JP6216196B2 - Polyamide resin composition and molded body containing the polyamide resin composition - Google Patents

Description

  The present invention relates to a polyamide resin composition and a molded body containing the polyamide resin composition.

  Polyamide resins have excellent mechanical properties, chemical resistance, moldability, etc., and are therefore widely used in various applications such as electrical and electronic, automotive, industrial materials, industrial materials, daily use, and household products. .

  In particular, in the automobile industry, to reduce carbon dioxide emissions as an environmental effort, vehicle weight reduction has been promoted by using resin for metal parts, and many automobile parts made of polyamide resin are likely to be used. It is becoming.

  The automobile parts made of polyamide resin are manufactured by various methods such as injection molding, extrusion molding, blow molding and the like. There are many hollow body parts in automobile parts. When the hollow body parts are obtained by injection molding, a method of joining two or more injection molded parts by welding or an adhesive is employed. However, this method has a problem in reliability of the joint, and there is a problem to be improved in terms of productivity, for example, when an adhesive is used, a curing step of the adhesive is required. On the other hand, according to extrusion molding, since a cylindrical molded product can be obtained continuously, it is excellent in production efficiency. However, when manufacturing a molded product other than a cylindrical product, bending or the like is necessary after extrusion molding. For example, there is a problem that productivity should be improved, and there is a problem that the degree of freedom of design of the molded product is low. Blow molding is superior to these other molding methods in that a molded product having no joint portion and a high degree of design freedom can be obtained with high productivity.

  Regarding the blow molding technology of polyamide resin for obtaining automobile parts, for example, Patent Literature 1 discloses a blow molding material containing an aromatic polyamide, and the blow molding material contains a filler such as glass fiber. And may contain a colorant. Patent Document 2 discloses a polyamide hollow molded article obtained by blow molding, and the polyamide resin composition for producing the hollow molded article contains a filler such as a fibrous inorganic compound. And may contain dyes. Furthermore, Patent Document 3 discloses a blow-moldable polyamide resin composition containing an aromatic polyamide, an impact modifier, and a stabilizer, and the polyamide resin composition contains a fibrous inorganic reinforcing material. It is described that it may be contained and that it may contain a dye.

JP 07-228691 A JP 04-153222 A JP-T-2006-523863

  However, automobile parts tend to increase in part size due to the trend of modularization to reduce the number of parts, and thus the molding cycle tends to become longer. For this reason, there is a growing demand for a polyamide resin composition excellent in melt residence stability, and there is room for improvement in melt residence stability in the polyamide resin composition used in conventional blow molding materials.

  This invention is made | formed in view of the said situation, and it aims at providing the molded object containing the polyamide resin composition which is excellent in melt residence stability, and the said polyamide resin composition.

The present invention provides: [1] Polyamide resin (A),
10 to 100 parts by mass of fibrous or needle-like filler (B) with respect to 100 parts by mass of the polyamide resin (A), and 0.05 to 5 parts by mass of dye with respect to 100 parts by mass of the polyamide resin (A) A polyamide resin composition containing (C),
A polyamide resin composition, wherein the dye (C) has a 5% heat loss temperature of 280 ° C. or higher;
[2] The polyamide resin (A) contains 50 to 100 mol% of an aliphatic diamine unit having 4 to 18 carbon atoms in all diamine units constituting the polyamide resin (A), and the polyamide resin (A The polyamide resin composition of the above-mentioned [1], which contains 50 to 100 mol% of aromatic dicarboxylic acid units and / or alicyclic dicarboxylic acid units in all dicarboxylic acid units constituting
[3] The aliphatic diamine units are 1,4-butanediamine units, 1,5-pentanediamine units, 1,6-hexanediamine units, 2-methyl-1,5-pentanediamine units, 1,8- The polyamide resin composition of [2] above, which is at least one selected from the group consisting of an octanediamine unit, a 1,9-nonanediamine unit, a 2-methyl-1,8-octanediamine unit, and a 1,10-decanediamine unit. object;
[4] The polyamide resin composition according to [3], wherein the aliphatic diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit;
[5] The polyamide resin composition according to any one of the above [2] to [4], wherein the aromatic dicarboxylic acid unit is a terephthalic acid unit;
[6] The polyamide resin composition according to any one of [2] to [5], wherein the alicyclic dicarboxylic acid unit is a 1,4-cyclohexanedicarboxylic acid unit;
[7] The polyamide resin composition according to any one of the above [2] to [6], wherein the polyamide resin (A) further contains a lactam unit and / or an aminocarboxylic acid unit;
[8] The polyamide resin composition according to any one of [1] to [7], wherein the polyamide resin (A) has a melting point of 260 to 350 ° C;
[9] The polyamide resin composition according to any one of [1] to [8], wherein the fibrous or needle-like filler (B) has an irregular cross-sectional shape;
[10] The polyamide according to [9], wherein the fibrous or needle-like filler (B) has a deformed ratio D1 / D2 of a deformed cross-sectional shape represented by a cross-sectional major axis D1 and a minor cross-sectional axis D2 of 1.2 to 10. Resin composition;
[11] The polyamide resin composition according to any one of [1] to [10], wherein the fibrous or needle-like filler (B) is a glass fiber;
[12] The polyamide resin composition according to any one of the above [1] to [11], wherein the dye (C) is an azine dye having a 5% heat loss temperature of 280 ° C. or higher;
[13] The polyamide resin composition according to any one of [1] to [12], wherein the chlorine content of the dye (C) is 0.08% by mass or less based on the total mass of the dye (C). ;
[14] The polyamide resin composition according to any one of [1] to [13], further containing 0.1 to 10 parts by mass of an anti-dripping agent (D) with respect to 100 parts by mass of the polyamide resin (A). object;
[15] A molded article containing the polyamide resin composition according to any one of [1] to [14] above;
[16] A blow molded article containing the polyamide resin composition of any one of [1] to [14]; and [17] An EGR pipe for automobiles including the blow molded article of [16] above;
About.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition excellent in melt residence stability and the molded object containing the said polyamide resin composition can be provided.

It is a perspective view of the container for measuring the thickness difference produced by blow molding in an Example and a comparative example.

  Hereinafter, the best mode for carrying out the present invention (the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The present invention relates to a polyamide resin (A), 10 to 100 parts by mass of a fibrous or acicular filler (B) and 0.05 to 5 parts by mass of a dye (C) with respect to 100 parts by mass of the polyamide resin (A). Is a polyamide resin composition in which the dye (C) has a 5% heat loss temperature of 280 ° C. or higher.

[Polyamide resin (A)]
Examples of the polyamide resin (A) used in the present invention include resins obtained using diamine, dicarboxylic acid, lactam, aminocarboxylic acid and the like as main raw materials.

  Examples of the diamine constituting the polyamide resin (A) include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, and 1,7-. Heptanediamine, 1,8-octadiamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1, Aliphatic diamines such as 13-tridecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 2,2,4 (or 2,4,4) -trimethylhexanediamine, 5-methylnonanediamine; 1 , 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3 Aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (amino And alicyclic diamines such as propyl) piperazine and aminoethylpiperazine; and aromatic diamines such as metaxylylenediamine and paraxylylenediamine.

  Examples of the dicarboxylic acid constituting the polyamide resin (A) include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, and 2,2-dimethylglutaric acid. Aliphatic dicarboxylic acids such as suberic acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid; alicyclic rings such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Formula dicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3 -Phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4 - dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, aromatic dicarboxylic acids such as 4,4'-biphenyl dicarboxylic acid.

  Examples of the lactam constituting the polyamide resin (A) include ε-caprolactam and ω-laurolactam, and examples of the aminocarboxylic acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraamino. And methyl benzoic acid.

  In the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

  Specific examples of the polyamide resin (A) include polycaproamide (polyamide 6), polyundecamide (polyamide 11), polylauramide (polyamide 12), polyhexamethylene adipamide (polyamide 66), poly Tetramethylene adipamide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene sebamide (polyamide 1010), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene terephthalamide / polyundecanamide copolymer (polyamide 6T / 11), polyhexamethylene terephthalamide / polyamide Dodecanamide copolymer (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), Polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 66 / 6I / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T) / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / poly (2 Methylpentamethylene) terephthalamide copolymer (polyamide 6T / M5T), polymetaxylylene adipamide (polyamide MXD6), polymetaxylene azeamide (polyamide MXD9), polymetaxylene sebacamide (polyamide MXD10), polyparaxylene azimuth Pamide (polyamide PXD6), polyparaxylene azelamide (polyamide PXD9), polyparaxylene sebamide (polyamide PXD10), polynonamethylene terephthalamide (polyamide 9T), poly (2-methyloctamethylene) terephthalamide (polyamide) M8T), polynonamethylene terephthalamide / poly (2-methyloctamethylene) terephthalamide copolymer (polyamide 9T / M8T), polydecamethylene terephthalamide (polyamide) 10T), polyundecamethylene terephthalamide (polyamide 11T), polydodecamethylene terephthalamide (polyamide 12T), polyhexamethylenecyclohexylamide (polyamide 6C), polyhexamethylenecyclohexylamide / polycaproamide copolymer (polyamide 6C) / 6), polyhexamethylenecyclohexylamide / polyundecanamide copolymer (polyamide 6C / 11), polyhexamethylenecyclohexylamide / polydodecanamide copolymer (polyamide 6C / 12), polyhexamethylene adipamide / polyhexamethylene Cyclohexylamide copolymer (polyamide 66 / 6C), polyhexamethylene adipamide / polyhexamethylenecyclohexylamide / polyhexamethylene isophthal Copolymer (polyamide 66 / 6C / 6I), polyhexamethylenecyclohexylamide / polyhexamethyleneisophthalamide copolymer (polyamide 6C / 6I), polyhexamethylenecyclohexylamide / poly (2-methylpentamethylene) cyclohexylamide Copolymer (Polyamide 6C / M5C), Polynonamethylenecyclohexylamide (Polyamide 9C), Poly (2-methyloctamethylene) cyclohexylamide (Polyamide M8C), Polynonamethylenecyclohexylamide / Poly (2-methyloctamethylene) cyclo Hexylamide copolymer (polyamide 9C / M8C), polydecamethylenecyclohexylamide (polyamide 10C), polyundecamethylenecyclohexylamide (polyamide 11C), Li dodecamethylene cycloheteroalkyl Kishiruamido (polyamide 12C) and mixtures thereof, and the like other than the above copolymer containing plural kinds of monomer units comprising these polyamides.

  The polyamide resin (A) preferably has a terminal amino group content in the range of 1 to 50 μmol / g, preferably in the range of 1 to 40 μmol / g, from the viewpoints of heat resistance and higher melt residence stability. Is more preferable.

  The polyamide resin (A) is preferably a semi-alicyclic polyamide resin containing a semi-aromatic and / or alicyclic ring containing an aromatic ring in the repeating structural unit from the viewpoint of heat resistance.

  Examples of the semi-aromatic and / or semi-alicyclic polyamide resin include polyamide resins containing an aliphatic diamine unit and an aromatic dicarboxylic acid unit and / or an alicyclic dicarboxylic acid unit as a dicarboxylic acid unit.

  As an aliphatic diamine unit, a C4-C18 aliphatic diamine unit is preferable. At this time, it is preferable that a C4-C18 aliphatic diamine unit is contained in 50-100 mol% in all the diamine units which comprise a polyamide resin (A), and it is contained in 60-100 mol%. More preferred.

  Examples of the aliphatic diamine unit having 4 to 18 carbon atoms include 1,4-butanediamine unit, 1,5-pentanediamine unit, 1,6-hexanediamine unit, 2-methyl-1,5-pentanediamine unit, At least one selected from the group consisting of 1,8-octanediamine units, 1,9-nonanediamine units, 2-methyl-1,8-octanediamine units and 1,10-decanediamine units is preferred, and 1,9- Nonanediamine units and / or 2-methyl-1,8-octanediamine units are more preferred. When both 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit are contained, these molar ratios (1,9-nonanediamine: 2-methyl-1,8-octanediamine) It is preferably 99: 1 to 1:99, more preferably 95: 5 to 50:50, and still more preferably 90:10 to 75:25. When the polyamide resin (A) containing the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit in the above proportion is used, the polyamide resin composition has excellent heat resistance and chemical resistance. Become.

  The aromatic dicarboxylic acid unit and / or the alicyclic dicarboxylic acid unit is preferably contained in an amount of 50 to 100 mol%, and preferably 60 to 100 mol% in all dicarboxylic acid units constituting the polyamide resin (A). It is more preferable.

  As aromatic dicarboxylic acid units, terephthalic acid units, isophthalic acid units, phthalic acid units, 1,4-naphthalenedicarboxylic acid units, 2,6-naphthalenedicarboxylic acid units, 2,7-naphthalenedicarboxylic acid units, 1,4 -Phenylenedioxydiacetic acid unit, 1,3-phenylenedioxydiacetic acid unit, diphenic acid unit, 4,4'-oxydibenzoic acid unit, diphenylmethane-4,4'-dicarboxylic acid unit, diphenylsulfone-4,4 At least one selected from the group consisting of a '-dicarboxylic acid unit and a 4,4'-biphenyldicarboxylic acid unit is preferable, and among these, a terephthalic acid unit is preferable.

  As the alicyclic dicarboxylic acid unit, a cyclohexanedicarboxylic acid unit such as a 1,3-cyclohexanedicarboxylic acid unit or a 1,4-cyclohexanedicarboxylic acid unit is preferable, and among them, a 1,4-cyclohexanedicarboxylic acid unit is preferable. When the polyamide resin (A) containing a terephthalic acid unit and / or a 1,4-cyclohexanedicarboxylic acid unit is used, the heat resistance of the polyamide resin composition becomes excellent.

  Further, as the polyamide resin (A), a semi-aromatic and / or semi-alicyclic polyamide resin containing an aromatic diamine unit and / or an alicyclic diamine unit and an aliphatic dicarboxylic acid unit as a diamine unit is used. You can also

  The semi-aromatic and / or semi-alicyclic polyamide resin may further contain a lactam unit and / or an aminocarboxylic acid unit as a monomer unit as long as the effects of the present invention are not impaired.

  In the polyamide resin (A), it is preferable that 10% or more of the terminal groups of the molecular chain are sealed with a terminal sealing agent. When the polyamide resin (A) having a terminal sealing rate of 10% or more is used, the melt residence stability of the obtained polyamide resin composition becomes more excellent.

Here, the terminal blocking rate is determined by measuring the number of terminal carboxyl groups, terminal amino groups, and terminal groups sealed with a terminal blocking agent present in the polyamide resin (A). It can be determined according to 1). The number of each terminal group can be determined by ¹ H-NMR based on the integral value of the characteristic signal corresponding to each terminal group. In Formula (1), X represents the total number of end groups of the molecular chain (this is usually equal to twice the number of polyamide molecules), and Y represents the remaining end carboxyl groups and seals. This represents the total number of terminal amino groups remaining without being stopped.
Terminal sealing ratio (%) = [(XY) / X] × 100 (1)

  The end capping agent for capping the end of the polyamide resin (A) is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide. From the viewpoints of stability of the sealing end and the like, monocarboxylic acid or monoamine is preferable, and from the viewpoint of ease of handling, monocarboxylic acid is more preferable. In addition, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can also be used.

The terminal amino group content [NH ₂ ] of the polyamide resin (A) is preferably 3 to 13 μmol / g, and the terminal carboxyl group content [COOH] is preferably 56 to 80 μmol / g. The relationship between the terminal carboxyl group content [COOH] and the terminal amino group content [NH ₂ ] is preferably 0.8 ≦ [COOH] / [NH ₂ ] + [COOH] ≦ 1.4, 0.82 It is more preferable that ≦ [COOH] / [NH ₂ ] + [COOH] ≦ 1.0. When a polyamide resin having a terminal group content within the above range is used, the polyamide resin composition is particularly excellent in melt residence stability.

  The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, laurin Aliphatic monocarboxylic acids such as acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid , Β-naphthalene carboxylic acid, methyl naphthalene carboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, and any mixture thereof. Above all, from the viewpoints of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, benzoic acid Acid is preferred.

  The monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; Cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; any mixtures thereof Is mentioned. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred from the viewpoints of reactivity, high boiling point, stability of the sealing end and price.

  A polyamide resin (A) can be manufactured using the arbitrary methods known as a method of manufacturing a polyamide resin. For example, it can be produced by a solution polymerization method or an interfacial polymerization method using acid chloride and diamine as raw materials, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid phase polymerization method, a melt extrusion polymerization method, or the like.

  As a method for producing the polyamide resin (A), for example, first, a dicarboxylic acid component, a diamine component, a catalyst, and optionally a terminal blocking agent are collectively added to produce a polyamide salt. A prepolymer having an intrinsic viscosity (ηinh) at 30 ° C. of 0.1 to 0.6 dL / g and a sample concentration in concentrated sulfuric acid of 0.2 g / dL is obtained by heat polymerization at a temperature of ˜250 ° C. Examples of the method include phase polymerization or polymerization using a melt extruder. Here, when ηinh of the prepolymer is in the range of 0.1 to 0.6 dL / g, there is little shift in the molar balance of the carboxyl group and amino group and a decrease in the polymerization rate in the subsequent polymerization stage, and the molecular weight A polyamide resin (A) having a small distribution and excellent in various physical properties and moldability can be obtained.

  When the final stage of the polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or in an inert gas atmosphere. If the polymerization temperature is in the range of 200 to 280 ° C., the polymerization rate is high and the productivity is increased. Excellent coloration and gelation can be effectively suppressed. The polymerization temperature when the final stage of the polymerization is performed by a melt extruder is preferably 370 ° C. or lower. When polymerized under such conditions, the polyamide resin (A) is hardly decomposed and a polyamide resin (A) having no deterioration is obtained.

  In the production of the polyamide resin (A), in addition to the above-described end-capping agent, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof can be added as a catalyst. Examples of the salt or ester include phosphoric acid, phosphorous acid or hypophosphorous acid and metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Salt of phosphoric acid, phosphorous acid or hypophosphorous acid; ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid, Examples of the ester include decyl ester, stearyl ester, and phenyl ester.

  The polyamide resin (A) preferably has a sample concentration in concentrated sulfuric acid of 0.2 g / dL and a ηinh measured at 30 ° C. in the range of 0.4 to 3.0 dL / g, 0.5 to 2 More preferably within the range of 0.0 dL / g, even more preferably within the range of 0.6 to 1.5 dL / g. When one having ηinh in the above range is used, a polyamide resin composition that gives a molded article having more excellent heat resistance, mechanical strength and the like can be obtained.

  The polyamide resin (A) preferably has a melting point of 260 to 350 ° C. from the viewpoint of heat resistance and moldability.

[Fibrous or needle filler (B)]
Examples of the fibrous or acicular filler (B) used in the present invention include glass fiber, carbon fiber, wholly aromatic polyamide fiber (for example, polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene). Fibrous fillers such as isophthalamide fiber, polymetaphenylene isophthalamide fiber, fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid), boron fiber, liquid crystal polyester fiber, basalt fiber, etc .; potassium titanate whisker, Examples thereof include needle-shaped fillers such as aluminum borate whisker, calcium carbonate whisker, wollastonite, and zonotlite. These may be used alone or in combination of two or more. Especially, since the mechanical characteristics, heat resistance, and dimensional characteristics of the obtained molded body are further improved, at least one selected from the following group is preferable, and glass fibers are more preferable.
Fibrous filler: glass fiber, carbon fiber, wholly aromatic polyamide fiber Needle-shaped filler: potassium titanate whisker, aluminum borate whisker, calcium carbonate whisker, wollastonite, zonotlite

  The average length of the fibrous or needle-like filler (B) is preferably in the range of 1 μm to 20 mm from the viewpoint of maintaining good moldability and improving the mechanical properties and heat resistance of the obtained molded body. More preferably, it is in the range of 5 μm to 10 mm, and still more preferably in the range of 10 μm to 5 mm. The aspect ratio is preferably in the range of 3 to 2000, and more preferably in the range of 10 to 600.

  The cross section of the fibrous or needle-like filler (B) is preferably an irregular cross-sectional shape. The cross section of the filler is a cut surface when cut along a plane perpendicular to the longitudinal direction of the filler, and the irregular cross sectional shape is, for example, an eyebrow, ellipse, semi-circle, rectangle, multiple Non-circular cross sections such as a square and a star are listed. The deformed cross-sectional shape is preferably such that the deformed ratio D1 / D2 represented by the cross-sectional major axis D1 and the cross-sectional minor axis D2 is in the range of 1.2 to 10, and more preferably in the range of 1.5 to 6. When the deformation ratio is within the above range, the draw-down resistance of the polyamide resin composition, the mechanical strength (particularly, the strength in the TD direction), and the surface property of the blow molded product are improved.

  Regarding the content of the fibrous or acicular filler (B), when the polyamide resin (A) is 100 parts by mass, the lower limit value needs to be 10 parts by mass, preferably 12 parts by mass, Part by mass is more preferable. The upper limit value needs to be 100 parts by mass, preferably 40 parts by mass, and more preferably 30 parts by mass. By setting the content of the fibrous or needle-like filler (B) to 10 parts by mass or more, the mechanical strength of the blow-molded product obtained by the present invention can be increased. The drawdown property can be improved.

  The fibrous or needle-like filler (B) may be subjected to a surface treatment from the viewpoint of improving adhesion with the polyamide resin (A) which is a matrix resin and improving the mechanical properties of the polyamide resin composition. Examples of the surface treatment agent in the surface treatment include coupling agents such as silane coupling agents, titanium coupling agents, and aluminate coupling agents, and bundling agents. Preferred coupling agents include aminosilane, epoxy silane, methyltrimethoxysilane, methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, and vinyltrimethoxysilane. Examples of the sizing agent that can be suitably used include epoxy compounds, urethane compounds, carboxylic acid compounds, urethane / maleic acid-modified compounds, and urethane / amine-modified compounds. These surface treatment agents may be used alone or in combination of two or more. In particular, when a coupling agent and a sizing agent are used in combination, the adhesion between the fibrous or needle-like filler (B) and the polyamide resin (A) is further improved, and the mechanical properties of the resulting polyamide resin composition are further improved. . The surface-treated fibrous or acicular filler (B) has a mass decrease when heated at 625 ± 20 ° C. for 10 minutes or more based on the total mass of the surface-treated fibrous or acicular filler (B). It is preferably within a range of 0.01 to 8.0% by mass, and more preferably within a range of 0.1 to 5.0% by mass.

[Dye (C)]
The dye (C) used in the present invention has a 5% heat loss temperature of 280 ° C. or higher. By using the dye (C) having such a 5% heat loss temperature, the resulting polyamide resin composition can be melted. Residence stability can be improved. The 5% heat loss temperature of the dye (C) is preferably 290 ° C or higher, more preferably 295 ° C or higher, and further preferably 300 ° C or higher.

  The reason why the melt residence stability of the polyamide resin composition obtained by using the dye (C) having a 5% heat loss temperature of 280 ° C. or higher can be improved is not clear. It is estimated that radicals, hydrochloric acid, etc.) accelerate the deterioration of the polyamide.

  As the dye (C), an azine dye is preferable from the viewpoint that the surface property of the molded product obtained by molding the polyamide resin composition of the present invention can be remarkably improved. Examples of the azine dye include aniline and A mixture of azine compounds such as triphenazine osazine and phenazine azine obtained by using nitrobenzene and hydrochloric acid as main raw materials and ferric oxide or the like as a catalyst can be used. Note that not all azine dyes such as the above azine compounds have a 5% heat loss temperature of 280 ° C. or higher as shown in Examples and Comparative Examples described later. Therefore, in order to obtain a dye (C) having a 5% heat loss temperature of 280 ° C. or higher, the 5% heat loss temperature may be actually measured for azine dyes and the like and appropriately selected. The 5% heat loss temperature can be obtained as a temperature at which the weight is reduced by 5%, for example, by using a thermogravimetric analyzer and measuring under an inert gas stream under a temperature rising rate of 10 ° C./min. .

  It is preferable to use a dye (C), particularly an azine dye, having a low chlorine content. Dye (C), especially azine dyes, tend to have a higher 5% heat loss temperature when the chlorine content is lower, and the amount of hydrochloric acid generated by heating during melt residence decreases, resulting in polyamide resin (A ) Is suppressed. For this reason, higher melt residence stability is obtained by using the dye (C) having a low chlorine content. As a chlorine content rate, 0.08 mass% or less is preferable with respect to the total mass of dye (C), and 0.06 mass% or less is more preferable. As the dye (C), for example, NUBIAN BLACK TH-827 (manufactured by Orient Chemical Industry Co., Ltd.) can be used.

  Regarding the amount of the dye (C) used, if the amount is too small, the surface properties of the resulting blow molded article are poor, and if too large, the mechanical strength of the polyamide resin composition and the blow molded article is lowered. A) When it is 100 parts by mass, the lower limit value needs to be 0.05 parts by mass, and 1 part by mass is preferable. The upper limit value needs to be 5 parts by mass, and is preferably 3 parts by mass.

[Anti-drip agent (D)]
The polyamide resin composition of the present invention may further contain an anti-dripping agent (D).

  The anti-dripping agent (D) is, for example, a polymer or copolymer containing a fluoroethylene structure. Specific examples thereof include a difluoroethylene polymer, a tetrafluoroethylene polymer, and a tetrafluoroethylene-hexafluoropropylene copolymer. And a polyfluoroolefin resin such as a copolymer of tetrafluoroethylene and an ethylene monomer containing no fluorine atom. Among these, tetrafluoroethylene polymer (PTFE) is preferable.

  When a polyfluoroolefin-based resin is used as the anti-dripping agent (D), high drawdown resistance can be imparted by using a fibril forming ability. Here, the “fibril forming ability” means a property showing a tendency that the resins are bonded to each other by an external action such as a shearing force to form a fiber.

  Examples of the polyfluoroolefin-based resin having fibril-forming ability include Teflon 6-J (Mitsui / DuPont Fluoro Chemical Co., Ltd.), Polyflon F-201, Polyflon MPA PA-5000H, Polyflon FA-100 (Daikin Industries, Ltd.). ), Fullon CD076 (manufactured by Asahi Glass Co., Ltd.), Algoflon F5 (manufactured by Solvay Solexis Co., Ltd.), methabrene A3000 and methabrene A3700 (manufactured by Mitsubishi Rayon Co., Ltd.) which are acrylic resin modified polytetrafluoroethylene. The polyfluoroolefin-based resin having fibril-forming ability is, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, etc., under a pressure of about 7 to 700 kPa, at a temperature of about 0 to 200 ° C., Preferably, it can be obtained by polymerizing at 20 to 100 ° C. or by modifying PTFE with an acrylic resin. These polyfluoroolefin-based resins may be used alone or in combination of two or more.

When the dripping inhibitor (D) is contained, the melt viscosity at a low shear rate of the polyamide resin composition is increased, while the melt viscosity at a high shear rate is decreased. That is, the slope of the melt viscosity with respect to the shear rate becomes steep, leading to improvement of blow moldability. For example, the increase in viscosity in the low shear rate region contributes to the stability of the parison and the suppression of uneven thickness of the molded body. On the other hand, the decrease in viscosity in the high shear rate region acts to suppress melt fracture at the time of parison formation, and a molded product with small uneven thickness can be obtained. The slope of the melt viscosity with respect to the shear rate can be calculated from the following formula (2) by measuring the melt viscosity at an shear rate of 0.1 radians / second and 100 radians / second using an ARES parallel plate rheometer.
Melt viscosity ratio = (melt viscosity at 0.1 radians / second) ÷ (melt viscosity at 100 radians / second) (2)

  The viscosity ratio is preferably 10 or more, and more preferably 20 or more.

  Regarding the content of the anti-dripping agent (D), from the viewpoint of drawdown resistance and surface properties of the molded article, when the polyamide resin (A) is 100 parts by mass, the lower limit is preferably 0.1 parts by mass, 0.3 parts by mass is more preferable. The upper limit is preferably 10 parts by mass, and more preferably 4 parts by mass.

[Other ingredients]
The polyamide resin composition of the present invention has an affinity for other thermoplastic resins, thermosetting resins, other inorganic fillers, inorganic fillers and resins, as necessary, as long as the effects of the present invention are not impaired. Coupling agent, crystal nucleating agent, copper stabilizer, hindered phenol antioxidant, hindered amine antioxidant, phosphorus antioxidant, thio antioxidant, UV absorber, light stability Other components such as an agent, an antistatic agent, a lubricant, a plasticizer, a lubricant, a flame retardant, a flame retardant aid, and a processing aid may be contained.

[Production Method of Polyamide Resin Composition]
The method for producing the polyamide resin composition of the present invention may be a method in which the polyamide resin (A), the fibrous or needle-like filler (B), the dye (C) and other components as required can be mixed uniformly. Usually, a melt kneading method is employed. The melt-kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, and the melt-kneading conditions are not particularly limited. For example, from the melting point of the polyamide resin (A) Also, the polyamide resin composition of the present invention can be obtained by kneading for 1 to 30 minutes at a temperature range of 30 to 50 ° C.

[Molded body]
The polyamide resin composition of the present invention is thermoplastic, such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, assist molding, etc., depending on the type, application, shape, etc. of the target molded product. Various molded bodies can be produced by applying a molding method generally used for the resin composition. Moreover, you may employ | adopt the shaping | molding method which combined said shaping | molding method. Furthermore, the polyamide resin composition of the present invention can be formed into a composite molded body obtained by bonding, welding, or bonding to various materials such as various thermoplastic resins, thermosetting resins, paper, metal, wood, and ceramics.

  The polyamide resin composition of the present invention is excellent in heat retention, mechanical strength, chemical resistance, and surface properties in addition to excellent melt residence stability. Moreover, since it is excellent also in drawdown resistance, it can utilize suitably for blow molding. As a method for obtaining a blow molded article, a conventionally known blow molding method can be used. Examples include a direct blow method, an accumulator blow method, a multidimensional blow method, and the like. It is also possible to apply a multilayer blow molding method, an exchange blow molding method or the like used in the combination. It is also possible to obtain a multilayer structure by co-extrusion with polyolefin such as polyethylene and other thermoplastic resins, followed by blow molding. In that case, an adhesive layer may be provided between the polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of a multilayer structure, a blow molded article having excellent heat resistance and chemical resistance can be obtained by arranging the layer of the polyamide resin composition of the present invention in the inner layer.

  Since the molded article of the present invention is excellent in heat resistance, mechanical strength, chemical resistance, and surface properties, it can be used for articles that come into contact with a high-temperature gas of 60 ° C. or higher and / or a high-temperature chemical solution. In particular, it can be used as an automobile pipe, for example, an intake / exhaust pipe through which a high-temperature gas passes, and is particularly suitable for an automobile EGR (exhaust gas recirculation) pipe. In recent years, the amount of exhaust gas returning to the intake manifold in EGR is increasing from the viewpoint of fuel efficiency improvement and exhaust gas regulation, and accompanying this, acidic condensed water derived from SOx or NOx may adhere to the pipe portion. The blow molded article of the present invention is also suitable for such an EGR pipe to which acidic condensed water adheres. The blow molded article of the present invention is also suitable for a refrigerant pipe for automobiles. For example, the blow molded article can be used for a cooling system refrigerant pipe through which a high-temperature radiator liquid passes and an air conditioner system refrigerant pipe through which a refrigerant for air conditioner such as chlorofluorocarbon passes. It is. The blow molding of the present invention is also used as an air conditioner system refrigerant pipe through which an air conditioner refrigerant containing a compound having a double bond between carbon atoms such as HFO-1234yf, which is planned to be introduced as an alternative refrigerant to conventional chlorofluorocarbons. The body is suitable from the viewpoint of chemical resistance. It can also be used for fuel system pipes that come into contact with high-temperature fuel in the engine room.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In the following examples and comparative examples, the 5% heat loss temperature and chlorine content of the dye, the melting point of the polyamide resin, the solution viscosity, the terminal amino group content, the viscosity ratio of the melt viscosity of the polyamide resin composition, and the melt viscosity The rate of change, the tensile strength, the chemical resistance, the thickness difference and the surface property of the molded article of the polyamide resin composition were measured by the following methods.

<5% heat loss temperature>
The 5% heat loss temperature of the dyes used in the following examples and comparative examples was measured using a thermogravimetric analyzer (TC15) manufactured by METTLER TOLEDO Co., Ltd. under a nitrogen stream under a temperature rising rate of 10 ° C / min. The weight change was measured while heating from 50 ° C. to 500 ° C., and the temperature (° C.) when the weight of the sample decreased by 5% was obtained.

<Chlorine content>
The chlorine content of the dyes used in the following examples and comparative examples is 10 times the sample solution obtained by the oxygen flask combustion method using 10 mg of the sample and 25 mL of ultrapure water as the absorbing solution with the eluent. It diluted and measured with the ion chromatograph (DX-500) by a Dionex company. The measurement conditions are described below.
Column: IonPac AG12A, AS12A (4 mmφ × 250 mm)
Eluent: 0.3 mM NaHCO ₃ and 2.7 mM Na ₂ CO ₃
Eluent flow rate: 1.2 mL / min
Detector: Electric conductivity detector

<Melting point>
Using a differential scanning calorimeter (DSC822) manufactured by METTLER TOLEDO Co., Ltd., using the polyamide resin used in the following examples and comparative examples, from 30 ° C. to 340 ° C. at 10 ° C./min under a nitrogen atmosphere The sample was heated at 340 ° C. and held at 340 ° C. for 2 minutes to completely melt the sample, then cooled to 30 ° C. at a rate of 10 ° C./min and held at 30 ° C. for 2 minutes. The peak temperature of the melting peak that appears when the temperature is raised again to 360 ° C. at a rate of 10 ° C./min is the melting point (° C.). If there are multiple melting peaks, the peak temperature of the melting peak at the highest temperature is the melting point (° C.) It was used as an index of heat resistance.

<Solution viscosity>
The polyamide resin 50 mg used in the following Examples and Comparative Examples was dissolved in 25 mL of 98% concentrated sulfuric acid in a measuring flask, and the falling time (t) of the obtained solution at 30 ° C. was measured with an Ubbelohde viscometer. The solution viscosity ηinh (dL / g) was calculated from the following formula (3) from the falling time (t ₀ ) of concentrated sulfuric acid.
ηinh (dL / g) = {ln (t / t ₀ )} / 0.2 (3)

<Terminal amino group content>
1 g of the polyamide resin used in the following examples and comparative examples was dissolved in 35 mL of phenol, and 2 mL of methanol was mixed therewith to obtain a sample solution. Titration was performed using thymol blue as an indicator and a 0.01 N hydrochloric acid aqueous solution, and the terminal amino group content ([NH ₂ ], unit: μmol / g) was measured.

<Terminal carboxyl group content>
0.2 g of polyamide resin used in the following Examples and Comparative Examples was added to 15 mL of o-cresol, and heated to 110 ° C. to dissolve. After cooling to near room temperature, 10 mL of benzyl alcohol, 50 mL of o-cresol and 50 μL of formaldehyde were added. The terminal carboxyl group content ([COOH], unit: μmol / g) was measured with a potentiometric titrator using 0.05N ethanolic potassium hydroxide as a titrant.

<Viscosity ratio of melt viscosity>
Using the polyamide resin compositions of the following examples and comparative examples, using a compression molding machine, the molding temperature is 150 mm long × 150 mm wide × 1 mm thick at a molding temperature 10-30 ° C. higher than the melting point of the polyamide resin. A flat plate was produced. From the obtained flat plate, a circular molded body having a diameter of 25 mm was cut out and subjected to measurement of melt viscosity. The melt viscosity was measured using an ARES parallel plate rheometer (Rheometrics) at a measurement temperature 15 ° C. higher than the melting point of the polyamide resin at 0.1 radians / second and 100 radians / second. Was measured respectively. The viscosity ratio was calculated from the above mathematical formula (2) and used as an index of the drawdown resistance.

<Change rate of melt viscosity>
About the polyamide resin composition of the following examples and comparative examples, using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a barrel temperature of 320 ° C. and a shear rate of 121.6 sec ⁻¹ (capillary: inner diameter 1.0 mm × length 10 mm) As an extrusion speed of 10 mm / min), a melt viscosity M1 having a melting time of 4 minutes and a melt viscosity M2 having a melting time of 15 minutes were determined. Using these M1 and M2, the change rate (%) of the melt viscosity was calculated from the following mathematical formula (4) and used as an index of melt residence stability.
Change rate of melt viscosity (%) = (M2−M1) / M1 × 100 (4)

<Tensile strength>
Using an injection molding machine manufactured by Toshiba Machine Co., Ltd. (clamping force: 80 tons, screw diameter: φ32 mm), the cylinder temperature is 20-30 ° C. higher than the melting point of the polyamide resin, and the glass transition temperature of the polyamide resin. Under the conditions of a mold temperature higher by 20 to 30 ° C., using a T-runner mold, an ISO multipurpose test piece A type dumbbell was prepared from the polyamide resin compositions (pellets) of the following examples and comparative examples, It was set as the test piece for tensile strength evaluation. Using the obtained test piece, the tensile strength (MPa) at 23 ° C. was measured according to ISO 527-1 using an autograph (manufactured by Shimadzu Corporation), and used as an index of mechanical strength. .

<Chemical resistance>
Using the polyamide resin compositions of the following examples and comparative examples, injection molding (mold temperature: 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of the polyamide resin to produce an ISO multipurpose test piece A type. . The tensile strength of this specimen was measured according to ISO 527. Subsequently, the ISO multipurpose test piece A produced in the same manner was immersed in an aqueous solution obtained by diluting a Toyota Super Long Life Coolant (pink) with water twice, and the tensile strength after being immersed at 130 ° C. for 500 hours was determined as ISO. Measured according to 527. By calculating the ratio (%) of the tensile strength of the test piece after immersion to the tensile strength of the test piece before immersion, it was used as an index of chemical resistance.

<Thickness difference>
Using the polyamide resin compositions of the following Examples and Comparative Examples, using a blow molding machine (JSW JB105, die diameter Φ21 mm, core diameter Φ18.5 mm), a molding temperature that is 10 to 30 ° C. higher than the melting point of the polyamide resin The 500 mL container 1 which has the narrow mouth 2 in the upper part was shape | molded (FIG. 1). The thickness of the container portion located 5 cm upward from the bottom surface 3 of the obtained container is T1, and the thickness of the container portion located further 5 cm upward from there is T2, and using the following formula (5), The thickness difference (mm) was calculated and used as an index of blow moldability.
Thickness difference (mm) = T1-T2 (5)

<Surface property>
The appearance of the container produced during the evaluation of the thickness difference was observed, and the surface property was evaluated using the following indices.
◎: No glass fiber fluffing ○: Some glass fiber fluffing is observed ×: Glass fiber fluffing, unevenness is observed

  The polyamide resin, fibrous or acicular filler, dye, and anti-dripping agent used in each example and comparative example are described below.

<Synthesis of Polyamide Resin A-1>
9870.6 g (59.42 mol) of terephthalic acid, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [former / latter = 80/20 (molar ratio)] 9497.4 g (60.00 Mol), 142.9 g (1.17 mol) of benzoic acid, 19.5 g of sodium hypophosphite monohydrate (0.1% by mass with respect to the total mass of the raw material) and 5 liters of distilled water in an internal volume of 40 It was put into a liter autoclave and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the temperature inside the autoclave was increased to 220 ° C. over 2 hours. At this time, the pressure inside the autoclave was increased to 2 MPa. The reaction was continued as it was for 2 hours, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2 MPa. Next, the pressure was reduced to 1 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer having ηinh of 0.16 dL / g. This was pulverized to a particle size of 2 mm or less using a flake crusher manufactured by Hosokawa Micron Corporation, dried at 100 ° C. under reduced pressure for 12 hours, and then solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours. Melting point is 304 ° C., ηinh is 1.30 dL / g, terminal amino group content ([NH ₂ ]) is 10 μmol / g, terminal carboxyl group content ([COOH]) is 60 μmol / g, and terminal blocking ratio is 46 % White polyamide resin was obtained.

<Synthesis of polyamide resin A-2>
According to the same production method as that for polyamide resin A-1, except that the ratio of the mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was changed to the former / the latter = 50/50 (molar ratio), the melting point Is 265 ° C., ηinh is 1.30 dL / g, terminal amino group content ([NH ₂ ]) is 10 μmol / g, terminal carboxyl group content ([COOH]) is 60 μmol / g, and terminal blocking ratio is 46%. A white polyamide resin was obtained.

<Synthesis of polyamide resin A-3>
The amount of terephthalic acid used was 9861.5 g (59.36 mol), and 1,9-nonanediamine and 2-methyl-1,8-octanediamine mixture 9497.4 (60.00 mol) were added to 1,10-decane. The amount of benzoic acid used is 156.3 g (1.28 mol), the amount of sodium hypophosphite monohydrate used is 20.4 g (total mass of raw materials) The melting point is 318 ° C., the intrinsic viscosity ηinh is 1.30 dL / g, and the terminal amino group content ([NH ₂ ]) is the same as in the polyamide resin A-1, except that the content is changed to 0.1% by mass. ) Was 10 μmol / g, the terminal carboxyl group content ([COOH]) was 58 μmol / g, and a white polyamide having a terminal blocking rate of 48% was obtained.

<Fibrous or needle filler (B)>
<B-1> “CS-3J-256” (glass fiber) manufactured by Nitto Boseki Co., Ltd., the cross-sectional shape is circular (amorphous ratio = 1), the diameter is 11 μm, and the fiber length is 3 mm.
<B-2> “CSH 3PA-870” (glass fiber) manufactured by Nitto Boseki Co., Ltd., fiber cross-sectional shape is eyebrows (different shape ratio = 2), major axis 20 μm, fiber length 3 mm
<B-3> “CSH 3PA-820” (glass fiber) manufactured by Nitto Boseki Co., Ltd., fiber cross-sectional shape is a rectangle (different shape ratio = 4), major axis 28 μm, fiber length 3 mm

<Dye>
<C-1> “Nubian Black TH-827” (azine-based dye) manufactured by Orient Chemical Industries, Ltd., 5% heat loss temperature = 301 ° C., chlorine content 0.04% by mass
<C-2> “Nubian Black AH-827” (azine dye) manufactured by Orient Chemical Co., Ltd., 5% heat loss temperature = 276 ° C., chlorine content 1.8% by mass
<C-3> “Nubian Black PA-2800” (azine dye) manufactured by Orient Chemical Industries, Ltd., 5% heat loss temperature = 268 ° C., chlorine content 2.3 mass%

<Anti-dripping agent>
“Metablene A3000” (acrylic modified PTFE) manufactured by Mitsubishi Rayon Co., Ltd.

(About Examples 1-10 and Comparative Examples 1-2)
After preliminarily mixing the polyamide resin and other components in the proportions shown in Table 1, they were put all together into the supply port of the same-direction rotating twin-screw extruder (“TEM-26SS” manufactured by Toshiba Machine Co., Ltd.). After melt-kneading under conditions of a cylinder temperature 30 ° C. higher than the melting point of the polyamide resin, it was extruded into a strand, cooled and cut to produce a pellet-like polyamide resin composition. The various physical property evaluations described above were performed using the obtained pellets. The results are shown in Table 1.

  Since Examples 1-10 contain the dye <C-1> having a 5% heat loss temperature of 280 ° C. or higher, heat resistance, drawdown resistance, melt residence stability, mechanical strength, chemical resistance, Blow moldability and surface properties were good. In Examples 4 to 7 and 10, the results of further improving the drawdown resistance and blow moldability were obtained while combining the melt retention stability and surface properties by further combining the anti-drip agent. On the other hand, Comparative Examples 1 and 2 were inferior in melt residence stability because the dyes <C-2> and <C-3> having a 5% heat loss temperature of less than 280 ° C. were used.

  Various molded articles can be provided using the polyamide resin composition of the present invention. In particular, the polyamide resin composition of the present invention is advantageous for providing a blow molded article. The molded body containing the polyamide resin composition of the present invention is useful as an automobile pipe or the like.

1 container 2 narrow mouth 3 bottom

Claims (17)

Polyamide resin (A),
10 to 100 parts by mass of fibrous or needle-like filler (B) with respect to 100 parts by mass of the polyamide resin (A), and 0.05 to 5 parts by mass of dye with respect to 100 parts by mass of the polyamide resin (A) A polyamide resin composition containing (C),
The polyamide resin composition, wherein the dye (C) is an azine dye having a 5% heat loss temperature of 290 ° C or higher.   The said polyamide resin (A) contains 50-100 mol% of C4-C18 aliphatic diamine units in all the diamine units which comprise the said polyamide resin (A), and comprises the said polyamide resin (A). 2. The polyamide resin composition according to claim 1, comprising 50 to 100 mol% of an aromatic dicarboxylic acid unit and / or an alicyclic dicarboxylic acid unit in all dicarboxylic acid units.   The aliphatic diamine units are 1,4-butanediamine units, 1,5-pentanediamine units, 1,6-hexanediamine units, 2-methyl-1,5-pentanediamine units, 1,8-octanediamine units. The polyamide resin composition according to claim 2, which is at least one selected from the group consisting of 1,9-nonanediamine units, 2-methyl-1,8-octanediamine units and 1,10-decanediamine units.   The polyamide resin composition according to claim 3, wherein the aliphatic diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit.   The polyamide resin composition according to any one of claims 2 to 4, wherein the aromatic dicarboxylic acid unit is a terephthalic acid unit.   The polyamide resin composition according to any one of claims 2 to 5, wherein the alicyclic dicarboxylic acid unit is a 1,4-cyclohexanedicarboxylic acid unit.   The polyamide resin composition according to any one of claims 2 to 6, wherein the polyamide resin (A) further contains a lactam unit and / or an aminocarboxylic acid unit.   The polyamide resin composition in any one of Claims 1-7 whose melting | fusing point of the said polyamide resin (A) is 260-350 degreeC.   The polyamide resin composition according to any one of claims 1 to 8, wherein the fibrous or acicular filler (B) has an irregular cross-sectional shape.   The polyamide resin composition according to claim 9, wherein a deformed ratio D1 / D2 of the deformed cross-sectional shape represented by the cross-sectional major axis D1 and the cross-sectional minor axis D2 of the fibrous or needle-like filler (B) is 1.2 to 10. object.   The polyamide resin composition according to any one of claims 1 to 10, wherein the fibrous or acicular filler (B) is a glass fiber. The polyamide resin composition according to any one of claims 1 to 11, wherein the azine dye (C) is an azine dye having a 5% heat loss temperature of 300 ° C or higher.   The polyamide resin composition in any one of Claims 1-12 whose chlorine content rate of the said dye (C) is 0.08 mass% or less with respect to the total mass of the said dye (C).   The polyamide resin composition according to any one of claims 1 to 13, further comprising 0.1 to 10 parts by mass of an anti-dripping agent (D) with respect to 100 parts by mass of the polyamide resin (A).   The molded object containing the polyamide resin composition in any one of Claims 1-14.   The blow molded object containing the polyamide resin composition in any one of Claims 1-14.   The EGR pipe for motor vehicles containing the blow molded object of Claim 16.

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