CN104231619A - Polyamide resin composition and forming body - Google Patents

Abstract

The present invention relates to a polyamide resin composition and a molded article. An object of the present invention is to provide a polyamide resin composition capable of obtaining a molded article having excellent dimensional accuracy and excellent appearance, and a molded article containing the polyamide resin composition. A polyamide resin composition comprising (A) a polyamide resin, (B) glass fibers, and (C) a non-fibrous filler, wherein 50% by mass or more of the (A) polyamide resin is carbon atoms In an aliphatic polyamide having a ratio of nitrogen atoms (C/N ratio) of 7 or more, the number average fiber diameter x (μm) of the (B) glass fiber and the number of the (C) non-fibrous filler The average particle size y (μm) satisfies the following formula: x≥5, y≥3, 0.8x+y≥11.

Description

Polyamide resin composition and molded article

technical field

The present invention relates to a polyamide resin composition and a molded article.

Background technique

Polyamide resin has excellent mechanical properties (mechanical strength, rigidity, impact resistance, etc.), toughness, heat resistance, and chemical resistance, so it is used in various fields such as clothing materials, industrial materials, automobiles, electrical and electronic components, and other industrial products. used in the industrial field. In particular, polyamide resins are superior to other resins in heat aging resistance. Therefore, it is used as a material for components in places with very high heat, such as the engine room of an automobile.

For materials used in the engine room of automobiles, use in cold regions is envisaged recently, and the suppression of resin deterioration (calcium chloride resistance) of calcium chloride as an antifreeze is more highly required, and it is used as an antifreeze in cooling system components. Inhibition of resin deterioration (hydrolysis resistance) due to long-term cooling liquid (LLC) of freezing liquid, etc. Polyamide resins are also required to have the above-mentioned calcium chloride resistance and hydrolysis resistance when used in parts related to automobile engine compartments.

Polyamides having long carbon chains (long-chain polyamides; polyamides having a high ratio of methylene chains to amide bonds) are conventionally known as techniques for improving the calcium chloride resistance and hydrolysis resistance of polyamide resins.

Regarding polyamide 610, which is one of long-chain polyamides, techniques for blending glass fibers, nucleating agents, heat stabilizers, and the like are disclosed (see, for example, Patent Document 1 and Patent Document 2).

prior art literature

patent documents

Patent Document 1: Japanese PCT Publication No. 2010-522259

Patent Document 2: Japanese Patent Laid-Open No. 2009-215514

Contents of the invention

The problem to be solved by the invention

However, long-chain polyamides have excellent calcium chloride resistance and hydrolysis resistance, but their crystallization speed is slower than general polyamide 66, polyamide 6, etc. Insufficient dimensional accuracy, etc. On the other hand, when the crystallization rate is too fast for improving mold releasability, the appearance of the molded article is impaired.

In addition, when the obtained polyamide resin composition is used as a material for automobile engine compartment parts, electric and electronic parts, etc., a polyamide resin composition with better dimensional accuracy than conventional ones is required, and existing The dimensional accuracy of the polyamide resin composition is insufficient.

Therefore, the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a polyamide resin composition capable of obtaining a molded article having excellent dimensional accuracy and excellent appearance, and a molded article containing the polyamide resin composition.

means of solving problems

The inventors of the present invention have conducted extensive and intensive studies in order to solve the above-mentioned problems. As a result, it was found that a polyamide resin composition containing a specified amount of specified aliphatic polyamide, the average fiber diameter x (μm) of the glass fiber and the average particle size y (μm) of the non-fibrous filler satisfying the specified relationship can solve the problem. The above problems have been solved, and the present invention has been accomplished.

That is, the present invention is as follows.

[1] A polyamide resin composition comprising (A) a polyamide resin, (B) glass fibers and (C) a non-fibrous filler,

50% by mass or more of the (A) polyamide resin is an aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more,

The number average fiber diameter x (μm) of the (B) glass fiber and the number average particle size y (μm) of the (C) non-fibrous filler material satisfy the following formula:

x≥5

y≥3

0.8x+y≥11.

[2] The polyamide resin composition according to the above item [1], wherein the (A) ratio of the number of carbon atoms/number of nitrogen atoms in the polyamide resin (C/N ratio) is 7 or more The aliphatic polyamide is at least one selected from the group consisting of polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, and polyamide 1012.

[3] The polyamide resin composition as described in [1] or [2] above, wherein the (C) non-fibrous filler is selected from glass flakes, talc, kaolin, mica, calcium carbonate, clay and one or more of the group consisting of silicon nitride.

[4] The polyamide resin composition according to any one of [1] to [3] above, wherein the (B) glass fibers are glass fibers treated with a sizing agent containing a copolymer, The copolymer contains a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer as constituent units.

[5] The polyamide resin composition according to any one of [1] to [4] above, wherein the (A) polyamide resin has a ratio of carbon atoms/nitrogen atoms (C/N ) ratio of less than 7 aliphatic polyamides,

The content of the aliphatic polyamide is 50% by mass or less with respect to 100% by mass of the total amount of the (A) polyamide resin.

[6] The polyamide resin composition according to any one of [1] to [5] above, wherein the (A) polyamide resin contains an amount of amino terminals relative to the amount of amino terminals and the amount of carboxyl terminals. A polyamide resin having a total ratio [amount of amino terminals/(amount of amino terminals+amount of carboxyl terminals)] of 0.3 or more and less than 1.0.

[7] The polyamide resin composition according to any one of [1] to [6] above, which contains 25 to 84% by mass of the (A ) polyamide resin, 15 to 74% by mass of the (B) glass fiber, and 1 to 20% by mass of the (C) non-fibrous filler.

[8] The polyamide resin composition according to any one of [1] to [7] above, further comprising (D) a mixture of a copper salt and an alkali metal halide and/or an alkaline earth metal halide mixture.

[9] The polyamide resin composition according to any one of [1] to [8] above, further comprising (E) boron nitride and/or carbon black.

[10] A molded article comprising the polyamide resin composition according to any one of [1] to [9].

[11] The molded article according to the above item [10], which has a cylindrical portion.

[12] The molded body according to the preceding item [11], wherein the cylindrical shape portion includes an undercut portion that is forcibly taken out.

Invention effect

According to the present invention, there can be provided a polyamide resin composition capable of obtaining a molded article having excellent dimensional accuracy and excellent appearance, and a molded article comprising the polyamide resin composition.

Detailed ways

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "the present embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement various deformation|transformation within the range of the summary.

[Polyamide resin composition]

The polyamide resin composition of this embodiment contains (A) polyamide resin, (B) glass fiber and (C) non-fibrous filler,

50% by mass or more of the (A) polyamide resin is an aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more,

The number average fiber diameter x (μm) of the (B) glass fiber and the number average particle size y (μm) of the (C) non-fibrous filler material satisfy the following formula:

x≥5

y≥3

0.8x+y≥11.

Hereinafter, each constituent element of the aforementioned polyamide resin composition will be described in detail.

[(A) polyamide resin]

"Polyamide resin" refers to a polymer compound having a -CO-NH-(amide) bond in the main chain. The (A) polyamide resin used in this embodiment is not particularly limited, and examples thereof include: (a) a polyamide resin obtained by ring-opening polymerization of a lactam, (b) a polyamide resin obtained by A polyamide resin obtained by condensation, (c) a polyamide resin obtained by condensing a diamine and a dicarboxylic acid, and a copolymer thereof. (A) The polyamide resin may be used singly or as a mixture of two or more kinds. Hereinafter, the raw material of (A) polyamide resin of this embodiment is demonstrated.

The lactam as a raw material of the polyamide resin (a) is not particularly limited, and examples thereof include pyrrolidone, caprolactam, undecalactam, and laurolactam.

In addition, the ω-aminocarboxylic acid used as a raw material of the above (b) polyamide resin is not particularly limited, and examples thereof include ω-amino fatty acid, which is a ring-opened compound obtained from the above-mentioned lactam with water. In addition, each of the above-mentioned (a) polyamide and (b) polyamide may be a polyamide obtained by condensing two or more lactams or ω-aminocarboxylic acids in combination.

Next, the diamine (monomer) used as the raw material of the above (c) polyamide resin is not particularly limited, and examples thereof include linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine. ; 2-methylpentamethylenediamine, 2-ethylhexamethylenediamine and other branched aliphatic diamines; p-phenylenediamine, m-phenylenediamine and other aromatic diamines; cyclohexanediamine , cyclopentanediamine, cyclooctanediamine and other alicyclic diamines.

On the other hand, the dicarboxylic acid (monomer) used as the raw material of the above (c) polyamide resin is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as adipic acid, heptanediamine, and sebacic acid. ; Aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc.

The above (c) polyamide may be a polyamide obtained by condensing a diamine and a dicarboxylic acid alone or in combination of two or more.

The (A) polyamide resin is not particularly limited, and examples thereof include polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecamide), polyamide 12 (polyamide Lauramide), polyamide 46 (polybutylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polydecane Hexamethylene diamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 1010 (polydecanediamide sebacamide), polyamide 1012 (polydecanediamide dodecamide), polyamide 6T ( Polyhexamethylene terephthalamide), polyamide 9T (polynonanediamide terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), and copolymers containing them as constituents amides etc.

The (A) polyamide resin used in this embodiment is an aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more in the (A) polyamide resin in an amount of 50% by mass or more. By containing such an aliphatic polyamide, the obtained molded article tends to be more excellent in dimensional accuracy and appearance. The ratio of the number of carbon atoms to the number of nitrogen atoms (C/N ratio) of the aliphatic polyamide is 7 or more, preferably 8 or more. In addition, the upper limit of the ratio of carbon atoms/nitrogen atoms (C/N ratio) is not particularly limited, but is preferably 15 or less, more preferably 12 or less, and still more preferably 10 or less. When the ratio of the number of carbon atoms/number of nitrogen atoms is within the above-mentioned range, the molded article obtained tends to have better dimensional accuracy and appearance. In addition, regarding the C/N ratio of the copolymerized polyamide, the average value calculated from the molar ratio of the copolymerization ratio can be obtained as the C/N ratio.

In addition, the content of the aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more is 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more. When the content is within the above range, the obtained molded article tends to have better dimensional accuracy and appearance.

In addition, the "aliphatic polyamide" in the present embodiment refers to a unit constituting a polyamide (when composed of a diamine and a dicarboxylic acid, a pair of diamine and a dicarboxylic acid are regarded as one unit) More than 50% by mass of polyamides are composed of aliphatic units.

The aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more is not particularly limited, and examples thereof include polyamide 610, polyamide 612, polyamide 11, and polyamide 12. , polyamide 1010, polyamide 1012, and the group consisting of copolyamides containing these as constituent components.

The polyamide resin composition of this embodiment preferably contains a polyamide having a C/N ratio of less than 7 as another polyamide resin. The polyamide having a C/N ratio of less than 7 is not particularly limited, and examples thereof include polyamides selected from polyamide 4, polyamide 6, polyamide 46, polyamide 56, polyamide 66, and copolymers containing these as constituents. One or more types from the group consisting of polyamides. Among them, polyamides having a C/N ratio of less than 7 are more preferred, and aliphatic polyamides having a C/N ratio of less than 7 are more preferred. By containing such a polyamide, the obtained molded article tends to be more excellent in mechanical strength and rigidity when heated.

The content of the polyamide having a C/N ratio of less than 7 is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and still more preferably 5 to 20% by mass. When the content is within the above range, the mechanical strength and the rigidity when heated tend to be more excellent without impairing the dimensional accuracy and appearance of the molded body obtained.

In addition, the polyamide resin composition of the present embodiment preferably contains a semi-aromatic polyamide having a C/N ratio of 7 or more as another polyamide resin. The semi-aromatic polyamide having a C/N ratio of 7 or more is not particularly limited, and examples thereof include polyamide 6T, polyamide 9T, and polyamide 6I. By containing such a semi-aromatic polyamide, the rigidity at the time of heating tends to be more excellent. Here, "semi-aromatic polyamide" refers to a polyamide composed of a combination of a diamine or a dicarboxylic acid, one of which is an aliphatic compound and the other is a compound having an aromatic structure, and polyamides containing these as constituents. The component copolyamide, in the case of a copolyamide, is called a semiaromatic polyamide when more than 50% by mass of the constituent units is a semiaromatic unit.

The content of the semi-aromatic polyamide having a C/N ratio of 7 or more is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and still more preferably 5 to 20% by mass. When the content is within the above range, the rigidity at the time of heating tends to be more excellent without impairing the dimensional accuracy and appearance of the molded body obtained.

The (A) terminal group of the polyamide resin used in this embodiment is not particularly limited, and amino or carboxyl groups generally exist. The ratio of the amount of amino terminals in the (A) polyamide resin used in this embodiment to the total amount of amino terminals and carboxyl terminals [amino terminal amount / (amino terminal amount + carboxy terminal amount)] is preferably 0.3 or more and less than 1.0, more preferably 0.3 to 0.8, still more preferably 0.3 to 0.6. When the ratio of the amount of terminal groups is within the above range, the molded article obtained from the polyamide resin composition tends to be more excellent in color tone, mechanical strength, and vibration fatigue resistance.

(A) The amino terminal amount of the polyamide resin is preferably 10 to 100 micromol/g, more preferably 15 to 80 micromol/g, and still more preferably 30 to 80 micromol/g. There exists a tendency for the mechanical strength of a polyamide resin composition to become more excellent when the amount of amino terminal exists in the said range.

Here, examples of methods for measuring the amount of amino-terminals and carboxy-terminals in the present specification include ¹ H-NMR and titration. In the ¹ H-NMR method, it is obtained from the integral value of the characteristic signal corresponding to each terminal group. The titration method includes titrating a phenol solution of polyamide resin with 0.1N hydrochloric acid for the amino terminal, and titrating a benzyl alcohol solution of polyamide resin with 0.1N sodium hydroxide for the carboxyl terminal. More specifically, it can be measured by the method described in the Example.

In addition, as a method of adjusting the concentration of the terminal group of (A) polyamide resin used in this embodiment, a known method can be used. The adjustment method is not particularly limited, and examples thereof include a method using a terminal adjuster. As a specific example, adding one or more terminal regulators selected from the group consisting of monoamine compounds, diamine compounds, monocarboxylic acid compounds, and dicarboxylic acid compounds during the polymerization of polyamide resins to achieve the specified method of the end concentration. The timing of adding the terminal regulator to the solvent is not particularly limited as long as it exhibits its original function as the terminal regulator. For example, it may be added when adding the raw material of the above-mentioned polyamide resin to the solvent.

The above-mentioned monoamine compound is not particularly limited, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and diethylamine. Aliphatic monoamines such as butylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and arbitrary mixtures thereof. Among them, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of blocking, price, and the like. These substances may be used alone or in combination of two or more.

The above-mentioned diamine compounds are not particularly limited, and examples thereof include straight-chain aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; 2-methylpentamethylenediamine, 2-ethylhexamethylenediamine; Branched-chain aliphatic diamines such as diamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine amines, etc. These compounds may be used alone or in combination of two or more.

The above-mentioned 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, tridecanoic acid, myristic acid, palmitic acid, stearic acid, Aliphatic monocarboxylic acids such as pentanoic acid and isobutyric acid; aliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, methylbenzoic acid, alpha-naphthoic acid, beta-naphthoic acid, methylnaphthoic acid and phenyl Aromatic monocarboxylic acids such as acetic acid, etc. In this embodiment, these carboxylic acid compounds may be used alone or in combination of two or more.

The above-mentioned dicarboxylic acid compound is not particularly limited, and examples thereof include: malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyl Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; 1, Alicyclic dicarboxylic acids such as 3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid; isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4 -Naphthalene dicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenylcarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone- Units derived from aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid. These compounds may be used alone or in combination of two or more.

(A) The sulfuric acid relative viscosity of the polyamide resin is preferably 1.0 to 6.0, more preferably 1.5 to 5.0, still more preferably 2.0 to 4.0. When the relative viscosity of sulfuric acid is within the above range, the balance between fluidity and mechanical strength tends to be more excellent. In addition, the relative viscosity of sulfuric acid can be measured by the method described in the Examples.

In this embodiment, the content of the polyamide resin in the polyamide resin composition is preferably 25 to 84% by mass, more preferably 35 to 74% by mass, and even more preferably 40 to 74% by mass relative to 100% by mass of the polyamide resin composition. %. When the content is within the above range, the fluidity of the polyamide resin composition and the mechanical strength and appearance of the molded article obtained tend to be more excellent.

[(B) glass fiber]

The polyamide resin composition of this embodiment contains (B) glass fiber whose number average fiber diameter is 5 micrometers or more. (B) The glass fiber has a number average fiber diameter of 5 μm or more, preferably 7 μm or more. When the number average fiber diameter of (B) glass fiber is 5 micrometers or more, the mechanical strength and rigidity of a polyamide resin composition can be improved further. In addition, the number average fiber diameter of (B) glass fiber is preferably 25 μm or less, more preferably 20 μm or less. By setting the number-average fiber diameter within the above-mentioned range, there is a tendency that the appearance and the like can be further improved while maintaining the mechanical strength and rigidity of the molded article obtained from the polyamide resin composition at a high level.

(B) The number average fiber diameter of a glass fiber can be measured by the method described in an Example.

(B) Glass fiber can be surface-treated with a surface treatment agent such as a silane coupling agent. The silane coupling agent is not particularly limited, and examples include: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl Aminosilanes such as methyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Among them, the above-mentioned aminosilanes are more preferable. The above-mentioned surface treatment agents may be used alone or in combination of two or more.

In addition, (B) glass fibers are preferably treated with a sizing agent. Such a sizing agent is not particularly limited, and for example, a copolymer containing a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer as constituent units , epoxy compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of homopolymers or copolymers of acrylic acid and primary, secondary and tertiary amines. These substances may be used alone or in combination of two or more. Among them, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer as a constituent unit, an epoxy compound or a polyurethane resin, or a combination thereof is preferable. The combination is more preferably a copolymer or a polyurethane resin containing a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer as constituent units, or a combination thereof. By using (B) glass fibers treated with such a sizing agent, the mechanical strength of the molded article obtained from the polyamide resin composition tends to be more excellent.

It does not specifically limit as said carboxylic acid anhydride containing unsaturated vinyl monomer, For example, maleic anhydride, itaconic anhydride, citraconic anhydride are mentioned. Among them, maleic anhydride is preferred.

The above-mentioned unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer is not particularly limited as long as it is an unsaturated vinyl monomer different from the above-mentioned carboxylic anhydride-containing unsaturated vinyl monomer, and examples thereof include : Styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene alkene, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate. Among them, styrene and butadiene are preferable.

Among the combinations of unsaturated vinyl monomers containing carboxylic anhydride and unsaturated vinyl monomers other than the unsaturated vinyl monomers containing carboxylic anhydride, copolymers of maleic anhydride and butadiene, maleic anhydride and Copolymers of ethylene, copolymers of maleic anhydride and styrene, and mixtures thereof.

In addition, the weight-average molecular weight of the copolymer of unsaturated vinyl monomers containing carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers other than the unsaturated vinyl monomers containing carboxylic acid anhydrides is preferably 2,000 or more, more preferably 2,000 to 1,000,000, and even more preferably 5000~500000. When the weight average molecular weight is within the above range, the fluidity of the glass fiber-reinforced polyamide resin composition tends to be further improved. In addition, the weight average molecular weight in this specification is the value measured by the gel permeation chromatography (GPC).

The epoxy compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butylene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, and decylene oxide. , undecene oxide, dodecene oxide, pentacene oxide and eicosene oxide and other aliphatic epoxy compounds; glycidol, epoxy amyl alcohol, 1-chloro-3,4-epoxybutane, 1- Chloro-2-methyl-3,4-epoxybutane, 1,4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctyl oxide Cycloaliphatic epoxy compounds such as alkene, methylcyclohexene oxide, vinylcyclohexene oxide, and epoxidized cyclohexene methanol; terpene epoxy compounds such as pinene oxide; styrene oxide, p-chlorine oxide Aromatic epoxy compounds such as styrene and m-chlorostyrene oxide; epoxidized soybean oil; and epoxidized linseed oil.

The above-mentioned polyurethane resin is not particularly limited as long as it is generally used as a sizing agent for (B) glass fibers, and can be preferably used. Polyurethane resin synthesized from isocyanate such as methyl bis(cyclohexyl isocyanate) (HMDI) or isophorone diisocyanate (IPDI) and polyester or polyether diol.

The weight average molecular weight of the homopolymer of the said acrylic acid becomes like this. Preferably it is 1,000-90,000, More preferably, it is 1,000-25,000.

The copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers is not particularly limited, and examples thereof include monomers having a hydroxyl group and/or carboxyl group, and ester monomers. Such a copolymerizable monomer is not particularly limited, and examples thereof include: , mesaconic acid and their ester compounds consisting of one or more species (except for acrylic acid alone). It is preferable to have one or more ester monomers among the above-mentioned monomers.

The amine constituting the salt of a homopolymer and/or copolymer of acrylic acid and a primary, secondary, or tertiary amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine. The degree of neutralization is preferably 20 to 90%, more preferably 40 to 60%, from the viewpoint of improving the stability of a mixed solution with other chemical reagents (silane coupling agent, etc.) used in combination and reducing amine odor.

Although the weight average molecular weight of the homopolymer or copolymer of the acrylic acid which forms a salt is not specifically limited, Preferably it is 3000-50000. When the weight average molecular weight is 3000 or more, there exists a tendency for the bundling property of (B) glass fiber to improve more. In addition, when the weight average molecular weight is 50,000 or less, there is a tendency that the mechanical properties of the molded article obtained from the polyamide resin composition are further improved.

The treatment method of (B) glass fiber is not particularly limited. For example, the above-mentioned sizing agent can be applied to the glass fiber by a known method such as a roll coater in a known glass fiber production process. bundles, and drying the manufactured fiber bundles, thereby continuously reacting to obtain.

In addition, the state of the (B) glass fiber is not particularly limited, and the above-mentioned fiber bundle may be used directly as a roving, or may be used as chopped glass strands after a cutting process. In addition, the fiber bundle may be dried after the cutting step, or may be cut after drying the fiber bundle.

The added amount of the surface treatment agent and/or sizing agent is preferably 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, more preferably 0.3 to 1 quality%. When the added amount of the sizing agent is 0.2% by mass or more, it tends to be possible to further maintain the sizing of the glass fibers. On the other hand, when the additive of the sizing agent is 3% by mass or less, the thermal stability of the polyamide resin composition tends to be further improved.

In the present embodiment, the content of (B) glass fibers in the polyamide resin composition is preferably 15 to 74 mass %, more preferably 25 to 64 mass %, based on 100 mass % of the polyamide resin composition. When the content of (B) glass fibers is within the above range, the fluidity of the polyamide resin composition and the mechanical strength, rigidity, dimensional accuracy and appearance of the molded article obtained can be further improved.

[(C) Non-fibrous filler material]

In the present embodiment, the polyamide resin composition contains (C) a non-fibrous filler having a number average particle diameter of 3 μm or more. (C) The number average particle diameter of the non-fibrous filler is 3 μm or more, preferably 4 μm or more, more preferably 5 μm or more, further preferably 7 μm or more. (C) When the number average particle diameter of the non-fibrous filler is 3 μm or more, the mechanical strength and rigidity of the molded article obtained from the polyamide resin composition can be further improved, and the dimensional accuracy of the molded article obtained can be further improved. . In addition, the number average particle diameter of the (C) non-fibrous filler is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less. When the number average particle diameter is within the above range, the dimensional accuracy, appearance, etc. of the molded article obtained from the polyamide resin composition can be further improved while maintaining the mechanical strength and rigidity of the molded article obtained from the polyamide resin composition at a high level. In addition, "fibrous" means, for example, a shape produced by cutting fibers, and "non-fibrous" means, for example, a shape other than fibrous.

(C) The number average particle diameter of the non-fibrous filler can be measured by the method described in the examples.

(C) The non-fibrous filler is not particularly limited, and examples thereof include glass flakes, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, Silicon, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, Ketjen black, acetylene black, furnace black, graphite, Brass, copper, silver, aluminum, nickel, iron, calcium fluoride, clay, and apatite.

Among them, glass flake, talc, kaolin, mica, calcium carbonate, clay, and silicon nitride are preferable, and glass flake, talc, mica, kaolin, calcium carbonate, and clay are more preferable. The aforementioned (C) non-fibrous fillers may be used alone or in combination of two or more. By using such a (C) non-fibrous filler, there exists a tendency for the dimensional accuracy and appearance of the molded object obtained from a polyamide resin composition to become more excellent.

The above (C) non-fibrous filler may be surface-treated with a silane coupling agent or the like. The above-mentioned silane coupling agent is not particularly limited, and examples thereof include: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl Aminosilanes such as methyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Among them, aminosilanes are more preferable. The above-mentioned surface treatment agents may be used alone or in combination of two or more.

In this embodiment, the content of the (C) non-fibrous filler in the polyamide resin composition is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 2% to 100% by mass of the polyamide resin composition. ~8% by mass. When the content of the (C) non-fibrous filler is within the above range, the molded article obtained from the polyamide resin composition tends to be more excellent in mechanical strength, rigidity, dimensional accuracy, and appearance.

In the present embodiment, the number average fiber diameter x (μm) of (B) glass fiber and the number average particle size y (μm) of (C) non-fibrous filler satisfy the relationship of the following formula (1). As a result, the unevenness on the surface of the molded article becomes smaller, and as a result, the molded article obtained from the polyamide resin composition is more excellent in dimensional accuracy and appearance.

0.8x+y≥11...(1).

When the value of "0.8x+y" is less than 11, the obtained molded article tends to have increased anisotropy, increased warpage, decreased dimensional accuracy, and also decreased appearance. On the other hand, the value of "0.8x+y" is 11 or more, preferably 11 or more and 30 or less, more preferably 14 or more and 26 or less, still more preferably 17 or more and 26 or less. When the value of "0.8x+y" is within the above range, not only the dimensional accuracy and appearance of the obtained molded body are more excellent, but also the mechanical strength of the molded body can be maintained at a high level.

[(D) Copper salts, halides of alkali metals and/or halides of alkaline earth metals]

The polyamide resin composition of the present embodiment may further contain a copper salt, an alkali metal halide and/or an alkaline earth metal halide (hereinafter simply referred to as a "halide"), or a mixture of a copper salt and a halide.

<copper salt>

The above-mentioned copper salt is not particularly limited, and examples include copper halides (copper iodide, cuprous bromide, copper bromide, cuprous chloride, etc.), copper acetate, copper propionate, copper benzoate, adipic acid Copper, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex formed by coordination of chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid with copper Salt. These substances may be used alone or in combination of two or more.

Among the copper salts listed above, preferably one or more selected from the group consisting of copper iodide, cuprous bromide, copper bromide, cuprous chloride and copper acetate, more preferably copper iodide and/or copper acetate . Use of the above-mentioned copper salt tends to provide a polyamide resin composition that is excellent in heat aging resistance and can suppress metal corrosion of the screw or barrel portion during extrusion (hereinafter simply referred to as "metal corrosion").

When a copper salt is used, the content of the copper salt in the polyamide composition is preferably 0.01 to 0.2 mass%, more preferably 0.01 to 0.1 mass%, based on 100 mass% of the polyamide resin composition. When the content of the copper salt is within the above-mentioned range, the thermal aging resistance of the polyamide resin composition can be further improved, and copper precipitation and metal corrosion tend to be suppressed.

In addition, the content concentration of the copper element is preferably 20 to 1000 ppm, more preferably 30 to 500 ppm, and still more preferably 50 to 300 ppm based on the total amount of the polyamide composition. When the content concentration of the copper element is within the above-mentioned range, the thermal aging resistance of the polyamide resin composition can be further improved, and the precipitation of copper and metal corrosion tend to be suppressed.

<Halides of alkali metals and/or halides of alkaline earth metals>

The alkali metal halide and/or the alkaline earth metal halide is not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and mixtures thereof. Among them, potassium iodide, potassium bromide, and mixtures thereof are preferred, and potassium iodide is more preferred. Use of such a halide tends to further improve the heat aging resistance of the polyamide resin composition and further suppress metal corrosion. In addition, one kind of halide may be used alone, or two or more kinds may be used in combination.

The content of alkali metal and/or alkaline earth metal halides in the polyamide resin composition is preferably 0.05 to 5% by mass, more preferably 0.05 to 2% by mass, and even more preferably 0.05 to 1% by mass relative to 100% by mass of the polyamide resin composition %. When the content of the halide is within the above range, the thermal aging resistance of the polyamide resin composition can be further improved, and the deposition of copper and metal corrosion tend to be further suppressed.

The components of the copper salts, alkali metals, and/or alkaline earth metal halides described above may be used alone or in combination of two or more. Among them, copper salts and alkalis are preferably used from the viewpoint of heat aging resistance. Mixtures of halides of metals and/or alkaline earth metals.

The molar ratio (halogen/copper) of the halogen to copper in the mixture is preferably 2-50, more preferably 5-30, still more preferably 5-20. When the molar ratio is within the above-mentioned range, there is a tendency that the heat aging resistance of the polyamide resin composition can be further improved. In addition, the "halogen" here refers to the total of the halogen derived from the copper halide and the halogen derived from the halides of alkali metals and alkaline earth metals when copper halide is used as the copper salt. When the molar ratio of the halogen to copper is 2 or more, the deposition of copper and the corrosion of metal tend to be further suppressed. On the other hand, when the molar ratio of the halogen to copper is 50 or less, it tends to be possible to further prevent corrosion of the screw of the molding machine, etc. without impairing mechanical properties such as heat resistance and toughness.

The content of the mixture of copper salt and alkali metal and/or alkaline earth metal halide in the polyamide resin composition is preferably 0.01 to 1% by mass, more preferably 0.05 to 1% by mass based on 100% by mass of the polyamide resin composition. When the content is within the above range, the heat aging resistance of the polyamide resin composition tends to be further improved.

[(E) boron nitride and/or carbon black]

The polyamide resin composition of this embodiment may further contain boron nitride and/or carbon black. By containing boron nitride and carbon black, there is a tendency that the crystallization rate of the polyamide resin (A) can be increased, the releasability of the polyamide resin composition during molding can be improved, or the cooling time of injection molding can be shortened.

The content of boron nitride and/or carbon black in the polyamide resin composition is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.8% by mass, and even more preferably 0.05 to 0.6% by mass relative to 100% by mass of the polyamide resin composition. When the content is within the above range, the moldability of the polyamide resin composition tends to be further improved without impairing the mechanical strength of a molded article obtained from the polyamide resin composition.

As boron nitride, the shape of the primary particles is not limited, and known boron nitride can be used. The average primary particle size of boron nitride is not particularly limited, but is preferably 1 to 20 μm, more preferably 3 to 20 μm.

The carbon black is not particularly limited, and known carbon blacks can be used. The average primary particle diameter of carbon black is not particularly limited, but is preferably 10 to 100 nm, more preferably 10 to 50 nm, and still more preferably 10 to 20 nm. When the average primary particle diameter is within the above range, the formability of the polyamide resin composition tends to be further improved without impairing the mechanical strength of a molded article obtained from the polyamide resin composition. In addition, the average primary particle diameter of carbon black can be measured with a transmission electron microscope.

[Other components that may be contained in the polyamide resin composition]

In addition to the above-mentioned components, other components may be further added as necessary within the range not impairing the effect of the present embodiment. Such other components are not particularly limited, and for example, phenolic heat stabilizers, phosphorus-containing heat stabilizers, amine-based heat stabilizers, sulfur-containing heat stabilizers, ultraviolet absorbers, photodegradation inhibitors, and plasticizers can be added. , Lubricants, crystal nucleating agents, mold release agents, flame retardants, colorants, dyes, pigments, etc., can also be mixed with other thermoplastic resins. Here, since the properties of each of the above-mentioned other components are largely different, the appropriate content rate of each component also varies. Furthermore, those skilled in the art can easily set the respective appropriate content rates of the above-mentioned other components.

[Manufacturing method of polyamide resin composition]

The method of producing the polyamide resin composition of the present embodiment is not particularly limited, and a method of kneading the polyamide resin in a molten state with a single-screw or multi-screw extruder can be used. For example, it is preferable to use a twin-screw extruder having an upstream feed port and a downstream feed port, supply the polyamide resin and the stabilizer from the upstream feed port and melt them, and then supply them from the downstream feed port. Glass fiber and melt kneading method. Moreover, when using the roving of glass fiber, it can also compound by a well-known method.

[Molded article of polyamide resin composition]

The molded article of this embodiment contains a polyamide resin composition. The polyamide resin composition is not particularly limited, and can be used as a molded product of various parts obtained by injection molding, blow molding, sheet molding, or the like. Among them, it is preferable that the molded body has a cylindrical portion from the viewpoint of obtaining a molded body having excellent roundness. In addition, the cylindrical shape portion preferably includes an undercut portion that is forcibly taken out.

These various parts are not particularly limited, and for example, they can be suitably used for automobiles, machinery industry, electric and electronic products, industrial materials, industrial materials, daily and household products.

The molded article obtained from the polyamide resin composition of this embodiment is excellent in dimensional accuracy and appearance, so it can be suitably used in intake manifolds, intercooler intake pipes, exhaust pipe covers, inner sleeves, bearings Lining, engine frame, engine cylinder head, muffler, and throttle body, chain guard, thermostat shell, discharge pipe, radiator tank, alternator, and water pipes, etc.

Example

Hereinafter, although an Example and a comparative example demonstrate this embodiment more concretely, this embodiment is not limited to these Examples.

First, the measurement methods, evaluation methods, and raw materials used in Examples and Comparative Examples are as follows.

[test methods]

<Measurement method of sulfuric acid relative viscosity of polyamide resin>

The sulfuric acid relative viscosity of the polyamide resin was measured according to JIS-K6920. Specifically, 98% sulfuric acid was used to prepare a solution having a concentration of 1% (ratio of (1 g of polyamide resin)/(100 mL of 98% sulfuric acid)), and the relative viscosity of sulfuric acid was measured at a temperature of 25°C.

<Measuring method of amino terminal amount and carboxyl terminal amount of polyamide resin>

The amount (micromoles/g) of the amino terminals of the polyamide resin was determined by titrating a phenol solution of the polyamide resin with 0.1N hydrochloric acid. In addition, the number (micromoles/g) of carboxyl terminals of the polyamide resin was determined by titrating a benzyl alcohol solution of the polyamide resin with 0.1 N sodium hydroxide.

<Measuring method of thermal weight loss of glass fiber>

10 g of the glass fibers used in Examples and Comparative Examples were accurately weighed, heated in an electric furnace at 650° C. for 2 hours for incineration treatment, and the amount of mass loss was taken as the intense thermal weight loss of the glass fibers.

<Measuring method of number average fiber diameter of glass fiber>

The glass fibers used in Examples and Comparative Examples were heated in an electric furnace at 650°C for 2 hours and incinerated, and 100 glass fibers were randomly selected from the residue components, and the fiber diameter was measured using a SEM photograph with a magnification of 1000 times, thereby obtaining Number average fiber diameter of glass fibers.

<Measuring method of number average particle diameter of non-fibrous filler>

The non-fibrous fillers used in Examples and Comparative Examples were dispersed in 1% soapy water, and the particle size distribution was measured with a laser particle size analyzer to obtain the number average particle size of the non-fibrous fillers.

[Evaluation method]

<tensile strength>

Using an injection molding machine (PS-40E: manufactured by Nissei Plastics Co., Ltd.), the pellets of the polyamide resin compositions obtained in Examples and Comparative Examples were molded into multipurpose test piece A-type molded pieces according to ISO3167. At this time, the injection and holding time were set to 25 seconds, the cooling time was set to 15 seconds, the mold temperature was set to 80°C, and the molten resin temperature was set to 290°C. Using the obtained multipurpose test piece (Type A), a tensile test was performed at a tensile speed of 5 mm/min according to ISO527 to measure tensile strength. The higher the tensile strength, the better the mechanical strength.

<Charpy Impact Strength>

The multi-purpose test piece (type A) obtained above was cut into width 10 mm x length 80 mm x thickness 4 mm, and a notched Charpy impact test was performed according to ISO179/1eA to measure the Charpy impact strength. The higher the Charpy impact strength, the better the impact resistance.

<Dimensional accuracy>

(anisotropy)

Using an injection molding machine (FN-3000: manufactured by Nissei Plastics Co., Ltd.), the pellets of the polyamide resin compositions obtained in Examples and Comparative Examples were molded into a molded sheet having a width of 100 mm x a length of 100 mm x a thickness of 2 mm. At this time, the injection and holding time were set at 10 seconds, the cooling time was set at 15 seconds, the mold temperature was set at 80°C, and the molten resin temperature was set at 290°C. After the obtained molded sheet was left to stand at 23°C and 50% RH for 24 hours, the lengths in the MD direction (flow direction) and the TD direction (direction perpendicular to the flow direction) were measured respectively, and the molding shrinkage rate (% ). The molding shrinkage rate was determined by (100 mm-dimension of molded piece after 24 hours)/100 mm×100. Then, the MD/TD ratio of molding shrinkage was calculated. The closer the MD/TD ratio is to 1, the smaller the anisotropy and the better the dimensional accuracy.

(warpage amount)

In addition, the same molded piece as used in the anisotropic dimensional accuracy test was prepared, an arbitrary corner of the molded piece was fixed on a smooth table, and the height at which the diagonal corner rose from the table was obtained as the amount of warpage. The measurement of the warpage amount was measured for each combination of different two diagonal corners. Let the average value be the amount of warpage. The smaller the amount of warpage, the better the dimensional accuracy.

(roundness)

Using an injection molding machine (FN-3000: manufactured by Nissei Plastics Co., Ltd.), the pellets of the polyamide resin compositions obtained in Examples and Comparative Examples were molded into cylindrical pellets with an inner diameter of 30 mm x a length of 60 mm x a thickness of 1.5 mm. In addition, as the mold, a gate is provided on the outer side of one end of the cylindrical part of the molded sheet, an undercut for forced extraction is arranged on the end opposite to the gate, and an undercut for forced extraction is arranged on the outer side of the cylindrical shape. of protruding stencils. The injection and holding time were set at 20 seconds, the cooling time was set at 15 seconds, the mold temperature was set at 80°C, and the molten resin temperature was set at 290°C. After leaving the obtained molded piece at 23° C. and 50% RH for 24 hours, measure the inner diameter of the molded piece opposite to the gate in the same direction as the direction of the gate and in the direction perpendicular to it, and calculate their Compared to true roundness. The closer the roundness is to 1, the better the dimensional accuracy.

<Appearance>

The appearance of the bottom portion with the protrusion for forced removal of the molded sheet used in the evaluation method of the above-mentioned roundness was observed. The evaluation of the appearance was performed on the basis of the following criteria.

+++: 20 formed pieces were observed, none of the formed pieces had a wrinkled shape, and the appearance was good

++: 20 molded pieces were observed, and a wrinkled form was observed in 1 or more and 5 or less molded pieces

+: 20 formed pieces were observed, and a wrinkled shape was observed in more than 5 formed pieces

[raw material]

(1) Polyamide resin

1-1. Polyamide 610 resin (hereinafter referred to as "PA610")

C/N ratio: 8

98% sulfuric acid relative viscosity (ηr): 2.5

N-terminal amount: 42 micromol/g

Carboxyl terminal amount: 65 micromol/g

[Amount of amino terminal / (amount of amino terminal + amount of carboxyl terminal)] = 0.39

1-2. Polyamide 612 resin (hereinafter referred to as "PA612")

C/N ratio: 9

98% sulfuric acid relative viscosity (ηr): 2.4

N-terminal amount: 45 micromol/g

Carboxyl terminal amount: 70 micromol/g

[Amount of amino terminal/(Amount of amino terminal+Amount of carboxyl terminal)]=0.31

1-3. Polyamide 66 resin (hereinafter referred to as "PA66")

C/N ratio: 6

98% sulfuric acid relative viscosity (ηr): 2.8

N-terminal amount: 46 micromol/g

Carboxyl terminal amount: 60 micromol/g

[Amount of amino terminal/(Amount of amino terminal+Amount of carboxy terminal)]=0.43

(2) Glass fiber

2-1. Glass fibers with an average fiber diameter of 6 μm treated with a sizing agent containing a copolymer of maleic anhydride and ethylene and a polyurethane resin (hereinafter referred to as "GF-1")

Strong thermal weight loss: 0.42%

2-2. Glass fibers with an average fiber diameter of 8 μm treated with a sizing agent containing a copolymer of maleic anhydride and ethylene and a polyurethane resin (hereinafter referred to as "GF-2")

Strong thermal weight loss: 0.41%

2-3. Glass fibers with an average fiber diameter of 10 μm treated with a sizing agent containing a copolymer of maleic anhydride and ethylene and a polyurethane resin (hereinafter referred to as "GF-3")

Strong thermal weight loss: 0.43%

2-4. Glass fibers with an average fiber diameter of 13 μm treated with a sizing agent containing a copolymer of maleic anhydride and ethylene and polyurethane resin (hereinafter referred to as "GF-4")

Strong thermal weight loss: 0.42%

2-5. Glass fibers with an average fiber diameter of 17 μm treated with a sizing agent containing a copolymer of maleic anhydride and ethylene and a polyurethane resin (hereinafter referred to as "GF-5")

Strong thermal weight loss: 0.40%

2-6. Glass fibers with an average fiber diameter of 10 μm treated with a sizing agent containing polyurethane resin (hereinafter abbreviated as "GF-6")

Strong thermal weight loss: 0.28%

(3) Non-fibrous filler material

3-1. Talc with an average particle diameter of 1.5 μm (hereinafter referred to as “T-1”)

3-2. Talc with an average particle diameter of 3.3 μm (hereinafter referred to as “T-2”)

3-3. Talc with an average particle diameter of 5.0 μm (hereinafter referred to as “T-3”)

3-4. Talc with an average particle diameter of 8.0 μm (hereinafter referred to as “T-4”)

3-5. Talc with an average particle diameter of 13 μm (hereinafter referred to as “T-5”)

3-6. Talc with an average particle diameter of 19 μm (hereinafter referred to as “T-6”)

(4) Copper iodide (hereinafter referred to as "CuI") (manufactured by Wako Pure Chemical Industries, Ltd.)

(5) Potassium iodide (hereinafter referred to as "KI") (manufactured by Wako Pure Chemical Industries, Ltd.)

(6) Carbon black (hereinafter referred to as "CB")

Product name: Mitsubishi (registered trademark) carbon black #980, average particle diameter 16nm (manufactured by Mitsubishi Chemical Corporation)

[Examples 1-20, Comparative Examples 1-4]

Use L/D (the length of the barrel of the extruder) having the upstream side feed port on the first barrel from the upstream side of the extruder and the downstream side feed port on the ninth barrel /Cylinder diameter of the extruder) = 48 (the number of barrels: 12) twin-screw extruder "ZSK-26MC: made by Kobelion (Germany)". In the above-mentioned twin-screw extruder, from the feed port on the upstream side to the die was set at 290° C., the screw rotation speed was set at 300 rpm, and the discharge amount was set at 25 kg/hour. Under the above conditions, the above-mentioned polyamide resin (PA), non-fibrous filler (T), CuI, KI and CB are respectively supplied from the upstream side feed port, and the glass fiber (GF) is supplied from the downstream side feed port. , to obtain the ratios recorded in the upper part of Table 1 below. Then, pellets of the polyamide resin composition were prepared by melt-kneading them. After drying so that the water content of the pellets of the obtained polyamide resin composition was 800 ppm or less, molding was carried out at a molten resin temperature of 290°C and a mold temperature of 80°C, and the tensile strength, anisotropy, warpage, and true roundness were evaluated. degree and appearance. These evaluation (count) results and the like are shown in Table 1 below.

It can be seen from Table 1 that when the average fiber diameter x (μm) of the glass fiber and the average particle size y (μm) of the non-fibrous filler satisfy x≥5, y≥3, and 0.8x+y≥11, the flat plate shape The anisotropy and warpage of the sheet are small, and the cylindrical molded sheet has high roundness and excellent dimensional accuracy. In addition, it can be seen that there are few appearance defects such as wrinkles in the undercut portion, and the appearance is excellent. It was also found that when 17≦0.8x+y≦26 is satisfied, the Charpy impact strength is also excellent.

[Examples 21-28, Comparative Examples 5-7]

Use on the first barrel from the upstream side of the extruder with the upstream side feed port and the downstream side first feed port on the sixth barrel, and the downstream side first feed port on the ninth barrel Twin-screw extruder "ZSK-26MC" with two feeding ports, L/D (length of barrel of extruder/diameter of barrel of extruder) = 48 (number of barrels: 12): manufactured by Koberion Co., Ltd. (Germany)". In the above-mentioned twin-screw extruder, from the feed port on the upstream side to the die was set at 290° C., the screw rotation speed was set at 300 rpm, and the discharge amount was set at 25 kg/hour. Under the said conditions, the above-mentioned polyamide resin (PA), CuI, KI and CB are respectively supplied from the upstream feed port, the non-fibrous filler (T) is supplied from the first feed port on the downstream side, and the non-fibrous filler (T) is supplied from the downstream feed port. The second feed port supplied glass fibers (GF) so as to obtain the ratios described in the upper part of Table 2 below. Then, pellets of the polyamide resin composition were prepared by melt-kneading them. After drying so that the water content of the pellets of the obtained polyamide resin composition was 800 ppm or less, molding was carried out at a molten resin temperature of 290°C and a mold temperature of 80°C, and the tensile strength, anisotropy, warpage, and true roundness were evaluated. degree and appearance. These evaluation (count) results and the like are shown in Table 2 below.

【Table 2】

It can be seen from Table 2 that even in the case of using PA612, when the average fiber diameter x (μm) of the glass fiber and the average particle size y (μm) of the non-fibrous filler satisfy x≥5, y≥3, 0.8x+ When y≥11, the dimensional accuracy and appearance are also excellent.

[Examples 29-34, Comparative Examples 8-12]

Use on the first barrel from the upstream side of the extruder with the upstream side feed port and the downstream side first feed port on the sixth barrel, and the downstream side first feed port on the ninth barrel Twin-screw extruder "ZSK-26MC" with two feeding ports, L/D (length of barrel of extruder/diameter of barrel of extruder) = 48 (number of barrels: 12): manufactured by Koberion Co., Ltd. (Germany)". In the above-mentioned twin-screw extruder, from the feed port on the upstream side to the die was set at 290° C., the screw rotation speed was set at 300 rpm, and the discharge amount was set at 25 kg/hour. Under the above conditions, the above-mentioned polyamide resin (PA), CuI, and KI are respectively supplied from the upstream feed port, the non-fibrous filler (T) is supplied from the first feed port on the downstream side, and the second feed port from the downstream side. The feed port supplied glass fibers (GF) so as to obtain the ratios described in the upper part of Table 3 below. Then, pellets of the polyamide resin composition were prepared by melt-kneading them. After drying so that the water content of the pellets of the obtained polyamide resin composition was 800 ppm or less, molding was performed at a molten resin temperature of 290° C. and a mold temperature of 80° C., and roundness and appearance were evaluated. These evaluation (count) results and the like are shown in Table 3 below.

【table 3】

It can be seen from Table 3 that when the average fiber diameter x (μm) of the glass fiber and the average particle size y (μm) of the non-fibrous filler satisfy x≥5, y≥3, 0.8x+y≥11, the dimensional accuracy and Good appearance. On the other hand, comparing Example 30 and Example 31 with Comparative Examples 10 to 12, it can be seen that when the aliphatic polyamide having a polyamide C/N ratio of 7 or more is 50% by mass or more in the polyamide, the dimensional accuracy is lower. And the appearance is remarkably fine.

As can be seen from the above, the polyamide resin composition of the present embodiment can significantly improve the dimensional accuracy and appearance of the obtained molded article, and can obtain a molded article with high dimensional accuracy suitable for use in automobile parts and various electronic parts.

Industrial applicability

The molded article obtained from the polyamide resin composition of the present invention has excellent dimensional accuracy and appearance, and thus has industrial applicability as a molded article requiring a high level of dimensional accuracy such as automobile parts.

Claims (12)

1. an Amilan polyamide resin composition, it contains (A) polyamide resin, (B) glass fibre and (C) Non-fibrous packing material,

More than 50 quality % in described (A) polyamide resin to be the ratio (C/N than) of carbonatoms/nitrogen-atoms number be more than 7 fatty polyamide,

The number equal Fibre diameter x (μm) of described (B) glass fibre and the number average bead diameter y (μm) of described (C) Non-fibrous packing material meet following formula:

x≥5

y≥3

0.8x+y≥11。

2. Amilan polyamide resin composition as claimed in claim 1, wherein, the ratio of the carbonatoms/nitrogen-atoms number in described (A) polyamide resin (C/N than) be more than 7 described fatty polyamide be selected from the group that is made up of polyamide 610, polyamide 612, polymeric amide 11, polymeric amide 12, polyamide 1010 and polymeric amide 1012 more than one.

3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein, described (C) Non-fibrous packing material be selected from the group that is made up of glass flake, talcum, kaolin, mica, calcium carbonate, clay and silicon nitride more than one.

4. the Amilan polyamide resin composition according to any one of claims 1 to 3, wherein, described (B) glass fibre is utilize the glass fibre after processing containing the collecting agent of multipolymer, and described multipolymer contains containing carboxylic acid anhydride unsaturated ethylene thiazolinyl monomer and the unsaturated ethylene thiazolinyl monomer except this contains carboxylic acid anhydride unsaturated ethylene thiazolinyl monomer as Component units.

5. the Amilan polyamide resin composition according to any one of Claims 1 to 4, wherein, described (A) polyamide resin contains the ratio (C/N) of carbonatoms/nitrogen-atoms number than the fatty polyamide being less than 7,

The content of this fatty polyamide is below 50 quality % relative to the total amount 100 quality % of described (A) polyamide resin.

6. the Amilan polyamide resin composition according to any one of Claims 1 to 5, wherein, described (A) polyamide resin contains N-terminal amount and is more than 0.3 relative to the ratio [N-terminal amount/(N-terminal amount+C-terminal amount)] of N-terminal amount with the total amount of C-terminal amount and is less than the polyamide resin of 1.0.

7. the Amilan polyamide resin composition according to any one of claim 1 ~ 6, wherein, relative to Amilan polyamide resin composition 100 quality %, containing (A) polyamide resin described in 25 ~ 84 quality %, described (B) glass fibre of 15 ~ 74 quality %, and (C) Non-fibrous packing material described in 1 ~ 20 quality %.

8. the Amilan polyamide resin composition according to any one of claim 1 ~ 7, wherein, also contains the halid mixture of (D) mantoquita and alkali-metal halogenide and/or alkaline-earth metal.

9. the Amilan polyamide resin composition according to any one of claim 1 ~ 8, wherein, also containing (E) boron nitride and/or carbon black.

10. a molding, it contains the Amilan polyamide resin composition according to any one of claim 1 ~ 9.

11. moldinies as claimed in claim 10, it has drum portion.

12. moldinies as claimed in claim 11, wherein, described drum portion comprises the undercut portions of forcing to take out.