JP2019011388A - Reinforced polyamide resin composition and molding thereof - Google Patents

Abstract

To provide a polyamide resin composition excellent in low warpage, besides being excellent in mechanical strength, impact resistance and appearance.SOLUTION: A reinforced polyamide resin composition comprises 0 to 150 parts by mass of glass fiber and/or carbon fiber (B) and 10 to 200 parts by mass of non-fibrous inorganic filler (C), relative to 100 parts by mass of a polyamide resin (A); the non-fibrous inorganic filler (C) having a number average particle diameter of 10 to 40 μm, and a (D-D)/number average particle diameter as a grain size distribution index of 2.8 or more.SELECTED DRAWING: None

Description

  The present invention relates to a reinforced polyamide resin composition and a molded article which are excellent in mechanical strength, impact resistance and appearance, and also excellent in low warpage.

  Polyamide resins have excellent mechanical properties (such as mechanical strength, rigidity and impact resistance), heat resistance, and chemical resistance, so they are used in clothing, industrial materials, automobiles, electrical and electronic parts, and other industrial products. It is used in various industrial fields.

  As a method for increasing the rigidity and strength of a polyamide resin, techniques for blending inorganic fillers such as glass fiber and talc are known (for example, see Patent Documents 1 and 2). In particular, glass fibers are excellent in improving strength. On the other hand, non-fibrous inorganic fillers such as talc are known as inorganic fillers that are superior in warping and appearance during injection molding, although the effect of improving strength is insufficient compared to glass fibers and the like. Therefore, a method of adjusting mechanical strength and appearance by using glass fiber and non-fibrous inorganic filler in combination is also known.

  Among non-fibrous inorganic fillers, those with a smaller average particle size are known to be more effective in terms of rigidity and appearance, and may be surface treated with a coupling agent to improve mechanical properties. It is known (see, for example, Patent Documents 3 and 4).

JP-A-7-97514 JP-A-8-199063 JP 11-343409 A JP 2010-31179 A

However, it is not sufficient in terms of improving the mechanical strength while maintaining the appearance.
An object of the present invention is to provide a reinforced polyamide resin composition and a molded article, which are suitable for automobile parts, small precision parts, etc., which are excellent in mechanical strength, impact resistance and appearance, and also excellent in low warpage. is there.

As a result of intensive studies to solve the above problems, the present inventors have found that the number average particle size of the non-fibrous inorganic filler is 10 to 40 μm, which is an index of particle size distribution (D ₉₀ -D ₁₀ ). The inventors have found that it is effective to obtain a reinforced polyamide resin composition excellent in the above-described properties when the number average particle size is 2.8 or more, and the present invention has been achieved.

That is, the reinforced polyamide resin composition of the present invention comprises (B) glass fiber and / or 0 to 150 parts by mass of carbon fiber and (C) non-fibrous inorganic filler 10 with respect to 100 parts by mass of (A) polyamide resin. It is a reinforced polyamide resin composition containing ˜200 parts by mass, and (C) the number average particle size of the non-fibrous inorganic filler is 10 to 40 μm, which is an index of particle size distribution (D ₉₀ -D ₁₀ ) / number The average particle size is 2.8 or more.

  (C) The non-fibrous inorganic filler is preferably at least one selected from talc, mica, kaolin and wollastonite.

(C) The non-fibrous inorganic filler is preferably surface-treated with one or more selected from an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.
(C) It is more preferable that the non-fibrous inorganic filler is surface-treated with an acid anhydride group-containing alkoxysilane compound.

  (A) It is preferable that the polyamide resin has a viscosity number of 80 to 150 ml / g measured with sulfuric acid having a mass fraction of 96% in accordance with ISO 307.

  The molded article of the present invention is formed by molding the reinforced polyamide resin composition of the present invention.

  According to the present invention, it is possible to provide a polyamide resin composition that is excellent in mechanical strength, impact resistance and appearance, and also excellent in low warpage.

  The present invention will be specifically described below. Hereinafter, the reinforced polyamide resin composition is also simply referred to as a polyamide resin composition.

First, each component that can be used in the present invention will be described in detail.
[(A) Polyamide]
“Polyamide” means a polymer compound having a —CO—NH— (amide) bond in the main chain. The polyamide used in the present invention is not particularly limited. For example, (a) polyamide obtained by ring-opening polymerization of lactam, (b) polyamide obtained by self-condensation of ω-aminocarboxylic acid, (c) diamine and Examples thereof include polyamides obtained by condensing dicarboxylic acids, and copolymers thereof. Polyamide may be used alone or as a mixture of two or more. Hereinafter, the raw material of the polyamide resin used in the present invention will be described.

  Although it does not specifically limit as a lactam used as the raw material of said (a) polyamide, For example, a pyrrolidone, a caprolactam, an undecaractam, a dodecaractam, etc. are mentioned.

  Moreover, it does not specifically limit as (omega) omega-aminocarboxylic acid used as the raw material of said (b) polyamide resin, For example, the omega-amino fatty acid etc. which are the ring-opening compounds by the said lactam with water are mentioned. The (a) polyamide and (b) polyamide may each be a condensation product of two or more lactams or ω-aminocarboxylic acids.

  Subsequently, the diamine (monomer) used as the raw material for the above (c) polyamide is not particularly limited. For example, a linear aliphatic diamine such as hexamethylene diamine or pentamethylene diamine; 2-methylpentane diamine; And branched aliphatic diamines such as 2-ethylhexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine. It is done.

On the other hand, the dicarboxylic acid (monomer) used as the raw material for the polyamide (c) is not particularly limited. For example, aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; phthalic acid and isophthalic acid Aromatic dicarboxylic acids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like.
The (c) polyamide may be a single type or a combination of two or more types of diamines and dicarboxylic acids.

  The polyamide is not particularly limited. For example, polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene). Adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 410 (polytetramethylene sebacamide), polyamide 412 (polytetramethylene dodecamide), polyamide 610 (Polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 1010 (polydecamethylene sebacamide), polyamide 1012 (polydecamethylene dodecamide), polyamide 6T (polyhexa Chi terephthalamide), polyamide 9T (poly nonane terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide), and the like copolymerized polyamides containing them as a component.

  Although it does not specifically limit as a terminal group of the polyamide used by this invention, Generally an amino group or a carboxyl group exists. The ratio of the amount of amino end groups to the total amount of amino end groups and carboxyl end groups in the polyamide used in the present invention [amino end group amount / (amino end group amount + carboxyl end group amount)] is 0.3 or more and 4 0.0 or less, preferably 0.3 or more and 1.5 or less, and more preferably 0.5 or more and 1.2 or less. When the ratio of the amount of terminal groups is within the above range, the color tone, mechanical strength, and vibration fatigue resistance of the molded product obtained from the polyamide resin composition tend to be more excellent. In addition, when two or more types of polyamide are included, the same effect is acquired because ratio of the amount of terminal groups as those mixtures becomes this range.

  The amount of amino end groups of the polyamide is preferably 10 to 100 μmol / g, more preferably 15 to 80 μmol / g, and further preferably 30 to 80 μmol / g. When the amino terminal group amount is within the above range, the mechanical strength of the polyamide resin composition tends to be more excellent. In addition, when two or more types of polyamide are included, the same effect is acquired because the amount of terminal groups as a mixture thereof falls within this range.

Here, as an example of the measuring method of the amount of amino terminal groups and the amount of carboxyl terminal groups in this specification, < ¹ > H-NMR method and titration method are mentioned. ^{In the 1} H-NMR method, it can be determined by the integral value of the characteristic signal corresponding to each terminal group. In the titration method, for the amino end group, a method of titrating a polyamide resin phenol solution with 0.1N hydrochloric acid, for the carboxyl end group, a method of titrating a polyamide resin benzyl alcohol solution with 0.1N sodium hydroxide, etc. Is mentioned.

  Furthermore, as a method for adjusting the concentration of the end groups of the polyamide used in the present invention, a known method can be used. Although it does not specifically limit as an adjusting method, For example, the method of using a terminal adjusting agent is mentioned. As a specific example, adding one or more terminal regulators selected from the group consisting of a monoamine compound, a diamine compound, a monocarboxylic acid compound, and a dicarboxylic acid compound so as to have a predetermined terminal concentration during polymerization of polyamide. Is mentioned. The timing of adding the terminal adjuster to the solvent is not particularly limited as long as it functions as a terminal adjuster. For example, the above-described polyamide raw material may be added to the solvent.

  The monoamine compound is not particularly limited, but examples thereof include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and any mixtures thereof. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline are preferable from the viewpoints of reactivity, boiling point, stability of the sealing end and price. These may be used alone or in combination of two or more.

  Although the said diamine compound is not specifically limited, For example, linear aliphatic diamines, such as hexamethylene diamine and pentamethylene diamine; Branched aliphatic diamines, such as 2-methylpentane diamine and 2-ethyl hexamethylene diamine; Aromatic diamines such as p-phenylenediamine and m-phenylenediamine; cycloaliphatic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine are listed. These may be used alone or in combination of two or more.

  The monocarboxylic acid compound is not particularly limited, and examples thereof include 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 isobutyl. Aliphatic monocarboxylic acids such as acids; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatics such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid A monocarboxylic acid etc. are mentioned. In this invention, these carboxylic acid compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The dicarboxylic acid compound is not particularly limited. For example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid. Aliphatic dicarboxylic acids such as 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, diphenylmethane 4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicar Units derived from aromatic dicarboxylic acids such as phosphate and 4,4'-biphenyl dicarboxylic acid (unit) and the like. These may be used alone or in combination of two or more.

 In the present invention, (A) the polyamide resin is based on ISO 307, and the viscosity number (VN) measured with sulfuric acid having a mass fraction of 96% is 80 to 180 ml / g. It is preferable from the viewpoints of fluidity and appearance during molding. More preferably, it is 80-150 ml / g, More preferably, it is 100-150 ml / g, Most preferably, it is 115-150 ml / g.

  The blending amount of the (A) polyamide resin used in the present invention is preferably 30 to 90% by mass with respect to 100% by mass of the polyamide resin composition from the viewpoint of fluidity and appearance. More preferably, it is 35-80 mass%, More preferably, it is 35-75 mass%, Most preferably, it is 40-70 mass%.

[(B) Glass fiber and / or carbon fiber]
The polyamide resin composition of the present invention may contain (B) glass fibers and / or carbon fibers. By containing glass fiber and / or carbon fiber, excellent mechanical strength, impact resistance and rigidity can be obtained.

  Among the glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical strength to the polyamide resin composition, the polyamide resin composition has a number average fiber diameter of 3 to 30 μm and a weight average fiber length of 100 to 750 μm. More preferably, the aspect ratio of the weight average fiber length to the number average fiber diameter (value obtained by dividing the weight average fiber length by the number average fiber diameter) is 10 to 100.

Further, the glass fiber and the carbon fiber may have a circular cross section or a flat shape (such as an elliptical shape or a saddle shape). A flat shape is preferable from the viewpoint of impact resistance and low warpage.
When the fiber diameter of the glass fiber is flat, the average minor axis is preferably 3 to 15 μm, more preferably 4 to 10 μm, and still more preferably, from the viewpoint of excellent mechanical strength, appearance, and low warpage. 5-9 μm.

The number average fiber diameter and the weight average fiber length in this specification can be measured by the following methods.
The polyamide resin composition is put into an electric furnace, the contained organic matter is incinerated, and, for example, 100 or more glass fibers and / or carbon fibers are arbitrarily selected from the residue, and SEM (Scanning Electron Microscope) The number average fiber diameter is measured by observing and measuring these fiber diameters. In addition, the weight average fiber length is determined by measuring the fiber length using an SEM photograph at a magnification of 1000 times.

Glass fiber and carbon fiber may be subjected to surface treatment with a silane coupling agent or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxy. Aminosilanes such as silane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
In particular, at least one selected from the above listed components is preferable, and aminosilanes are more preferable.

  Further, for glass fibers and carbon fibers, as sizing agents, structural units include unsaturated vinyl monomers containing carboxylic anhydride and unsaturated vinyl monomers excluding unsaturated vinyl monomers containing carboxylic anhydride. Copolymers, epoxy compounds, polycarbodiimide compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and their primary, secondary and tertiary amines Or a salt thereof. These may be used alone or in combination of two or more.

Glass fiber and carbon fiber are obtained by continuously reacting in a known glass fiber and carbon fiber production process.
Specifically, glass fibers and carbon fibers are obtained by drying fiber strands produced by applying a sizing agent to glass fibers and carbon fibers using a known method such as a roller-type applicator.
The fiber strand may be used as it is as roving, or may be used as a chopped glass strand after further cutting.

  The sizing agent preferably gives (adds) a solid content of 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, with respect to 100% by mass of glass fiber or carbon fiber. (Added.

  From the viewpoint of maintaining the bundling of the glass fiber and the carbon fiber, the addition amount of the sizing agent is preferably equivalent to 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or the carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition of the present invention, the content is preferably 3% by mass or less. Moreover, drying of a strand may be performed after a cutting process, or a cutting process may be performed after drying of a strand.

  The compounding quantity of the glass fiber and / or carbon fiber used by this invention is 0-150 mass parts with respect to 100 mass parts of (A) polyamide resin from a viewpoint of mechanical strength, impact resistance, or an external appearance. Preferably it is 15-150 mass parts, More preferably, it is 25-120 mass parts, More preferably, it is 30-100 mass parts. Moreover, it is preferable that it is 0-57 mass% with respect to 100 mass% of polyamide resin compositions, More preferably, it is 10-55 mass%, More preferably, it is 15-55 mass%, Most preferably, it is 20-50 mass. %.

[(C) Non-fibrous inorganic filler]
The polyamide resin composition of the present invention contains (C) a non-fibrous inorganic filler. By including the non-fibrous inorganic filler, excellent mechanical strength, appearance and rigidity can be obtained.

The non-fibrous inorganic filler is preferably spherical, plate-shaped, rod-shaped, needle-shaped, granular or scale-shaped.
The non-fibrous inorganic filler is not limited to the following, for example, flaky glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, Wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, graphite, brass, copper, silver, aluminum, nickel, iron , Calcium fluoride, mica, montmorillonite, swellable fluorine mica and apatite.
These may be used alone or in combination of two or more.

  Among them, from the viewpoint of increasing the mechanical strength and rigidity of the polyamide resin composition of the present invention, flaky glass, talc, kaolin, mica, calcium carbonate, wollastonite, graphite, montmorillonite, swellable fluoromica and apatite 1 or more types selected from the group which consists of are preferable. More preferably, it is at least one selected from talc, mica, kaolin and wollastonite, and still more preferably at least one selected from talc, mica and kaolin.

 The non-fibrous inorganic filler used in the present invention has a number average particle diameter of 10 to 40 μm from the viewpoint that excellent mechanical strength, impact resistance, and low warpage can be imparted to the polyamide resin composition. When it is 10 μm or more, in addition to mechanical strength, it tends to be excellent in impact resistance and low warpage. On the other hand, when it is 40 μm or less, the mechanical strength tends to be excellent. Preferably it is 10-30 micrometers, More preferably, it is 15-30 micrometers, More preferably, it is 15-25 micrometers. Here, the number average particle diameter of the non-fibrous inorganic filler is a value measured with a laser particle size meter. For example, by using SALD-2100 manufactured by Shimadzu Corporation, a residue obtained by incinerating an organic substance contained in a non-fibrous inorganic filler as a raw material or a polyamide resin composition in an electric furnace is used as a dispersant. It can be obtained from a particle size distribution measured by using a flow cell after dispersing in purified water containing 0.2% by mass of sodium and 0.1% by mass of a neutral detergent as a surfactant.

Further, the non-fibrous inorganic filler used in the invention is measured using the above laser particle size meter, and D ₉₀ (volume cumulative 90% particle diameter), D ₁₀ (volume cumulative 10% particle diameter) and number average particles. (D ₉₀ -D ₁₀ ) / number average particle diameter, which is an index of particle size distribution using the diameter, is 2.8 or more. By setting it to 2.8 or more, a polyamide resin composition having both mechanical strength and impact resistance and excellent in appearance and low warpage can be obtained. Preferably they are 2.8 or more and 5.0 or less, More preferably, they are 2.8 or more and 4.0 or less, More preferably, they are 2.9 or more and 3.5 or less. D ₉₀ -D ₁₀ indicates the spread of the particle distribution as an absolute value, and a larger value means that the particle distribution is wider. By dividing this value by the number average particle diameter, distributions having different particle diameter ranges can be considered as an index for comparison. The particle size distribution of these non-fibrous inorganic fillers can be adjusted using methods such as dry pulverization and wet pulverization.

  The non-fibrous inorganic filler may be subjected to a surface treatment with a surface treatment agent or the like. The preferred surface treatment agent is at least one selected from an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound, and among them, excellent mechanical strength and impact resistance. From the viewpoint, an organosilane compound is more preferable.

  Specific examples of organic silane compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Mercapto group-containing alkoxysilane compounds such as alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2- Ureido group-containing alkoxysilane compounds such as ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane Isocyanato group-containing alkoxysilane compounds such as lan, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and other amino group-containing alkoxysilane compounds, γ-hydroxypropyltrimethoxysilane, γ -Hydroxyl-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl)- Examples include unsaturated group-containing alkoxysilane compounds such as γ-aminopropyltrimethoxysilane / hydrochloride and acid anhydride group-containing alkoxysilane compounds such as 3-trimethoxysilylpropyl succinic acid. Among them, amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane, 3-trimethoxy An acid anhydride group-containing alkoxysilane compound such as silylpropyl succinic acid is preferred, and an acid anhydride group-containing alkoxysilane compound is more preferred.

  These surface treatment agents are preferably used by a method in which a non-fibrous inorganic filler is surface-treated in advance and then melt-kneaded with a polyamide resin, but the non-fibrous inorganic filler is not subjected to a surface treatment in advance. When melt-kneading the fibrous inorganic filler and the polyamide resin, they may be used in a so-called integral blend method in which these surface treatment agents are added.

The treatment amount of these surface treatment agents is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the non-fibrous inorganic filler. More preferably, it is 0.1-5 mass parts, More preferably, it is 0.2-1.5 mass parts. When the amount is less than 0.05 parts by mass, the effect of improving the mechanical properties by the surface treatment is small. When the amount exceeds 10 parts by mass, the dispersion of the non-fibrous inorganic filler and the appearance defect due to the generated gas are poor. It tends to occur easily.
The non-fibrous inorganic filler having a specific particle size distribution used in the present invention tends to further improve the mechanical strength and impact resistance by the surface treatment.

  The blending amount of the non-fibrous inorganic filler used in the present invention is 10 to 200 parts by mass with respect to 100 parts by mass of the (A) polyamide resin from the viewpoint of mechanical strength, impact resistance and appearance. Preferably it is 15-150 mass parts, More preferably, it is 15-100 mass parts, More preferably, it is 20-80 mass parts. Moreover, it is preferable that it is 10-65 mass% with respect to 100 mass% of polyamide resin compositions, More preferably, it is 10-50 mass%, More preferably, it is 10-45 mass%, Most preferably, it is 10-40 mass %.

Examples of additional components are listed below.
Antioxidants, UV absorbers, heat stabilizers, photodegradation inhibitors, lubricants, plasticizers, mold release agents, nucleating agents, flame retardants, colorants, etc. can be added, and other thermoplastic resins are blended May be.
Examples of the heat stabilizer include, but are not limited to, phenolic heat stabilizers, phosphorus heat stabilizers, amine heat stabilizers, groups Ib, IIb, and IIIa of the periodic table. Group, group IIIb, group IVa and group IVb element metal salts, alkali metal halides and alkaline earth metal halides, and the like.
These may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a phenol type heat stabilizer, For example, a hindered phenol compound is mentioned.

Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), 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- -T-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1, 3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
In particular, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.

  When using a phenol-based heat stabilizer, the blending amount of the phenol-based heat stabilizer in the polyamide resin composition is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the (A) polyamide resin. Preferably it is 0.1-1 mass part. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  Examples of the phosphorus-based heat stabilizer include, but are not limited to, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl Diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, 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-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite , Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono , Dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebi (2-t-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'-isopropylidene diphenyl 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′-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'-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphos Fight is mentioned.

When using a phosphorus heat stabilizer, the compounding quantity of the phosphorus heat stabilizer in the polyamide resin composition of this invention is 0.01-1 mass part with respect to 100 mass parts of (A) polyamide resin, More preferably, it is 0.1-1 mass part.
When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  Examples of amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethyl Piperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl Piperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 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 (2,2,6,6) Tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetra Methyl-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-tri Carboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) Pionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

 When the amine heat stabilizer is used, the compounding amount of the amine heat stabilizer in the polyamide resin composition of the present invention is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) polyamide resin. Yes, more preferably 0.1 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of generated gas can be further reduced.

  The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt. .

Examples of copper salts include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, copper benzoate. , Copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
These may be used alone or in combination of two or more.

  Among the copper salts listed above, one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred, and copper iodide is more preferred. And / or copper acetate.

When using a copper salt, the compounding amount of the copper salt in the polyamide resin composition of the present invention is preferably 0.01 to 0.2 parts by mass, more preferably 100 parts by mass of the (A) polyamide resin. Is 0.02-0.15 parts by mass.
When it is within the above range, the heat aging resistance can be further improved.

  Further, from the viewpoint of improving the heat aging resistance, the copper element content is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and even more preferably 50, based on the total amount of the polyamide resin composition of the present invention. ~ 300 ppm.

Examples of alkali metal halides and alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof.
In particular, from the viewpoint of improving the heat aging resistance, potassium iodide and potassium bromide, and mixtures thereof are preferable, and potassium iodide is more preferable.

  When an alkali metal halide and / or an alkaline earth metal halide is used, the blending amount of the alkali metal halide and / or alkaline earth metal halide in the polyamide resin composition of the present invention is: A) Preferably it is 0.05-5 mass parts with respect to 100 mass parts of polyamide resins, More preferably, it is 0.2-2 mass parts. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

 The lubricant is not particularly limited, and examples thereof include fatty acid metal salts, fatty acid esters, fatty acid amides, and polyethylene waxes. From the viewpoint of excellent appearance and molding processability, one or more selected from fatty acid metal salts, fatty acid esters, and fatty acid amides are preferable, and two or more types are more preferable, and the fatty acid metal salt and the fatty acid ester are used in combination. More preferably.

Fatty acid refers to an aliphatic monocarboxylic acid. In particular, fatty acids having 8 or more carbon atoms are preferred. More preferably, it is a C8-C40 fatty acid.
Examples of fatty acids include, but are not limited to, saturated or unsaturated, linear or branched aliphatic monocarboxylic acids.
Examples of fatty acids include, but are not limited to, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid.

A fatty acid ester is an ester compound of a fatty acid and an alcohol.
Examples of the alcohol include, but are not limited to, 1,3-butanediol, trimethylolpropane, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.

  Examples of fatty acid esters include, but are not limited to, stearyl stearate, behenyl behenate, montanic acid-1,3-butanediol ester, montanic acid-trimethylolpropane ester, trimethylolpropane trilaurate. And butyl stearate.

A fatty acid amide is an amidated product of a fatty acid.
Examples of the fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Etc. In particular, stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucamide are preferable, and ethylene bisstearyl amide and N-stearyl erucamide are more preferable.

The fatty acid metal salt is a metal salt of the fatty acid described above.
Examples of metal elements that form salts with fatty acids include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), Group 3 elements, zinc, and aluminum in the Periodic Table of Elements.
As the metal element, alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; aluminum are preferable.

Examples of the fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, aluminum montanate, zinc montanate, and montan. Examples thereof include magnesium acid, calcium behenate, sodium behenate, zinc behenate, calcium laurate, zinc laurate, and calcium palmitate.
These fatty acid metal salts may be used alone or in combination of two or more.

 Although there is no restriction | limiting in particular in the compounding quantity of these lubricants, from a viewpoint of the outstanding external appearance and moldability, 0.01-1 mass% is preferable with respect to 100 mass% of polyamide resin compositions, and 0.03-0.6 % By mass is more preferable, and 0.05 to 0.5% by mass is more preferable.

 Although it does not restrict | limit especially as a coloring agent, For example, carbon black, a titanium oxide, an azine dye etc. are mentioned. Although there is no restriction | limiting in particular in the compounding quantity of these coloring agents, 0.01-3 mass% is preferable with respect to 100 mass% of polyamide resin compositions from a viewpoint of the outstanding external appearance and moldability, 0.05-2 mass % Is more preferable, and 0.1 to 2% by mass is more preferable.

In the present invention, the polyamide resin composition can be produced by a method of kneading the polyamide resin in a melted state using a single-screw or multi-screw extruder. Using a twin screw extruder equipped with an upstream supply port and a downstream supply port, after supplying polyamide resin from the upstream supply port and melting it, supplying inorganic filler from the downstream supply port and melt kneading Can be preferably used. Moreover, also when using glass fiber roving, it can compound by a well-known method.
The composition thus obtained can be molded as molded parts of various parts by various conventionally known methods such as injection molding.

These various parts can be suitably used for, for example, automobiles, machine industries, electric / electronics, industrial materials, industrial materials, and daily / household goods.
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Raw materials used)
(1) Polyamide (1-1) Polyamide 66 / 6I (hereinafter abbreviated as PA-1)
Copolymerized polyamide with hexamethylene adipamide unit: hexamethylene isophthalamide unit = 75: 25 (mass ratio) VN (sulfuric acid): 90 ml / kg, amino end group: 30 mmol / kg,
Carboxylic acid end group: 100 mmol / kg
(1-2) Polyamide 66 / 6I / 6 (hereinafter abbreviated as PA-2)
Hexamethylene adipamide unit: hexamethylene isophthalamide unit: ε capramide unit = 75: 17: 8 (mass ratio) copolymer polyamide VN (sulfuric acid): 105 ml / kg, amino end group: 40 mmol / kg,
Carboxylic acid end group: 90 mmol / kg

(2) Glass fiber Glass fiber having an average fiber diameter of 13 μm (hereinafter abbreviated as GF)

(3) Inorganic filler (3-1) Talc with a number average particle diameter of 17.0 μm (hereinafter abbreviated as T-1)
D ₉₀ : 55.8 μm, D ₁₀ : 4.4 μm
_(D 90 _{-D 10)} / number average particle diameter: 3.02
Mode length: 21.1 μm
(3-2) Talc with a number average particle diameter of 17.0 μm (hereinafter abbreviated as T-2)
D ₉₀ : 55.8 μm, D ₁₀ : 4.4 μm
_(D 90 _{-D 10)} / number average particle diameter: 3.02
Mode diameter: 21.1 μm
Surface treated with 0.5% by mass of an acid anhydride group-containing alkoxysilane compound (3-trimethoxysilylpropyl succinic anhydride) (3-3) Talc (hereinafter referred to as T) having a number average particle diameter of 17.4 μm -3)
D ₉₀ : 51.8 μm, D ₁₀ : 4.9 μm
_(D 90 _{-D 10)} / number average particle diameter: 2.70
Mode diameter: 21.2 μm
(3-4) Talc with a number average particle diameter of 13.1 μm (hereinafter abbreviated as T-4)
D ₉₀ : 38.6 μm, D ₁₀ : 3.9 μm
_(D 90 _{-D 10)} / number average particle diameter: 2.65
Mode diameter: 17.2 μm
(3-5) Talc with a number average particle diameter of 13.1 μm (hereinafter abbreviated as T-5)
D ₉₀ : 38.6 μm, D ₁₀ : 3.9 μm
_(D 90 _{-D 10)} / number average particle diameter: 2.65
Mode diameter: 17.2 μm
Surface treated with 0.5% by mass of an acid anhydride group-containing alkoxysilane compound (3-trimethoxysilylpropyl succinic anhydride) (3-6) Talc (hereinafter referred to as T) having a number average particle size of 4.8 μm (Abbreviated as -6)
D ₉₀ : 10.0 μm, D ₁₀ : 2.1 μm
_(D 90 _{-D 10)} / number average particle diameter: 1.65
Mode diameter: 6.1 μm

(4) Lubricant Calcium montanate [Licomont (registered trademark) CaV102 (manufactured by Clariant Chemicals)] (hereinafter abbreviated as WAX)

(5) Colorant Polyamide 6 (VN (sulfuric acid): 150 ml / g); 80% by mass, CB (Mitsubishi Carbon (registered trademark) 52B); 15% by mass, ethylenebisstearic acid amide; 5% by mass Master batch (hereinafter abbreviated as CMB)

(Evaluation method)
The evaluation method is described below.
<Tensile strength>
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the polyamide resin composition pellets obtained in the examples and comparative examples were injected + holding time 25 seconds, cooling time 15 seconds, mold temperature. A molded piece of ISO 3167, a multi-purpose test piece A type was molded at 80 ° C. and a molten resin temperature of 290 ° C. Using the obtained molded piece, in accordance with ISO 527, a tensile test was performed at a tensile speed of 5 mm / min, and the tensile strength was measured.

<Charpy impact strength>
The multipurpose test piece A type was cut and used, and a Charpy impact strength with a notch was measured using a test piece of 80 mm × 10 mm × 4 mm in accordance with ISO 179 / 1eA.

<Appearance>
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the mold temperature was set to 80 ° C. and the molten resin temperature 290 ° C. for the polyamide resin composition pellets obtained in the examples and comparative examples. According to ISO 294-3, using a mold of type D1, a molded piece of 60 mm × 60 mm × 2 mm was molded with a filling time at injection of 1 second and a holding pressure of 5 seconds, respectively, and the appearance was visually determined. Observe both sides of the 10 molded pieces (20 in total), A is the one where no whitening due to filler floatation or silver streak is observed on all sides, and 5 is the number of surfaces where whitening is observed The following were designated B, and those with 6 or more surfaces where whitened portions were observed were designated C.

<Low warpage>
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the polyamide resin composition pellets obtained in the examples and comparative examples were injected and held for 10 seconds, cooled for 15 seconds, and mold temperature. Was set to 80 ° C. and the molten resin temperature was 290 ° C., and a molded piece of 60 mm × 60 mm × 2 mm was molded using a mold of type D1 in accordance with ISO 294-3. This test piece is left in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere for 24 hours, placed on a horizontal surface, and an arbitrary one of the four corners is fixed to the horizontal surface. Is measured as the amount of warpage, AA is less than 0.2 mm, A is 0.2 mm or more and less than 0.5 mm, B is 0.5 mm or more and less than 1.0 mm, B is 1.0 mm or more Was designated C.

[Examples 1 to 4, Comparative Examples 1 to 7]
There is an upstream supply port in the first barrel from the upstream side of the extruder, a first supply port on the downstream side in the sixth barrel, a second supply port on the downstream side in the ninth barrel, and a vacuum devolatilization in the 11th barrel L / D (extruder cylinder length / extruder cylinder diameter) = 48 (barrel number: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] with a mouth was used. The temperature from the upstream supply port to the die is set to 300 ° C., and the polyamide, lubricant, and colorant are added from the upstream supply port so that the screw rotation speed is 300 rpm and the discharge amount is 25 kg / h and the ratio shown in Table 1 is obtained. Then, the inorganic filler was supplied from the downstream first supply port, and the glass fiber was supplied from the downstream second supply port. The mixture was melt-kneaded under reduced pressure from the vacuum devolatilization port to prepare a resin composition pellet. The obtained resin composition was molded at a resin temperature of 290 ° C. and a mold temperature of 80 ° C., and evaluated for tensile strength, Charpy impact strength, appearance, and low warpage. The physical properties and the like are shown in Table 1 together with the composition.

  As is apparent from Table 1, it can be seen that the reinforced polyamide resin composition of the present invention is excellent in mechanical strength, impact resistance and appearance, and is also excellent in low warpage.

  The polyamide resin composition of the present invention is excellent in mechanical strength, impact resistance and appearance, and is also excellent in low warpage. Therefore, it is a molded product requiring mechanical strength and good appearance such as automobile parts and small electric and electronic parts. Can be suitably used.

Claims (6)

(A) A reinforced polyamide resin composition comprising (B) 0 to 150 parts by mass of glass fiber and / or carbon fiber and (C) 10 to 200 parts by mass of non-fibrous inorganic filler with respect to 100 parts by mass of polyamide resin. And
The number average particle diameter of the (C) non-fibrous inorganic filler is 10 to 40 μm, and (D ₉₀ -D ₁₀ ) / number average particle diameter as an index of particle size distribution is 2.8 or more. Resin composition.   The reinforced polyamide resin composition according to claim 1, wherein the non-fibrous inorganic filler (C) is at least one selected from talc, mica, kaolin and wollastonite.   The (C) non-fibrous inorganic filler is surface-treated with at least one selected from an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Or the reinforced polyamide resin composition of 2.   The reinforced polyamide resin composition according to claim 3, wherein the non-fibrous inorganic filler (C) is surface-treated with an acid anhydride group-containing alkoxysilane compound.   The reinforcement according to any one of claims 1 to 4, wherein the (A) polyamide resin has a viscosity number of 80 to 150 ml / g measured with sulfuric acid having a mass fraction of 96% in accordance with ISO 307. Polyamide resin composition.   The molded object formed by shape | molding the reinforced polyamide resin composition of any one of Claims 1-5.