 parts by mass or less, the resin composition having more excellent toughness can be obtained.

[(J4) Heat stabilizer]
The heat stabilizer (J4) that can be included in the resin composition of the present embodiment is not limited to the following, but includes, for example, a phenol heat stabilizer, a phosphorus heat stabilizer, an amine heat stabilizer, and an element periodic table. And metal salts of the elements of Groups 3, 4 and 11 to 14, and halides of alkali metals and alkaline earth metals.

(Phenolic heat stabilizer)
The phenolic heat stabilizer is not limited to the following, but examples include a hindered phenol compound. The hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins and fibers such as polyamide.
Examples of the hindered phenol compound include, but are not limited to, N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionate). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, and the like can be mentioned.
These may be used alone or in combination of two or more of the hindered phenol compounds.
Particularly, from the viewpoint of improving heat aging resistance, hindered phenol compounds include N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )] Is preferred.

When a phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the resin composition is preferably 0.01% by mass or more and 1% by mass or less with respect to the total mass of the resin composition. The content is more preferably from 1% by mass to 1% by mass.
When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the resin composition can be further improved, and the amount of generated gas can be further reduced.

(Phosphorus heat stabilizer)
Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol type phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris isodecyl Phosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl (tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4'-butylidene- Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, 4,4'-isopropylidenebis (2 -T-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) Butanediphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite , Tris (mono- and di-mixed nonylphenyl) phosphite, 4,4'-isopropylidene Tris (3-tert-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) -bis (4,4'-butylidenebis (3-methyl- 6-t-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4 4,4'-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphite And the like.
One of these phosphorus-based heat stabilizers may be used alone, or two or more thereof may be used in combination.
Above all, as the phosphorus-based heat stabilizer, from the viewpoint of further improving the heat aging resistance of the resin composition and reducing the amount of generated gas, a pentaerythritol type phosphite compound and tris (2,4-di-t-butylphenyl) are used. ) One or more members selected from the group consisting of phosphites are preferred.

Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl -4-methylphenyl-stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl Carbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl・ Pentaerythritol diphosphite, bis (2,6-di t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite Phyte, 2,6-di-tert-butyl-4-methylphenyl-2,4-di-tert-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2 -Cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl pentaeryth Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight and the like.
These pentaerythritol type phosphite compounds may be used alone or in combination of two or more.
Above all, pentaerythritol type phosphite compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2 , 6-Di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6 And at least one member selected from the group consisting of -di-t-octyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite Fight is more preferred.

When a phosphorus-based heat stabilizer is used, the content of the phosphorus-based heat stabilizer in the resin composition is preferably 0.01% by mass or more and 1% by mass or less based on the total mass of the resin composition. The content is more preferably from 1% by mass to 1% by mass.
When the content of the phosphorus-based heat stabilizer is within the above range, the heat aging resistance of the resin composition can be further improved, and the amount of generated gas can be further reduced.

(Amine heat stabilizer)
Examples of the amine heat stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetraamine. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6, 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2 , 6,6-Tetramethyl-4-piperidyloxy) -ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2, 6,6-tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris ( 2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1, 3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di- t-butyl-4-hydroxyfe Le) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and condensates with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
One of these amine heat stabilizers may be used alone, or two or more thereof may be used in combination.

When an amine-based heat stabilizer is used, the content of the amine-based heat stabilizer in the resin composition is preferably 0.01% by mass or more and 1% by mass or less based on the total mass of the resin composition. The content is more preferably from 1% by mass to 1% by mass.
When the content of the amine-based heat stabilizer is within the above range, the heat aging resistance of the resin composition can be further improved, and the amount of generated gas can be further reduced.

(Metal salts of elements of Groups 3, 4 and 11 to 14 of the Periodic Table of the Elements)
The metal salts of the elements belonging to Groups 3, 4 and 11 to 14 of the periodic table are not particularly limited as long as they are salts of metals belonging to these groups.
Among them, a copper salt is preferred from the viewpoint of further improving the heat aging resistance of the resin composition. Examples of such copper salts include, but are not limited to, copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, and stearic acid. Copper and a copper complex salt in which copper is coordinated with a chelating agent.

Examples of the copper halide include copper iodide, cuprous bromide, cupric bromide, cuprous chloride and the like.
Examples of the chelating agent include ethylenediamine, ethylenediaminetetraacetic acid and the like.
These copper salts may be used alone or in combination of two or more.
Among them, the copper salt is preferably at least one selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, and is composed of copper iodide and copper acetate. One or more selected from the group is more preferable. When the above-mentioned preferred copper salt is used, it is more excellent in heat aging resistance, and more effectively suppresses metal corrosion (hereinafter, sometimes simply referred to as “metal corrosion”) of a screw or a cylinder during extrusion. The resulting resin composition is obtained.

(J4) When a copper salt is used as the heat stabilizer, the content of the copper salt in the resin composition is 0.01% based on the total mass of the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide). The mass is preferably from 0.6% by mass to 0.60% by mass, more preferably from 0.02% by mass to 0.40% by mass.
When the content of the copper salt is within the above range, the heat aging resistance of the resin composition can be further improved, and the precipitation of copper and metal corrosion can be more effectively suppressed.

Also, concentration of the copper elements derived from the copper salts described above, from the viewpoint of improving the thermal aging resistance of the resin composition, the polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) 10 ⁶ parts by weight (100 10 parts by mass or more and 2000 parts by mass or less, more preferably 30 parts by mass or more and 1500 parts by mass or less, even more preferably 50 parts by mass or more and 500 parts by mass or less.

(Halides of alkali metals and alkaline earth metals)
Examples of the alkali metal and alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride.
These alkali metal and alkaline earth metal halides may be used alone or in combination of two or more.
Among them, as the halides of alkali metals and alkaline earth metals, one or more selected from the group consisting of potassium iodide and potassium bromide are preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion. Potassium is more preferred.

When a halide of an alkali metal and an alkaline earth metal is used, the content of the halide of the alkali metal and the alkaline earth metal in the resin composition is determined by using polyamide ((A) aliphatic polyamide and (B) MXD6 polyamide) 100 It is preferably from 0.05 to 20 parts by mass, more preferably from 0.2 to 10 parts by mass with respect to parts by mass.
When the content of the halide of the alkali metal and the alkaline earth metal is within the above range, the heat aging resistance of the resin composition is further improved, and the precipitation of copper and metal corrosion can be more effectively suppressed. it can.

As the components of the heat stabilizer (J4) described above, only one kind may be used alone, or two or more kinds may be used in combination.
Above all, as the heat stabilizer (J4), a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable from the viewpoint of further improving the heat aging resistance of the resin composition.

The content ratio of the copper salt to the halide of an alkali metal and an alkaline earth metal is preferably from 2/1 to 40/1 as a molar ratio of halogen to copper (halogen / copper), and more preferably from 5/1 to 30/30. 1 or less is more preferable.
When the molar ratio of halogen to copper (halogen / copper) is within the above range, the heat aging resistance of the resin composition can be further improved.
In addition, when the molar ratio of halogen to copper (halogen / copper) is equal to or more than the above lower limit, precipitation of copper and metal corrosion can be more effectively suppressed. On the other hand, when the molar ratio of halogen to copper (halogen / copper) is equal to or less than the above upper limit, corrosion of screws and the like of a molding machine can be more effectively prevented without substantially impairing mechanical properties (toughness or the like).

[(J5) Other resins]
The (J5) other resin that can be included in the resin composition of the present embodiment is not particularly limited, and examples thereof include thermoplastic resins other than the above-described components (A) to (H).

(Thermoplastic resin)
Examples of the thermoplastic resin include a polyester resin, a condensation resin, a polyolefin resin, a halogen-containing vinyl compound resin, a phenol resin, and an epoxy resin.
Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and the like.
Examples of the condensation resin include polyphenylene sulfide and polyoxymethylene.
Examples of the polyolefin-based resin include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and the like.
Examples of the halogen-containing vinyl compound-based resin include polyvinyl chloride and polyvinylidene chloride.
One of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.

<Production method of resin composition>
The method for producing the resin composition of the present embodiment includes (A) an aliphatic polyamide, each of the components (B) to (D2), and, if necessary, each of the components (E) to (J). The method is not particularly limited as long as the method is a mixture of
As a method of mixing the component (A), the components (B) to (D2), and, if necessary, the components (E) to (J), for example, the following (1) ) Or (2).
(1) The component (A) and the components (B) to (D2) and, if necessary, the components (E) to (J) are mixed using a Henschel mixer or the like. And kneading by feeding to a melt kneader.
(2) In a single-screw or twin-screw extruder, the component (A) and each of the components (B) to (D2) and, if necessary, the components (E) to (G) and (J) Each component is previously mixed using a Henschel mixer or the like, and the component (A) and the components (B) to (D2) and, if necessary, (E) to (G) A method comprising preparing a mixture containing the components (A) and (J), supplying the mixture to a melt kneader, kneading the mixture, and optionally compounding a filler (H) from a side feeder.

In the method of supplying the components constituting the resin composition to the melt kneader, all the components may be supplied to the same supply port at a time, or the components may be supplied from different supply ports.
The melting and kneading temperature is preferably about 1 ° C. to 100 ° C. higher than the melting point of the aliphatic polyamide (A), and more preferably about 10 ° C. to 50 ° C. higher than the melting point of the (A) aliphatic polyamide.
The shear rate in the kneader is preferably about 100 sec ^-1 or more. The average residence time during kneading is preferably about 0.5 to 5 minutes.
As a device for performing the melt-kneading, a known device may be used, and for example, a single-screw or twin-screw extruder, a Banbury mixer, a melt-kneader (mixing roll and the like) and the like are preferably used.
The amount of each component when producing the resin composition of the present embodiment is the same as the content of each component in the above-described resin composition.

≪Molded product≫
The molded article of the present embodiment is obtained by molding the resin composition of the above embodiment.
Further, the molded article of the present embodiment has a high surface gloss value. The surface gloss value of the molded article of the present embodiment is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more. When the surface gloss value of the molded product is not less than the lower limit value, the obtained molded product can be used as various parts such as for automobiles, electric and electronic, industrial materials, industrial materials, and daily and household products. It can be suitably used.

The method for obtaining the molded product is not particularly limited, and a known molding method can be used.
Known molding methods include, for example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, foam injection molding, low pressure molding, ultra-thin wall injection molding (Ultra high-speed injection molding), composite molding in a mold (insert molding, outsert molding), and the like.

<Application>
The molded article of the present embodiment contains the resin composition of the above embodiment, is excellent in mechanical properties (particularly, tensile strength, flexural modulus, Charpy impact), surface appearance, and the like, and can be used for various applications.
As a use of the molded article of the present embodiment, for example, it can be suitably used in the automotive field, the electric and electronic field, the mechanical and industrial field, the office equipment field, the aviation and space field.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
Hereinafter, each component of the resin compositions used in the present examples and comparative examples will be described.

<Components>
[(A) Aliphatic polyamide]
A-1: Polyamide 66 (PA66)

[(B) MXD6 polyamide]
B-1: Polyamide MXD6 (PAMXD6) (manufactured by Toyobo, trade name: Toyobo nylon, T-600)

[(C) Amorphous resin]
C-1: Polystyrene (PS) (manufactured by Polystyrene Japan, trade name: GPPS, 680, glass transition temperature 105 ° C, Mw (C) = 200000)
C-2: Acrylonitrile-styrene copolymer (AS) (manufactured by Asahi Kasei, trade name: Stylac, T8804, glass transition temperature 110 ° C, Mw (C) = 80000)
C-3: acrylonitrile-butadiene-styrene copolymer (ABS) (manufactured by Asahi Kasei, trade name: Stylac, 190, glass transition temperature 110 ° C, Mw (C) = 125000)
C-4: Polymethyl methacrylate (PMMA) (manufactured by Asahi Kasei, trade name: Delpet, 720V, glass transition temperature 105 ° C, Mw (C) = 60000)
C-5: Polycarbonate (PC) (manufactured by Teijin, trade name: L-1225L, glass transition temperature 150 ° C, Mw (C) = 31600)
C-6: Polyphenylene ether (PPE) (manufactured by Asahi Kasei, trade name: Zylon, S203A, glass transition temperature 205 ° C, Mw (C) = 30,000)
In addition, (C) the glass transition temperature of the amorphous resin is measured by increasing the temperature at 20 ° C./min in differential scanning calorimetry according to JIS-K7121.

[(C ') elastomer]
C′-1: Ethylene-propylene rubber (EPM) (manufactured by JSR, trade name: JSR EP331, glass transition temperature −55 ° C.)

[(D1) Flame retardant]
D1-1: Brominated polystyrene (Br-PS) (manufactured by ALBEMALE CORPORATION, trade name: “SAYTEX (registered trademark) HP-7010G” (bromine content determined by elemental analysis: 67% by mass))

[(D2) Flame retardant aid]
D2-1: Antimony trioxide (Sb ₂ O ₃ ) (trade name: “antimony trioxide” manufactured by Dai-ichi FRL Co., Ltd.)

[(E) pigment]
E-1: Zinc sulfide (ZnS) (SACHTOLITH HD-S)

[(F) UV absorber]
F-1: Benzotriazole UV absorber (UVA-1) (Tinuvin 234)

[(G) Polymer containing α, β unsaturated dicarboxylic anhydride units]
G-1: Maleic anhydride-modified polyphenylene ether

[(H) filler]
H-1: Glass fiber (GF) (manufactured by Nippon Electric Glass, trade name “ECS03T275H”, average fiber diameter 10 μmφ, cut length 3 mm)

<Manufacture of polyamide>
The method for producing the aliphatic polyamide A-1 and the polymer (G) containing an α, β unsaturated dicarboxylic anhydride unit will be described in detail below. The aliphatic polyamide A-1 obtained by the following production method was dried in a stream of nitrogen to adjust the water content to about 0.2% by mass, and then the resin composition in Examples and Comparative Examples described later was used. It was used as a raw material.

Synthesis Example 1 Synthesis of Aliphatic Polyamide A-1 (Polyamide 66) A polymerization reaction of a polyamide was carried out by the “hot melt polymerization method” as follows.
First, an equimolar salt of adipic acid and hexamethylenediamine: 1500 g was dissolved in distilled water: 1500 g to prepare an equimolar 50% by mass homogeneous aqueous solution of the raw material monomer. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L, and was replaced with nitrogen. Subsequently, while stirring at a temperature of 110 ° C. or more and 150 ° C. or less, water vapor was gradually removed to a solution concentration of 70% by mass, followed by concentration. Next, the internal temperature was raised to 220 ° C. At this time, the pressure in the autoclave was increased to 1.8 MPa. The reaction was allowed to proceed for 1 hour while maintaining the pressure at 1.8 MPa by gradually removing steam until the internal temperature reached 245 ° C. for 1 hour. Then, the pressure was reduced over 1 hour. Next, the inside of the autoclave was maintained for 10 minutes under a reduced pressure of 650 torr (86.66 kPa) by a vacuum device. At this time, the final internal temperature of the polymerization was 265 ° C. Subsequently, the mixture is pressurized with nitrogen to form a strand from the lower spinneret (nozzle), water-cooled, cut, discharged in the form of a pellet, dried at 100 ° C. under a nitrogen atmosphere for 12 hours, and dried with an aliphatic polyamide A-1 (polyamide 66). ) Got.
The obtained aliphatic polyamide A-1 (polyamide 66) had Mw (A) = 35000 and Mw (A) / Mn (A) = 2.0.

[Synthesis Example 2] Synthesis of maleic anhydride-modified polyphenylene ether Oxidative polymerization of 2,6-dimethylphenol resulted in 0.52 poly (2) having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C). , 6-dimethyl-1,4-phenylene ether) (hereinafter sometimes abbreviated as "polyphenylene ether"): 100 parts by mass, and maleic anhydride: 1.0 part by mass as a compatibilizer. One outlet (hereinafter sometimes abbreviated as “top-F”) on the upstream side and two outlets on the central part of the extruder and on the downstream side near the die (hereinafter the central part of the extruder is “side-1”). , The downstream side close to the die may be abbreviated as “side-2” in some cases) in a state where side-1 and side-2 of a twin-screw extruder (manufactured by Werner & Pfleiderer: ZSK-40) are closed. A dry blend of polyphenylene ether and maleic anhydride was supplied from top-F under the conditions of a cylinder set temperature of 320 ° C., a screw rotation of 300 rpm, and a discharge rate of 20.15 kg / hr. Next, the mixture was melt-kneaded, taken out in a strand shape, and cooled in a strand bath (water tank). Next, the mixture was granulated by a cutter to obtain maleic anhydride-modified polyphenylene ether pellets.

<Physical properties and evaluation>
First, pellets of the resin compositions obtained in the examples and comparative examples were dried in a nitrogen stream to reduce the water content in the resin compositions to 500 ppm or less. Next, various physical properties and various evaluations were performed using the pellets of each resin composition whose water content was adjusted, using the following methods.

[Physical property 1] tan δ peak temperature Using a PS40E injection molding machine manufactured by Nissei Industry Co., Ltd., the cylinder temperature was set to 290 ° C., the mold temperature was set to 100 ° C., and the injection molding conditions were 10 seconds for injection and 10 seconds for cooling under JIS-injection conditions. A molded product according to K7139 was molded. Using a dynamic viscoelasticity evaluation apparatus (manufactured by GABO, EPLEXOR500N), the molded article was measured for storage elastic modulus E1 and loss elastic modulus E2 under the following conditions.

(Measurement condition)
Measurement mode: tensile Measurement frequency: 8.00 Hz
Heating rate: 3 ° C / min Temperature range: minus 100 to 250 ° C

  The ratio (E2 / E1) of the loss modulus E2 to the storage modulus E1 was defined as tan δ, and the highest temperature was defined as the tan δ peak temperature.

[Property 2] Number average molecular weight and weight average molecular weight of resin composition The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin compositions obtained in Examples and Comparative Examples were measured using GPC under the following measurement conditions. Next, the molecular weight distribution Mw / Mn was calculated based on the value obtained by GPC.

(Measurement condition)
Measuring device: HLC-8020 manufactured by Tosoh Corporation
Solvent: Hexafluoroisopropanol solvent Standard sample: PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratory) GPC column: TSK-GEL GMHHR-M and G1000HHR

[Evaluation 1] Moldability and appearance (1) Production of molded product "FN3000" manufactured by Nissei Industry Co., Ltd. was used. Cylinder temperature was set at 290 ° C, mold temperature was set at 100 ° C, and molding was performed up to 100 shots using each resin composition under injection molding conditions of injection 10 seconds and cooling 10 seconds, and a molded product (ISO test piece) I got

(2) Evaluation of moldability The moldability was evaluated on the basis of the following evaluation criteria as to what percentage of the 100 shots when the mold was released during molding.

(Evaluation criteria)
A: 10% or less B: More than 10% and 20% or less C: More than 20% and 50% or less D: More than 50%

(3) Evaluation of Appearance Regarding the appearance of the obtained molded article, the grip of the molded article was measured for gloss at 60 degrees using a gloss meter (IG320 manufactured by HORIBA) according to JIS-K7150. The appearance was evaluated from the measured surface gloss value according to the following evaluation criteria.

(Evaluation criteria)
A: 60 or more B: 55 or more and less than 60 C: 50 or more and less than 55 D: less than 50

[Evaluation 2] Flame retardancy Measurement was performed using the method of UL94 (a standard defined by Under Writers Laboratories Inc, USA). In addition, the test piece (127 mm in length, 12.7 mm in width, 1.6 mm in thickness) is prepared by attaching a mold for a UL test piece (mold temperature = 100 ° C.) to an injection molding machine (PS40E manufactured by Nissei Industry Co., Ltd.). Each resin composition was produced by molding at a cylinder temperature of 290 ° C. The injection pressure was set to a pressure of + 2% of the complete filling pressure at the time of molding the UL test piece. According to the UL94 standard (vertical combustion test), the flame-retardant grade was evaluated to be any one of V-0, V-1, and V-2. The smaller the numerical value of the grade, the higher the flame retardancy.

[Evaluation 3] Measurement of Flexural Elasticity Using the ISO test pieces from 20 shots to 25 shots obtained in the above “Evaluation 1”, the bending elastic modulus was measured in an environment of 80 ° C. in accordance with ISO 178. . The measured value was an average value of n = 6.

[Evaluation 4] Measurement of Charpy Impact Strength Charpy impact strength was measured in accordance with ISO 179 using the ISO test pieces from 20 shots to 25 shots obtained in the above “Evaluation 1”. The measured value was an average value of n = 6.

<Production of resin composition>
Example 1 Production of Resin Composition P-a1 Using a TEM 35 mm twin screw extruder (set temperature: 280 ° C., screw rotation speed 300 rpm) manufactured by Toshiba Machine Co., Ltd., a top feed port provided at the most upstream part of the extruder (A) Aliphatic polyamide A-1, (B) MXD6 polyamide B-1, (C) amorphous resin C-1, (D1) flame retardant, (D2) flame retardant auxiliary, (E) A pigment, (F) an ultraviolet absorber, and (G) a polymer previously blended with a polymer containing α, β unsaturated dicarboxylic anhydride units were supplied. Further, the filler (H) was supplied from the side feed port on the downstream side of the extruder (the state in which the resin supplied from the top feed port was sufficiently melted). Next, the melt-kneaded product extruded from the die head was cooled in a strand shape and pelletized to obtain a pellet of the resin composition P-a1. The blending amounts are (A) aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) amorphous resin C-1: 5.0% by mass. , (D1) flame retardant: 4.5% by mass, (D2) flame retardant auxiliary: 1.2% by mass, (E) pigment: 3.5% by mass, (F) ultraviolet absorber: 0.2% by mass , (G) a polymer containing α, β unsaturated dicarboxylic anhydride units: 1.0% by mass, and (H) a filler: 50% by mass.
Using the pellets of the obtained resin composition P-a1, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 2 Production of Resin Composition P-a2 (C) Amorphous resin C-1: 5.0% by mass was changed to (C) Amorphous resin C-2: 5.0% by mass. Except for using the same method as in Example 1, pellets of the resin composition P-a2 were obtained. Using the pellets of the obtained resin composition P-a2, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 3 Production of Resin Composition P-a3 (C) Amorphous resin C-1: 5.0% by mass was changed to (C) Amorphous resin C-3: 5.0% by mass. Except for using the same method as that of Example 1, pellets of the resin composition P-a3 were obtained. Using the pellets of the obtained resin composition P-a3, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 4 Production of Resin Composition P-a4 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide A-1 Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 10.3% by mass, (B) MXD6 polyamide B-1: 24.3% by mass, and (C) A pellet of the resin composition P-a4 was obtained in the same manner as in Example 1, except that the amorphous resin C-4 was changed to 5.0% by mass. Using the pellets of the obtained resin composition P-a4, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 5 Production of Resin Composition P-a5 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 6.9% by mass, (B) MXD6 polyamide B-1: 27.7% by mass, and (C) A pellet of the resin composition P-a5 was obtained in the same manner as in Example 1, except that the amorphous resin C-4 was changed to 5.0% by mass. Using the pellets of the obtained resin composition P-a5, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 6 Production of Resin Composition P-a6 (C) Amorphous resin C-1: 5.0% by mass was changed to (C) Amorphous resin C-4: 5.0% by mass. Except for using the same method as in Example 1, pellets of the resin composition Pa-6 were obtained. Using the pellets of the obtained resin composition Pa-6, a molded article was produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 7 Production of Resin Composition P-a7 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide A-1 Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 3.5% by mass, (B) MXD6 polyamide B-1: 31.1% by mass, and (C) A pellet of the resin composition P-a7 was obtained in the same manner as in Example 1, except that the amorphous resin C-4 was changed to 5.0% by mass. Using the pellets of the obtained resin composition P-a7, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 8 Production of Resin Composition P-a8 (C) Amorphous resin C-1: 5.0% by mass was changed to (C) Amorphous resin C-5: 5.0% by mass. Except for using the same method as in Example 1, pellets of the resin composition Pa-8 were obtained. Using the pellets of the obtained resin composition P-a8, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 9 Production of Resin Composition P-a9 (C) Amorphous resin C-1: 5.0% by mass was changed to (C) Amorphous resin C-6: 5.0% by mass. Except for using the same method as that of Example 1, pellets of the resin composition Pa-9 were obtained. Using the pellets of the obtained resin composition Pa-9, a molded article was produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 10 Production of Resin Composition P-a10 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 4.9% by mass, (B) MXD6 polyamide B-1: 32.7% by mass, and (C) Amorphous resin C-4: A pellet of resin composition P-a10 was obtained in the same manner as in Example 1, except that the mass was changed to 2.0% by mass. Using the pellets of the obtained resin composition P-a10, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 1 below.

Example 11 Production of Resin Composition P-a11 (A) 4.5% by mass of aliphatic polyamide A-1; (B) 30.1% by mass of MXD6 polyamide B-1; Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 3.8% by mass, (B) MXD6 polyamide B-1: 25.8% by mass, (C) amorphous Pellets of the resin composition P-a11 were obtained by using the same method as in Example 1 except for changing the conductive resin C-4 to 10.0% by mass. Using the pellets of the obtained resin composition P-a11, molded articles were produced by the above method, and various physical properties and evaluations were performed. The evaluation results are shown in Table 1 below.

Comparative Example 1 Production of Resin Composition P-b1 (A) Aliphatic polyamide A-1: 4.5% by mass and (B) MXD6 polyamide B-1: 30.1% by mass, (A) Aliphatic polyamide A-1: 0% by mass, and (B) MXD6 polyamide B-1: 39.6% by mass, except that it was changed to 39.6% by mass, using the same method as in Example 1 to prepare the resin composition P-b1. A pellet was obtained. Using the pellets of the obtained resin composition P-b1, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 2 below.

Comparative Example 2 Production of Resin Composition P-b2 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 0% by mass, (B) MXD6 polyamide B-1: 34.5% by mass, and (C) amorphous Pellets of the resin composition P-b2 were obtained using the same method as in Example 1 except that the amount of the resin was changed to 5.1% by mass. Using the pellets of the obtained resin composition P-b2, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 2 below.

Comparative Example 3 Production of Resin Composition P-b3 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 34.5% by mass, (B) MXD6 polyamide B-1: 0% by mass, and (C) amorphous Pellets of the resin composition P-b3 were obtained by using the same method as in Example 1 except that the resin was changed to C-4: 5.1% by mass. Using the pellets of the obtained resin composition P-b3, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 2 below.

Comparative Example 4 Production of Resin Composition P-b4 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 5.1% by mass, (B) MXD6 polyamide B-1: 34.5% by mass, and (C) A pellet of the resin composition P-b4 was obtained using the same method as in Example 1 except that the amorphous resin C-1 was changed to 0% by mass. Using the pellets of the obtained resin composition P-b4, molded articles were produced by the above method, and various physical properties and evaluations were performed. The evaluation results are shown in Table 2 below.

[Comparative Example 5] Production of resin composition P-b5 (A) Aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C) Non-polyamide Crystalline resin C-1: 5.0% by mass, (A) aliphatic polyamide A-1: 4.5% by mass, (B) MXD6 polyamide B-1: 30.1% by mass, and (C ′) ) Elastomer: A pellet of the resin composition P-b5 was obtained in the same manner as in Example 1 except that the mass was changed to 5.0% by mass. Using the pellets of the obtained resin composition P-b5, molded articles were produced by the above method, and various physical properties and evaluation were performed. The evaluation results are shown in Table 2 below.

From Table 1, resin compositions P-a1 to P-a11 (Examples 1 to 11) containing (A) an aliphatic polyamide, (B) an MXD6 polyamide, and (C) an amorphous resin were obtained. The molded product had good appearance, flame retardancy, flexural modulus at 80 ° C., and impact resistance.
On the other hand, from Table 2, the molded articles obtained from the resin compositions P-b1 and P-b2 (Comparative Examples 1 and 2) containing (B) the MXD6 polyamide but not (A) the aliphatic polyamide Had insufficient moldability and impact resistance.
(B) The molded product obtained from the resin composition P-b3 containing no MXD6 polyamide (Comparative Example 3) had insufficient appearance, flame retardancy, and flexural modulus at 80 ° C.
Moldings obtained from resin compositions P-b4 and P-b5 (Comparative Examples 4 and 5) comprising (A) an aliphatic polyamide and (B) an MXD6 polyamide, but not containing (C) an amorphous resin. The product was insufficient in any of the flexural modulus at 80 ° C. and the impact resistance.

Further, in the resin compositions P-a1 to P-a3, P-a6, P-a8 and P-a9 containing different (C) amorphous resins, C-2, C-3, C-4 or C -5-containing resin compositions P-a2, P-a3, P-a6 and P-a8 are 80 ° C. higher than the resin compositions P-a1 and P-a9 containing C-1 or C-6. The flexural modulus was particularly good.
In the resin compositions Pa-A4 to Pa-a7 having different contents of (A) the aliphatic polyamide and (B) the MXD6 polyamide, the content of the (A) aliphatic polyamide is reduced and the content of the (B) MXD6 polyamide is reduced. As the amount increases, the 80 ° C. flexural modulus tends to be better. On the other hand, with the increase in the content of the aliphatic polyamide (A) and the decrease in the content of the MXD6 polyamide (B), And a tendency that the impact resistance became better.
(C) In the resin compositions P-a6, P-a10 and P-a11 having different contents of the amorphous resin C-4, the bending elasticity at 80 ° C. was increased with the increase of the content of C-4. Both the modulus and the impact resistance tended to be better.

  From the above, it was confirmed that according to the resin composition of the present embodiment, a molded article having good appearance, flame retardancy, flexural modulus at 80 ° C., and impact resistance was obtained.

  The resin composition of the present embodiment contains an MXD6 polyamide and a flame retardant, and a molded article having good rigidity at heat and excellent surface appearance, flame retardancy, and impact resistance as a molded article can be obtained. The molded article of the present embodiment contains the resin composition and is suitably used as various parts for automobiles, electric and electronic products, industrial materials, and daily and household products.

Claims (20)

(A) an aliphatic polyamide;
(B) MXD6 polyamide;
(C) In a differential scanning calorimetry according to JIS-K7121, an amorphous resin having a glass transition temperature of not less than 80 ° C and not more than 250 ° C obtained when the temperature is increased at 20 ° C / min;
(D1) a flame retardant;
(D2) a flame retardant auxiliary,
And a tan δ peak temperature of 90 ° C. or higher.   The resin composition according to claim 1, wherein the (A) aliphatic polyamide includes an aliphatic polyamide containing a dicarboxylic acid unit and a diamine unit.   The resin composition according to claim 1, wherein the (A) aliphatic polyamide includes polyamide 66. 4.   The resin according to any one of claims 1 to 3, wherein the content of the (A) aliphatic polyamide is more than 0% by mass and 50% by mass or less based on the total mass of the polyamide in the resin composition. Composition.   The resin composition according to any one of claims 1 to 4, wherein the content of the (B) MXD6 polyamide is 50% by mass or more and less than 100% by mass based on the total mass of the polyamide in the resin composition. object.   The resin composition according to any one of claims 1 to 5, wherein the resin composition has a weight average molecular weight Mw of 10,000 or more and 60,000 or less.   The resin according to any one of claims 1 to 6, wherein the content of the (C) amorphous resin is 0.1% by mass or more and 30% by mass or less based on the total mass of the resin composition. Composition.   The resin composition according to any one of claims 1 to 7, wherein the (C) amorphous resin does not contain a polyamide.   The resin composition according to any one of claims 1 to 8, wherein the (C) amorphous resin is at least one selected from the group consisting of a polystyrene resin, an acrylic resin, and a polyether resin. .   The (C) amorphous resin is at least one selected from the group consisting of polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polyphenylene ether and polycarbonate. 10. The resin composition according to any one of 1 to 9. (D1) The flame retardant is brominated polystyrene, and the content of the brominated polystyrene is 2% by mass or more and 7% by mass or less based on the total mass of the resin composition;
(D2) The flame retardant aid is Sb ₂ O ₃ , and the content of Sb ₂ O ₃ is 0.1% by mass or more and 4% by mass or less based on the total mass of the resin composition. The resin composition according to claim 1. (E) further containing a white pigment,
The resin composition according to any one of claims 1 to 11, wherein the content of the (E) white pigment is 0.5% by mass or more and 5% by mass or less based on the total mass of the resin composition. object.   The resin composition according to claim 12, wherein the (E) white pigment is at least one selected from the group consisting of zinc sulfide, zinc oxide, and titanium oxide. (F) further containing an ultraviolet absorber,
The resin according to any one of claims 1 to 13, wherein the content of the (F) ultraviolet absorber is 0.1% by mass or more and 5% by mass or less based on the total mass of the resin composition. Composition.   The resin composition according to claim 14, wherein the (F) ultraviolet absorber is at least one selected from the group consisting of benzotriazole and triazine-based ultraviolet absorbers.   The resin composition according to any one of claims 1 to 15, further comprising (G) a polymer containing an α, β unsaturated dicarboxylic anhydride unit.   The resin composition according to claim 16, wherein the polymer (G) containing an α, β unsaturated dicarboxylic anhydride unit is a maleic anhydride-modified polyphenylene ether.   The resin composition according to any one of claims 1 to 17, further comprising (H) a filler. (H) the filler is glass fiber,
The resin composition according to claim 18, wherein the content of the glass fiber is 40% by mass or more and 60% by mass or less based on the total mass of the resin composition.   A molded article obtained by molding the resin composition according to any one of claims 1 to 19 and having a surface gloss value of 50 or more.