CN104761886A - Polyamide resin composition and formed product - Google Patents

Abstract

The present invention relates to a polyamide resin composition and a molded article. The present invention provides a polyamide resin composition and a molded article having excellent creep properties, appearance, mold release properties, and mechanical strength in an underwater environment. A polyamide resin composition comprising: (A) 100 parts by mass of an aliphatic polyamide resin having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more, (B) 1 to 200 parts by weight of glass fibers Parts by mass, (C) 0.1-10 parts by mass of inorganic fillers other than glass fiber, and (D) 0.01-10 parts by mass of lubricant.

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 resins are excellent in moldability, mechanical properties, and chemical resistance, so they have been widely used as materials for various parts such as clothing, industrial materials, automobiles, electrical and electronic, and industrial.

In recent years, polyamide resins have been widely used in the automotive field, especially polyamide resins reinforced with glass fibers, which have excellent mechanical properties, heat resistance, oil resistance, and toughness, so they are used in radiator tanks, water valves, etc. and antifreeze The material used for the parts in contact.

However, conventional glass fiber-reinforced polyamide resins have disadvantages in that their strength decreases due to long-term contact with antifreeze in a high-temperature environment, and that their strength decreases significantly even in a dry heat state in a high-temperature environment.

Therefore, there is a demand for a polyamide resin that suppresses the above-mentioned decrease in strength due to long-term contact with an antifreeze solution in a high-temperature environment and a decrease in strength in a dry heat state in a high-temperature environment.

To meet such demands, polyamide resin compositions using polyamide 610 resins have conventionally been disclosed (for example, see Patent Documents 1 to 3).

prior art literature

patent documents

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

Patent Document 2: Japanese Patent Laid-Open No. 2008-222290

Patent Document 3: Japanese Patent Laid-Open No. 60-32847

Contents of the invention

The problem to be solved by the invention

However, although the polyamide resin compositions disclosed in the above-mentioned Patent Documents 1 to 3 have an improvement effect on antifreeze resistance, they have not yet obtained sufficient characteristics for creep characteristics in an underwater environment. A polyamide resin excellent in properties is still unknown, and thus such a polyamide resin composition is required.

In addition, the polyamide resin compositions disclosed in the aforementioned Patent Documents 1 to 3 are insufficient in appearance and mold release properties, and polyamide resin compositions satisfying these points are required.

Therefore, in view of the problems of the prior art described above, an object of the present invention is to provide a polyamide resin composition and a molded article thereof which are excellent in creep characteristics, appearance, and mold releasability in an underwater environment.

means of solving problems

The inventors of the present invention conducted extensive and intensive studies to solve the above-mentioned problems peculiar to the polyamide resin composition. The polyamide resin composition of an inorganic filler and (D) a lubricant can solve the aforementioned problems, and the present invention has been accomplished.

That is, the present invention is as follows.

[1] A polyamide resin composition comprising:

(A) 100 parts by mass of aliphatic polyamide resin having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more,

(B) 1 to 200 parts by mass of glass fibers,

(C) 0.1 to 10 parts by mass of inorganic fillers other than glass fibers, and

(D) 0.01 to 10 parts by mass of lubricant.

[2] The polyamide resin composition as described in [1] above, wherein:

The (D) lubricant has a melting point of 110-150°C.

[3] The polyamide resin composition according to [1] or [2] above, wherein:

The (D) lubricant is a higher fatty acid metal salt with a metal content of 3.5-11.5% by mass.

[4] The polyamide resin composition according to any one of [1] to [3] above, wherein

The outer surface of the (A) polyamide resin in the polyamide resin composition was measured by differential scanning calorimetry (in which the cooling rate was set to 20° C./min for cooling) according to JIS K7121. The crystallization initiation temperature (T _ic ) is expected to be 200° C. or higher.

[5] The polyamide resin composition according to any one of [1] to [4] above, wherein

The relative viscosity of the (A) polyamide resin measured in 98% sulfuric acid is 2.0-3.0.

[6] The polyamide resin composition according to any one of [1] to [5] above, wherein

The (A) polyamide resin is at least one selected from the group consisting of polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, and polyamide 1012.

[7] The polyamide resin composition according to any one of [1] to [6] above, wherein

The (B) glass fibers are glass fibers treated with a sizing agent, and the sizing agent contains a copolymer having a carboxylic anhydride-containing unsaturated vinyl monomer and a carboxylic anhydride-containing unsaturated vinyl monomer Unsaturated vinyl monomers other than monomers serve as polymerized units.

[8] The polyamide resin composition according to any one of [1] to [7] above, wherein

It also contains (E) 0.002 to 2 parts by mass of copper compounds and halogen compounds (except for copper halides).

[9] The polyamide resin composition as described in [8] above, wherein:

The (E) molar ratio x/y of the halogen element content x to the copper element content y in the copper compound and the halogen compound (except copper halide) is 2/1˜50/1.

[10] The polyamide resin composition as described in [8] or [9] above, wherein:

The (E) copper compound and halogen compound (except copper halide) are added in the form of polyamide masterbatch.

[11] The polyamide resin composition according to any one of [1] to [10] above, wherein,

It also contains (F) 0.01 to 5 parts by mass of a coloring agent.

[12] A molded article comprising the polyamide resin composition according to any one of [1] to [11].

Invention effect

According to the present invention, it is possible to provide a polyamide resin composition and a molded article having excellent creep properties in an underwater environment, appearance, releasability, and mechanical strength.

Detailed ways

Hereinafter, a mode for implementing the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.

The present embodiment below is an illustration for explaining the present invention, and does not intend to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Polyamide resin composition]

The polyamide resin composition of this embodiment contains

(A) 100 parts by mass of aliphatic polyamide resin having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more,

(B) 1 to 200 parts by mass of glass fibers,

(C) 0.1 to 10 parts by mass of inorganic fillers other than glass fibers, and

(D) 0.01 to 10 parts by mass of lubricant

polyamide resin composition.

Hereinafter, the constituent components of the polyamide resin composition of the present embodiment will be described.

((A) Aliphatic polyamide resin having a carbon number/nitrogen atom ratio (C/N ratio) of 7 or more)

The (A) polyamide resin used in this embodiment is an aliphatic polyamide having a carbon number/nitrogen atom ratio (C/N ratio) of 7 or more. By containing such an aliphatic polyamide, the molded article obtained tends to be excellent in creep characteristics, appearance, and mechanical strength in an underwater environment. 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 the number of carbon atoms to the number of nitrogen atoms (C/N ratio) is not particularly limited, but it 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 obtained molded body tends to be more excellent in creep characteristics, appearance, and mechanical strength in an underwater environment. 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, in the present embodiment, "aliphatic polyamide" refers to a unit constituting polyamide (when composed of diamine and dicarboxylic acid, a pair of diamine and dicarboxylic acid is 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, polyamide 12, One or more of polyamide 1010, polyamide 1012, polyamide 410, polyamide 412, polyamide 69, and a group consisting of copolyamides containing these as constituent components. Among them, one or more selected from the group consisting of polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, polyamide 1012, and copolymerized polyamides containing these components are preferred, and more preferably At least one selected from the group consisting of polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and copolyamides containing these components, more preferably selected from polyamide 610, polyamide 612, and polyamide 1010 and polyamide 1012, and polyamide 610 is particularly preferred.

(A) The aliphatic polyamide having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more may contain a fat having 6 or less carbon atoms within a range that does not impair the purpose of the present embodiment. Dibasic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, aliphatic diamines with less than 6 carbon atoms, aromatic diamines, polycondensable amino acids, lactams, etc. body.

The aforementioned aliphatic dicarboxylic acid having 6 or less carbon atoms is not limited to the following, and examples include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2, 2-Diethylsuccinic acid, glutaric acid and adipic acid.

The above-mentioned alicyclic dicarboxylic acid is not limited to the following substances, for example, esters such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid, etc. The ring structure has 3 to 10 carbon atoms, preferably an alicyclic dicarboxylic acid having 5 to 10 carbon atoms.

The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

The aforementioned aromatic dicarboxylic acids are not limited to the following, and examples include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5 C8-C20 aromatic dicarboxylic acids unsubstituted or substituted with various substituents, such as methyl isophthalic acid and isophthalic acid-5-sodium sulfonate, etc.

Examples of the aforementioned various substituents include alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, halogen groups such as chloro and bromo groups, Alkylsilyl groups having 3 to 10 carbon atoms, sulfonic acid groups and salts thereof such as sodium salts, etc.

The aforementioned aliphatic diamines having 6 or less carbon atoms are not limited to the following, and examples include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. And straight-chain saturated aliphatic diamines such as 2-methylpentamethylenediamine, etc.

As said aromatic diamine, it is not limited to the following thing, For example, m-xylylenediamine etc. are mentioned.

The polycondensable amino acid is not limited to the following, and examples thereof include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and p-aminomethylbenzoic acid.

The aforementioned lactam is not limited to the following, and examples thereof include butyrolactam, pivalolactam, caprolactam, capryllactam, enantholactam, undecanolactam, and laurolactam.

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

<Blocking agent>

As a raw material of the aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more, an end-blocking agent may be further added in order to adjust molecular weight and improve hot water resistance.

For example, when the polyamide 610 resin of this embodiment is polymerized, the amount of polymerization can be controlled by further adding a known terminal blocking agent.

The aforementioned blocking agent is not limited to the following substances, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacyl halides, monoesters, and monohydric alcohols.

Among these, monocarboxylic acids and monoamines are preferable from the viewpoint of productivity.

These end-blocking agents may be used alone or in combination of two or more.

The monocarboxylic acid used as the aforementioned end-blocking agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, and lauric acid , tridecanoic acid, myristic acid, palmitic acid, stearic acid, trimethylacetic acid and isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other aliphatic monocarboxylic acids; benzoic acid, toluic acid, Aromatic monocarboxylic acids such as α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid, etc.

These monocarboxylic acids may be used alone or in combination of two or more.

The monoamine used as the aforementioned end-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, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine and naphthylamine, etc. Aromatic monoamine, etc.

These monoamines may be used alone or in combination of two or more.

((A) Method for producing aliphatic polyamide resin having a carbon number/nitrogen atom ratio (C/N ratio) of 7 or more)

(A) A method for producing an aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more includes, for example, mixing a dicarboxylic acid, a diamine, and, if necessary, A method in which an aqueous solution or an aqueous suspension of a mixture of catalysts, apatite, and other components described later is heated and polymerized while maintaining a molten state (hot melt polymerization method); the polyamide obtained by the hot melt polymerization method is A method of increasing the degree of polymerization while maintaining a solid state at a temperature below the melting point (hot-melt polymerization, solid-state polymerization method); an aqueous solution or water of a mixture of dicarboxylic acid, diamine, and other components as required A method in which the suspension is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (prepolymer extrusion polymerization method); dicarboxylic acid, diamine, and A method in which a mixture of other required components, a solid salt, or a polycondensate is polymerized while maintaining a solid state (solid-state polymerization method), etc.

The polymerization method is not particularly limited, and may be either a batch type or a continuous type.

In addition, the polymerization apparatus is not particularly limited, and known apparatuses such as autoclave type reactors, drum type reactors, extruder type reactors such as kneaders and the like can be used.

(A) For the production of aliphatic polyamide resins (including polyamide copolymers, the same below) having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more, a prescribed catalyst can be used.

The catalyst is not particularly limited as long as it is a known catalyst used for polyamides. 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 their metal salts, etc.

The metal of the metal salt is not limited to the following, and examples thereof include metal salts or ammonium salts of potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, and the like.

In addition, phosphoric acid esters such as ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, stearyl ester, stearyl ester, and phenyl ester can also be used as the catalyst.

((A) Physical properties of aliphatic polyamide resins having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more)

(A) The 98% sulfuric acid solution viscosity (JIS K6920) of the aliphatic polyamide resin having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more is preferably 2.0 to 3.0, more preferably 2.0 to 2.9, More preferably, it is 2.2-2.6.

When the viscosity of the sulfuric acid solution is 2.0 or more, a molded article having practically sufficient mechanical properties can be obtained, and when the viscosity of the sulfuric acid solution is 3.0 or less, the fluidity during molding is good, and a molded article with excellent surface appearance can be obtained.

The polyamide resin composition of this embodiment may contain 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 copolymerized polyamides containing these as constituents. More than one of the groups formed. Among them, polyamides having polyamide 6 and polyamide 66 as main constituents and 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 further preferred. By containing such a polyamide, the obtained molded article tends to be more excellent in mechanical strength and rigidity during heating.

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, based on 100% by mass of the total polyamide resin. When the content is within the above range, the mechanical strength and rigidity during heating 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 may contain 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, there exists a tendency for the rigidity at the time of heating to become more excellent. Here, "semi-aromatic polyamide" refers to a polyamide composed of a combination of a diamine or a dicarboxylic acid as an aliphatic compound and the other as a compound having an aromatic structure, and a polyamide containing these as The copolymerized polyamide as a constituent component, in the case of a copolymerized polyamide, when more than 50% by mass of the constituent units are semi-aromatic units, is called a semi-aromatic polyamide.

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, based on 100% by mass of the total polyamide resin. %. When the content is within the above-mentioned range, the dimensional accuracy and appearance of the molded body obtained tend to be more excellent in rigidity during heating.

((B) Fiberglass)

The polyamide resin composition of this embodiment contains 1 to 200 mass parts Part (B) Fiberglass.

Excellent rigidity can be obtained by containing said (B) glass fiber.

The above-mentioned (B) glass fiber has a number average fiber diameter of preferably 3 to 30 μm, more preferably 3 to 25 μm, and still more preferably 5 to 20 μm, from the viewpoint of being able to exhibit excellent mechanical strength and vibration fatigue resistance. The fiber length is preferably 100 to 750 μm, more preferably 100 to 700 μm, even more preferably 200 to 600 μm.

(B) The glass fiber has an aspect ratio (L/D) of weight average fiber length (L) to number average fiber diameter (D) of preferably 10-100, more preferably 10-90, even more preferably 20-90.

(B) 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 weight-average fiber length (L) of the (B) glass fibers can be measured by microscopy.

For example, by heating a granular polyamide resin composition containing glass fibers above the decomposition temperature of the polyamide resin composition, taking pictures of the remaining (B) glass fibers with a microscope, and measuring the diameter of the glass fibers and length method to measure.

Examples of methods for calculating the number-average fiber diameter (D) and weight-average fiber length (L) from the measured values obtained by microscopy include the following formulas (I) and (II).

Number average fiber diameter (D) = total glass fiber diameter / number of glass fibers... (I)

Weight-average fiber length (L) = sum of squares of glass fiber lengths/sum of glass fiber lengths... (II)

The content of (B) glass fiber in the polyamide resin composition of the present embodiment is an aliphatic polyamide having a carbon number/nitrogen atom ratio (C/N ratio) of 7 or more relative to (A) as described above. 100 mass parts of resin is 1-200 mass parts, Preferably it is 2-200 mass parts, More preferably, it is 2-180 mass parts, More preferably, it is 5-100 mass parts.

By setting the content of (B) glass fiber to 1 part by mass or more relative to (A) 100 parts by mass of aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more, The mechanical strength and the like of the polyamide resin composition of this embodiment are improved, and the polyamide resin composition excellent in formability can be obtained by setting the content to 200 parts by weight or less.

In addition, the content of (B) glass fiber can be calculated by burning a polyamide resin composition, taking out and measuring remaining (B) glass fiber.

The specific composition of the aforementioned (B) glass fiber is not limited to the following composition, and examples thereof include E glass composition, C glass composition, S glass composition, and alkali-resistant glass composition.

Among them, E glass is preferable from the viewpoint of easy availability.

In addition, from the viewpoint of the mechanical strength of the polyamide resin composition of the present embodiment, the tensile strength of the (B) glass fiber is preferably 290 kg/mm ² or more.

The aforementioned (B) glass fibers are preferably made of silanes such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The coupling agent is used for surface treatment, but is not limited to these silane coupling agents, and its adhesion amount is preferably 0.01% by mass or more based on the weight of the glass fiber (the total amount of the glass fiber and the surface treatment agent).

In addition, the aforementioned (B) glass fibers may be treated with a sizing agent as needed. The sizing agent is not limited to the following examples, and examples include: a copolymer having a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer as polymerized units , epoxy compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers and their salts with primary, secondary and tertiary amines.

These substances may be used alone or in combination of two or more.

In particular, from the viewpoint of the mechanical strength of the polyamide resin composition of this embodiment, it is preferable to have a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic anhydride-containing unsaturated vinyl monomer. Copolymers, epoxy compounds, and polyurethane resins as polymerized units, and combinations thereof, more preferably have carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers other than the carboxylic anhydride-containing unsaturated vinyl monomers. Copolymers as polymerized units and polyurethane resins and combinations thereof.

((C) Inorganic filler other than glass fiber)

The polyamide resin composition of the present embodiment contains 0.1 to 10 mass parts of aliphatic polyamide resin with respect to 100 mass parts of the above-mentioned (A) ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more. Part (C) Inorganic filler other than glass fiber.

The (C) content of inorganic fillers other than glass fibers is preferably 0.18 per 100 parts by mass of the above-mentioned (A) aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more. -10 parts by mass, more preferably 0.18-8 parts by mass, still more preferably 0.18-5 parts by mass, still more preferably 2.0-5.0 parts by mass.

The effect of improving the strength of the polyamide resin composition of the present embodiment can be exhibited by setting the content of the inorganic filler other than the (C) glass fibers to 0.1 parts by mass or more. On the other hand, by setting the above-mentioned content to 10 parts by mass or less, a polyamide resin composition excellent in extrudability and formability can be obtained.

Examples of inorganic fillers other than (C) glass fibers include wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay (as silicon montmorillonite, which is a layered clay layered with salt layers, etc.).

The (C) inorganic fillers other than glass fibers may be used alone or in combination of two or more.

As the inorganic filler other than the aforementioned (C) glass fibers, from the viewpoint of improving strength, etc., preferably one or more selected from the group consisting of wollastonite, kaolin, mica, and talc, more preferably selected from wollastonite, One or more of the group consisting of kaolin and talc. Moreover, wollastonite and talc are still more preferable from the viewpoint of improving the surface appearance of the molded article of the polyamide resin composition of the present embodiment.

It is preferable that the average particle diameter of the inorganic filler other than the said (C) glass fiber is 0.01-38 micrometers. It is more preferably 0.03 to 30 μm, still more preferably 0.05 to 25 μm, still more preferably 0.10 to 20 μm, still more preferably 0.15 to 13 μm.

By setting the average particle size of the above (C) inorganic filler other than the glass fiber to 38 μm or less, a polyamide resin composition having excellent toughness and surface appearance of a molded article can be obtained.

On the other hand, by setting the average particle diameter to 0.01 μm or more, a polyamide resin composition having an excellent balance between cost, powder handling, and mechanical properties (strength, toughness, etc.) can be obtained.

In addition, among the inorganic fillers other than (C) glass fibers, the number average fiber diameter (hereinafter simply referred to as “average fiber diameter”) is the average particle diameter for materials having acicular shapes such as wollastonite. In addition, when the cross section is not circular, the maximum value of the length is taken as the fiber diameter, and the number-average fiber diameter obtained using this is taken as the average particle diameter.

The average particle diameter (number-average fiber diameter) can be determined by arbitrarily selecting 100 or more inorganic fillers other than the aforementioned (C) glass fibers, observing them with a scanning electron microscope (SEM), and measuring the particle size of these inorganic fillers. Diameter (fiber diameter), and calculate the arithmetic mean to find out.

Among the aforementioned inorganic fillers, the weight-average fiber length (hereinafter simply referred to as "average fiber length") of materials having acicular shapes such as wollastonite is preferably determined from the above-mentioned preferred range of number-average fiber diameter and the following weight-average fiber length: The numerical range calculated from the preferred range of the aspect ratio (L/D) of the average fiber length (L) to the number average fiber diameter (D).

Regarding the aspect ratio (L/D) of the weight-average fiber length (L) to the number-average fiber diameter (D) of the aforementioned needle-like material, it improves the surface appearance of the molded product and prevents metal damage such as injection molding machines. From the viewpoint of wear of permanent parts, it is preferably 1.5-10, more preferably 2.0-5, and even more preferably 2.5-4.

In addition, the aspect ratio of the material having acicular shape among inorganic fillers other than (C) glass fibers is preferably 10-20, more preferably 15-20.

Here, the number average fiber diameter (D) in this specification can be measured by arbitrarily selecting 100 or more inorganic fillers as raw materials, observing them with a scanning electron microscope (SEM), as described above. The fiber diameters of these inorganic fillers were obtained. In addition, the weight-average fiber length (L) in this specification can be calculated|required by selecting 100 or more inorganic fillers arbitrarily for a fibrous inorganic filler, and measuring a fiber length using a SEM photograph.

(C) Inorganic fillers other than glass fiber can be surface-treated with a silane coupling agent or a titanate coupling agent.

As the aforementioned silane coupling agent, it is not limited to the following examples, for example: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and N-β-(aminoethyl)-γ- Aminosilanes such as aminopropylmethyldimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxysilanes, and vinylsilanes.

Among these, aminosilanes are more preferable from the viewpoint of being able to express excellent mechanical strength.

These substances may be used alone or in combination of two or more.

Such a surface treatment agent may be treated in advance on the surface of (C) an inorganic filler other than glass fibers, or may be prepared on (A) the ratio of the number of carbon atoms/number of nitrogen atoms (C/N ratio) to 7 or more. It is added when aliphatic polyamide resin is mixed with (C) inorganic fillers other than glass fibers.

It is preferable that the addition amount of a surface treatment agent is 0.05-1.5 mass % with respect to 100 mass % of inorganic fillers other than (C) glass fiber.

((D) lubricant)

The polyamide resin composition of the present embodiment contains 0.01 to 10 Part (D) Lubricant.

The content of the (D) lubricant is preferably 0.03 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (A) aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more, More preferably, it is 0.03-5 mass parts, More preferably, it is 0.05-3 mass parts.

By setting the content of the (D) lubricant within the above range, a polyamide resin composition having more excellent appearance, releasability, mechanical strength, and plasticizability can be obtained.

As (D) the lubricant, at least one selected from the group consisting of higher fatty acid, higher fatty acid metal salt, higher fatty acid ester, and higher fatty acid amide 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 number of carbon atoms of the higher fatty acid is preferably 8-40. The higher fatty acid is not limited to the following examples, and examples thereof include saturated or unsaturated, linear or branched aliphatic monocarboxylic acids. For example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, montanic acid, etc. are mentioned as a higher fatty acid.

The higher fatty acid metal salt is a metal salt of the above-mentioned higher fatty acid.

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. As the metal element, alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; and aluminum are preferable.

As the higher fatty acid metal salt, it is not limited to the following examples, for example: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, aluminum montanate, Zinc montanate, magnesium montanate, calcium behenate, sodium behenate, zinc behenate, calcium laurate, zinc laurate, calcium palmitate, etc.

As the higher fatty acid metal salt, preferably use montanic acid metal salt, behenic acid metal salt and stearic acid metal salt, wherein, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, Calcium montanate, zinc montanate, magnesium montanate, calcium behenate, zinc behenate, more preferably aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, zinc montanate, behenic acid Calcium, zinc behenate, more preferably calcium montanate, zinc montanate, 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 preferably 3.5 to 11.5% by mass relative to 100% by mass of the higher fatty acid metal salt from the viewpoint of obtaining a polyamide resin composition with better appearance and releasability. 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 esterification product of the above-mentioned higher fatty acid and alcohol.

As the higher fatty acid ester, an esterified product of an aliphatic monocarboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.

The aliphatic alcohol is not limited to the following examples, and examples thereof include stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like. Examples of higher fatty acid esters include stearyl stearate, behenyl behenate, and the like.

The higher fatty acid amides are amidated products of the above-mentioned higher fatty acids.

The aforementioned higher fatty acid amides are not limited to the following examples, for example: stearamide, oleamide, erucamide, ethylenebisstearamide, ethylenebisoleamide, N-stearyl stearamide, N-stearyl erucamide, etc. As higher fatty acid amides, stearamide, erucamide, ethylene bisstearamide, and N-stearyl erucamide are preferable, and ethylene bisstearamide and N-stearyl erucamide are more preferable.

As the (D) lubricant, metal salts of higher fatty acids and higher fatty acid amides are preferable from the viewpoint of better formability, and among them, metal salts of higher fatty acids are more preferable from the viewpoint of better appearance and releasability.

From the viewpoint of better appearance and releasability, the (D) lubricant has a melting point of preferably 110 to 150°C, more preferably 115 to 145°C, even more preferably 115 to 140°C.

In addition, (D) the melting point of the lubricant can be measured by differential scanning calorimetry (DSC) or the like.

((E) Copper compounds and halogen compounds (except for copper halides))

The polyamide resin composition of the present embodiment may further contain (E) a copper compound and a halogen compound (except copper halide).

Copper compounds used in the aforementioned (E) copper compounds and halogen compounds (except for copper halides) are not limited to the following examples, for example: copper halide, copper acetate, copper propionate, copper benzoate, adipic acid Copper, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, etc., and copper complexes formed by coordination with chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid salt etc.

These copper compounds may be used alone or in combination of two or more.

Among these, copper iodide, cuprous bromide, copper bromide, cuprous chloride, and copper acetate are preferable from the viewpoint of thermal stability.

The content of the above-mentioned copper compound in the above-mentioned (E) copper compound and halogen compound (except for copper halide), relative to (A) the ratio of the number of carbon atoms to the number of nitrogen atoms (C/N ratio) is 7 or more. 0.001-1.999 mass parts of copper compounds are preferable for 100 mass parts of amide resins, More preferably, they are 0.0025-0.5 mass parts, More preferably, they are 0.01-0.1 mass parts. By setting it in this range, the polyamide resin composition of this embodiment and its molded article can realize sufficient heat aging resistance improvement, and copper precipitation and corrosion can be suppressed.

The halogen compounds (other than copper halides) used in the aforementioned (E) copper compounds and halogen compounds (except copper halides) are not limited to the following examples, for example: potassium iodide, sodium iodide, potassium bromide, Potassium chloride, sodium chloride, etc.

These halogen compounds may be used alone or in combination of two or more.

Aliphatic polyamides in which the content of halogen compounds in (E) copper compounds and halogen compounds (excluding copper halides) is 7 or more relative to (A) the ratio of carbon atoms to nitrogen atoms (C/N ratio) 100 parts by mass of the resin is preferably 0.001 to 1.999 parts by mass of a halogen compound, more preferably 0.01 to 1.999 parts by mass, still more preferably 0.03 to 1 part by mass. By setting it in this range, the polyamide resin composition of this embodiment and its molded article can realize sufficient heat aging resistance improvement, and copper precipitation and corrosion can be suppressed.

In order to improve the performance of the polyamide resin composition of this embodiment, it is preferable to contain both of the above-mentioned copper compound and a halogen compound (except copper halide).

100 wt. The part is preferably 0.002 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, still more preferably 0.03 to 1.5 parts by mass, and even more preferably 0.03 to 1 part by mass. By setting it as this range, the polyamide resin composition of this embodiment and its molded article can acquire sufficient heat aging resistance improvement effect, and copper precipitation and corrosion can be suppressed.

In the polyamide resin composition of this embodiment, the molar ratio of the content x of the halogen element to the content y of the copper element in the aforementioned (E) copper compound and the halogen compound (excluding copper halide) (the content x of the halogen element/copper The element content y) is preferably 2/1 to 50/1, more preferably 3/1 to 30/1, still more preferably 4/1 to 25/1, still more preferably 5/1 to 23/1.

When the molar ratio (x/y) of the content x of the halogen element to the content y of the copper element is 2 or more, copper precipitation and metal corrosion can be suppressed, which is preferable. In addition, when the molar ratio (x/y) of the above-mentioned halogen to copper is 50 or less, the corrosion of the screw of the molding machine and the like can be suppressed without impairing mechanical properties such as toughness.

The aforementioned (E) copper compound and halogen compound (except for copper halide) are preferably added in the form of a masterbatch.

By adding the aforementioned (E) copper compound and halogen compound in the form of a masterbatch, the dispersibility of the (E) component can be improved, heat aging resistance can be improved, corrosion can be prevented, and copper precipitation can be further suppressed.

The polyamide resin used in the polyamide masterbatch is not limited to the following examples, for example: polycaprolactam (polyamide 6), polybutylene adipamide (polyamide 46), polyadipamide adipamide Amine (polyamide 66), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecane adipamide (polyamide 116) , polyundecalactam (polyamide 11), polylaurolactam (polyamide 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide ( Polyamide 6I), polynonanediamine terephthalamide (9T), polyhexamethylene terephthalamide (6T), polybis(4-aminocyclohexyl)methane dodecane diamide (nylon PACM12) , polybis(3-methylaminocyclohexyl)methane dodecane diamide (nylon dimethyl PACM12), polym-xylylene adipamide (polyamide MXD6) and polyhexahydroterephthalamide One carbon diamine (polyamide 11T(H)), etc.

In addition, examples of the polyamide resin used in the aforementioned polyamide masterbatch include polyamide copolymers containing at least two different polyamide-forming components among these, and mixtures of these polyamides and/or polyamide copolymers wait.

Among the above-mentioned polyamide resins, for the polyamide resin composition and its molded article according to the present embodiment, from the viewpoint of suppressing a decrease in mechanical properties caused by contact with an antifreeze solution for a long time and a decrease in mechanical properties under high-temperature drying, preferably Polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), etc., and polyhexamethylene sebacamide (polyamide 610) is particularly preferable.

Regarding the polyamide masterbatch containing the aforementioned (E) copper compound and halogen compound (except copper halide) contained in the polyamide resin composition of the present embodiment, the polyamide resin contained in the polyamide masterbatch The main component is preferably polyamide 610 resin. Here, the "main component" means that the content of polyamide 610 resin in the polyamide constituting the polyamide masterbatch is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more.

The content of the copper compound in the polyamide masterbatch is preferably 0.1 to 5 parts by mass of the copper compound, more preferably 0.25 to 5 parts by mass, and even more preferably 0.40 parts by mass relative to 100 parts by mass of the polyamide resin constituting the polyamide masterbatch. ~4 parts by mass. By setting it as this range, the polyamide resin composition of this embodiment and its molded article can realize sufficient aging resistance, and copper precipitation and corrosion can be suppressed.

The content of the halogen compound in the polyamide masterbatch is preferably 1 to 50 parts by mass of the halogen compound, more preferably 5 to 45 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the polyamide resin constituting the polyamide masterbatch. ~40 parts by mass. By setting it as this range, the polyamide resin composition of this embodiment and its molded article can realize sufficient aging resistance, and copper precipitation and corrosion can be suppressed.

The (E) copper compound and halogen compound contained in the polyamide masterbatch are preferably in the form of particles.

In addition, the maximum particle size of the copper compound and the halogen compound contained in (E), that is, the particle size of the largest particle of the copper compound and the halogen compound contained in the masterbatch is preferably 50 μm or less, more preferably 20 μm or less , and more preferably 10 μm or less.

In the polyamide masterbatch, the particle refers to the average diameter of the two axes, that is, the average value of the short diameter and the long diameter. Here, the minor axis and the major axis are respectively the shorter side and the longer side of a circumscribed rectangle having the smallest area circumscribing the particles. The measurement of the maximum particle size of the aforementioned (E) copper compound and halogen compound can be obtained by observing at least 50 particles using a scanning electron microscope (SEM).

By setting the maximum particle size of the (E) copper compound and the halogen compound to 50 μm or less, the (E) copper compound and the halogen compound can be finely dispersed in the polyamide in the polyamide masterbatch. The amide resin composition and its molded product can further improve metal precipitation and corrosion problems, and can further improve toughness, heat aging resistance, appearance, and color tone.

<Organic compound having at least one amide group>

In the aforementioned polyamide masterbatch, an organic compound having at least one amide group may be mixed in the melt-kneading of the polyamide masterbatch.

The aforementioned organic compound having at least one amide group is a compound having at least one amide group in the molecular chain. The organic compound having at least one amide group is not limited to the following examples, and examples thereof include monoamides, substituted amides, methylol amides, and bisamides.

The aforementioned monoamides are represented by the general formula R-CONH ₂ (wherein, R is a saturated aliphatic, unsaturated aliphatic, or aromatic group with 8 to 30 carbon atoms, or a group in which part of their -H is replaced by -OH) . Examples of the monoamides include, without limitation, lauramide, palmitamide, stearamide, behenamide, hydroxystearamide, etc., oleamide, erucamide, and ricinamide.

The aforementioned substituted amides are represented by the general formula R ₁ -CONHR ₂ (wherein, R ₁ and R ₂ are each independently a saturated aliphatic, unsaturated aliphatic, aromatic or a part of their -H with 8 to 30 carbon atoms group substituted by -OH). The substituted amides are not limited to the following examples, for example: N-lauryl lauramide, N-palmityl palmitamide, N-stearyl stearamide, N-oleyl oleamide, N-stearyl Oleyl amide, N-oleyl stearamide, N-stearyl erucamide, N-oleyl palmitamide, N-stearyl 12-hydroxystearamide, N-oleyl 12-hydroxystearamide, etc. .

The aforementioned methylol amides are represented by the general formula R-CONHCH ₂ OH (wherein, R is a saturated aliphatic, unsaturated aliphatic, or aromatic group with 8 to 30 carbon atoms, or a part of their -H is substituted by -OH group). The methylolamides are not limited to the following examples, and examples thereof include methylol stearamide, methylol behenamide, and the like.

The aforementioned bisamides are represented by the general formula (R-CONH) ₂ (CH ₂ ) _n (wherein, R is a saturated aliphatic, unsaturated aliphatic, or aromatic group with 8 to 30 carbon atoms, or a part of their -H is replaced by A group substituted with -OH. In addition, n is 1 to 8). The bisamides are not limited to the following examples, and examples include: methylenebislauric amide, methylenebishydroxystearamide, ethylenebiscaprylamide, ethylenebislauricamide, ethylenebisylamide Stearamide, ethylene bisisostearamide, ethylene bishydroxystearamide, ethylene bisbehenamide, hexamethylene bisstearamide, hexamethylene bisbehenamide, hexaethylene Methyl bishydroxystearamide, butylene bishydroxystearamide, N,N'-distearyl adipamide, N,N'-distearyl sebacamide, methylene bisoleamide, Ethyl bisoleamide, Ethylene biserucamide, Hexamethylene bisoleamide, N,N'-Dioleyl adipamide, N,N'-Dioleyl sebacamide, Metaphthalamide Bis stearylamide, N,N'-distearyl isophthalamide, etc.

The aforementioned organic compounds having at least one amide group may be used alone or in combination of two or more. Among the above-mentioned organic compounds having at least one amide group, bisamides are preferred from the viewpoint of further improving the dispersibility of copper compounds and halogen compounds.

The content of the aforementioned organic compound having at least one amide group is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass relative to 100 parts by mass of the polyamide resin constituting the polyamide masterbatch. parts by mass.

By setting this range, the dispersibility of the copper compound and the halogen compound constituting the polyamide masterbatch in the polyamide resin constituting the polyamide masterbatch is further improved. In other words, 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 aforementioned copper compound, halogen compound, and if necessary, the aforementioned organic compound having at least one amide group with a polyamide resin.

The copper compound, the halogen compound, and the organic compound having at least one amide group can be independently compounded with the polyamide resin, at least two of the three compounds can be pre-mixed with the polyamide resin, and at least two of the three compounds can be mixed with the polyamide resin. The three compounds are pre-mixed and pulverized to be compounded with the polyamide resin, and at least two of the three compounds can also be pre-mixed and pulverized into tablets and then compounded with the polyamide resin.

As a method of mixing the aforementioned copper compound, halogen compound, and organic compound having at least one amide group, a known method can be applied. For example, any of drum, Henschel, plowshare mixer, Nauta mixer, jet mixer, etc. can be used.

As the pulverization method described above, known methods can be applied. For example, any of a hammer mill, a knife mill, a ball mill, a jaw crusher, a cone crusher, a tumble mill, a jet mill, a hand mill, and the like can be used.

A known method can be applied to the aforementioned method of forming a tablet. For example, any of compression granulation method, tablet molding method, dry extrusion granulation method, melt extrusion granulation method and the like can be used.

A polyamide masterbatch can be produced by blending and melt-kneading each compound with a polyamide resin as described above.

There are no particular limitations on the apparatus for melt-kneading, and known apparatuses can be used. For example, melt-kneading machines such as single-screw or twin-screw extruders, Banbury mixers, and kneading rolls are preferably used. Among them, it is preferable to use a twin-screw extruder.

In addition, in the melt kneader, a degassing mechanism (vent) device and a side feeder device can be installed.

The melting and kneading temperature is preferably about 1°C to about 100°C higher than the melting point or softening point of the polyamide obtained by differential scanning calorimetry (DSC) measurement according to JIS K7121.

The shear rate of the kneader is preferably about 100 (sec ⁻¹ ) or higher, and the average residence time during kneading is preferably about 1 minute to about 15 minutes.

The moisture content of the polyamide masterbatch is preferably 0.06 to 1.0% by mass, more preferably 0.10 to 0.75% by mass, and even more preferably 0.15 to 0.75% by mass.

Moisture in the polyamide masterbatch may exist as moisture in a state bound to polyamide molecules, or as moisture attached to the surface of the polyamide masterbatch, such as the surface of masterbatch particles or masterbatch powder.

By adjusting the water content of the polyamide masterbatch to this range, aggregation of copper compounds and halogen compounds can be suppressed. Accordingly, the polyamide resin composition of the present embodiment and its molded product have a high effect of improving mechanical properties such as toughness and heat aging resistance, and can further suppress copper precipitation and metal corrosion.

The moisture content of the aforementioned polyamide masterbatch can be adjusted by the vacuum degree of the extruder, the immersion time in the strand bath during cooling, the control of the immersion length or the control of the amount of water spray.

((F) colorant)

The polyamide resin composition of this embodiment may further contain (F) a colorant.

(F) The content of the coloring agent is preferably 0.01 to 5.0 parts by mass, more preferably 0.02 to 4.0 parts by mass, more preferably 0.03 to 2.0 parts by mass.

(Deterioration Inhibitor)

To the polyamide resin composition of the present embodiment, if necessary, within a range not impairing the object of the present embodiment, a deterioration inhibitor for preventing thermal deterioration, discoloration during heating, and improving heat aging resistance and weather resistance may be added. .

Examples of the deterioration inhibitor include, without being limited to the following, phenolic stabilizers such as hindered phenol compounds; phosphite stabilizers; hindered amine stabilizers; triazine stabilizers; and sulfur-containing stabilizers.

These deterioration inhibitors may be used alone or in combination of two or more.

(other resins)

In the polyamide resin composition of the present embodiment, other resins may be added as needed within a range not impairing the purpose of the present embodiment.

Such resins are not limited to the following examples, and include thermoplastic resins, rubber components, and the like described later.

The above-mentioned thermoplastic resin is not limited to the following examples, and examples thereof include polystyrene-based resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, and ABS resin. , polyester resins such as polyethylene terephthalate and polybutylene terephthalate, other polyamides such as nylon 6, 66, and 612 (polyamides other than the polyamide of this embodiment), polyamide Carbonate, polyether resins such as polyphenylene ether, polysulfone, and polyethersulfone, condensation resins such as polyphenylene sulfide, and polyoxymethylene, acrylic resins such as polyacrylic acid, polyacrylate, and polymethyl methacrylate, poly Polyolefin resins such as ethylene, polypropylene, polybutene, and ethylene-propylene copolymers, halogen-containing vinyl compound resins such as polyvinyl chloride and polyvinylidene chloride, phenolic resins, and epoxy resins.

These thermoplastic resins may be used alone or in combination of two or more.

The rubber component is not limited to the following, and examples thereof include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, polysulfide rubber (チオオコールゴム), acrylic rubber , polyurethane 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 Segment 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-Butene Random Copolymer, Ethylene-Propylene Copolymer (EPR), Ethylene -(1-butene) copolymer, ethylene-(1-hexene) copolymer, ethylene-(1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM), 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 ester-butadiene-styrene core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene core-shell rubber (SBR), and Core-shell rubber materials such as silicone-containing core-shell rubber represented by methyl methacrylate-butyl acrylate silicone.

These rubber components may be used alone or in combination of two or more.

[Manufacturing method of polyamide resin composition]

The polyamide resin composition of the present embodiment can be obtained by blending (B) glass fiber, (C) Inorganic fillers other than glass fibers, (D) Lubricants, (E) Copper compounds and halogen compounds (except for copper halides), (F) Colorants, deterioration inhibitors, and other resins as required .

As a compounding method, a known extrusion technique can be used.

For example, the melt-kneading temperature is preferably about 250°C to about 350°C in terms of resin temperature. The melt-kneading time is preferably about 1 minute to about 30 minutes.

In addition, in the method of supplying the components constituting the reinforced polyamide to the melt-kneader, all the constituent components may be supplied to the same supply port at once, or the constituent components may be supplied from different supply ports.

Specific mixing methods include (A) an aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more using a Henschel mixer, (B) glass fiber, (C) A method of mixing inorganic fillers other than glass fiber, (D) lubricants, and other components, and supplying them to a melt kneader for kneading; in a single-screw or twin-screw extruder with a pressure reducing device (A) Aliphatic polyamide resin having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more in a molten state, (D) lubricant mixed with (B) glass fiber from a side feeder , (C) Inorganic fillers other than glass fibers, methods of other components, etc.

[Physical properties of polyamide resin composition]

With regard to the polyamide resin composition of the present embodiment, according to JIS K7121, measured by differential scanning calorimetry (in which the cooling rate is set to 20 ° C / min for cooling), the polyamide resin composition in the The extrapolated crystallization initiation temperature (T _ic ) of the aforementioned (A) aliphatic polyamide resin having a ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more is 200°C or higher, which leads to appearance and detachment. A polyamide resin composition having better moldability is preferable. More preferably, it is 201°C or more and 220°C or less, still more preferably 202°C or more and 220°C or less, still more preferably 203°C or more and 220°C or less.

In order to adjust the extrapolated crystallization start temperature of the aliphatic polyamide resin having (A) the ratio of carbon atoms/nitrogen atoms (C/N ratio) of 7 or more in the polyamide resin composition to within a preferable range, 100 mass of aliphatic polyamide resin containing (C) an inorganic filler other than glass fibers, (D) a lubricant, and having a carbon number/nitrogen number ratio (C/N ratio) of 7 or more relative to (A) It is effective to contain 0.1 to 10 parts by mass of (C) an inorganic filler other than glass fiber and 0.01 to 10 parts by mass of (D) a lubricant.

In addition, by containing (D) a lubricant, there is a tendency to obtain a more preferable extrapolated crystallization start temperature, and a polyamide resin composition having better appearance and releasability can be obtained.

[Molded article of polyamide resin composition]

A predetermined molded article is obtained by molding the polyamide resin composition of the present embodiment.

The method for obtaining a molded article is not particularly limited, and known molding methods can be used.

Examples include: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, dissimilar material molding (other material molding), gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin injection molding Forming (ultra-high-speed injection molding) and in-mold composite molding (insert molding, insert-on-molding) and other forming methods.

The polyamide resin composition and its molded article of this embodiment are characterized in that, as described above, specific amounts of (C) inorganic fillers other than glass fibers and (D) lubricants are used. Ambient creep behavior, appearance, mold release and mechanical strength.

[use]

The molded article of the polyamide resin composition of the present embodiment is excellent in the stability of the surface appearance and impact resistance of the molded article under severe molding conditions, and can be used in various applications.

For example, it can be suitably used in the automotive field, the electrical and electronic field, the machinery industry field, the commercial equipment field, and the aerospace field.

Example

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, the constituent elements, physical property measurement methods, and characteristic evaluation methods of polyamide resins are as follows.

<Viscosity of sulfuric acid solution>

Dissolve polyamide resin in 98% sulfuric acid, and measure according to JIS K6920.

<Extrapolated crystallization start temperature>

Evaluation was performed using pellets of polyamide resin compositions produced in Examples and Comparative Examples described later.

For differential scanning calorimetry, "DSC7" manufactured by Perkin-Elmer was used.

Using JIS K7121 as a reference, heat 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 to 100°C at a cooling rate of 20°C per minute, and draw DSC curve.

The temperature at the intersection of the straight line obtained by extending the base line on the high temperature side to the low temperature side during the cooling process and the tangent line drawn at the point where the gradient is the largest in the curve on the high temperature side of the crystallization peak was used as the extrapolated crystallization start temperature (T _ic ).

<Evaluation of Tensile Creep Properties in Water at 23°C>

Evaluation was performed using a JIS No. 3 test piece.

The cylinder temperature was set at 280° C., the mold temperature was set at 80° C., and under the injection molding conditions of injection for 17 seconds and cooling for 20 seconds, a JIS No. 3 test piece was obtained.

The test piece was immersed in a 50% aqueous solution of long-term cooling liquid (LLC) for 450 hours in an environment of 130 ° C, and a tensile creep test was performed in water at 23 ° C to measure the stress at rupture 40 hours from the start of the test. Determination.

<Appearance (near the undercut)>

Molded articles for evaluation were produced using an injection molding machine.

As the injection molding machine, "FN-3000" manufactured by Nissei Plastics Co., Ltd. was used.

Set the barrel temperature to 290°C, the mold temperature to 80°C, and under the injection conditions of injection and pressure holding time of 20 seconds and cooling time of 15 seconds, a cylindrical shape with an inner diameter of 30mm x length of 60mm x thickness of 1.5mm is obtained. Shaped sheet. In addition, as the mold, a gate is provided on the outside of one end of the cylindrical part of the forming sheet, an undercut for forced extraction is arranged at 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 appearance of the root portion with the protrusion for forced removal of the obtained molded sheet was observed.

The evaluation of the appearance was performed on the basis of the following criteria.

+++: 20 molded pieces were observed, and all molded pieces were not wrinkled but had a good appearance

++: 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

<Appearance (near the center)>

The appearance of the cylindrical center portion of the molded sheet obtained above was observed.

The evaluation of the appearance was performed on the basis of the following criteria.

+++: 20 formed pieces were observed, all formed pieces had good appearance without filler swelling

++: 20 molded pieces were observed, and filler lifting was observed in 1 or more and 5 or less molded pieces

+: 20 formed pieces were observed, and filler lifting was observed in more than 5 formed pieces

<Releasability>

Evaluation was performed using an injection molding machine.

As the injection molding machine, "FN-3000" manufactured by Nissei Plastics Co., Ltd. was used.

Set the barrel temperature to 290°C, the mold temperature to 80°C, and under the injection conditions of injection and pressure holding time of 20 seconds and cooling time of 10 seconds, a cylindrical shape with an inner diameter of 30mm×length of 60mm×thickness of 1.5mm is obtained. Shaped sheet. The releasability from the mold at this time was evaluated. The evaluation of mold releasability was performed based on the following criteria.

+++: Formed 20 formed pieces, all formed pieces were released from the mold without problems

++: 20 molded pieces were molded, and mold release failure occurred in 1 or more and 5 or less molded pieces

+: 20 molded pieces were molded, and mold release failure occurred in more than 5 molded pieces

<Measurement of Charpy impact strength>

As an injection molding machine, "PS40E" manufactured by Nissei Plastics Co., Ltd. was used to manufacture test pieces for evaluation.

The cylinder temperature was set at 280°C, the mold temperature was set at 80°C, and the ISO test piece was obtained under the injection conditions of injection + holding time of 25 seconds and cooling for 15 seconds.

The Charpy impact strength was measured according to ISO179 using the ISO test piece.

The measured value is the average value of n (measurement sample number)=6.

[(A) polyamide resin]

(A1): Polyamide 610 resin with 98% sulfuric acid viscosity 2.5

Ratio of polymerized units composed of sebacic acid and hexamethylenediamine: 100 mol%

(A2): Polyamide 610 resin with 98% sulfuric acid viscosity 2.3

Ratio of polymerized units composed of sebacic acid and hexamethylenediamine: 100 mol%

(A3): 98% sulfuric acid polyamide 610 resin with a viscosity of 2.5

Ratio of polymerized units composed of sebacic acid and hexamethylenediamine: 100 mol%

Copper iodide: 0.03% by mass, potassium iodide: 0.5% by mass

Iodine/copper molar ratio = 20 Copper iodide and potassium iodide are added during polymerization.

(A4): Polyamide 610 resin with 98% sulfuric acid viscosity 2.3

Ratio of polymerized units composed of sebacic acid and hexamethylenediamine: 100 mol%

Copper iodide: 0.03% by mass, potassium iodide: 0.5% by mass

Iodine/copper molar ratio = 20 Copper iodide and potassium iodide are added during polymerization.

(A5): 98% sulfuric acid polyamide 66 resin with a viscosity of 2.5

Copper iodide: 0.03% by mass, potassium iodide: 0.5% by mass

Iodine/copper molar ratio = 20 Copper iodide and potassium iodide are added during polymerization.

[(B) glass fiber]

(B1): Number-average fiber diameter of glass fibers treated with a sizing agent containing a maleic anhydride copolymer: 10 μm

(B2): Number-average fiber diameter of glass fibers treated with a sizing agent containing polyurethane resin: 10 μm

[(C) Inorganic fillers other than inorganic fibers]

(C1) Talc

Product name: ミクロエース (registered trademark) L-1 (manufactured by Nippon Talc Co., Ltd.)

[(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 stearate melting point: 125°C, metal content: 2.5% by mass

(D5) Zinc montanate has a melting point of 120°C and a metal content of 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% by mass

(D8) Zinc laurate melting point: 134°C, metal content: 14.0% by mass

(D9) Zinc oleate melting point: 85°C, metal content: 10.5% by mass

The melting points of the aforementioned lubricants (D) were measured by differential scanning calorimetry (DSC).

[Polyamide masterbatches containing (E) copper compounds and halogen compounds (excluding copper halides)]

(E1) Polyamide 610 resin with 98% sulfuric acid viscosity of 2.3 copper iodide: 3% by mass, potassium iodide: 15% by mass, iodine/copper molar ratio=8, ethylenebisstearamide: 2% by mass

(E2) Polyamide 610 resin with 98% sulfuric acid viscosity of 2.3 Copper iodide: 3% by mass, Potassium iodide: 30% by mass, Iodine/copper molar ratio=20, Ethylenebisstearamide: 2% by mass

[(F) colorant]

(F1) carbon black

Product name: Mitsubishi (registered trademark) カーボンブラック #2600 (manufactured by Mitsubishi Chemical Corporation)

[Embodiments 1 to 11]

The aforementioned (A) polyamide resin was supplied from a feed hopper to a TEM35 twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: 280° C., screw rotation speed: 300 rpm).

Moreover, the said (B) glass fiber was supplied from the side feed port at the ratio shown in the following Table 1 with respect to 100 mass parts of said (A) polyamide resins, and it melt-kneaded.

With respect to 100 parts by mass of the (A) polyamide resin, the (C) inorganic filler and the (D) lubricant were supplied from the feeding hopper at the ratios shown in Table 1 below.

The other additives were fed simultaneously with the aforementioned (A) polyamide resin from the addition funnel at the ratios shown in Table 1 below.

The melt-kneaded product extruded from the spinning nozzle was cooled in a strand form and pelletized to obtain a pelletized polyamide resin composition.

In addition, using the obtained polyamide resin composition, the measurement of the extrapolated crystallization start temperature was carried out by the method described above, and a molded product was produced, and evaluation of tensile creep characteristics in water at 23°C, appearance, and mold release properties were carried out. And the determination of Charpy impact strength.

The evaluation results are shown in Table 1 below.

[Comparative examples 1 to 13]

The aforementioned (A) polyamide resin was supplied from a feed hopper to a TEM35 twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: 280° C., screw rotation speed: 300 rpm).

Moreover, the said (B) glass fiber was supplied from the side feed port at the ratio shown in the following Table 2 with respect to 100 mass parts of said (A) polyamide resins, and it melt-kneaded.

If necessary, the (C) inorganic filler and the (D) lubricant were supplied from the feeding funnel at a ratio shown in Table 2 below with respect to 100 parts by mass of the (A) polyamide resin.

The other additives were fed simultaneously with the aforementioned (A) polyamide resin from the addition funnel at the ratios shown in Table 2 below.

The melt-kneaded product extruded from the spinning nozzle was cooled in a strand form and pelletized to obtain a pelletized polyamide resin composition.

In addition, using the obtained polyamide resin composition, the measurement of the extrapolated crystallization start temperature was carried out by the method described above, and a molded product was produced, and evaluation of tensile creep characteristics in water at 23°C, appearance, and mold release properties were carried out. And the determination of Charpy impact strength.

The evaluation results are shown in Table 2 below.

[Example 12-24]

The aforementioned (A) polyamide resin was supplied from a feed hopper to a TEM35 twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: 280° C., screw rotation speed: 300 rpm).

Moreover, the said (B) glass fiber was supplied from the side feed port at the ratio shown in the following Table 3 with respect to 100 mass parts of said (A) polyamide resins, and it melt-kneaded.

With respect to 100 parts by mass of the (A) polyamide resin, the (C) inorganic filler and the (D) lubricant were supplied from the feeding hopper at the ratios shown in Table 3 below.

The other additives were fed simultaneously with the aforementioned (A) polyamide resin from the addition funnel at the ratios shown in Table 3 below.

The melt-kneaded product extruded from the spinning nozzle was cooled in a strand form and pelletized to obtain a pelletized polyamide resin composition.

In addition, using the obtained polyamide resin composition, the measurement of the extrapolated crystallization start temperature was carried out by the method described above, and a molded product was produced, and evaluation of tensile creep characteristics in water at 23°C, appearance, and mold release properties were carried out. And the determination of Charpy impact strength.

The evaluation results are shown in Table 3 below.

As shown in Table 1 and Table 3 above, it has been confirmed that the molded articles of the polyamide resin compositions of Examples 1 to 22 all have extremely excellent tensile creep properties in water at 23° C., appearance, releasability, and mechanical properties.

On the other hand, it was confirmed that molded articles of the polyamide resin compositions of Comparative Examples 1 to 11 shown in Table 2 had significantly lower 23° C. underwater tensile creep properties, appearance, mold release properties, and mechanical properties.

Industrial applicability

The polyamide resin composition of the present invention and molded articles using the composition have industrial applicability in the fields of automobiles, electrical and electronic fields, machinery industry, office equipment, aviation, space, and the like.

Claims (12)

1. an Amilan polyamide resin composition, it contains:

(A) ratio of carbonatoms/nitrogen-atoms number and C/N than aliphatic polyamide resin 100 mass parts being more than 7,

(B) glass fibre 1 ~ 200 mass parts,

(C) inorganic filling material 0.1 ~ 10 mass parts beyond glass fibre, and

(D) lubricant 0.01 ~ 10 mass parts.

2. Amilan polyamide resin composition as claimed in claim 1, wherein,

The fusing point of described (D) lubricant is 110 ~ 150 DEG C.

3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein,

The higher fatty acid metal salt of described (D) lubricant to be metal content be 3.5 ~ 11.5 quality %.

4. Amilan polyamide resin composition as claimed any one in claims 1 to 3, wherein,

Obtain by measuring according to the means of differential scanning calorimetry of JIS K7121, the extrapolation crystallization of (A) polyamide resin described in described Amilan polyamide resin composition starts temperature (T _ic) be more than 200 DEG C, in described means of differential scanning calorimetry measures, speed of cooling is set as 20 DEG C/min cool.

5. the Amilan polyamide resin composition according to any one of Claims 1-4, wherein,

The relative viscosity measured in 98% sulfuric acid of described (A) polyamide resin is 2.0 ~ 3.0.

6. the Amilan polyamide resin composition according to any one of claim 1 to 5, wherein,

Described (A) polyamide resin 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.

7. the Amilan polyamide resin composition according to any one of claim 1 to 6, wherein,

Described (B) glass fibre is the glass fibre after utilizing collecting agent to process, described collecting agent contains multipolymer, described multipolymer have containing carboxylic acid anhydride unsaturated ethylene thiazolinyl monomer and except this containing the unsaturated ethylene thiazolinyl monomer except carboxylic acid anhydride unsaturated ethylene thiazolinyl monomer as polymerized unit.

8. the Amilan polyamide resin composition according to any one of claim 1 to 7, wherein,

Also containing (E) copper compound and halogen compounds 0.002 ~ 2 mass parts, described halogen compounds does not comprise copper halide.

9. Amilan polyamide resin composition as claimed in claim 8, wherein,

Halogen element content x in described (E) copper compound and halogen compounds and the mol ratio x/y of copper content y is 2/1 ~ 50/1, and described halogen compounds does not comprise copper halide.

10. Amilan polyamide resin composition as claimed in claim 8 or 9, wherein,

Described (E) copper compound and halogen compounds are added with the form of polyamide master-batch, and described halogen compounds does not comprise copper halide.

11. Amilan polyamide resin compositions according to any one of claim 1 to 10, wherein, also containing (F) tinting material 0.01 ~ 5 mass parts.

12. 1 kinds of molding, it contains the Amilan polyamide resin composition according to any one of claim 1 to 11.