JP2019116607A - Polyamide resin composition and molded article comprising the same - Google Patents

Abstract

To provide a polyamide resin composition excellent in mechanical characteristics and also excellent in long-term heat aging resistance and surface glossiness.SOLUTION: The polyamide resin composition contains, based on 100 pts.mass of a polyamide resin (A), 0.01-15 pts.mass of a polyethyleneimine resin (B), 0.01-0.12 pt.mass of iron oxalate (C), 0.01-0.12 pt.mass of iron (III) oxide (D), 0.01-0.15 pt.mass of a copper halide (E), and 0.04-0.60 pt.mass of an alkali metal or alkaline earth metal halide (F). A molded article obtained by molding the polyamide resin composition is also provided.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition excellent in long-term heat aging resistance and surface gloss and a molded article made of them.

  Polyamide resins are excellent in mechanical strength such as mechanical strength, rigidity, toughness, impact resistance, etc., heat resistance and chemical resistance, so they are used in various industrial fields such as clothing, industrial materials, automobiles, electricity and electronics. It's being used. In addition, since polyamide resins are relatively excellent in heat aging resistance as compared with other resins, polyamide resins are used as materials for parts of very heat-consuming places such as in an automobile engine room. However, since the polyamide resin alone is insufficient as the component material, the heat aging resistance is improved by various techniques.

  As a technique for improving the heat aging resistance of the polyamide resin, for example, a technique of blending a halide of copper and a halide of potassium with a polyamide resin (Patent Document 1), and a halide of copper with two types of polyamide resins having different melting points. Technology to mix iron halide with potassium and iron oxide (patent document 2), technology to mix fine grained elemental iron with polyamide resin (patent document 3), technology to mix finely dispersed metal powder to polyamide resin (patent document 4) ), A technique of blending a halide of copper with a halide of alkali or alkaline earth metal and iron (II) oxide in a polyamide resin (Patent Document 5), a technique of blending iron oxalate in a polyamide resin (Patent Document 6) Patent Document 7 discloses a technique of blending a polyethyleneimine resin with a polyamide resin.

JP-A-8-325382 Japanese Patent Application Publication No. 2008-527129 Japanese Patent Application Publication No. 2006-528260 Japanese Patent Application Publication No. 2008-527127 JP, 2010-270318, A JP-A-2015-516477 Japanese Patent Application Publication No. 2012-508314

In recent years, the environmental temperature in the engine room has been getting higher as the density of parts and the engine power increase in the automobile engine room, and it is 180-220 ° C, far exceeding the level required so far Long-term heat aging resistance of 3000 hours or more at high temperature is required for the polyamide resin composition. However, the polyamide resin compositions of Patent Documents 1 to 7 can not satisfy the long-term heat aging resistance requirement of 3000 hours or more described above.
Further, in recent years, it has been required that parts in the engine room of automobiles have a good appearance such as surface glossiness, but in the case of molded articles made of the polyamide resin compositions of Patent Documents 1 to 7, It could not meet the requirement of surface gloss.

  An object of the present invention is to provide a polyamide resin composition which is excellent in mechanical properties and is also excellent in long-term heat aging resistance and surface glossiness in view of the prior art.

  As a result of intensive studies to solve such problems, the inventors of the present invention have studied polyamide resin, polyethyleneimine resin, iron oxalate, iron (III) oxide, copper halide, alkali metal or It has been found that it is possible to obtain a polyamide resin composition which is excellent in mechanical properties and remarkably improved in long-term heat aging resistance and surface glossiness by blending a specific amount of an alkaline earth metal halide and the like. The invention has been reached.

That is, the gist of the present invention is as follows.
(1) 100 parts by mass of polyamide resin (A),
0.01 to 15 parts by mass of polyethyleneimine resin (B),
0.01 to 0.12 parts by mass of iron oxalate (C),
0.01 to 0.12 parts by mass of iron oxide (III) (D),
0.01 to 0.15 parts by mass of copper halide (E),
A polyamide resin composition comprising: 0.04 to 0.60 parts by mass of a halide (F) of an alkali metal or an alkaline earth metal.
(2) The polyamide resin composition according to (1), wherein the polyamide resin (A) is a mixture of a crystalline polyamide resin and an amorphous polyamide resin.
(3) The polyamide resin composition according to (1) or (2), which further contains a polyhydric alcohol.
(4) The polyamide resin composition according to any one of (1) to (3), which further contains a coupling agent.
(5) The polyamide resin composition according to any one of (1) to (4), further comprising a reinforcing material.
(6) The polyamide resin composition according to any one of (1) to (5), which further contains a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and a hindered amine-based light stabilizer.
The molded object formed by shape | molding the polyamide resin composition in any one of (7) (1)-(6).

  According to the present invention, it is possible to provide a polyamide resin composition which is excellent in mechanical properties and remarkably improved in long-term heat aging resistance and surface gloss.

  The polyamide resin composition of the present invention comprises a polyamide resin (A), a polyethyleneimine resin (B), iron oxalate (C), iron oxide (III) (D) and a halide of copper (E) And an alkali metal or alkaline earth metal halide (F).

  The polyamide resin (A) used in the present invention is a homopolyamide or copolyamide having an amide bond, and a mixture thereof. The homopolyamide or copolyamide having an amide bond can be obtained by polymerizing a lactam, an aminocarboxylic acid, a diamine, a dicarboxylic acid or the like. The polyamide resin (A) may be a crystalline polyamide resin, an amorphous polyamide resin alone, or a mixture thereof. From the viewpoint of mechanical properties, a crystalline polyamide resin or a mixture of a crystalline polyamide resin and an amorphous polyamide resin is preferred.

  In the present invention, the crystalline polyamide resin refers to a polyamide resin having a heat of fusion value measured at a temperature rising rate of 16 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (DSC) of more than 1 cal / g. Amorphous polyamide resin means a polyamide resin whose value of heat of fusion measured at a temperature rising rate of 16 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (DSC) is less than 1 cal / g. Means

  As crystalline polyamide resin, for example, polytetramethylene isophthalamide (polyamide 4I), polytetramethylene terephthalamide (polyamide 4T), polycupramide (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene azidamide Pamide (polyamide 66), polycoupler / polyhexamethylene adipamide copolymer (polyamide 6/66), polyundecamide (polyamide 11), polycoupler / polyundecamide copolymer (polyamide 6/11), polydodecamide (polyamide 12), polycoupler / Polydodecamide copolymer (polyamide 6/12), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), porundere camera Lenadipamide (polyamide 116), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene terephthalamide (polyamide 6T), polyco-pramide / poly-tetramethylene terephthalamide copolymer (polyamide 6/4 T), poly-co-pramide / poly-tetramethylene isophthalamide copolymer Polyamide 6 / 4I), polyhexamethylene adipamide / polytetramethylene terephthalamide copolymer (polyamide 66 / 4T), polyhexamethylene adipamide / polytetramethylene isophthalamide copolymer (polyamide 66 / 4I), polyhexamethylene terephthal Amide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), poly coupleramide / polyhexamethylene terephthalate Copolymer (polyamide 6 / 6T), polycoupler / polyhexamethylene isophthalamide copolymer (polyamide 6 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / Polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polytrimethylhexamethylene terephthalamide (polyamide TMDT), polybis (4-aminocyclohexyl) methandodecamide (polyamide PACM 12), polybis (3-methyl-4-aminocyclohexyl ) Methododecamide (polyamide dimethyl PACM 12), polymetaxylylene adipamide (polyamide MXD 6), polyoctamethylene terephthalamide (polyamide) 8T), polynonamethylene terephthalamide (polyamide 9T), polydecamethylene terephthalamide (polyamide 10T), polyundecamethylene terephthalamide (polyamide 11T) and mixtures thereof. Among them, polyamide 6 and polyamide 66 are more preferable. The crystalline polyamide resin may be used singly or in combination of the above.

  As the amorphous polyamide resin, for example, isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane copolymer, terephthalic acid / 2,2,4-trimethyl- 1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine copolymer, isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-laurolactam copolymer, isophthalic acid Acid / terephthalic acid / 1,6-hexanediamine copolymer, isophthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine copolymer , Isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexene Njiamin copolymer, isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / .omega.-laurolactam copolymer, a copolymer of isophthalic acid / terephthalic acid / other diamine components. Among them, isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane copolymer, terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2 2,4,4-Trimethyl-1,6-hexanediamine copolymer, isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane copolymer and terephthalic acid / 2 , A mixture with 2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine copolymer, isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymer Isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane is preferred. Polymer, isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymer is more preferable. The non-crystalline polyamide resin may be used singly or in combination of the above.

  When a mixture of a crystalline polyamide resin and an amorphous polyamide resin is used as the polyamide resin (A), the content of the amorphous polyamide resin is 5 to 50 mass based on the total of the crystalline polyamide resin and the amorphous polyamide resin. It is preferable to set it as%, and it is preferable to set it as 5 to 20 mass%.

  The relative viscosity of the polyamide resin (A) used in the present invention is not particularly limited, but the relative viscosity measured under conditions of a temperature of 25 ° C. and a concentration of 1 g / dL using 96 parts by mass concentrated sulfuric acid as a solvent is 1.6 It is preferable that it is more than. If the relative viscosity is less than 1.6, mechanical properties and heat resistance may be reduced when forming a molded article.

  The polyamide resin composition of the present invention is required to contain a polyethyleneimine resin (B). The polyethyleneimine resin (B) can be obtained by polymerizing ethyleneimine. Examples of the polyethyleneimine resin (B) include linear polyethyleneimine resin and polyethyleneimine resin having a branched structure, but from the viewpoint of improving long-term heat aging resistance, polyethyleneimine resin having a branched structure is more preferable. preferable. The molecular weight of the polyethyleneimine resin (B) is preferably 200 to 800.

  The content of the polyethyleneimine resin (B) in the polyamide resin composition is required to be 0.01 to 15 parts by mass with respect to 100 parts by mass of the polyamide resin (A), and 0.1 to 4 parts It is preferable to set it as a part, and it is more preferable to set it as 0.2-2 mass parts. When the content of the polyethyleneimine resin (B) is less than 0.01 parts by mass, the improvement effect of the long-term heat aging resistance and the surface gloss is small, which is not preferable. On the other hand, when the content is more than 15 parts by mass, mechanical properties are deteriorated or the handleability is deteriorated, which is not preferable.

  The polyamide resin composition of the present invention is required to contain iron oxalate (C). Examples of iron oxalate include iron oxalate (II) and iron oxalate (III), but iron oxalate (II) is preferable from the viewpoint of improving long-term heat aging resistance. As iron (II) oxalate, iron (II) oxalate dihydrate is preferred.

  The content of iron oxalate (C) in the polyamide resin composition is required to be 0.01 to 0.12 parts by mass with respect to 100 parts by mass of the polyamide resin (A), and 0.02 to 0 It is preferable to use .06 parts by mass. If the content of iron oxalate (C) is less than 0.01 parts by mass, the effect of improving long-term heat aging resistance and surface gloss is small, which is not preferable. On the other hand, when the content exceeds 0.12 parts by mass, the effect of improving long-term heat aging resistance is saturated, which is economically disadvantageous.

The polyamide resin composition of the present invention is required to contain iron oxide (III) (D). The iron oxide (III) (D) may be any iron oxide containing iron oxide (III) in the compound, or a complex oxide consisting of a combination with other oxides. Examples of iron oxide containing iron (III) oxide in the compound include, for example, iron (III) oxide (ferric oxide: Fe ₂ O ₃ ), iron oxide (II, III) (iron trioxide trioxide: Fe ₃ O ₄ ). The complex oxide containing iron (III) oxide is a complex oxide consisting of iron oxide and other metal oxides, and examples of the other metal oxides include Ti, Mg, Mn, Zn, and Co. And oxides of Cr, Sb, Ni, Al and Cu. Among them, Fe ₂ O ₃ is more preferable.

  The content of iron oxide (III) (D) in the polyamide resin composition is required to be 0.01 to 0.12 parts by mass with respect to 100 parts by mass of the polyamide resin (A), 0.02 It is preferable to set it as -0.06 mass part. When the content of iron oxide (III) (D) is less than 0.01 parts by mass, the effect of improving long-term heat aging resistance and surface gloss is small, which is not preferable. On the other hand, when the content exceeds 0.12 parts by mass, the effect of improving long-term heat aging resistance is saturated, which is economically disadvantageous.

  The polyamide resin composition of the present invention is required to contain a copper halide (E). As a copper halide (E), for example, copper iodide, cuprous bromide, cupric bromide, cuprous chloride, copper acetate, copper propionate, copper benzoate, copper adipate, terephthalic acid Examples thereof include copper, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, and copper complexes in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. Among them, copper iodide is preferable from the viewpoint of the improvement of long-term heat aging resistance. The copper halide (E) may be used alone or in combination of the above.

  The content of the halide (E) of copper in the polyamide resin composition is required to be 0.01 to 0.15 parts by mass with respect to 100 parts by mass of the polyamide resin (A). Preferably, it is 0.06 parts by mass. If the content is less than 0.01 parts by mass, the effect of improving long-term heat aging resistance and surface gloss is small, which is not preferable. On the other hand, when the content exceeds 0.15 parts by mass, the effect of improving long-term heat aging resistance is saturated, which is economically disadvantageous.

  The polyamide resin composition of the present invention needs to contain an alkali metal or alkaline earth metal halide (F). Examples of the halide (F) include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and among them, potassium iodide and bromide from the viewpoint of improving long-term heat aging resistance. Potassium is preferred, and potassium iodide is more preferred. The said halide (F) may be used individually by 1 type in the above, and may be used together.

  The content of the halide (F) of an alkali metal or alkaline earth metal in the polyamide resin composition needs to be 0.04 to 0.60 parts by mass with respect to 100 parts by mass of the polyamide resin (A) Preferably, it is 0.04 to 0.24 parts by mass. If the content is less than 0.04 parts by mass, the effect of improving long-term heat aging resistance is small, which is not preferable. On the other hand, when the content exceeds 0.60 parts by mass, the effect of improving long-term heat aging resistance and surface glossiness is saturated, which is economically disadvantageous.

  The polyamide resin composition of the present invention may contain a reinforcing material in order to improve mechanical properties. Examples of the reinforcing material include fibrous fillers and particulate fillers.

  As a fibrous filler, for example, glass fiber, carbon fiber, graphitized carbon fiber, aramid fiber, metal fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, kenaf or the like Natural fibers such as cellulose can be mentioned. Among them, glass fibers are preferable from the viewpoint of mechanical properties, heat resistance and cost, and carbon fibers are preferable from the viewpoint of mechanical properties and heat resistance.

  As a particulate filler, for example, talc, layered silicate, calcium carbonate, zinc carbonate, wollastonite, silica, calcium silicate, graphite, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, Antimony trioxide, zeolite, hydrotalcite may be mentioned. Among them, talc and layered silicate are preferable from the viewpoint of mechanical properties and heat resistance.

  The fibrous filler or the particulate filler may be surface-treated with a coupling agent in order to improve the adhesion between the polyamide resin (A) and the filler. As a coupling agent, a silane coupling agent and a titanium coupling agent are mentioned, for example. As a silane coupling agent, for example, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyldimethoxymethyl Epoxysilane coupling agents such as aminosilane coupling agents such as silane, γ-glycidoxypropyltrimethoxysilane, γ-glyricidoxypropylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like Can be mentioned. Examples of titanium-based coupling agents include isopropyl tristearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate. The coupling agent may be used alone or in combination of any of the above. The coupling agent may be added to the polyamide resin composition to adjust the viscosity of the polyamide resin (A).

  When a polyamide resin composition contains a reinforcing material, the content thereof is preferably 10 to 175 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the polyamide resin (A). preferable. When the content is more than 175 parts by mass, mechanical properties may be reduced or molding flowability may be significantly reduced.

  The polyamide resin composition of the present invention may further contain a polyhydric alcohol in order to further improve the long-term heat aging resistance. Examples of polyhydric alcohols include monopentaerythritol, dipentaerythritol, and tripentaerythritol. Among them, dipentaerythritol is preferable from the viewpoint of the improvement of long-term heat aging resistance. The polyhydric alcohols may be used alone or in combination of any of the above.

  When making a polyamide resin composition contain polyhydric alcohol, it is preferable to make the content into 0.01-6.0 mass parts with respect to 100 mass parts of polyamide resin (A), and 0.01-0. It is more preferable to use 5 parts by mass. When the content is less than 0.01 parts by mass, the long-term heat aging resistance may not be improved. On the other hand, when the said content exceeds 6.0 mass parts, mechanical characteristics and heat resistance may fall.

  The polyamide resin composition of the present invention further comprises iron oxalate, iron (III) oxide, a halide of copper, a halide of an alkali metal or an alkaline earth metal or the like to further improve long-term heat aging resistance. A heat stabilizer, an antioxidant, or a light stabilizer may be contained. Examples of heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, phosphites and sulfur compounds. Among them, hindered phenols and hindered amines are preferable because the effect of improving long-term heat aging resistance is large. Examples of the light stabilizer include hindered amine (HALS) and benzophenone. Among them, HALS is preferable because the improvement effect of long-term heat aging resistance is further improved. The heat stabilizer, the antioxidant and the light stabilizer may be used alone or in combination of any of the above.

  When a polyamide resin composition contains a heat stabilizer, an antioxidant, and a light stabilizer, the content thereof is 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the polyamide resin (A). Is preferable, and 0.1 to 2.0 parts by mass is more preferable. If the content is less than 0.05 parts by mass, the long-term heat aging resistance may not be improved. On the other hand, when the content exceeds 3.0 parts by mass, the effect of improving long-term heat aging resistance is saturated, which is economically disadvantageous.

  In the polyamide resin composition of the present invention, the combined use of a hindered phenol-based antioxidant, a hindered amine-based antioxidant and a hindered amine-based light stabilizer only enhances the effect of improving long-term heat aging resistance and surface gloss. Can. In addition, since the releasability during injection molding can be improved, the cooling time during injection molding can be shortened and the molding cycle can be improved.

  In the polyamide resin composition of the present invention, as long as the properties thereof are not significantly impaired, the pigment, weathering agent, flame retardant, plasticizer, lubricant, releasing agent, antistatic agent, crystal nucleating material, high value other than polyethyleneimine resin Additives such as molecular compounds may be added. Examples of the pigment include nigrosine. As the flame retardant, for example, halogen flame retardants, non-halogen flame retardants, phosphorus flame retardants, and inorganic flame retardants are preferable, and from the environmental point of view, non-halogen flame retardants are more preferable. Examples of non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, nitrogen compounds such as melamines and guanidines, and inorganic compounds such as oxalates and molybdenum compounds. Be Examples of the crystal nucleus material include an inorganic crystal nucleus material and an organic crystal nucleus agent. Examples of the inorganic crystal nucleus material include kaolin. Examples of the organic crystal nucleus material include sorbitol compounds, benzoic acid and metal salts of the compounds, metal salts of phosphoric acid esters, and rosin compounds. Examples of the polymer compound include polyethylene, polypropylene, polybutadiene, polystyrene, AS resin, ABS resin, poly (acrylic acid) resin, poly (acrylic acid ester) resin, poly (methacrylic acid) resin, poly (methacrylic acid ester) And the like) resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polycarbonate resins, and copolymers thereof.

  The polyamide resin composition of the present invention can be produced by melt-kneading using a general extruder such as a single screw extruder, a twin screw extruder, a roll kneader, Brabender and the like. Among them, in order to improve the kneading state, it is preferable to use a twin-screw extruder. Also, a static mixer or a dynamic mixer may be used in combination. The ingredients may each be added from the hopper or from a side feeder. Also, polyamide resin (A) and polyethylene imine resin (B), polyamide resin (A) and iron oxalate (C), polyamide resin (A) and iron oxide (III) (D), polyamide resin (A) and copper A masterbatch may be prepared from each of the halides (E) of the above and the halides of alkali metals or alkaline earth metals (F), and these may be used after being diluted with the polyamide resin (A) at the time of molding and processing.

  The polyamide resin composition of the present invention can be molded into a desired shape using a generally known melt molding method such as injection molding, compression molding, extrusion molding, transfer molding, sheet molding and the like.

  The molded body may be vibration-welded from parts to parts to form a final molded body, but in that case, the polyamide resin composition used is required to have vibrational weldability. The vibration welding property can be improved by using the above-mentioned coupling agent. The vibration weldability can be further improved by using the above-mentioned coupling agent and the above-mentioned amorphous polyamide resin in combination.

  A molded article obtained by molding the polyamide resin composition of the present invention is excellent in mechanical properties, and also excellent in long-term heat aging resistance and surface gloss, and thus, for example, for automobile, machine industry, electricity, It can be suitably used for various parts such as for electronics, for industrial materials, for industrial materials, for household goods and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

A. Evaluation Method (1) Relative Viscosity The sample solution was dissolved in 96% sulfuric acid to prepare a sample solution having a concentration of 1 g / dL. Subsequently, using an Ubbelohde viscometer, the falling time of the sample solution and the solvent was measured at a temperature of 25 ° C., and the relative viscosity was determined using the following equation.
Relative viscosity = (dropping time of sample solution) / (dropping time of solvent only)

(2) Tensile strength A fully dried resin composition pellet was subjected to a cylinder temperature of 280 ° C., a mold temperature of 100 ° C., an injection time of 15 seconds, and a cooling time using an injection molding machine (Nisei Resin Industry Co., Ltd .: NEX 110-12E). It injection-molded in 20 seconds and the dumbbell test piece (test part 127 mm x 12.7 mm x 3.2 mm) was produced.
It measured according to ISO standard 527 using the obtained dumbbell test piece.
The tensile strength before heat treatment is preferably 100 MPa or more, and more preferably 110 MPa or more.

(3) Tensile strength retention rate The dumbbell test piece obtained in (2) was placed in a hot air dryer set at 220 ° C. and heat treated. The tensile strength was measured by the method described in (2) after taking out after a predetermined time has elapsed and sufficiently cooling, and calculated by the following equation.
Tensile strength retention (%) = tensile strength after heat treatment / tensile strength before heat treatment × 100
The tensile strength retention after heat treatment for 3000 hours is preferably 80% or more, and more preferably 90% or more.

(4) Gloss A sufficiently dried resin composition pellet was subjected to a cylinder temperature of 280 ° C., a mold temperature of 100 ° C., an injection time of 15 seconds, and a cooling time using an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd .: NEX 110-12E). It injection-molded in 20 seconds and produced the color plate (90 mm x 60 mm x 2 mm).
It measured by making an incident angle into 60 degree based on JIS-K7105 using the obtained color plate.
The gloss is preferably 70% or more, more preferably 90% or more. The higher the gloss, the higher the surface gloss.

(5) The shortest cooling time to obtain a target molded piece The resin composition pellet sufficiently dried is subjected to a cylinder temperature of 280 ° C., a mold temperature, using an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd .: NEX 110-12E). Injection molding is performed at 100 ° C, injection time 15 seconds, and cooling time 20 seconds, and when a test piece (target molded piece, 100 mm × 100 mm × 3 mm) is molded, the shortest cooling time that the target molded piece can be collected is determined. The
If the cooling time is too short, the formed piece may be deformed when protruding or the protruding pin portion may be largely dented, and the intended formed piece can not be obtained.
The shortest cooling time is preferably 20 seconds or less, more preferably 15 seconds or less. The shorter the shortest cooling time, the higher the releasability.

(6) Vibration welding strength The dumbbell test piece obtained in (2) was cut in half, and the cut surface was polished. Thereafter, using a vibration welding machine, cut surfaces of the dumbbell test pieces cut in half were put together and vibration welded.
Using a test piece obtained by vibration welding, in accordance with ISO standard 527, the tensile speed was measured at 1 mm / sec.

B. Raw material (1) Polyamide resin (A)
PA6: Polyamide resin 6 (A1030BRL manufactured by Unitika, relative viscosity 2.6) PA66: Polyamide resin 66 (A125 manufactured by Unitika, relative viscosity 2.8)
Amorphous PA1: Amorphous polyamide (isophthalic acid / terephthalic acid / 1,6-hexanediamine copolymer, manufactured by DSM, X21)
Amorphous PA2: Amorphous polyamide (isophthalic acid / terephthalic acid / 1,6-hexamethylenediamine cocondensate, manufactured by EMS G21)

(2) Polyethyleneimine resin (B)
PEI-1: polyethylene imine resin (SP-600, manufactured by Nippon Shokuhin Co., Ltd., having a molecular weight of 600, and having a branched structure)
PEI-2: polyethyleneimine resin (SP-300 manufactured by Nippon Shokuhin Co., Ltd., molecular weight 300, having a branched structure)

(3) Iron oxalate (C)
Fe (C ₂ O ₄ ) ₂ H ₂ O: iron (II) oxalate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.)

(4) Iron oxide (III) (D)
Fe ₂ O ₃ : ferric oxide (manufactured by Wako Pure Chemical Industries, Ltd.)

(5) Copper halide (E)
・ CuI: Copper iodide (made by Nippon Chemical Industrial Co., Ltd.)

(6) Alkali metal or alkaline earth metal halide (F)
・ KI: Potassium iodide (Mitsui Chemical Fine Co., Ltd.)

(7) Reinforcing material · GF: Glass fiber (JAFT 692, manufactured by Owens Corning, average fiber diameter 10 μm, average fiber length 3 mm)
・ Tc: Talc (manufactured by Nippon Talc, average particle size 5 μm)

(8) Additives · DPE: dipentaerythritol (dipentarit manufactured by Hiroei Chemical Industry Co., Ltd.)
・ KBM: Epoxysilane coupling agent (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.)
-NH-815: Nigrosine (NUBIAN BLACK NH-815 manufactured by Orient Chemical Industries, Ltd.)
· AO-60: hindered phenolic antioxidant (ADEKA STAV AO-60 manufactured by ADEKA, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate])
-NAU: hindered amine antioxidant (Naugard 445 manufactured by Addivant, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine)
SEED: hindered amine light stabilizer (Nylostab S-EED manufactured by CLARIANT, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide)

Example 1
100 parts by mass of polyamide 6 resin (PA6), 0.6 parts by mass of polyethyleneimine resin (PEI-1), iron (II) oxalate dihydrate (Fe (C ₂ O ₄ ) · 2H ₂ O) 0 .04 parts by mass, 0.04 parts by mass of iron (III) oxide (Fe ₂ O ₃ ), 0.04 parts by mass of copper iodide (CuI), and 0.12 parts by mass of potassium iodide (KI) It dry-blended, and supplied the mixture to the main hopper of a twin-screw extruder (made by Toshiba Machine: TEM26SS, screw diameter 26 mm), and it melt-kneaded at 260 degreeC. On the way, 18 parts by mass of glass fiber (GF) was supplied from a side feeder, sufficiently melt-kneaded, extruded in a strand shape, cooled and solidified, and then cut with a pelletizer to obtain pellets of a polyamide resin composition.

Examples 2 to 41, Comparative Examples 1 to 10
The same operation as in Example 1 was carried out except that the resin composition was changed as shown in Tables 1 to 3, to obtain pellets of a polyamide resin composition.
In addition, all glass fiber was supplied by the side feeder on the way, and the other raw material was dry-blended and supplied from the main hopper.

The polyamide resin compositions of Examples 1 to 41 contained (B) to (F) in the range specified in the present invention, so the tensile strength before heat treatment was 100 MPa or more, and after aging treatment for 3000 hours. The tensile strength retention was 80% or more.
Comparison of polyamide resin compositions having the same content of reinforcing material, that is, Examples 1-14, 18-29, 31-41 and Comparative Example 1, Example 16 and Comparative Example 2, Example 17 and Comparative Example From the comparison of the polyamide resin composition of 3, it is understood that the gloss becomes high by containing (B) to (F) in the range specified in the present invention.
From the comparison of the polyamide resin compositions of Example 1 and Examples 18 to 20, it is understood that the tensile strength retention after aging treatment for 3000 hours is increased by further containing dipentaerythritol which is a polyhydric alcohol. .
From the comparison of the polyamide resin composition in which the content of the reinforcing material is the same, that is, the comparison of the polyamide resin compositions of Example 1 and Example 21 and Example 34 and Example 35, by containing the coupling agent , It can be seen that the vibration welding strength is high. Further, from the comparison of the polyamide resin compositions of Example 21 and Example 32, Example 36 and Examples 37 to 40, 41, vibration is caused by using a mixture of crystalline polyamide and amorphous polyamide resin as the polyamide resin. It turns out that welding strength becomes high.
From the comparison of the polyamide resin compositions of Examples 1, 2 to 26 and Examples 27 to 29, further, by containing a hindered phenol-based antioxidant, a hindered amine-based antioxidant and a hindered amine-based light stabilizer, It can be seen that not only the tensile strength retention after aging for 3000 hours increases, but also the releasability during injection molding is improved.

Since the polyamide resin compositions of Comparative Examples 1 to 3 did not contain (B) to (F), deterioration of the resin after aging treatment for 3000 hours was severe, and the tensile strength could not be measured.
Since the polyamide resin composition of Comparative Example 4 did not contain (B) to (D), deterioration of the resin after aging treatment for 3000 hours was severe, and tensile strength could not be measured.
In the polyamide resin compositions of Comparative Examples 5 and 7 to 10, since the content of any of (B) to (F) was small, deterioration of the resin after aging treatment for 3000 hours was severe, and the tensile strength could be measured. could not.
The polyamide resin composition of Comparative Example 6 had a low tensile strength because the content of the polyethyleneimine resin was too large.

Claims (7)

Per 100 parts by mass of polyamide resin (A),
0.01 to 15 parts by mass of polyethyleneimine resin (B),
0.01 to 0.12 parts by mass of iron oxalate (C),
0.01 to 0.12 parts by mass of iron oxide (III) (D),
0.01 to 0.15 parts by mass of copper halide (E),
A polyamide resin composition comprising: 0.04 to 0.60 parts by mass of a halide (F) of an alkali metal or an alkaline earth metal. The polyamide resin composition according to claim 1, wherein the polyamide resin (A) is a mixture of a crystalline polyamide resin and an amorphous polyamide resin. The polyamide resin composition according to claim 1, further comprising a polyhydric alcohol. Furthermore, the coupling agent is contained, The polyamide resin composition in any one of the Claims 1-3 characterized by the above-mentioned. Furthermore, the reinforcing material is contained, The polyamide resin composition in any one of the Claims 1-4 characterized by the above-mentioned. The polyamide resin composition according to any one of claims 1 to 5, further comprising a hindered phenol antioxidant, a hindered amine antioxidant and a hindered amine light stabilizer. The molded object formed by shape | molding the polyamide resin composition in any one of Claims 1-6.