JP2019108526A - Polyamide resin composition for deposition, and molded article using the same - Google Patents

Abstract

To provide a polyamide resin composition for deposition capable of providing a molded article excellent in balance of tensile elongation and tensile strength of a weld part.SOLUTION: There is provided a polyamide resin composition for deposition by blending a glass fiber (C) of 3 to 9 pts.wt. to total 100 pts.wt. of a polyamide resin (A) of 90 to 99.99 pts.wt. and an amide-based wax (B) of 0.01 to 10 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition for welding, which is obtained by blending specific amounts of a polyamide resin, an amide wax and a glass fiber, and a molded article formed by molding the same.

  Polyamide resins are widely used as injection molded articles in the fields of automobiles and machine parts, taking advantage of their excellent injection moldability, heat resistance, toughness, oil and gasoline resistance, abrasion resistance, etc. . Basically, the development process of polyamide resin in the above-mentioned field mainly substitutes for metal materials, and the practical use has been advanced from parts having many advantages such as weight reduction and rustproofing. Furthermore, as the development of high performance and molding processing technology of polyamide resin materials has recently been made, application of polyamide resin to parts with large and complicated shapes, for which resinification has been difficult in the prior art, is considered. It has become. In order to resinify parts with such a high degree of difficulty, it is not enough to use only single molding techniques such as injection molding, extrusion molding and blow molding, but it is necessary to combine post processing techniques such as cutting, bonding and welding. . However, the design of the conventional polyamide resin material can not be considered in consideration of the applicability to such post-processing, for example, in the case of welding and using a glass fiber reinforced polyamide resin molded product consisting of two or more parts, There is a problem that the use is limited because the tensile strength of the welded portion is insufficient.

  As a material which is excellent in flowability and high cycleability at the time of molding and which has high strength by various welding methods, for example, a polyamide resin composition comprising a crystalline polyamide resin having a specific amino end group concentration and an inorganic filler is examined. (See, for example, Patent Document 1).

  Moreover, as a material which can express welding characteristics such that the welded portion does not become a defect in strength and can improve the durability of the welded joint, for example, polyxylene adipamide, hexamethylene diamine and terephthalic acid and ε-caprolactam The polyamide based molding material which consists of a copolyamide of these, and a filler is examined (for example, refer patent document 2).

Japanese Patent Application Laid-Open No. 2002-30215 JP, 2009-96903, A

  When a molded article made of a glass fiber reinforced polyamide resin composition is used by welding, for example, in the use, such as a high pressure tank liner where strain is applied at the time of use, the tensile elongation is If this is insufficient, there is a problem that a crack is generated from the weld and the use is limited. Therefore, not only high tensile strength of the weld but also high tensile elongation of the weld is required in applications where strain is applied during use.

  However, the polyamide resin composition described in Patent Document 1 has a problem that although the tensile strength of the welded portion is high, the tensile elongation is low.

  Moreover, the polyamide-based molding material described in Patent Document 2 similarly has a problem that although the tensile strength of the welded portion is high, the tensile elongation is low.

  An object of the present invention is to provide a polyamide resin composition capable of obtaining a molded article excellent in the balance between tensile strength and tensile elongation of a welded portion, in view of the above-mentioned problems of the prior art.

  In order to achieve the above object, the present invention has the following constitution.

  3 to 9 parts by weight of glass fiber (C) with respect to a total of 100 parts by weight of polyamide resin (A) 90 to 99.99 parts by weight and amide-based wax (B) 0.01 to 10 parts by weight Polyamide resin composition for welding.

  The present invention includes a molded article having a weld formed of the above polyamide resin composition.

  The present invention includes a method for producing a molded article in which a molded article having the above-mentioned welded portion is joined by any welding method selected from hot plate welding, infrared welding, vibration welding, laser welding and infrared / vibration welding. .

  The polyamide resin composition for welding of the present invention is excellent in the balance between tensile strength and tensile elongation at the welded portion, and can take advantage of the property of being able to suppress the generation of cracks at the welded portion even when used under an environment where strain is applied. It becomes possible to develop usefully as a molded article which has a welding part.

  Hereinafter, the present invention will be described in more detail.

  The polyamide resin composition for welding of the present invention (hereinafter sometimes referred to as "polyamide resin composition") comprises 90 to 99.99 parts by weight of a polyamide resin (A) and an amide wax (B) 0.01 to 10 3 to 9 parts by weight of glass fiber (C) is blended with 100 parts by weight in total of parts by weight. By blending a specific amount of an amide-based wax (B) with the polyamide resin (A) excellent in the balance of moldability, rigidity and toughness, a dense and uniform crystal is formed, so the tensile elongation of the welded portion Excellent. Furthermore, by compounding the glass fiber (C) which is excellent in rigidity in a specific amount, it is possible to obtain a molded article which is excellent in the balance between the tensile strength and the tensile elongation at the welded portion. On the other hand, when the combination of only the polyamide resin (A) and the glass fiber (C) or the blending amount of the glass fiber (C) is large, the tensile strength of the welded portion is improved but the tensile elongation is lowered.

  The polyamide resin (A) used in the present invention is a resin composed of a polymer having an amide bond, and is mainly composed of an amino acid, a lactam or a diamine and a dicarboxylic acid. Representative examples of the raw material include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, lactams such as ε-caprolactam, ω-laurolactam, tetramethylene diamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylene Diamines, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4 -Aminocyclohexene Aliphatic, alicyclic or aromatic such as sil) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine Family diamines and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid And aliphatic, alicyclic and aromatic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, and in the present invention, polyamide homopolymers or copolymers derived from these raw materials may be used alone. Or in the form of a mixture. Two or more such polyamide resins may be blended.

  In the present invention, specific examples of the polyamide resin (A) particularly useful include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), Polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polyhexamethylene dodecamide (polyamide 612), porundecane amide (polyamide 11) Polydodecane amide (polyamide 12), polycaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhe Samethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 66 / 6I / 6), polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / polydodecane amide copolymer (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide MXD6), polyhexamethylene terephthalamide / poly-2-methylpentamethyle Terephthalamide copolymer (polyamide 6T / M5T), polyhexamethylene terephthalamide / poly pentamethylene terephthalamide copolymer (polyamide 6T / 5T), and mixtures thereof or copolymers, and the like.

  Particularly preferable examples include polyamide 6 resin, polyamide 66 resin, polyamide 610 resin, polyamide 11 resin, polyamide 12 resin, polyamide 6/66 copolymer, polyamide 6/12 copolymer and the like. Particularly preferable examples include polyamide 6 resin, polyamide 66 resin, and polyamide 610 resin, and more preferably polyamide 6 resin. Furthermore, it is also practically preferable to use these polyamide resins as a mixture.

  The degree of polymerization of the polyamide resin (A) is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Is preferred. When the relative viscosity is 1.5 or more, the melt viscosity of the polyamide resin composition at the time of molding is appropriately increased, air entrainment at the time of molding can be suppressed, and the moldability can be further improved. The relative viscosity is more preferably 1.8 or more. On the other hand, when the relative viscosity is 7.0 or less, the melt viscosity at the time of molding of the polyamide resin composition becomes appropriately low, and the moldability can be further improved.

There is no particular limitation on the amino end groups of the polyamide resin (A), the it is preferably in the range of ^{1.0 × 10 -5 ~10.0 × 10 -5} mol / g. If the amount of amino end groups is in the range of 1.0 × 10 ^{−5 to} 10.0 × 10 ⁻⁵ mol / g, a sufficient degree of polymerization can be obtained, and the mechanical strength of the molded article can be improved. Here, the amount of amino end groups of the polyamide resin can be determined by dissolving the polyamide resin in a phenol / ethanol mixed solvent (83.5: 16.5 (volume ratio)) and titrating with a 0.02 N hydrochloric acid aqueous solution. It can be asked.

  The amide wax (B) used in the present invention includes an amide compound obtained by reacting a monocarboxylic acid and a diamine, an amide compound produced by reacting a monoamine and a polybasic acid, a monocarboxylic acid, a polybasic acid and a diamine. The amide compound etc. which are made to react are mentioned. These can be obtained by the dehydration reaction of corresponding amines and carboxylic acids.

  The monoamine is preferably a monoamine having 5 or more carbon atoms, and specific examples thereof include pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, stearylamine, cyclohexylamine and benzylamine. These may be used in combination of two or more. Among them, higher aliphatic monoamines having 10 to 20 carbon atoms are particularly preferable. When the carbon number is more than 20, the compatibility with the polyamide resin (A) is reduced, and there is a risk of precipitation.

  The monocarboxylic acid is preferably an aliphatic monocarboxylic acid having 5 or more carbon atoms and a hydroxycarboxylic acid. Specific examples thereof include valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, olein An acid, linoleic acid, behenic acid, montanic acid, 12-hydroxystearic acid, benzoic acid and the like may be mentioned, and two or more of these may be used in combination. Among them, higher aliphatic monocarboxylic acids having 10 to 30 carbon atoms are particularly preferable. When the carbon number is more than 30, the compatibility with the polyamide resin (A) is reduced, and there is a possibility of precipitation.

  Specific examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine And p-xylylenediamine, tolylenediamine, phenylenediamine, isophoronediamine and the like, and two or more of these may be used in combination. Among them, ethylenediamine is particularly preferable.

  The polybasic acid is a carboxylic acid having a dibasic acid or more, and specific examples thereof include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, azelaic acid, phthalic acid, and terephthalic acid Examples thereof include acids, aromatic dicarboxylic acids such as isophthalic acid, and cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid, and two or more of these may be used in combination.

  Among them, amide compounds obtained by reacting higher aliphatic monocarboxylic acids, polybasic acids and diamines are particularly preferable, and for example, amide compounds obtained by reacting stearic acid, sebacic acid and ethylenediamine are preferable. The mixing ratio of each component at that time is preferably in the range of 0.18 mol to 1.0 mol of polybasic acid and 1.0 mol to 2.2 mol of diamine with respect to 2 mol of higher aliphatic monocarboxylic acid. The range of 0.5 mol to 1.0 mol of a polybasic acid and 1.5 mol to 2.0 mol of a diamine is more preferable with respect to 2 mol of a higher aliphatic monocarboxylic acid.

  The glass fiber (C) used in the present invention is not particularly limited, and known ones can be used. By blending glass fiber with the polyamide resin composition of the present invention, the mechanical strength of the molded article can be enhanced. The glass fibers may be in the form of chopped strands, roving strands, milled fibers or the like cut to a predetermined length, and any of them may be used. The fiber diameter is not particularly limited, but preferably 4 to 20 μm. If the fiber diameter is 4 μm or more, the filling rate to the thin part of the molded product can be increased. On the other hand, if it is 20 μm or less, the number of glass fibers in the polyamide resin composition can be increased, and the reinforcing effect by the glass fibers can be easily obtained, whereby the mechanical strength can be enhanced. Here, the fiber diameter of glass fiber refers to the number average value of the fiber diameter of each glass fiber, and can be determined by the following method. The cross section (surface perpendicular to the longitudinal direction of the fiber) of the glass fiber is observed using SEM (scanning electron microscope), the maximum diameter and the minimum diameter are measured, and the average value is the fiber of each glass fiber Let the diameter. The fiber diameter of the glass fibers can be determined by calculating the number average value of the fiber diameters of ten glass fibers randomly selected. When using a chopped strand, the fiber length is not particularly limited, but a glass fiber with a strand length of 3 mm, which has high extrusion kneading workability, is preferably used. If roving strands are used, they can be compounded by known techniques in which the roving strands are introduced directly into the extruder. Two or more of these glass fibers may be used in combination.

  The glass fiber is preferably surface-treated with a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent to further improve the mechanical strength of the molded article. be able to. As a silane coupling agent, an aminosilane, an epoxysilane, an acrylsilane etc. are mentioned, for example.

  Moreover, it is preferable that glass fiber is coat | covered with a sizing agent (binding agent), and the workability at the time of melt-kneading can be improved. Furthermore, the effect of improving the mechanical strength of a molded article may be exhibited. Examples of the sizing agent (binding agent) include urethane resins, epoxy resins, acrylic resins, amino resins, vinyl acetate resins, and polyolefin resins.

  The polyamide resin composition of the present invention comprises 3 to 3 parts of glass fiber (C) per 100 parts by weight in total of 90 to 99.99 parts by weight of polyamide resin (A) and 0.01 to 10 parts by weight of amide wax (B). 9 parts by weight is blended.

  When the blending amount of the polyamide resin (A) is less than 90 parts by weight, the toughness of a molded article made of the obtained polyamide resin composition is lowered. 93 weight parts or more are preferable, and, as for the compounding quantity of a polyamide resin (A), 95 weight parts or more are more preferable. On the other hand, when the blending amount of the polyamide resin (A) is more than 99.99 parts by weight, the mold release property at the time of molding of the obtained polyamide resin composition, and the tensile strength and tensile elongation at the welded portion at the time of welding decrease. Do. 99.95 weight part or less is preferable, and, as for the compounding quantity of a polyamide resin (A), 99.9 weight part or less is more preferable. The compounding amount of the amide-based wax (B) is 0.01 to 10 parts by weight, preferably 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more. Also, 7 parts by weight or less is preferable, and 5 parts by weight or less is more preferable. When the amount of the amide-based wax (B) is less than 0.01 parts by weight, the mold release property at the time of molding of the resulting polyamide resin composition, and the tensile strength and tensile elongation at the welded portion at the time of welding decrease. . On the other hand, if the compounding amount of the amide-based wax (B) is more than 10 parts by weight, the toughness of a molded article made of the obtained polyamide resin composition is lowered. If the blending amount of glass fiber (C) is less than 3 parts by weight with respect to a total of 100 parts by weight of polyamide resin (A) and amide-based wax (B), the obtained polyamide resin composition in the welded portion at the time of welding The tensile strength is reduced. The compounding amount of the glass fiber (C) is preferably 4 parts by weight or more. On the other hand, if the compounding amount of the glass fiber (C) is more than 9 parts by weight, the tensile elongation at the welding portion at the time of welding of the obtained polyamide resin composition is lowered. The blending amount of the glass fiber (C) is preferably 8 parts by weight or less.

  The polyamide resin composition preferably further comprises an impact resistant material (D). By blending the impact resistant material (D), the impact resistance of the molded article can be improved.

  As the impact resistant material (D), for example, olefin resin, acrylic rubber, silicone rubber, fluorine rubber, styrene rubber, nitrile rubber, vinyl rubber, urethane rubber, polyamide elastomer, polyester elastomer, ionomer Etc. Two or more of these may be blended.

  Among these, olefin resins are preferably used because they are excellent in compatibility with the polyamide resin (A) and the amide wax (B) and have a high impact resistance improvement effect. The olefin resin is a thermoplastic resin obtained by polymerizing olefin monomers such as ethylene, propylene, butene, isoprene and pentene. The copolymer of 2 or more types of olefin monomers may be sufficient, and the copolymer of these olefin monomers and another monomer may be sufficient. Specific examples of the olefin resin include polymers such as polyethylene, polypropylene, polystyrene, poly 1-butene, poly 1-pentene and polymethylpentene or copolymers thereof; ethylene / α-olefin copolymer, ethylene / α, β-unsaturated carboxylic acid ester copolymer, α-olefin / α, β-unsaturated carboxylic acid ester copolymer, [copolymer of ((ethylene and / or propylene) and vinyl alcohol ester)] Polyolefins obtained by hydrolyzing a portion, copolymers of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), [(ethylene and / or propylene) and (unmodified Copolymer with saturated carboxylic acid and / or unsaturated carboxylic acid ester] Polyolefins obtained by at least a portion of the cyclohexyl group and a metal chloride, such as a block copolymer or its hydrogenation product of a conjugated diene and a vinyl aromatic hydrocarbons. Among these, ethylene / α-olefin copolymer and ethylene / α, β-unsaturated carboxylic acid ester copolymer are more preferable, and ethylene / α-olefin copolymer is more preferable.

  The olefin resin may be modified with an unsaturated carboxylic acid and / or a derivative thereof. Here, the derivative of unsaturated carboxylic acid is a compound in which the hydroxy group part of the carboxyl group of unsaturated carboxylic acid is substituted with another substituent, and metal salts of unsaturated carboxylic acid, acid halides, esters, acids Anhydrides, amides and imides etc. By using such a modified olefin-based resin, the compatibility with the polyamide resin (A) and the amide-based wax (B) can be further improved, and the impact resistance can be further improved. As unsaturated carboxylic acid or derivatives thereof, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid and carboxylic acids thereof Metal salts; methyl maleate, methyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, meta Unsaturated carboxylic acid esters such as hydroxyethyl acrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate; maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5 -Hepten- Acid anhydrides such as 3-dicarboxylic acid and endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride; maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl Maleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconate, 5-norbornene-2,3-dicarboxylic acid and the like can be mentioned. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid or maleic anhydride is particularly preferable.

  As a method of introducing these unsaturated carboxylic acids or derivatives thereof into olefin resins, for example, a method of copolymerizing an olefin monomer with an unsaturated carboxylic acid and / or a derivative thereof, using a radical initiator, The method etc. which graft-in unsaturated carboxylic acid and / or its derivative (s) etc. can be mentioned to unmodified | non_denatured olefin resin.

  As the ethylene / α-olefin copolymer, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferable. Specifically as a C3-C20 alpha-olefin, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like.Two or more of these may be used. Among these α-olefins, α-olefins having 3 to 12 carbon atoms are preferable from the viewpoint of improving mechanical strength. Furthermore, non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1'-propenyl) -2-norbornene and the like Or at least one of them may be copolymerized. Copolymer of ethylene modified with unsaturated carboxylic acid and / or derivative thereof and α-olefin having 3 to 12 carbon atoms further improves the compatibility with polyamide resin (A) and amide-based wax (B) And impact resistance can be further improved, which is more preferable. The α-olefin content in the ethylene / α-olefin copolymer is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, still more preferably 3 to 20 mol%.

  The structure of the impact resistant material (D) is not particularly limited. For example, a multilayer structure called a so-called core-shell type comprising at least one layer of rubber and one or more layers of different polymers therefrom. It may be The number of layers constituting the multilayer structure may be two or more, and may be three or more or four or more, but it is preferable to have one or more rubber layers (core layer) inside . The kind of rubber which comprises the rubber layer of a multilayer structure is not specifically limited, For example, an acryl component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene component, a propylene component, isobutene The rubber obtained by polymerizing a component etc. is mentioned. The types of different polymers constituting the layers other than the rubber layer of the multilayer structure are not particularly limited as long as they are thermoplastic polymers, but polymers having a glass transition temperature higher than that of the rubber layer are preferred. preferable. As the polymer having thermoplasticity, for example, unsaturated carboxylic acid alkyl ester unit, unsaturated carboxylic acid unit, unsaturated glycidyl group-containing unit, unsaturated dicarboxylic acid anhydride unit, aliphatic vinyl unit, aromatic vinyl unit, Included are polymers containing vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units.

  The compounding amount of the impact resistant material (D) in the polyamide resin composition is preferably 1 to 50 parts by weight with respect to 100 parts by weight in total of the polyamide resin (A) and the amide wax (B). Impact resistance can be further improved by setting the blending amount of the impact resistant material (D) to 1 part by weight or more. The blending amount of the impact resistant material (D) is more preferably 5 parts by weight or more, and further preferably 10 parts by weight or more. On the other hand, the rigidity can be further improved by setting the blending amount of the impact resistant material (D) to 50 parts by weight or less. The blending amount of the impact resistant material (D) is more preferably 45 parts by weight or less, still more preferably 40 parts by weight or less, and still more preferably 35 parts by weight or less.

  In the polyamide resin composition, other components other than the components (A), (B), (C) and (D) may be blended, if necessary, as long as the properties of the composition are not impaired. Examples of other components include fillers other than the components (A) to (D), thermoplastic resins, and various additives.

  For example, by blending a filler into the polyamide resin composition as another component, it is possible to further improve the strength, dimensional stability and the like of the resulting molded article. In addition, the filler applicable here does not contain what corresponds to (C) glass fiber. The shape of the filler may be fibrous or non-fibrous, and a fibrous filler and a non-fibrous filler may be used in combination. Examples of fibrous fillers include carbon fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, etc. Be Non-fibrous fillers include, for example, warastenite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, silicates such as alumina silicate; alumina, silicon oxide, magnesium oxide, oxide Metal oxides such as zirconium, titanium oxide and iron oxide; metal carbonates such as calcium carbonate, magnesium carbonate and dolomite; metal sulfates such as calcium sulfate and barium sulfate; magnesium hydroxide, calcium hydroxide and aluminum hydroxide And metal hydroxides, glass flakes, glass beads, ceramic beads, boron nitride and silicon carbide. These may be hollow. Also, it is preferable to use these fibrous and / or non-fibrous fillers by pre-treating with a coupling agent in the sense of obtaining better mechanical properties. Examples of the coupling agent include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, epoxy compounds and the like.

  As thermoplastic resins, for example, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polyacetal resin, polysulfone resin, tetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin Polyether sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, styrene resin such as polystyrene resin and ABS resin, polyalkylene oxide resin, etc. may be mentioned. It is also possible to blend two or more of such thermoplastic resins.

  As various additives, for example, anti-coloring agents, antioxidants such as hindered phenols and hindered amines, mold release agents, plasticizers, heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants, foaming agents, etc. Can be mentioned.

  It is preferable to add a copper compound to the polyamide resin composition because long-term heat resistance can be improved. As the copper compound, for example, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, cupric nitrate , Copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and the above inorganic copper halide and xylylene diamine, 2-mercaptobenzimidazole, benzimidazole And complex compounds such as Two or more of these may be blended. Among them, monovalent copper compounds, particularly monovalent copper halide compounds, are preferable, and cuprous acetate, cuprous iodide and the like are preferable. 0.01 weight part or more is preferable with respect to 100 weight part of polyamide resin (A), and, as for the compounding quantity of a copper compound, 0.015 weight part or more is more preferable. On the other hand, the amount of the copper compound is preferably 2 parts by weight or less, more preferably 1 part by weight or less, from the viewpoint of suppressing the coloration caused by the release of metallic copper during molding.

  Moreover, you may mix | blend a halogenated alkali compound with a copper compound. Examples of the halogenated alkali compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Two or more of these may be blended. Potassium iodide or sodium iodide is particularly preferred.

  Examples of the method for producing the polyamide resin composition of the present invention include production in a molten state and production in a solution state. From the viewpoint of productivity, production in the molten state can be preferably used. For production in the molten state, melt kneading using an extruder, a Banbury mixer, a kneader, mixing rolls, etc. can be used, and from the viewpoint of productivity, melt kneading using an extruder that can be continuously produced can be preferably used. Examples of the extruder include multi-screw extruders such as single-screw extruders, twin-screw extruders and four-screw extruders, and twin-screw single-screw composite extruders. A plurality of these extruders may be combined. From the viewpoint of improving the kneadability, reactivity, and productivity, multi-screw extruders such as a twin-screw extruder and a four-screw extruder are preferable, and a twin-screw extruder is more preferable.

  As a melt-kneading method using a twin-screw extruder, for example, components other than polyamide resin (A), amide wax (B), glass fiber (C) and, if necessary, (A) (B) (C) Are mixed in advance, and then supplied to a twin-screw extruder whose cylinder temperature is set to the melting point or more of the polyamide resin (A) to melt and knead. The mixing order of the raw materials is not particularly limited, and all raw materials are melt-kneaded by the above method, some raw materials are melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded, Any method may be used such as a method of mixing the remaining raw materials using a side feeder while melt-kneading some raw materials. Extruder root (The raw material is supplied on the upstream side, the molten resin is discharged on the side where the molten resin is discharged.) The polyamide resin (A), the amide wax (B) and, if necessary, other components other than (A) (B) It is preferable to adopt a method in which glass fibers (C) are introduced from the middle of the extruder using a side feeder and melt-kneaded after being melt-kneaded after being introduced downstream from the position of the upstream end of the screw). In addition, a method of removing the gas generated by exposing to vacuum state in the middle of the extruder is also preferably used.

  The polyamide resin composition of the present invention can be molded by any method to obtain a molded part. Examples of the molding method include extrusion molding, injection molding, hollow molding, calender molding, compression molding, vacuum molding, foam molding, blow molding, rotational molding and the like. Examples of molded parts include injection molded parts, extrusion molded parts, hollow molded parts, blow molded parts, films, sheets, fibers and the like.

  A molded article can be obtained by welding the molded parts obtained in this manner. Examples of the method for welding the molded part of the present invention include hot plate welding, infrared welding, vibration welding, laser welding and infrared / vibration welding. The infrared / vibration positive attachment is a welding method in which vibration welding is performed after the welded portion is warmed by infrared light. Among these, infrared welding, vibration welding, and infrared / vibration welding are preferable because they are more excellent in the balance of tensile strength and tensile elongation at the welded portion.

  In the present invention, the above-mentioned various molded articles can be used in various applications such as automobile members, electric / electronic members, building members, various containers, daily necessities, household goods and sanitary goods. In particular, the polyamide resin composition of the present invention is excellent in the balance of tensile strength and tensile elongation in the welded portion, and can take advantage of the property of being able to suppress the generation of cracks in the welded portion even when used under an environment where strain is applied. It is suitable as a high pressure tank liner having a welded portion, and is particularly suitable as a high pressure hydrogen tank liner.

  Hereinafter, the effects of the present invention will be more specifically described by way of examples. The present invention is not limited to the following examples. Evaluation in each example and comparative example was performed by the following method.

(1) Welded area tensile elongation From the molded article (3 mm in thickness) having the welded area obtained in each of the Examples and the Comparative Example, a portion joined by welding with a height of 100 mm and a width of 10 mm is the center in the height direction After conditioning the humidity for 30 minutes under conditions of a temperature of 23 ° C and a humidity of 50%, set the specimen to be a weld in the center of a tensile tester set at a distance between chucks of 50 mm. A tensile test was performed at a speed of 10 mm / min to evaluate the distance between chucks at break. The average value of five measurements was taken as the distance between chucks at break. Using the measured distance between chucks at break, the tensile elongation at weld was calculated by the following equation.
Formula 1) x = 100 x (L-Lo) / Lo
x: Weld tensile elongation (%)
Lo: Chuck distance before test (mm)
L: Distance between chucks at break (mm)

(2) Welded area tensile strength From the molded article (3 mm in thickness) having the welded area obtained in each Example and Comparative Example, a portion joined by welding is 100 mm in height and 10 mm in width, the center in the height direction For 5 test pieces cut out as above, after adjusting the humidity for 30 minutes under the conditions of temperature 23 ° C and humidity 50%, set the test piece to be the welded part at the center of the tensile tester set at 50mm distance between chucks, 10mm Tensile tests were performed at a rate of 1 / min to evaluate the maximum strength to failure. The average value of five measurements was taken as the weld zone tensile strength.

The raw materials and abbreviations used in each example and comparative example are shown below.
PA6: Polyamide 6 resin (melting point 223 ° C., relative viscosity 2.70 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA 66: Polyamide 66 resin (melting point 265 ° C., relative viscosity 2.80 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA 610: polyamide 610 resin (melting point 226 ° C., relative viscosity 3.50 at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml)
PA (MXD6): Polyamide MXD6 resin "Nylon T-600" (manufactured by Toyobo Co., Ltd.)
PA (6T / 6): Polyamide 6T / 6 resin "" Ultramid "(registered trademark) T KR 4350" (manufactured by BASF, melting point 295 ° C)
Amide-based wax: Ethylenediamine · stearic acid · sebacic acid polycondensate ““ Light Amide ”WH-255 (manufactured by Kyoeisha Chemical Co., Ltd .; melting point 255 ° C.)
Impact resistant material 1: Maleic anhydride-modified ethylene / 1-butene copolymer "" Tafmer "(registered trademark) MH 7020" (Mitsui Chemical Co., Ltd.)
Impact resistant material 2: glycidyl methacrylate modified polyethylene copolymer "" Bond first "(registered trademark) 7 L" (manufactured by Sumitomo Chemical Co., Ltd.)
Impact Resistant Material 3: Ionomer "High Milan" (registered trademark) 1706 (manufactured by DuPont)
Glass fiber: "T249H" (fiber diameter: 10.5 μm, fiber length 3 mm, surface-treated with a silane coupling agent) (manufactured by Nippon Electric Glass Co., Ltd.)
Glass flakes: "Micro Glass Flexa REFG-101" (manufactured by Nippon Sheet Glass Co., Ltd.).

[Examples 1-4, 6-10, Comparative Examples 1-5]
Each raw material of Table 1 and Table 2 is set as a screw arrangement in which cylinder temperature is set to 240 ° C., two kneading zones are provided, and screw rotational speed is 200 rpm (JEX TEX30α-). The mixture was supplied to 35BW-7V) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)), and was melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 240 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel, and heat the parallel faces for 25 seconds with infrared rays, and the amount of penetration is 2 mm It vibrated so that it might become and welding (infrared / vibration welding) was performed, and the molded article which has a welding part was obtained. The results evaluated by the above-mentioned method using the obtained molded articles are shown in Table 1 and Table 2.

[Example 5]
Each raw material of Table 1 sets cylinder temperature to 280 degreeC, sets it as screw arrangement provided with two kneading zones, and sets screw rotation speed to 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 280 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel, and heat the parallel faces for 25 seconds with infrared rays, and the amount of penetration is 2 mm It vibrated so that it might become and welding (infrared / vibration welding) was performed, and the molded article which has a welding part was obtained. The result evaluated by the above-mentioned method using the obtained molded article was described in Table 1.

[Examples 11 and 15 to 18]
Each raw material of Table 1 sets a cylinder temperature to 240 degreeC, sets it as the screw arrangement which provided two kneading zones, and the screw rotation speed was 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 240 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel, and heat the parallel faces for 30 seconds with infrared rays, and the amount of penetration is 2 mm It pressure-welded so that it might become and welding (infrared rays welding) was performed, and the molded article which has a welding part was obtained. The result evaluated by the above-mentioned method using the obtained molded article was described in Table 1.

[Example 12]
Each raw material of Table 1 sets a cylinder temperature to 240 degreeC, sets it as the screw arrangement which provided two kneading zones, and the screw rotation speed was 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 240 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel, vibrate so that the amount of penetration is 2 mm, and perform welding (vibration welding). A molded article having The result evaluated by the above-mentioned method using the obtained molded article was described in Table 1.

[Example 13]
Each raw material of Table 1 sets a cylinder temperature to 240 degreeC, sets it as the screw arrangement which provided two kneading zones, and the screw rotation speed was 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 240 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel and the parallel faces are heated with a hot plate having a hot plate temperature of 280 ° C. Pressure was applied so that the amount of penetration was 2 mm, and welding (hot plate welding) was performed to obtain a molded article having a welded portion. The result evaluated by the above-mentioned method using the obtained molded article was described in Table 1.

Example 14
Each raw material of Table 1 sets a cylinder temperature to 240 degreeC, sets it as the screw arrangement which provided two kneading zones, and the screw rotation speed was 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 240 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa, using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd., from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm on the laser beam transmitting side was injection molded under molding conditions of 20 seconds. In addition, using a material obtained by blending 0.4 parts by weight of carbon black with 100 parts by weight of the obtained pellets, cylinder temperature: 240 using an injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd. ° C, mold temperature: 80 ° C, injection speed: 40 mm / sec, holding pressure: 20 MPa, cooling time: 20 seconds, injection molded of square plate molded product of 80 mm x 80 mm x 3 mm thickness on the laser beam absorption side . Using the obtained square plate molded product on the laser beam transmission side and one square plate molded product on the laser beam absorption side, the 80 mm × thickness 3 mm faces are arranged to be parallel to each other, and the amount of penetration becomes 2 mm. As a result, a laser beam was irradiated for welding (laser welding) to obtain a molded product having a welded portion. The result evaluated by the above-mentioned method using the obtained molded article was described in Table 1.

[Comparative Examples 6 and 7]
Each raw material of Table 2 sets a cylinder temperature to 300 degreeC, sets it as the screw arrangement which provided two kneading zones, and the screw rotation speed was 200 rpm. Twin screw extruder (TEX30 alpha-35 BW-7V made by JSW) ) (L / D = 45 (here, L is the length from the raw material supply port to the discharge port)) and melt-kneaded. After quenching the gut discharged from the die at a speed of 20 kg / h for 10 seconds through a cooling bath filled with water heated to 10 ° C., it was pelletized with a strand cutter to obtain pellets . The obtained pellet was vacuum dried in a vacuum dryer at a temperature of 80 ° C. for 12 hours to obtain a pellet after drying. Cylinder temperature: 300 ° C., mold temperature: 80 ° C., injection speed: 40 mm / sec, holding pressure: 20 MPa using the injection molding machine “SE75DUZ-C250” manufactured by Sumitomo Heavy Industries, Ltd. from the obtained pellets Cooling time: A square plate molded article of 80 mm × 80 mm × thickness 3 mm was injection molded under molding conditions of 20 seconds. Two pieces of the obtained square plate molded product are used, arranged so that faces of 80 mm × thickness 3 mm face each other in parallel, and heat the parallel faces for 25 seconds with infrared rays, and the amount of penetration is 2 mm It vibrated so that it might become and welding (infrared / vibration welding) was performed, and the molded article which has a welding part was obtained. The result evaluated by the above-mentioned method using the obtained molded article was described in Table 2.

  From the above results, a molded article having a welded portion obtained by molding a polyamide resin composition obtained by blending a polyamide resin (A), an amide wax (B) and a glass fiber (C) It was found that the balance between tensile strength and tensile elongation of the part was excellent.

  Furthermore, it turned out that the molded article which has a weld part obtained by shape | molding the polyamide resin composition obtained by mix | blending an impact-resistant material (D) is excellent in tensile elongation more.

  The polyamide resin composition for welding of the present invention is excellent in the balance of tensile strength and tensile elongation at the welded portion, and makes use of the property of being able to suppress the generation of cracks at the welded portion even when used in an operating environment where strain is applied. It can be usefully developed as a molded article having a weld.

Claims (7)

3 to 9 parts by weight of glass fiber (C) with respect to a total of 100 parts by weight of polyamide resin (A) 90 to 99.99 parts by weight and amide-based wax (B) 0.01 to 10 parts by weight Polyamide resin composition for welding. The polyamide resin composition for welding according to claim 1, wherein the polyamide resin (A) is at least one selected from polyamide 6 resin, polyamide 610 resin, and polyamide 66 resin. Furthermore, 1 to 50 parts by weight of an impact resistant material (D) is compounded with respect to a total of 100 parts by weight of the polyamide resin (A) and the amide wax (B), for welding according to claim 1 or 2. Polyamide resin composition. The polyamide resin composition for welding according to claim 3, wherein the impact resistant material (D) comprises an ethylene / α-olefin copolymer modified with an unsaturated carboxylic acid and / or a derivative thereof. The molded article which has a weld part which consists of a polyamide resin composition in any one of Claims 1-4. A high pressure tank liner having a welded portion comprising the polyamide resin composition according to any one of claims 1 to 4. The method for manufacturing a molded article according to claim 5 or 6, wherein the welded portion is joined by any welding method selected from hot plate welding, infrared welding, vibration welding, laser welding and infrared / vibration welding.