JP2014037526A - Polyamide resin composition and formed part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition and a formed part that have a characteristic excellent in a creep property in a water atmosphere, appearance, releasability, and mechanical strength.SOLUTION: A polyamide resin composition includes: (A) 100 pts.mass of a polyamide 610 resin; (B) 1-200 pts.mass of a fiber glass; (C) 0.1-10 pts.mass of an inorganic filler other than the fiber glass; and (D) 0.01-10 pts.mass of a lubricant.

Description

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

Polyamide resins have been widely used as various component materials for clothing, industrial materials, automobiles, electrical / electronics, and industrial use because of their excellent molding processability, mechanical properties, and chemical resistance. It has been.
In recent years, polyamide resins have been widely used in the automotive field, and in particular, polyamide resins reinforced with glass fibers have excellent mechanical properties, heat resistance, oil resistance, and toughness. It is used as a material for parts that come into contact with antifreeze.

However, the conventional glass fiber reinforced polyamide resin has the disadvantage that the strength is reduced by contact with the antifreeze solution for a long time in a high temperature atmosphere, and even in a dry heat state in a high temperature atmosphere. Also, it has a drawback that the strength is greatly reduced.
Therefore, there is a demand for a polyamide resin that suppresses a decrease in strength due to contact with an antifreeze solution for a long time in a high temperature atmosphere as described above and a decrease in strength in a dry heat state under a high temperature atmosphere.
Conventionally, a polyamide resin composition using a polyamide 610 resin has been disclosed in response to such demands (see, for example, Patent Documents 1 to 3).

Special table 2010-522259 gazette JP 2008-222290 A JP 60-32847 A

However, the polyamide resin compositions disclosed in Patent Documents 1 to 3 have an improvement effect with respect to antifreeze resistance, but have not yet obtained sufficient characteristics with respect to creep characteristics in an underwater atmosphere. In fact, a polyamide resin composition excellent in both characteristics is not yet known, and such a polyamide resin composition is desired.
Further, the resin compositions disclosed in Patent Documents 1 to 3 are not sufficient in appearance and releasability, and a polyamide resin composition that satisfies these requirements is desired.

  In view of the above-described problems of the prior art, an object of the present invention is to provide a polyamide resin composition excellent in creep characteristics, appearance, and releasability in an underwater atmosphere, and a molded product thereof.

As a result of intensive studies to solve the problems peculiar to the polyamide resin composition, the present inventors have (A) polyamide 610 resin, (B) glass fiber, and (C) inorganic filler other than glass fiber. The present inventors have found that a polyamide resin composition containing a material and (D) a lubricant in a specific ratio can solve the above-mentioned problems, and has completed the present invention.
That is, the present invention is as follows.

[1]
(A) Polyamide 610 resin: 100 parts by mass;
(B) Glass fiber: 1 to 200 parts by mass;
(C) Inorganic filler other than glass fiber: 0.1 to 10 parts by mass;
(D) Lubricant: 0.01 to 10 parts by mass;
A polyamide resin composition.
[2]
The polyamide resin composition according to the above [1], wherein the melting point of the (D) lubricant is 110 to 150 ° C.
[3]
The polyamide resin composition according to [1] or [2], wherein (D) the lubricant is a higher fatty acid metal salt having a metal content of 3.5 to 11.5% by mass.
[4]
Extrapolated crystallization start temperature of the (A) polyamide 610 resin in the polyamide resin composition obtained by differential scanning calorimetry according to JIS K7121 (however, cooling is performed at a cooling rate of 20 ° C./min) ( The polyamide resin composition according to any one of [1] to [3], wherein T _ic ) is 200 ° C. or higher.
[5]
The polyamide resin composition according to any one of [1] to [4], wherein the (A) polyamide 610 resin has a relative viscosity measured in 98% sulfuric acid of 2.0 to 3.0.
[6]
Copolymer comprising the (B) glass fiber having a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as polymerized units. The polyamide resin composition according to any one of the above [1] to [5], which is a glass fiber treated with a sizing agent containing coalescence.
[7]
(E) Copper compound and halogen compound (excluding copper halide): The polyamide resin composition according to any one of [1] to [6], further including 0.002 to 2 parts by mass. .
[8]
The molar ratio x / y between the content x of the halogen element in the copper compound and the halogen compound (excluding the halogen compound) and the content y of the copper element is 2/1 to 50/1. The polyamide resin composition according to the above [7].
[9]
The polyamide resin composition according to [7] or [8], wherein (E) the copper compound and the halogen compound (excluding the halogen compound) are added in the form of a polyamide masterbatch.
[10]
(F) Colorant: The polyamide resin composition according to any one of [1] to [9], further including 0.01 to 5 parts by mass.
[11]
A molded article comprising the polyamide resin composition according to any one of [1] to [10].

  ADVANTAGE OF THE INVENTION According to this invention, the polyami resin composition and the molded article which have the characteristic excellent also in the creep characteristic in water atmosphere, an external appearance, mold release property, and mechanical strength can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A) Polyamide 610 resin: 100 parts by mass;
(B) Glass fiber: 1 to 200 parts by mass;
(C) Inorganic filler other than glass fiber: 0.1 to 10 parts by mass;
(D) Lubricant: 0.01 to 10 parts by mass;
Is a polyamide resin composition containing
Hereinafter, the components of the polyamide composition of the present embodiment will be described.

((A) polyamide 610 resin)
The polyamide resin composition of this embodiment contains (A) polyamide 610 resin as described above, and the (A) polyamide 610 resin has hexamethylene diamine as a diamine and sebacic acid as a dicarboxylic acid as a polymerization monomer. And a polyamide resin having a unit composed of hexamethylenediamine and sebacic acid.

<Copolymerization components other than sebacic acid and hexamethylenediamine>
(A) The polyamide 610 resin may contain a dicarboxylic acid other than the sebacic acid as a polymerization monomer as long as the object of the present embodiment is not impaired.
Examples of such dicarboxylic acids include aliphatic dicarboxylic acids other than adipic acid and isophthalic acid, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
Moreover, (A) polyamide resin 610 resin may contain diamine other than the said hexamethylenediamine as a polymerization monomer in the range which does not impair the objective of this embodiment. As such a diamine, a diamine having a substituent branched from a main chain other than hexamethylenediamine, an aliphatic diamine, an aromatic diamine, a polycondensable amino acid, a lactam, or the like can be used.
The (A) polyamide 610 resin used in the present embodiment mainly contains a polymerization monomer composed of sebacic acid and hexamethylenediamine in amounts described later, and as described above, dicarboxylic acid other than sebacic acid and hexamethylene. Even when a diamine other than a diamine is contained, it is regarded as a polyamide 610 resin as a whole.

  Examples of the aliphatic dicarboxylic acid other than adipic acid and isophthalic acid include, but are not limited to, for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3- Dimethyl glutaric acid, 2,2-diethyl succinic acid, 2,3-diethyl glutaric acid, glutaric acid, 2,2-dimethyl glutaric acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

Examples of the alicyclic dicarboxylic acid include, but are not limited to, alicyclic structures such as 1,3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. Examples thereof include alicyclic dicarboxylic acids having 10 and preferably 5 to 10 carbon atoms.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

Examples of the aromatic dicarboxylic acid include, but are not limited to, for example, terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfo Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms which are unsubstituted or substituted with various substituents such as isophthalic acid.
Examples of the various substituents include halogen groups such as alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, chloro groups and bromo groups, and carbon numbers. Examples thereof include 3 to 10 alkylsilyl groups, and sulfonic acid groups and groups such as sodium salts thereof.

  The diamine having a substituent branched from the main chain other than the hexamethylene diamine is not limited to the following. For example, 2-methylpentamethylene diamine (also referred to as 2-methyl-1,5-diaminopentane) is used. 2) 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, etc. And branched saturated aliphatic diamines.

  Examples of the aliphatic diamine include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undeca Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as methylene diamine, dodecamethylene diamine, and tridecamethylene diamine.

  Examples of the aromatic diamine include, but are not limited to, metaxylylenediamine and the like.

  Examples of the amino acid capable of polycondensation include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.

  Examples of the lactam include, but are not limited to, butyl lactam, pivalolactam, caprolactam, capryl lactam, enantolactam, undecanolactam, dodecanolactam, and the like.

  Each of the above-described dicarboxylic acid component, diamine component, amino acid component, and lactam component may be used alone or in combination of two or more.

  In the (A) polyamide 610 resin, the proportion of units consisting of sebacic acid and hexamethylenediamine is preferably 70 to 100 mol%, and 90 to 100 mol%, in 100 mol% of the component (A). Is more preferable.

<End sealant>
As a raw material for the polyamide 610 resin, an end-capping agent can be further added to adjust the molecular weight or improve hot water resistance.
For example, when polymerizing the polyamide 610 resin of this embodiment, the polymerization amount can be controlled by further adding a known end-capping agent.

Examples of the end capping agent include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. And the like.
Among them, monocarboxylic acid and monoamine are preferable from the viewpoint of productivity.
These end capping agents may be used alone or in combination of two or more.

The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group. For example, 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 aliphatic monocarboxylic acid such as isobutyric acid; cycloaliphatic monocarboxylic acid such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α- And aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
These monocarboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more types.

The monoamine used as the terminal blocking agent is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Examples include aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.
These monoamines may be used alone or in combination of two or more.

((A) Manufacturing method of polyamide 610 resin)
(A) As a manufacturing method of polyamide 610 resin, for example, an aqueous solution of a mixture of other components such as sebacic acid, hexamethylene diamine, and a catalyst described later, and apatite as necessary, or a suspension of water is heated. A method of polymerizing while maintaining a molten state (thermal melt polymerization method); a method of increasing the degree of polymerization of a polyamide obtained by the hot melt polymerization method while maintaining a solid state at a temperature below the melting point (thermal melt polymerization Solid-phase polymerization method): Heat an aqueous solution of a mixture of sebacic acid, hexamethylenediamine, and other components as necessary, or a water suspension, and melt the precipitated prepolymer again with an extruder such as a kneader. To increase the degree of polymerization (prepolymer / extrusion polymerization method); a mixture of sebacic acid, hexamethylenediamine, and other components as necessary, solid salt It is a polycondensate, a method of polymerizing while maintaining the solid state (solid-phase polymerization method).
It does not specifically limit as a polymerization form, Either a batch type and a continuous type may be sufficient.
The polymerization apparatus is not particularly limited, and a known apparatus such as an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

(A) In the production of polyamide 610 resin (including polyamide copolymer, the same shall apply hereinafter), a predetermined catalyst can be used.
The catalyst is not particularly limited as long as it is a known one used for polyamide. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphorous acid, pyrophosphorous acid, phenylphosphinic acid, phenylphosphonic acid , 2-methoxyphenylphosphonic acid, 2- (2′-pyridyl) ethylphosphonic acid, and metal salts thereof.
Examples of the metal of the metal salt include, but are not limited to, metal salts such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony, and ammonium salts. Can be mentioned.
In addition, as the catalyst, phosphate esters such as ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, octadecyl ester, stearyl ester, and phenyl ester can also be used.

(Physical properties of (A) polyamide 610 resin)
(A) Polyamide 610 resin has a 98% sulfuric acid solution viscosity (JIS K 6920) of preferably 2.0 to 3.0, more preferably 2.0 to 2.9, and still more preferably 2. 2 to 2.6.
When the sulfuric acid solution viscosity is 1.8 or more, a molded article having practically sufficient mechanical properties is obtained, and when the sulfuric acid solution viscosity is 3.0 or less, the fluidity during molding becomes good. A molded article having excellent surface appearance can be obtained.

((B) Glass fiber)
The polyamide resin composition of the present embodiment contains (B) glass fibers: 1 to 200 parts by mass with respect to (A) polyamide 610 resin: 100 parts by mass described above.
By containing the (B) glass fiber, excellent rigidity can be obtained.
The (B) glass fiber has a number average fiber diameter of preferably 3 to 30 μm, more preferably 3 to 25 μm, and even more preferably 5 to 20 μm, from the viewpoint of exhibiting excellent mechanical strength and vibration fatigue resistance. The weight average fiber length is preferably 100 to 750 μm, more preferably 100 to 700 μm, and still more preferably 200 to 600 μm.
(B) The aspect ratio (L / D) of the weight average fiber length (L) and the number average fiber diameter (D) of the glass fiber is preferably 10 to 100, more preferably 10 to 90, and still more preferably. 20-90.
(B) Only one type of glass fiber may be used alone, or two or more types having different number average fiber diameters and weight average fiber lengths may be used in combination.
The number average fiber diameter (D) and the weight average fiber length (L) of the glass fiber (B) described above can be measured by microscopy.
For example, a polyamide resin composition containing pelletized glass fibers is heated at a temperature equal to or higher than the decomposition temperature of the polyamide resin composition, and the remaining (B) glass fibers are photographed using a microscope, and the diameter of the glass fibers is determined. And it can measure by the method of measuring length.
Examples of the method for calculating the number average fiber diameter (D) and the weight average fiber length (L) from the measurement values obtained by the microscopy include the following formulas (I) and (II).
Number average fiber diameter (D) = total diameter of glass fibers / number of glass fibers (I)
Weight average fiber length (L) = sum of squares of glass fiber length / total of glass fiber length (II)

As described above, the content of (B) glass fiber in the polyamide resin composition of the present embodiment is 1 to 200 parts by mass, preferably 2 to 200 parts by mass with respect to (A) polyamide 610 resin: 100 parts by mass. 200 parts by mass, more preferably 2 to 180 parts by mass, and even more preferably 5 to 100 parts by mass.
(B) By making the content of glass fiber 1 part by mass or more with respect to (A) polyamide 610 resin: 100 parts by mass, the mechanical strength and the like of the polyamide resin composition of the present embodiment are improved, By setting the content to 200 parts by mass or less, a polyamide resin composition having excellent moldability can be obtained.
In addition, content of (B) glass fiber can be calculated by burning a polyamide resin composition, taking out the remaining (B) component, and measuring.

The specific composition of the (B) glass fiber is not limited to the following, and examples thereof include an E glass composition, a C glass composition, an S glass composition, and an alkali-resistant glass composition.
Among these, E glass is preferable from the viewpoint of easy availability.
Moreover, it is preferable that the tensile strength of (B) glass fiber is 290 kg / mm < ² > or more from a viewpoint of the mechanical strength of the polyamide resin composition of this embodiment.

Although the (B) glass fiber is not limited to the following, for example, silane cups such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. It is preferable that the surface treatment is performed with a ring agent, and the adhesion amount is preferably 0.01% by mass or more with respect to the glass fiber weight (total amount of the glass fiber and the surface treatment agent).
Furthermore, the (B) glass fiber can also be processed with a sizing agent as required. Examples of the sizing agent include, but are not limited to, for example, carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymer of acrylic acid and other copolymerizable monomers, and primary, secondary, and tertiary amines thereof. Of the salt.
These may be used individually by 1 type and may be used in combination of 2 or more type.
In particular, from the viewpoint of mechanical strength of the polyamide resin composition of the present embodiment, the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer. And a combination of these as a polymer unit, an epoxy compound and a polyurethane resin, and combinations thereof are preferable, and the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer are excluded. More preferred are copolymers and polyurethane resins containing saturated vinyl monomers as polymerized units, and combinations thereof.

((C) Inorganic filler other than glass fiber)
The polyamide resin composition of this embodiment contains (C) inorganic filler other than glass fiber: 0.1 to 10 parts by mass with respect to (A) polyamide 610 resin: 100 parts by mass described above.
It is preferable that content of inorganic fillers other than the said (C) glass fiber is 0.18-10 mass parts with respect to 100 mass parts of (A) polyamide 610 resin mentioned above, 0.18-8 masses Part is more preferable, 0.18 to 5 parts by mass is further preferable, and 2.0 to 5.0 parts by mass is even more preferable.
(C) By making content of inorganic fillers other than glass fiber into 0.1 mass part or more, the effect of improving the intensity | strength of the polyamide resin composition of this embodiment is expressed. On the other hand, by setting the content to 10 parts by mass or less, a polyamide resin composition excellent in extrudability and moldability can be obtained.

Examples of inorganic fillers other than (C) glass fiber include, but are not limited to, for example, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate and And clay (layered clay formed by laminating silicate layers, such as montmorillonite).
Such inorganic fillers other than (C) glass fiber may be used alone or in combination of two or more.
The inorganic filler other than (C) glass fiber is preferably one or more selected from the group consisting of wollastonite, kaolin, mica and talc from the viewpoint of improving strength and the like, and wollastonite, kaolin and talc. One or more selected from the group consisting of Further, wollastonite and talc are even more preferable from the viewpoint of improving the surface appearance of the molded article of the polyamide resin composition of the present embodiment.

The average particle diameter of the inorganic filler other than the (C) glass fiber is preferably 0.01 to 38 μm. More preferably, it is 0.03-30 micrometers, More preferably, it is 0.05-25 micrometers, More preferably, it is 0.10-20 micrometers, More preferably, it is 0.15-13 micrometers.
By setting the average particle size of the inorganic filler other than the (C) glass fiber to 38 μm or less, a polyamide resin composition excellent in toughness and surface appearance of a molded product can be obtained.
On the other hand, when the average particle size is 0.01 μm or more, a polyamide resin composition having an excellent balance between cost and powder handling surface and mechanical properties (strength, toughness, etc.) can be obtained.
In addition, among inorganic fillers other than (C) glass fiber, those having a needle-like shape such as wollastonite have an average number average fiber diameter (hereinafter also simply referred to as “average fiber diameter”). The particle size. If the cross section is not a circle, the maximum value of the length is regarded as the fiber diameter, and the number average fiber diameter using this is taken as the average particle diameter.
For the average particle diameter (number average fiber diameter), inorganic fillers other than the (C) glass fibers of 100 pieces (numbers) or more are arbitrarily selected and observed with a scanning electron microscope (SEM). It is obtained by measuring the particle size (fiber diameter) of the filler and calculating the arithmetic average value.

Among the inorganic fillers, the weight average fiber length (hereinafter, also simply referred to as “average fiber length”) of the needle-like shape such as the wollastonite is preferably in the above-mentioned number average fiber diameter. And the numerical range calculated from the preferable range of the aspect ratio (L / D) of the following weight average fiber length (L) and number average fiber diameter (D) is preferable.
Regarding the aspect ratio (L / D) between the weight average fiber length (L) and the number average fiber diameter (D) of the needle-shaped one, the surface appearance of the molded product is improved, and an injection molding machine or the like is used. From the viewpoint of preventing wear of metallic parts, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.
Furthermore, (C) the aspect ratio of the inorganic filler other than glass fiber having a needle-like shape is 10 from the viewpoint of reducing the occurrence of warpage in the molded article of the polyamide resin composition of the present embodiment. -20 are preferable and 15-20 are more preferable.
Here, as described above, the number average fiber diameter (D) in the present specification is arbitrarily selected from 100 inorganic fillers as raw materials and observed with a scanning electron microscope (SEM). Thus, it is obtained by measuring the fiber diameter of these inorganic fillers. In addition, the weight average fiber length (L) in the present specification is for a fibrous inorganic filler, and 100 or more inorganic fillers are arbitrarily selected, and the fiber length is measured using an SEM photograph. Is required.

(C) The inorganic filler other than the glass fiber may be surface-treated using a silane coupling agent, a titanate coupling agent, or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Examples include aminosilanes such as dimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes.
Among these, aminosilanes are more preferable from the viewpoint of exhibiting excellent mechanical strength.
These may use only 1 type and may use it in combination of 2 or more type.
Such a surface treatment agent may be previously treated on the surface of an inorganic filler other than (C) glass fiber, or (A) polyamide 610 resin and (C) an inorganic filler other than glass fiber are mixed. You may add at the time.
The addition amount of the surface treatment agent is preferably 0.05 to 1.5% by mass with respect to 100% by mass of the inorganic filler other than (C) glass fiber.

((D) Lubricant)
The polyamide resin composition of this embodiment contains (D) lubricant: 0.01-10 mass parts with respect to (A) polyamide 610 resin: 100 mass parts mentioned above.
The content of the (D) lubricant is preferably 0.03 to 10 parts by mass, and 0.03 to 5 parts by mass with respect to 100 parts by mass of the above-mentioned (A) polyamide 610 resin. More preferably, it is 0.05-3 mass parts.
(D) By making content of a lubricant into the said range, the polyamide resin composition which is further excellent in an external appearance, mold release property, mechanical strength, and plasticization property is obtained.

(D) As the lubricant, at least one selected from the group consisting of higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides can be used.
The (D) lubricant may be used alone or in combination of two or more.

The higher fatty acid refers to an aliphatic monocarboxylic acid having 8 or more carbon atoms.
The higher fatty acid preferably has 8 to 40 carbon atoms. Examples of the higher fatty acid include, but are not limited to, a saturated or unsaturated, linear or branched aliphatic monocarboxylic acid. For example, examples of higher fatty acids include stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid.

The higher fatty acid metal salt is a metal salt of the higher fatty acid described above.
Examples of metal elements that form salts with higher 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 higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, aluminum montanate, and zinc montanate. , Magnesium montanate, calcium behenate, sodium behenate, zinc behenate, calcium laurate, zinc laurate, calcium palmitate and the like.
As the higher fatty acid metal salt, a metal salt of montanic acid, a metal salt of behenate, and a metal stearate are preferably used. Among them, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, montan Zinc acid, magnesium montanate, calcium behenate, zinc behenate are preferable, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, zinc montanate, calcium behenate, zinc behenate are more preferable, and montanic acid More preferred are calcium, zinc montanate, and zinc behenate.
These higher fatty acid metal salts may be used alone or in combination of two or more.
The metal content in the higher fatty acid metal salt is 3.5 to 11.5% by mass with respect to 100% by mass of the higher fatty acid metal salt, thereby obtaining a polyamide resin composition having further improved appearance and releasability. From the viewpoint of More preferably, it is 3.5-10.0 mass%, More preferably, it is 4.0-9.0 mass%.

The higher fatty acid ester is an esterified product of the above-described higher fatty acid and alcohol.
The higher fatty acid ester is preferably an esterified product of an aliphatic monocarboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like. Examples of the higher fatty acid ester include stearyl stearate, behenyl behenate, and the like.

The higher fatty acid amide is an amidation product of the higher fatty acid described above.
Examples of the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, and N-stearyl. Examples include erucamide. As the higher fatty acid amide, 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.

  As the lubricant (D), higher fatty acid metal salts and higher fatty acid amides are preferable from the viewpoint of further improving moldability. Among them, higher fatty acid metal salts are preferable from the viewpoint of further improving the appearance and releasability. More preferred.

The melting point of the (D) lubricant is preferably 110 to 150 ° C., more preferably 115 to 145 ° C., and still more preferably 115 to 140 ° C. from the viewpoint of further improving the appearance and releasability. .
The melting point of (D) lubricant can be measured by differential scanning calorimetry (DSC) or the like.

((E) Copper compound and halogen compound (however, excluding copper halide))
The polyamide resin composition of this embodiment may further contain (E) a copper compound and a halogen compound (however, excluding copper halide).
The copper compound used in the (E) copper compound and halogen compound (excluding copper halide) is not limited to the following, but examples include copper halide, copper acetate, copper propionate, Examples thereof include copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts coordinated to chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid.
These copper compounds may be used independently and may mix 2 or more types.
Among these, copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate are preferable from the viewpoint of thermal stability.

  Content of the said copper compound in said (E) copper compound and a halogen compound (however, except a copper halide) is (A) polyamide resin 610 resin: Copper compound 0.001-1. 999 mass parts is preferable, More preferably, it is 0.0025-0.5 mass part, More preferably, it is 0.01-0.1 mass part. By setting it as this range, in the polyamide resin composition of this embodiment and the molded product thereof, sufficient heat aging resistance can be improved, and copper precipitation and corrosion can be suppressed.

The halogen compound (excluding copper halide) used in the (E) copper compound and halogen compound (excluding copper halide) is not limited to the following. Examples include potassium iodide, sodium iodide, potassium bromide, potassium chloride, sodium chloride and the like.
These halogen compounds may be used alone or in combination of two or more.

  The content of the halogen compound in the (E) copper compound and the halogen compound (excluding the copper halide) is (A) polyamide 610 resin: 0.001 to 1.999 mass of the halogen compound with respect to 100 mass parts. Part is preferable, more preferably 0.01 to 1.999 parts by mass, and still more preferably 0.03 to 1 part by mass. By setting it as this range, in the polyamide resin composition of this embodiment and its molded article, sufficient heat aging resistance can be improved, and copper precipitation and corrosion can be suppressed.

Both of the copper compound and the halogen compound (excluding the copper halide) are preferably contained in order to improve the performance of the polyamide resin composition of the present embodiment.
The total content of the (E) copper compound and the halogen compound (excluding the copper halide) is preferably 0.002 to 2 parts by mass with respect to 100 parts by mass of the (A) polyamide 610 resin. Preferably it is 0.01-2 mass parts, More preferably, it is 0.03-1.5 mass parts, More preferably, it is 0.03-1 mass parts. By setting it within this range, a sufficient effect of improving the heat aging resistance can be obtained in the polyamide resin composition of the present embodiment and the molded product thereof, and copper precipitation and corrosion can be suppressed.

In the polyamide resin composition of the present embodiment, the molar ratio of the content x of the halogen element and the content y of the copper element in the (E) copper compound and the halogen compound (excluding copper halide) ( Halogen element content x / copper element content y) is preferably 2/1 to 50/1, more preferably 3/1 to 30/1, and 4/1 to 25/1. Is more preferable, and 5/1 to 23/1 is even more preferable.
It is preferable that the molar ratio (x / y) of the halogen element content x and the copper element content y is 2 or more because copper precipitation and metal corrosion can be suppressed. Further, when the molar ratio (x / y) of the halogen and copper is 50 or less, corrosion of the screw or the like of the molding machine can be suppressed without impairing mechanical properties such as toughness.

The (E) copper compound and halogen compound (excluding the halogen compound) are preferably added in the form of a masterbatch.
By adding the (E) copper compound and the halogen compound in the form of a masterbatch, the dispersibility of the (E) component is improved, heat aging characteristics are improved, corrosion is prevented, and copper precipitation can be further suppressed.

The polyamide resin used in the polyamide masterbatch is not limited to the following. For example, polycaprolactam (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide) 66), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polyundecalactam (polyamide 11), polydodecalactam (polyamide) 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (polyamide 6I), polynonanemethylene terephthalamide (9T), polyhexamethylene terephthalamide ( T), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (polyamide MXD6), and polyun Examples include decamethylene hexahydroterephthalamide (polyamide 11T (H)).
Examples of the polyamide resin used in the polyamide masterbatch include polyamide copolymers containing at least two different polyamide-forming components, and mixtures of these polyamides and / or polyamide copolymers. .
Among the polyamide resins described above, in the polyamide resin composition and the molded product thereof according to the present embodiment, from the viewpoint of deterioration of mechanical properties due to contact with antifreeze liquid for a long time and suppression of deterioration of mechanical properties under high temperature drying, polyhexa Methylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612) and the like are preferable, and polyhexamethylene sebacamide (polyamide 610) is particularly preferable.
The polyamide masterbatch containing the (E) copper compound and halogen compound (excluding copper halide) contained in the polyamide resin composition of the present embodiment is the main component in the polyamide resin contained in the polyamide masterbatch. The component is preferably a polyamide 610 resin. Here, the “main component” means that the content of the polyamide 610 resin in the polyamide constituting the polyamide master batch is 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more. .

  The content of the copper compound in the polyamide master batch is preferably 0.1 to 5 parts by mass of the copper compound, more preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the polyamide resin constituting the polyamide master batch. More preferably, it is 0.40-4 mass parts. By setting it as this range, in the polyamide resin composition of this embodiment and the molded product thereof, sufficient heat aging resistance can be improved, and copper precipitation and corrosion can be suppressed.

  The content of the halogen compound in the polyamide master batch is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, further preferably 10 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin constituting the polyamide master batch. 40 parts by mass. By setting it as this range, in the polyamide resin composition of this embodiment and its molded product, sufficient heat aging resistance can be improved, and copper precipitation and corrosion can be suppressed.

The (E) copper compound and halogen compound contained in the polyamide master batch are preferably in the form of particles.
Further, the maximum particle diameter of the copper compound and halogen compound to be contained (E), that is, the maximum particle diameter of the copper compound and halogen compound particles contained in the masterbatch is preferably 50 μm or less. More preferably, it is 20 micrometers or less, More preferably, it is 10 micrometers or less.
In the polyamide master batch, the particle diameter refers to the biaxial average diameter, that is, the average value of the short diameter and the long diameter. Here, the minor axis and the major axis are the short side and the long side of the circumscribed rectangle that minimizes the area circumscribing the particle, respectively. The measurement of the maximum particle diameter of the (E) copper compound and the halogen compound can be obtained by observing at least 50 particles using a scanning electron microscope (SEM).
(E) By setting the maximum particle size of the copper compound and the halogen compound to 50 μm or less, in the polyamide master batch, the (E) copper compound and the halogen compound can be finely dispersed in the polyamide. In the resin composition and the molded product thereof, problems of metal precipitation and corrosion are further improved, and toughness, heat-resistant aging property, appearance, and color tone are further improved.

<Organic compound having at least one amide group>
In the polyamide master batch, an organic compound having at least one amide group may be mixed during the melt kneading of the polyamide master batch.
The organic compound having at least one amide group is a compound having at least one amide group in the molecular chain. Examples of the organic compound having at least one amide group include, but are not limited to, monoamides, substituted amides, methylol amides, and bisamides.
The monoamides are represented by the general formula R—CONH ₂ (where R is a saturated aliphatic, unsaturated aliphatic, aromatic having 8 to 30 carbon atoms, or a part of —H is —OH 2. It has been replaced.) Examples of the monoamides include, but are not limited to, for example, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, etc. An acid amide etc. are mentioned.
The substituted amides are represented by the general formula R ₁ —CONH—R ₂ (wherein R ₁ and R ₂ are each independently a saturated aliphatic or unsaturated aliphatic group having 8 to 30 carbon atoms, Aromatics or those in which a part of —H is substituted with —OH). Examples of the substituted amides include, but are not limited to, for example, N-lauryl lauric acid amaad, N-paltimyl palmitic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N- Examples include stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, N-stearyl 12 hydroxystearic acid amide, N-oleyl 12 hydroxystearic acid amide and the like.
The methylol amides are represented by the general formula R—CONHCH ₂ OH (where R is a saturated aliphatic, unsaturated aliphatic, aromatic having 8 to 30 carbon atoms, or a part of —H— Substituted with OH). Examples of the methylol amides include, but are not limited to, methylol stearic acid amide and methylol behenic acid amide.
The bisamides are represented by the general formula (R—CONH) ₂ (CH ₂ ) _n (where R is a saturated aliphatic, unsaturated aliphatic, aromatic or —H of 8 to 30 carbon atoms). In which n is 1 to 8). Examples of the bisamides include, but are not limited to, for example, methylene bis lauric acid amide, methylene bis lauric acid amide, methylene bishydroxystearic acid amide, ethylene biscaprylic acid amide, ethylene bis lauric acid amide, ethylene Bistearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, butylene bishydroxystearic acid Acid amide, N, N′-distearyl adipate amide, N, N′-distearyl sebacic acid amide, methylene bisoleic acid amide , Ethylene bisoleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sebacic acid amide, m-xylylene bis stearic acid amide N, N′-distearylisophthalic acid amide and the like.
The organic compound having at least one amide group described above may be used alone or in combination of two or more. Among the above organic compounds having at least one amide group, bisamides may be mentioned from the viewpoint of further improving the dispersibility of the copper compound and the halogen compound.

The content of the organic compound having at least one amide group is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyamide resin constituting the polyamide master batch. The amount is 5.0 parts by mass, and more preferably 1.0 to 4.0 parts by mass.
By making it within this range, the dispersibility of the copper compound constituting the polyamide masterbatch and the polyamide resin constituting the polyamide masterbatch of the halogen compound is further improved, and in the polyamide resin composition of the present embodiment and the molded product thereof, Thus, sufficient heat aging resistance can be improved, and copper precipitation and corrosion can be suppressed.

(Manufacturing method of polyamide masterbatch)
A method for producing a polyamide masterbatch will be described.
The polyamide masterbatch is obtained by mixing the above-described copper compound, halogen compound, and, if necessary, the organic compound having at least one amide group with a polyamide resin.
A copper compound, a halogen compound, and an organic compound having at least one amide group may be blended alone in the polyamide resin, or at least two of the three compounds are premixed before blending in the polyamide resin. Alternatively, at least two of the three types of compounds may be premixed and pulverized before blending with the polyamide resin, or at least two of the three types of compounds may be premixed and pulverized into tablets. You may mix | blend with a polyamide resin after making it into a shape.

A known method can be applied to the method of mixing the copper compound, the halogen compound, and the organic compound having at least one amide group. For example, any of a tumbler, a Henschel, a pro shear mixer, a nauter mixer, a flow jet mixer, and the like may be used.
As the pulverization method, a known method can be applied. For example, any of a hammer mill, a knife mill, a ball mill, a jaw crusher, a cone crusher, a roller mill, a jet mill, a tool mill and the like may be used.
A known method can be applied to the tablet. For example, any of compression granulation method, tableting molding method, dry extrusion granulation method, melt extrusion granulation method and the like may be used.

A polyamide masterbatch can be produced by blending each compound in a polyamide resin as described above and performing melt kneading.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus can be used. For example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll is preferably used. Of these, a twin screw extruder is preferably used.
The melt kneader may be equipped with a deaeration mechanism (vent) device and side feeder equipment.
The melt kneading temperature is preferably about 1 to 100 ° C. higher than the melting point or softening point determined by differential scanning calorimetry (DSC) measurement of polyamide according to JIS K7121.
The shear rate in the kneader is preferably about 100 (SEC ⁻¹ ) or more, and the average residence time during kneading is preferably about 1 to 15 minutes.
The moisture content of the polyamide master batch is preferably 0.06 to 1.0% by mass, more preferably 0.10 to 0.75% by mass, and still more preferably 0.15 to 0.75% by mass. It is.
The moisture in the polyamide master batch may be present as moisture bonded to the polyamide molecules, or may be moisture attached to the surface of the polyamide master batch, for example, the master batch pellet or the master batch powder.
By setting the moisture content of the polyamide master batch within this range, aggregation of copper compounds and halogen compounds can be suppressed. As a result, the effect of improving the mechanical properties such as toughness and the heat aging resistance of the polyamide resin composition of the present embodiment and the molded product thereof is high, and the copper precipitation and the metal corrosiveness can be further suppressed.
The moisture content of the polyamide master batch can be adjusted by controlling the degree of decompression of the extruder, the dipping time in the strand bath during cooling, the dipping length, or the water spray amount.

((F) Colorant)
The polyamide resin composition of this embodiment may further contain (F) a colorant.
(F) The content of the colorant is preferably 0.01 to 5.0 parts by mass, and 0.02 to 4.0 parts by mass with respect to 100 parts by mass of the (A) polyamide 610 resin. Is more preferred,
More preferably, it is 0.03-2.0 mass parts.

(Degradation inhibitor)
In the polyamide resin composition of the present embodiment, if necessary, the deterioration is suppressed for the purpose of improving thermal deterioration, preventing discoloration during heat, heat aging resistance, and weather resistance, as long as the purpose of the present embodiment is not impaired. An agent may be added.
Examples of the degradation inhibitor include, but are not limited to, phenolic stabilizers such as hindered phenol compounds, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, and sulfur stabilizers. Etc.
One of these deterioration inhibitors may be used alone, or two or more thereof may be used in combination.

(Other resins)
If necessary, other resins may be added to the polyamide resin composition of the present embodiment as long as the purpose of the present embodiment is not impaired.
Examples of such resins include, but are not limited to, thermoplastic resins and rubber components described later.

Examples of the thermoplastic resin include, but are not limited to, polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, and ABS resin; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as nylon 6, 66, 612 and other polyamides (polyamides other than the polyamide of this embodiment); polyether resins such as polycarbonate, polyphenylene ether, polysulfone, polyether sulfone; polyphenylene sulfide, polyoxy Condensation resins such as methylene; Acrylic resins such as polyacrylic acid, polyacrylic acid ester, and polymethyl methacrylate; polyethylene, polypropylene, polybutene, ethylene-propylene Polyvinyl chloride, halogen-containing vinyl compound resin polyvinylidene chloride; a copolymer polyolefin resins such as body phenol resins, epoxy resins and the like.
One type of these thermoplastic resins may be used alone, or two or more types may be used in combination.

Examples of the rubber component include, but are not limited to, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, Styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) ), Styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene. Block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene-propylene copolymer Polymer (EPR), ethylene- (1-butene) copolymer, ethylene- (1-hexene) copolymer, ethylene- (1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM) And butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene- Core shell types such as ash-containing rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane, etc. It is done.
These rubber components may be used alone or in combination of two or more.

[Production method of polyamide resin composition]
The polyamide resin composition of the present embodiment comprises (A) polyamide 610 resin, (B) glass fiber, (C) inorganic filler other than glass fiber, (D) lubricant, and (E) copper as required. It can be produced by blending a compound and a halogen compound (excluding copper halide), (F) a colorant, a deterioration inhibitor, and other resins.
As a blending method, a known extrusion technique can be used.
For example, the melt kneading temperature is preferably about 250 to 350 ° C. as the resin temperature. The melt kneading time is preferably about 1 to 30 minutes.
Moreover, the method of supplying the components constituting the reinforced polyamide to the melt kneader may supply all the components to the same supply port at a time, or may supply the components from different supply ports. .
A specific mixing method is as follows: (A) polyamide 610 resin and (B) glass fiber, (C) inorganic filler other than glass fiber, (D) lubricant, and other components are mixed using a Henschel mixer or the like. A method of feeding and kneading to a melt kneader, a melted state with a single or twin screw extruder equipped with a decompression device (A) polyamide 610 resin, (D) lubricant, side feeder (B) glass fiber (C) Inorganic fillers other than glass fibers, methods of blending other components, and the like.

[Physical properties of polyamide resin composition]
In the polyamide resin composition of this embodiment, according to JIS K7121, the said (A in the polyamide resin composition measured by performing differential scanning calorimetry (however, it cooled at the cooling rate of 20 degrees C / min.). ) The extrapolation crystallization start temperature (T _ic ) of the polyamide 610 resin is preferably 200 ° C. or higher from the viewpoint of obtaining a polyamide resin composition having further improved appearance and releasability. More preferably, it is 201 degreeC or more and 220 degrees C or less, More preferably, it is 202 degreeC or more and 220 degrees C or less, More preferably, it is 203 degreeC or more and 220 degrees C or less.
In order to make the extrapolation crystallization start temperature of the (A) polyamide 610 resin in the polyamide resin composition within a preferable range, (C) an inorganic filler other than glass fiber, and (D) a lubricant, ) Polyamide 610 resin: It is effective to contain 0.1 to 10 parts by mass of (C) an inorganic filler other than glass fiber and (D) 0.01 to 10 parts by mass of a lubricant with respect to 100 parts by mass. .
In addition, by including (D) a lubricant, a more preferable extrapolation crystallization start temperature tends to be obtained, and a polyamide resin composition having further improved appearance and releasability can be obtained.

[Molded product of polyamide resin composition]
A predetermined molded product is obtained by molding the polyamide resin composition of the present embodiment.
It does not specifically limit as a method of obtaining a molded article, A well-known shaping | molding method can be used.
For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, gunshot injection molding, low pressure molding, ultra thin injection molding (ultra high speed injection molding), And molding methods such as in-mold composite molding (insert molding, outsert molding) and the like.

  As described above, the polyamide resin composition and molded product of the present embodiment are characterized in that a specific amount of (C) an inorganic filler other than glass fibers and (D) a lubricant are used. Excellent creep characteristics, appearance, releasability, and mechanical strength in an underwater atmosphere can be obtained.

[Use]
The molded article of the polyamide resin composition of the present embodiment is excellent in stability of the surface appearance and impact resistance characteristics of the molded body under severe molding conditions, and can be used for various applications.
For example, it can be suitably used in the automotive field, electrical / electronic field, machine / industrial field, office equipment field, aerospace field.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

First, constituent elements of a polyamide resin, methods for measuring physical properties, and methods for evaluating characteristics are shown below.
<Sulfuric acid solution viscosity>
Polyamide 610 resin was dissolved in 98% sulfuric acid and measured according to JIS K6920.

<Extrapolation crystallization start temperature>
Evaluation was performed using the polyamide resin composition pellets produced in Examples and Comparative Examples described below.
For suggestion scanning calorimetry, “DSC7” manufactured by Perkin-Elmer was used.
Referring to JIS K7121, heat up to a temperature 30 ° C higher than the temperature at the end of the melting peak of the polyamide resin, hold this temperature for 3 minutes, then cool the cooling rate to 100 ° C at 20 ° C per minute, Painted.
Extrapolation crystallization start temperature (T _ic ).

<Evaluation of 23 ° C underwater tensile creep characteristics>
Evaluation was performed using a JIS No. 3 test piece.
A cylinder temperature was set at 280 ° C., a mold temperature was set at 80 ° C., and a JIS No. 3 test piece was obtained under injection molding conditions of 17 seconds for injection and 20 seconds for cooling.
The test piece was subjected to a tensile creep test in a long-life coolant (LLC) 50% aqueous solution for 450 hours in a 130 ° C. atmosphere and in an atmosphere of 23 ° C. in water, and the stress at which fracture occurred in 40 hours from the start of the test was measured.

<Appearance>
A molded article for evaluation was produced using an injection molding machine.
As the injection molding machine, “FN-3000” manufactured by Nissei Resin Co., Ltd. was used.
A cylindrical molded piece with an inner diameter of 30 mm, a length of 60 mm, and a thickness of 1.5 mm under the injection conditions of a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., injection and pressure holding time of 20 seconds, and cooling time of 15 seconds. Got. In addition, as a mold, the gate is set to the outside of one end of the cylindrical portion of the molded piece, an undercut portion that is forcibly removed is arranged on the end opposite to the gate, and a projection for forcibly removing is provided on the outside of the cylindrical shape. I used the ones I arranged.
The appearance of the protrusion root for forced removal of the obtained molded piece was observed.
The appearance was evaluated according to the following criteria.
++++: Observation of 20 molded pieces, no appearance of wrinkle-like pattern in any molded piece ++: Observation of 20 molded pieces, 1 to 5 molded pieces , Wrinkled pattern was observed +: 20 molded pieces were observed and wrinkled patterns were observed with more than 5 molded pieces

<Measurement of Charpy impact strength>
A test piece for evaluation was manufactured using “PS40E” manufactured by Nissei Resin Co., Ltd. as an injection molding machine.
An ISO test piece was obtained under injection conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and injection and pressure holding time of 25 seconds and cooling of 15 seconds.
Charpy impact strength was measured according to ISO 179 using an ISO test piece.
The measurement value was an average value of n (number of measurement samples) = 6.

[(A) Polyamide 610 resin]
(A1): Polyamide 610 resin with a 98% sulfuric acid viscosity of 2.5 Ratio of polymerized units consisting of sebacic acid and hexamethylenediamine: 100 mol%
(A2): Polyamide 610 resin with 98% sulfuric acid viscosity 2.3 Ratio of polymerized units consisting of sebacic acid and hexamethylenediamine: 100 mol%
(A3): 98% sulfuric acid viscosity 2.5 polyamide 610 resin Ratio of polymerized units consisting of sebacic acid and hexamethylenediamine: 100 mol%
Copper iodide: 0.03% by mass, potassium iodide: 0.5% by mass,
Iodine / copper ratio molar ratio = 20 Copper iodide and potassium iodide were added during polymerization.
(A4): Polyamide 610 resin with 98% sulfuric acid viscosity 2.3 Ratio of polymerized units consisting of sebacic acid and hexamethylenediamine: 100 mol%
Copper iodide: 0.03% by mass, potassium iodide: 0.5% by mass,
Iodine / copper ratio molar ratio = 20 Copper iodide and potassium iodide were added during polymerization.
(A5): Polyamide 66 resin with 98% sulfuric acid viscosity 2.5 Copper iodide: 0.03% by mass, Potassium iodide: 0.5% by mass,
Iodine / copper ratio molar ratio = 20 Copper iodide and potassium iodide were added during polymerization.

[(B) Glass fiber]
(B1) Glass fiber treated with sizing agent containing maleic anhydride copolymer Number average fiber diameter: 10 μm
(B2) Glass fiber treated with sizing agent containing urethane resin Number average fiber diameter: 10 μm

[(C) Inorganic filler other than glass fiber]
(C1) Talc Product name: Microace (registered trademark) L-1 (manufactured by Nippon Talc)

[(D) Lubricant]
(D1) Calcium montanate Melting point: 135 ° C., metal content: 4.8% by mass
(D2) Calcium behenate Melting point: 148 ° C, metal content: 5.6% by mass
(D3) Calcium stearate Melting point: 155 ° C, metal content: 6.7% by mass
(D4) Magnesium montanate Melting point: 125 ° C., metal content: 2.5% by mass
(D5) Zinc montanate Melting point: 120 ° C., metal content: 7.5% by mass
(D6) Zinc behenate Melting point: 126 ° C., metal content: 8.8% by mass
(D7) Zinc stearate Melting point: 123 ° C, metal content: 10.7 mass%
The melting point of each (D) lubricant was measured by differential scanning calorimetry (DSC).

[(E) Polyamide masterbatch containing copper compound and halogen compound (excluding copper halide)]
(E1) Polyamide 610 resin with 98% sulfuric acid viscosity 2.3 Copper iodide: 3% by mass, Potassium iodide: 15% by mass, Iodine / copper ratio molar ratio = 8 Ethylene bisstearylamide: 2% by mass
(E2) Polyamide 610 resin with 98% sulfuric acid viscosity 2.3 Copper iodide: 3% by mass, Potassium iodide: 30% by mass, Iodine / copper ratio molar ratio = 20 Ethylene bisstearylamide: 2% by mass

[(F) Colorant]
(F1) Carbon black Product name: Mitsubishi (registered trademark) carbon black # 2600 (manufactured by Mitsubishi Chemical Corporation)

[Examples 1 to 11]
The (A) polyamide 610 resin was supplied from a feed hopper to a TEM35 twin screw extruder (set temperature: 280 ° C., screw rotation speed: 300 rpm) manufactured by Toshiba Machine.
Furthermore, from the side feed port, the (B) glass fiber was supplied at a ratio shown in Table 1 below with respect to 100 parts by mass of the (A) polyamide 610 resin, and melt kneading was performed.
The (C) inorganic filler and the (D) lubricant were supplied from a feed hopper at a ratio shown in Table 1 below with respect to 100 parts by mass of the (A) polyamide 610 resin.
Other additives were fed simultaneously with the (A) polyamide 610 resin from a feed hopper in the proportions shown in Table 1 below.
The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
Further, by using the obtained polyamide resin composition, by the method described above, measurement of extrapolation crystallization start temperature, production of a molded product, evaluation of 23 ° C. water tensile creep property, appearance, releasability, and Charpy impact strength was measured.
The evaluation results are shown in Table 1 below.

[Comparative Examples 1 to 11]
The (A) polyamide 610 resin was supplied from a feed hopper to a TEM35 twin screw extruder (set temperature: 280 ° C., screw rotation speed: 300 rpm) manufactured by Toshiba Machine.
Further, from the side feed port, the (B) glass fiber was supplied at a ratio shown in Table 2 below with respect to 100 parts by mass of the (A) polyamide 610 resin, and melt kneading was performed.
Other additives were supplied at the same time as the following Table 2 from a feed hopper at the same time as the (A) polyamide 610 resin.
The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
Further, by using the obtained polyamide resin composition, by the method described above, measurement of extrapolation crystallization start temperature, production of a molded product, evaluation of 23 ° C. water tensile creep property, appearance, releasability, and Charpy impact strength was measured.
The evaluation results are shown in Table 2 below.

[Examples 12 to 22]
The (A) polyamide 610 resin was supplied from a feed hopper to a TEM35 twin screw extruder (set temperature: 280 ° C., screw rotation speed: 300 rpm) manufactured by Toshiba Machine.
Further, from the side feed port, the (B) glass fiber was supplied at a ratio shown in Table 3 below with respect to 100 parts by mass of the (A) polyamide 610 resin, and melt kneading was performed.
The (C) inorganic filler and the (D) lubricant were supplied from a feed hopper at a ratio shown in Table 3 below with respect to 100 parts by mass of the (A) polyamide 610 resin.
Other additives were fed simultaneously with the (A) polyamide 610 resin from a feed hopper in the proportions shown in Table 3 below.
The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
Further, by using the obtained polyamide resin composition, by the method described above, measurement of extrapolation crystallization start temperature, production of a molded product, evaluation of 23 ° C. water tensile creep property, appearance, releasability, and Charpy impact strength was measured.
The evaluation results are shown in Table 3 below.

As shown in Tables 1 and 3 above, the molded articles of the polyamide resin compositions of Examples 1 to 22 all have extremely excellent 23 ° C underwater tensile creep properties, appearance, releasability, and mechanical properties. Was confirmed.
On the other hand, it was confirmed that the molded articles of the polyamide resin compositions of Comparative Examples 1 to 11 shown in Table 2 were greatly reduced in 23 ° C. water tensile creep properties, appearance, releasability, and mechanical properties.

  The polyamide resin composition of the present invention and a molded article using the same have industrial applicability in the automotive field, electrical / electronic field, mechanical / industrial field, office equipment field, aerospace field, and the like.

Claims (11)

(A) Polyamide 610 resin: 100 parts by mass;
(B) Glass fiber: 1 to 200 parts by mass;
(C) Inorganic filler other than glass fiber: 0.1 to 10 parts by mass;
(D) Lubricant: 0.01 to 10 parts by mass;
A polyamide resin composition.   The polyamide resin composition according to claim 1, wherein the melting point of the (D) lubricant is 110 to 150 ° C.   The polyamide resin composition according to claim 1 or 2, wherein the (D) lubricant is a higher fatty acid metal salt having a metal content of 3.5 to 11.5 mass%. Extrapolated crystallization start temperature of the (A) polyamide 610 resin in the polyamide resin composition obtained by differential scanning calorimetry according to JIS K7121 (however, cooling is performed at a cooling rate of 20 ° C./min) ( The polyamide resin composition according to any one of claims 1 to 3, wherein T _ic ) is 200 ° C or higher.   The polyamide resin composition according to any one of claims 1 to 4, wherein a relative viscosity of the (A) polyamide 610 resin measured in 98% sulfuric acid is 2.0 to 3.0.   Copolymer comprising the (B) glass fiber having a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as polymerized units. The polyamide resin composition according to any one of claims 1 to 5, which is a glass fiber treated with a sizing agent containing coalescence.   The polyamide resin composition according to any one of claims 1 to 6, further comprising (E) a copper compound and a halogen compound (excluding copper halide): 0.002 to 2 parts by mass.   The molar ratio x / y between the content x of the halogen element in the copper compound and the halogen compound (excluding the halogen compound) and the content y of the copper element is 2/1 to 50/1. The polyamide resin composition according to claim 7, wherein   The polyamide resin composition according to claim 7 or 8, wherein the (E) copper compound and the halogen compound (excluding the halogen compound) are added in the form of a polyamide masterbatch.   (F) Colorant: The polyamide resin composition as described in any one of Claims 1 thru | or 9 which further contains 0.01-5 mass parts.   The molded article containing the polyamide resin composition as described in any one of Claims 1 thru | or 10.