JP2021172017A - Method for manufacturing hollow molding in contact with high-pressure hydrogen - Google Patents

Abstract

To provide a method for manufacturing a hollow molding in contact with high-pressure hydrogen which suppresses occurrences of defective points and cracks even with repeated filling and pressure release of high-pressure hydrogen, and is composed of a polyamide resin composition.SOLUTION: A method for manufacturing a hollow molding in contact with high-pressure hydrogen includes a step of forming a hollow molding using a polyamide resin composition by a press blow molding method, in which the polyamide resin composition is blended with 0.005-1 pts.wt. of a metal halide (C) with respect to 100 pts.wt. of the total of 70-99 pts.wt. of a polyamide 6 resin (A) and 1-30 pts.wt. of an impact-resistant material (B), a melt tension of the polyamide resin composition when being measured at 260°C is 20 mN or more, and take-off speed at break when being measured at 260°C is 50 m/min or more.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a hollow molded product made of a polyamide resin composition and in contact with high-pressure hydrogen. More specifically, a polyamide resin composition obtained by blending a specific amount of a polyamide 6 resin, an impact resistant material, and a metal halide and controlling a specific melt tension and a take-up speed at break is used, and hollow molding is performed by a press blow molding method. It relates to a method for manufacturing a hollow molded product that forms a product.

In recent years, in order to respond to the depletion of petroleum fuels and the demand for reduction of harmful gas emissions, fuel cells that generate electricity by electrochemically reacting hydrogen with oxygen in the air are installed in automobiles, and the fuel cells generate electricity. Fuel cell electric vehicles, which supply the generated electricity to a motor and use it as a driving force, are attracting attention. As a tank for high-pressure hydrogen for mounting a fuel cell electric vehicle, a resin tank in which the outside of a resin liner is reinforced with carbon fiber reinforced resin is being studied. However, since hydrogen has a small molecular size, it is easier to permeate through the resin than natural gas, which has a relatively large molecular size, and high-pressure hydrogen accumulates in the resin in a larger amount than normal-pressure hydrogen. For this reason, conventional resin tanks have a problem that the tank is deformed or destroyed when high-pressure hydrogen is repeatedly filled and released.

As a material for a hydrogen tank liner having excellent gas barrier properties and excellent impact resistance even at low temperatures, for example, a material for a hydrogen tank liner composed of a polyamide resin composition containing polyamide 6, a copolymerized polyamide, and an impact resistant material has been studied. (See, for example, Patent Document 1).

Further, as a liner for a gas storage tank having excellent gas barrier properties, for example, a liner for a gas storage tank containing a polymer composition containing a polyamide, a nucleating agent and an impact resistance improving agent has been studied (for example, Patent Documents). 2).

Japanese Unexamined Patent Publication No. 2009-191871 Special Table 2014-501818

Examples of a method for producing a molded product made of a resin composition that comes into contact with high-pressure hydrogen include injection molding, extrusion molding, blow molding and the like. Among them, when molding a large molded product, it may be molded by blow molding, but when drawdown occurs during blow molding and the molded product cannot be obtained, or when air is blown, the molded product is torn and obtained. It may not be possible. Therefore, in order to blow-mold a large-sized molded product, a material having excellent draw-down resistance and blow-moldability such as not being torn when air is blown is required.

Further, in blow molding, the residence time of the resin composition during molding tends to be longer than that in injection molding, and the resin may be decomposed during retention and the toughness may be lowered. Therefore, a resin composition for blow molding is required to have a material that does not easily decompose when staying. Furthermore, the direct blow molding method, which is a general blow molding method, has a problem that the number of steps increases because, for example, when forming a tank for high-pressure hydrogen, secondary processing of a joint portion with a mouthpiece is required. .. Further, it is difficult to control the thickness at the time of molding, and there is a problem that the variation in thickness becomes large. If the thickness variation of the obtained hollow molded product becomes large, defect points and cracks may occur from a thin portion when the filling and releasing pressure of high-pressure hydrogen are repeated. Therefore, there is a demand for a manufacturing method that does not require secondary processing of the joint portion with the base and can suppress variations in the thickness of the hollow molded product.

However, the hydrogen tank liner described in Patent Document 1 is prone to permeation of hydrogen gas and dissolution of hydrogen in the resin, and repeated filling and releasing of high-pressure hydrogen causes defects in the hydrogen tank liner. There was a challenge. Further, there is a problem that the melt tension of the polyamide resin composition is low, the drawdown resistance is inferior, and a hollow molded product cannot be obtained by the blow molding method.

Further, although the liner for a gas storage tank described in Patent Document 2 is excellent in helium gas permeation resistance, hydrogen gas permeation and hydrogen dissolution in the resin are likely to occur, and high-pressure hydrogen is filled and released. Repeatedly, there was a problem that a defect point was generated in the hydrogen tank liner. Further, there is a problem that the melt tension of the polyamide resin composition is low, the drawdown resistance is inferior, and a hollow molded product cannot be obtained by the blow molding method.

In view of the above problems of the prior art, the present invention is excellent in blow moldability and retention stability, has small variation in thickness, and suppresses the occurrence of defect points and cracks even when high-pressure hydrogen is repeatedly filled and released. An object of the present invention is to provide a method for manufacturing a hollow molded product.

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

A method for producing a hollow molded product, which comprises a step of forming a hollow molded product by a press blow molding method using a polyamide resin composition, wherein the polyamide resin composition comprises 70 to 99 parts by weight of the polyamide 6 resin (A). A polyamide resin composition obtained by blending 0.005 to 1 part by weight of a metal halide (C) with a total of 100 parts by weight of 1 to 30 parts by weight of the impact resistant material (B). A hollow molded product that comes into contact with high-pressure hydrogen, characterized in that the melt tension of the product when measured at 260 ° C. is 20 mN or more, and the take-back speed at break when measured at 260 ° C. is 50 m / min or more. Production method.

According to the method for producing a hollow molded product made of the polyamide resin composition of the present invention that comes into contact with high-pressure hydrogen, the blow moldability and retention stability are excellent, the thickness variation is small, and the high-pressure hydrogen is repeatedly filled and released. However, it is possible to provide a hollow molded product in which the occurrence of defect points and cracks is suppressed.

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

The present invention is a method for producing a hollow molded product, which comprises a step of forming a hollow molded product by a press blow molding method using a polyamide resin composition, wherein the polyamide resin composition is a polyamide 6 resin (A) 70 to 70 to A polyamide resin composition obtained by blending 0.005 to 1 part by weight of a metal halide (C) with a total of 100 parts by weight of 99 parts by weight and 1 to 30 parts by weight of the impact resistant material (B). A hollow in contact with high-pressure hydrogen, characterized in that the melt tension of the polyamide resin composition measured at 260 ° C. is 20 mN or more, and the take-back speed at break when measured at 260 ° C. is 50 m / min or more. This is a method for manufacturing a molded product.

The press blow molding method of the present invention will be described. In the press blow molding method, in order to first mold the mouth of a hollow molded product, the mouth of the hollow molded product is injection-molded using an injection molding mold that is abutted against the extrusion head, and the mouth after molding is injection-molded. While separating from the extrusion head together with the mold, a parison continuous from the extrusion head to the mouth is extruded into a tube shape, and then the parison is sandwiched between blow molding molds and air blown to form a hollow molding continuous with the mouth. This is a molding method for obtaining a molded product by molding the body of the product.

The press blow molding method does not require secondary processing of the mouth part by forming the mouth part with an injection molding die, and the press blow molding method generally pushes the parison upward from the extrusion head (gravity). It is based on the form of extrusion (in the direction against), and the variation in thickness can be controlled by adjusting the moving speed of the injection molding die, the extrusion speed of the resin, and the degree of opening of the extrusion port.

In the polyamide resin composition of the present invention, the metal halide (C) 0.005 to 5 parts by weight is 100 parts by weight in total of 70 to 99 parts by weight of the polyamide 6 resin (A) and 1 to 30 parts by weight of the impact resistant material (B). It is made by blending 1 part by weight. The polyamide 6 resin (A) has an excellent balance of moldability, gas barrier property, rigidity and toughness. The polyamide 6 resin (A) can withstand a high take-up speed, but if the relative viscosity is made too high in order to increase the melt tension, kneading defects are likely to occur. Furthermore, since it has a high crystallinity and can suppress the permeation of hydrogen gas and the dissolution of hydrogen in the resin, it is possible to create a hollow molded product in which defects are unlikely to occur even if high-pressure hydrogen is repeatedly filled and released. Obtainable. The impact-resistant material (B) has good compatibility with the polyamide 6 resin (A), and it is desirable that the dispersion diameter of the impact-resistant material (B) becomes smaller when kneaded with the polyamide 6 resin (A). As a result of diligent studies, it was found that the melt tension of the polyamide resin composition at a high temperature can be an index of moldability during flow molding. In the present invention, the polyamide resin composition containing the polyamide (A) and the impact resistant material (B) has a high melt tension, and as a result, is excellent in drawdown resistance. Further, the toughness can be improved by blending a specific amount of the impact resistant material (B) with the polyamide 6 resin (A). Hollow molded products used for applications that come into contact with high-pressure hydrogen repeatedly shrink and expand due to the filling and release of high-pressure hydrogen, so cracks are likely to occur. By blending a specific amount of the impact-resistant material (B), cracking can be suppressed even if such high-pressure hydrogen filling, shrinkage due to release pressure, and expansion are repeated. Further, by blending a specific amount of the metal halide (C), the retention stability can be improved. Hollow molded products used for applications that come into contact with high-pressure hydrogen tend to have a long residence time of the resin composition during blow molding, and the toughness tends to decrease. By blending a specific amount of the metal halide (C), it is possible to suppress a decrease in toughness even if the residence time is long during such blow molding.

The polyamide 6 resin (A) used in the present invention is a polyamide resin mainly composed of 6-aminocaproic acid and / or ε-caprolactam. Other monomers may be copolymerized as long as the object of the present invention is not impaired. Here, "as the main raw material" means that the total of 100 mol% or more of the units derived from 6-aminocaproic acid or the unit derived from ε-caprolactam is contained in the total of 100 mol% of the monomer units constituting the polyamide resin. Means. It is more preferable to contain 70 mol% or more of units derived from 6-aminocaproic acid or ε-caprolactam, and even more preferably 90 mol% or more.

Other monomers to be copolymerized include, for example, amino acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ω-laurolactam; tetramethylenediamine, pentamethylenediamine, etc. An aliphatic diamine such as hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine; Aromatic diamines such as metaxylenediamine and paraxylylenediamine; 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 (aminopropyl) piperazine, aminoethyl piperazine, etc. Alicyclic diamines; aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid Aromatic dicarboxylic acids such as acids, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1 , 3-Cyclopentanedicarboxylic acid and other alicyclic dicarboxylic acids. Two or more kinds of these may be copolymerized.

The degree of polymerization of the polyamide 6 resin (A) is not particularly limited, but the relative viscosity (ηr) of a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml measured at 25 ° C. is 3.3 to 7. It is preferably in the range of 0. When the relative viscosity is 3.3 or more, the melt tension of the polyamide resin composition at the time of blow molding becomes moderately high, and the draw-down property can be further improved. On the other hand, when the relative viscosity is 7.0 or less, the melt viscosity of the polyamide resin composition at the time of blow molding becomes appropriately low, and the blow moldability can be further improved. From the viewpoint of further improving blow moldability, the relative viscosity is more preferably in the range of 4.0 to 7.0, and the relative viscosity is further preferably in the range of 4.0 to 6.5.

The amount of amino-terminal groups of the polyamide 6 resin (A) is not particularly limited, but is preferably in the range of ^{1.0 × 10-5 to} 10.0 × ^{10-5 mol / g.} When the amount of amino-terminal 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 hollow molded product can be improved. Here, the amount of amino terminal groups of the polyamide 6 resin (A) is such that the polyamide 6 resin (A) is dissolved in a phenol / ethanol mixed solvent (83.5: 16.5 (volume ratio)) and 0.02N hydrochloric acid is used. It can be obtained by titrating with an aqueous solution.

The impact resistant material (B) used in the present invention refers to a polymer having a glass transition temperature of 0 ° C. or lower. Here, the glass transition temperature can be determined from the inflection point that occurs when the temperature is raised at a temperature rising rate of 20 ° C./min with the measurement start temperature as −70 ° C. by a differential scanning calorimeter (DSC). For example, olefin resin, acrylic rubber, silicone rubber, fluorine rubber, styrene rubber, nitrile rubber, vinyl rubber, urethane rubber, polyamide elastomer, polyester elastomer, ionomer and the like can be mentioned. Two or more of these may be blended.

Among these, an olefin resin is preferably used because it has excellent compatibility with the polyamide 6 resin (A) and has a high toughness improving effect. The olefin resin is a thermoplastic resin obtained by polymerizing an olefin monomer such as ethylene, propylene, butene, isoprene, and pentene. It may be a copolymer of two or more kinds of olefin monomers, or it may be a copolymer of these olefin monomers and other monomers. Specific examples of the olefin resin include polymers such as polyethylene, polypropylene, polystyrene, poly1-butene, poly1-pentene, and polymethylpentene, or polymers thereof; ethylene / α-olefin copolymer, ethylene / At least of α, β-unsaturated carboxylic acid ester copolymer, α-olefin / α, β-unsaturated carboxylic acid ester copolymer, [polymer of (ethylene and / or propylene) and vinyl alcohol ester] Polypolymers obtained by partially hydrolyzing, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), [(ethylene and / or propylene) and (non-saturated carboxylic acid ester). Polymers with saturated carboxylic acids and / or unsaturated carboxylic acid esters)] Polypolymers obtained by metally chloride at least a part of the carboxyl groups, block copolymers of conjugated diene and vinyl aromatic hydrocarbons or blocks thereof. Examples include hydrides. Among these, ethylene / α-olefin copolymers and ethylene / α, β-unsaturated carboxylic acid ester copolymers are more preferable, and ethylene / α-olefin copolymers are even more preferable.

Further, it is desirable that the olefin resin is modified with an unsaturated carboxylic acid and / or a derivative thereof. As described above, the impact-resistant material (B) has good compatibility with the polyamide 6 resin (A), and when kneaded with the polyamide 6 resin (A), the dispersion diameter of the impact-resistant material (B) is small. Although desirable, in order to reduce the dispersion diameter, the points of mixing with the polyamide 6 resin (A) and the type of elastomer of the impact resistant material (B) are important points. For example, the impact-resistant material modified with an unsaturated carboxylic acid and / or a derivative thereof has good reactivity with the polyamide 6 resin (A) and enhances compatibility with the polyamide 6 resin.

Here, the derivative of the unsaturated carboxylic acid is a compound in which the hydroxy group portion of the carboxyl group of the unsaturated carboxylic acid is replaced with another substituent, and is a metal salt, an acid halide, an ester, or an acid of the unsaturated carboxylic acid. Such as anhydrides, amides and imides. By using such a modified olefin resin, the compatibility with the polyamide 6 resin (A) can be further improved, and the blow moldability can be further improved. Examples of unsaturated carboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid and these carboxylic acids. Metal salts of; methyl hydrogen maleate, methyl hydrogen 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 metaacrylate, dimethyl maleate, dimethyl itacone; maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5 Acid anhydrides such as −hepten-2,3-dicarboxylic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride; maleimide, N-ethylmaleimide, N-butylmaleimide , N-Phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl etacrilate, glycidyl itaconate, glycidyl citraconic acid, 5-norbornene-2,3-dicarboxylic acid and the like. Among these, unsaturated dicarboxylic acids and their acid anhydrides are preferable, and maleic acid or maleic anhydride is particularly preferable.

As a method for introducing these unsaturated carboxylic acids or derivatives thereof into an olefin resin, for example, a method for copolymerizing an olefin monomer with an unsaturated carboxylic acid and / or a derivative thereof, or a radical initiator is used. Examples thereof include a method of graft-introducing an unsaturated carboxylic acid and / or a derivative thereof into an unmodified olefin resin.

The olefin-based resin into which some unsaturated carboxylic acids and / or derivative components thereof are introduced contributes to the dispersion of the olefin-based resin in the polyamide 6 resin in addition to the improvement of impact resistance, and the resin thereof. It also has the effect of reducing local residual strain when the composition is a molded product.

The amount of the unsaturated carboxylic acid and / or its derivative component introduced is, for example, 0.1 part by weight to 2.5 parts by weight of the unsaturated carboxylic acid and / or its derivative with respect to 100 parts by weight of the olefin resin. Is. Specifically, an unsaturated carboxylic acid and / or a derivative thereof is introduced by an unsaturated carboxylic acid and / or a derivative thereof, and a modified ethylene / α-olefin co-weight modified with the unsaturated carboxylic acid and / or a derivative thereof. When the weight of the coalescence is 100 parts by weight, the weight of the introduced unsaturated carboxylic acid and / or the modified portion thereof is preferably 0.1 to 2.5 parts by weight. Further, more preferably, the weight of the introduced unsaturated carboxylic acid and / or its derivative modified portion is 0.3 parts by weight to 2.3 parts by weight.

In the weight range of the unsaturated carboxylic acid-modified portion, the particle dispersion diameter of the impact-resistant material (B) becomes smaller when the polyamide 6 resin (A) and the impact-resistant material (B) are kneaded. The dispersion diameter will be described later.

As an effect, by setting the amount to 0.1 parts by weight or more, the compatibility with the polyamide 6 resin (A) is improved, the dispersion diameter of the impact resistant material (B) is small, the melt tension is high, and during blow molding. The problem of drawdown is less likely to occur. Further, the take-up speed at the time of breakage becomes high, and the problem of breakage when air is blown during blow molding is less likely to occur, which is preferable. By setting the weight to 2.5 parts by weight or less, it is possible to suppress an abnormal reaction with the polyamide 6 resin (A) and gelation, and the melt fluidity is lowered, so that the load becomes large during blow molding and the machine Is less likely to stop. Further, the take-up speed at the time of breakage becomes high, and the problem of breakage when air is blown during blow molding is less likely to occur, which is preferable.

As the ethylene / α-olefin copolymer, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferable. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, and 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-hexene, 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 Examples thereof include -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. 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. In addition, non-conjugated diene such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornene, 5- (1'-propenyl) -2-norbornene. At least one of may be copolymerized. A copolymer of ethylene modified with an unsaturated carboxylic acid and / or a derivative thereof and an α-olefin having 3 to 12 carbon atoms further improves the compatibility with the polyamide 6 resin (A), resulting in blow moldability and blow moldability. It is more preferable because the toughness can be further improved. Further, even if filling and releasing pressure are repeated with higher pressure hydrogen, the occurrence of defective points can be suppressed. 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 composition and structure of the fine particles of the impact resistant material (B) are not particularly limited, and for example, a so-called core-shell type composed of at least one layer made of rubber and one or more layers made of polymers different from the same. It may be a multi-layer structure called. 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 layers) inside. .. The type of rubber constituting the rubber layer of the multilayer structure is not particularly limited, and for example, an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene component, a propylene component, and isobutylene. Examples thereof include rubber obtained by polymerizing components and the like. The type of the heterogeneous polymer constituting the layer other than the rubber layer of the multilayer structure is not particularly limited as long as it is a polymer having thermoplasticity, but a polymer having a glass transition temperature higher than that of the rubber layer is used. preferable. The copolymer composition, the amount of modification, and the structure used as the impact-resistant material may have a glass transition temperature of 0 ° C. or lower. Examples of the polymer having thermoplasticity include unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic acid anhydride units, aliphatic vinyl units, and aromatic vinyl units. Polymers containing vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units and other vinyl units can be mentioned.

Examples of the metal halide (C) used in the present invention include lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, lithium chloride, sodium chloride, potassium chloride and the like. Alkali metal halides, magnesium iodide, calcium iodide, magnesium bromide, calcium bromide, magnesium chloride, calcium chloride and other alkaline earth metal halides; manganese iodide (II), manganese bromide (II), chloride Group 7 metal halides such as manganese (II); Group 8 metal halides such as iron (II) iodide, iron (II) bromide, iron (II) chloride; cobalt iodide (II), bromide Group 9 metal halides such as cobalt (II) and cobalt (II) chloride; Group 10 metal halides such as nickel iodide (II), nickel bromide (II) and nickel chloride (II); copper iodide Group 11 metal halides such as (I), copper (I) bromide and copper (I) chloride; Group 12 metal halides such as zinc iodide, zinc bromide and zinc chloride; aluminum iodide (III) Group 13 metal halides such as aluminum (III) bromide and aluminum (III) chloride; Group 14 metal halides such as tin iodide (II), tin bromide (II) and tin (II) chloride; Group 15 metal halides such as antimony triiodide, antimony tribromide, antimony trichloride, bismuth iodide (III), bismuth bromide (III), and bismuth chloride (III) can be mentioned. Two or more of these can be used in combination.

Among these, alkali metal halides and / from the viewpoints of being easily available, having excellent dispersibility in the polyamide 6 resin (A), having higher reactivity with radicals, and further improving retention stability. Alternatively, copper iodide is preferable. From the viewpoint of reducing the amount of gas generated, alkali metal iodide is more preferably used among alkali metal halides.

The polyamide resin composition of the present invention has a total of 100 parts by weight of 70 to 99 parts by weight of the polyamide 6 resin (A) and 1 to 30 parts by weight of the impact resistant material (B), and 0.005 to 5 parts by weight of the metal halide (C). It is made by blending 1 part by weight.

When the blending amount of the polyamide 6 resin (A) is less than 70 parts by weight, the gas barrier property of the hollow molded product made of the obtained polyamide resin composition is lowered, and defects occur when filling and releasing pressure are repeated with high-pressure hydrogen. do. The blending amount of the polyamide 6 resin (A) is preferably 75 parts by weight or more, more preferably 80 parts by weight or more. On the other hand, when the blending amount of the polyamide 6 resin (A) is more than 99 parts by weight, the toughness of the hollow molded product made of the obtained polyamide resin composition decreases, and cracks occur when the hollow molded product is repeatedly filled and released with high-pressure hydrogen. do. The blending amount of the polyamide 6 resin (A) is preferably 97 parts by weight or less, more preferably 95 parts by weight or less.

The blending amount of the impact resistant material (B) is 1 to 30 parts by weight, preferably 3 parts by weight or more, and more preferably 5 parts by weight or more. Further, 25 parts by weight or less is preferable, and 20 parts by weight or less is more preferable. If the blending amount of the impact resistant material (B) is less than 1 part by weight, the toughness of the hollow molded product made of the obtained polyamide resin composition is lowered, and cracks occur when filling and releasing pressure with high-pressure hydrogen are repeated. On the other hand, if the blending amount of the impact resistant material (B) is more than 30 parts by weight, the gas barrier property of the hollow molded product made of the obtained polyamide resin composition is lowered, and if the hollow molded product is repeatedly filled and released with high-pressure hydrogen, a defect point is obtained. Occurs.

The blending amount of the metal halide (C) is 0.005 to 1 part by weight with respect to 100 parts by weight of the total of the polyamide 6 resin (A) and the impact resistant material (B), and the blending amount of the metal halide (C). When is less than 0.005 parts by weight, the retention stability of the obtained polyamide resin composition during blow molding is lowered, and the toughness of the hollow molded product is lowered. The blending amount of the metal halide (C) is preferably 0.02 parts by weight or more, more preferably 0.04 parts by weight or more, from the viewpoint of further improving the retention stability. On the other hand, when the blending amount of the metal halide (C) is more than 1 part by weight, the dispersion diameter becomes coarse due to the progress of self-aggregation of the metal halide (C), and the hollow molded product made of the obtained polyamide resin composition. The mechanical properties of the Further, since the surface area is lowered due to the coarse dispersion and the reaction between the metal halide (C) and the radical is lowered, the retention stability of the obtained polyamide resin composition during blow molding is lowered, and the hollow molded product is manufactured. Toughness decreases. The blending amount of the metal halide (C) is preferably 0.5 parts by weight or less, more preferably 0.3 parts by weight or less.

Further, as a method for obtaining a polyamide resin composition having a high melt tension and a high take-up rate at break, it is desirable that the dispersion diameter of the impact resistant material (B) is small. As a method for reducing the dispersion diameter of the impact resistant material (B), for example, it is preferable that the resin temperature is controlled to a relatively high temperature in the range of 235 ° C. to 330 ° C. for kneading. The resin temperature referred to here is a value measured by directly inserting a contact-type resin thermometer into the die hole. The dispersion diameter of the impact-resistant material (B) dispersed in the polyamide resin composition can be finely controlled, the interface between the polyamide 6 resin (A) and the impact-resistant material (B) increases, the melt tension increases, and the melt tension becomes uniform. Since it is easily stretched, it can withstand a high take-up speed at break, which is preferable. Here, the average dispersion diameter of the impact-resistant material (B) dispersed in the polyamide resin composition is preferably 0.01 μm or more and 0.5 μm or less, more preferably 0.02 μm or more and 0.3 μm or less, and 0.05 μm or more and 0. .2 μm or less is more preferable.

For the average dispersion diameter of the impact resistant material (B), for example, an ultrathin section is cut out from a polyamide resin composition pellet, the section cross section is dyed with the impact resistant material (B), and a transmission electron microscope is used. It is possible to observe and calculate the dispersed particle size by image analysis. If the particles are not a perfect circle, the average value of the major axis and the minor axis is calculated, and the average dispersion diameter is calculated as the average value of the major axis and the minor axis.

The polyamide resin composition of the present invention may contain other components other than the above components (A), (B) and (C), if necessary, as long as the characteristics are not impaired. Examples of other components include fillers, thermoplastic resins other than the above (A), and various additives.

For example, by blending a filler, the strength and dimensional stability of the molded product can be improved. The shape of the filler may be fibrous or non-fibrous, and the fibrous filler and the non-fibrous filler may be used in combination. Examples of the fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, and stone wool. Examples include fibers and metal fibers. Examples of the non-fibrous filler include silicates such as wallastenite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, and alumina silicate, alumina, silicon oxide, magnesium oxide, and oxidation. 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, aluminum hydroxide, etc. Examples include metal hydroxides, glass beads, ceramic beads, boron nitride and silicon carbide, which may be hollow. Further, it is preferable to use these fibrous and / or non-fibrous fillers after pretreatment 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.

Examples of the thermoplastic resin include polyamide resins other than the polyamide 6 resin (A), polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, polyacetal resins, polysulfone resins, and tetrafluoride polyethylene resins. Polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, styrene resin such as polystyrene resin and ABS resin, polyalkylene oxide resin, etc. Can be mentioned. It is also possible to blend two or more kinds of such thermoplastic resins. When a polyamide resin other than the polyamide 6 resin (A) is blended, it is preferably 4 parts by weight or less with respect to 100 parts by weight of the polyamide 6 resin (A).

Examples of various additives include color inhibitors, antioxidants such as hindered phenol and hindered amine, mold release agents such as ethylene bisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants, and UV inhibitors. Examples include colorants, flame retardants, and foaming agents.

The polyamide resin composition of the present invention has a melt tension of 20 mN or more when measured at 260 ° C., and a take-back speed at break when measured at 260 ° C. is 50 m / min or more. If the melt tension of the polyamide resin composition measured at 260 ° C. is 20 mN or more and the take-up speed at break when measured at 260 ° C. is 50 m / min or more, the polyamide resin composition is uniformly stretched during blow molding. It is easy to suppress the occurrence of defect points and cracks when the high-pressure hydrogen is repeatedly filled and released.

The polyamide resin composition of the present invention preferably has a melt tension of 20 to 500 mN, more preferably 25 to 500 mN, and even more preferably 30 to 300 mN. When the melt tension of the polyamide resin composition measured at 260 ° C. is 20 mN or more, drawdown during blow molding can be suppressed, a hollow molded product can be obtained, and high-pressure hydrogen filling and release pressure are repeated. At that time, it is possible to suppress the occurrence of defective points and cracks. Further, if the melt tension of the polyamide resin composition measured at 260 ° C. is 500 mN or less, the decrease in stretchability can be suppressed.

The polyamide resin composition of the present invention preferably has a take-up speed at break of 50 m / min or more, more preferably 60 m / min or more, and further preferably 80 m / min or more. If the take-up speed at break when the polyamide resin composition is measured at 260 ° C. is 50 m / min or more, it will not be broken when air is blown during blow molding, and a hollow molded product can be obtained. Therefore, no matter how high the value is. good.

In the present invention, the melt tension of the polyamide resin composition is measured as follows. Using a Capillograph 1C manufactured by Toyo Seiki Seisakusho (cylinder inner diameter 9.55 mm, orifice length 10.0 mm, inner diameter 1.0 mm), the test temperature is set to 260 ° C. A polyamide resin composition is filled in a cylinder and melted by compacting and holding for 20 minutes, and then a molten resin at 260 ° C. is extruded from an orifice in a strand shape at a piston speed of 10 mm / min. This strand is wound by passing through the circular guide of the lower tension detection pulley at a take-up speed of 10 m / min, and the detected tension is defined as the melt tension of the polyamide resin composition.

The means for setting the melt tension of the polyamide resin composition within the above range is not particularly limited as long as such a polyamide resin composition can be obtained, but 25 in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml. A method using a polyamide 6 resin (A) having a relative viscosity in the range of 3.3 to 7.0 measured at ° C., or as an impact resistant material (B), unsaturated carboxylic acid and / or a derivative thereof modified ethylene / α. -A method using an olefin copolymer is preferably used. Then, a modified ethylene / α-olefin copolymer modified with 0.1 to 2.5 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof is used with respect to 100 parts by weight of the ethylene / α-olefin copolymer. The method is preferably used. Specifically, the unsaturated carboxylic acid and / or its derivative portion introduced from the modification is 0 with respect to 100 parts by weight of the unsaturated carboxylic acid and / or its derivative modified ethylene / α-olefin copolymer. The impact resistant material (B), which is 1 to 2.5 parts by weight, is preferably used.

In the present invention, the take-back speed of the polyamide resin composition at break is measured as follows. Using a Capillograph 1C manufactured by Toyo Seiki Seisakusho (cylinder inner diameter 9.55 mm, orifice length 10.0 mm, inner diameter 1.0 mm), the test temperature is set to 260 ° C. A polyamide resin composition is filled in a cylinder and melted by compacting and holding for 20 minutes, and then a molten resin at 260 ° C. is extruded from an orifice in a strand shape at a piston speed of 10 mm / min. This strand is wound through a circular guide of the lower tension detection pulley at a take-up speed of 10 m / min to stabilize the detected tension. After stabilization, winding is performed while accelerating the take-up speed at an acceleration of 400 m / min ² , and the take-up speed at the time when the strand is broken is defined as the take-up speed at break of the polyamide resin composition. The limit value for measuring the take-back speed of the polyamide resin composition at break in the above measuring method is 200 m / min, but it may be 200 m / min or more if other device specifications are used. In the present invention, if it is 50 m / min or more, a hollow molded product can be obtained without tearing when air is blown during blow molding.

The means for setting the take-back rate of the polyamide resin composition at break to the above range is not particularly limited as long as such a polyamide resin composition can be obtained, but as the impact resistant material (B), an unsaturated carboxylic acid and / Alternatively, a method using a modified ethylene / α-olefin copolymer modified with the derivative thereof is preferably used. Then, a modified ethylene / α-olefin copolymer modified with 0.1 to 2.5 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof is used with respect to 100 parts by weight of the ethylene / α-olefin copolymer. The method is preferably used. Specifically, the unsaturated carboxylic acid and / or its derivative 0.1 introduced from the modification with respect to 100 parts by weight of the modified ethylene / α-olefin copolymer. A method using an impact resistant material (B) having an amount of ~ 2.5 parts by weight is preferable.

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 a molten state can be preferably used. For production in the molten state, melt-kneading with an extruder, a Banbury mixer, a kneader, a mixing roll or the like can be used, and from the viewpoint of productivity, melt-kneading with an extruder capable of continuously producing can be preferably used. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, and a twin-screw single-screw compound extruder. A plurality of these extruders may be combined. From the viewpoint of improving kneadability, reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder is preferable, and a twin-screw extruder is more preferable.

Examples of the melt-kneading method using a twin-screw extruder include polyamide 6 resin (A), impact-resistant material (B), metal halide (C), and if necessary, other than (A), (B), and (C). Examples thereof include a method in which the components of the above are premixed and supplied to a twin-screw extruder whose cylinder temperature is set to be equal to or higher than the melting point of the polyamide 6 resin (A) to be melt-kneaded. The mixing order of the raw materials is not particularly limited, and all the 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 further mixed and melt-kneaded. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder during melt-kneading of some raw materials. Further, a method of removing the gas generated by exposing the extruder to a vacuum state in the middle of the extruder is also preferably used.

The resin temperature during melt-kneading using a twin-screw extruder is preferably controlled in the range of 235 ° C to 330 ° C. By controlling the resin temperature during melt-kneading to 235 ° C. or higher, the dispersion diameter of the impact-resistant material (B) dispersed in the polyamide resin composition can be finely controlled, and the polyamide 6 resin (A) and the impact-resistant material (A) Since the number of interfaces of B) increases, the melt tension becomes high, and the resin is easily stretched uniformly, it can withstand a high take-up speed at break, which is preferable. Further, by controlling the resin temperature during melt-kneading to 330 ° C. or lower, the decomposition of the polyamide 6 resin (A) and the impact-resistant material (B) is suppressed, the melt tension becomes higher, and the resin is uniformly stretched. It is preferable because it can withstand a high take-up speed at break. The resin temperature referred to here is a value measured by directly inserting a contact-type resin thermometer into the die hole.

The hollow molded product obtained in the present invention is used for a hollow molded product that comes into contact with high-pressure hydrogen by taking advantage of its excellent feature that the generation of defective points is suppressed even if the filling and releasing pressure of high-pressure hydrogen is repeated. The hollow molded product that comes into contact with high-pressure hydrogen here is a hollow molded product that comes into contact with hydrogen at a pressure higher than normal pressure. Since it has the effect of suppressing the occurrence of defective points when high-pressure hydrogen is repeatedly filled and released, it is preferably used for hollow molded products that come into contact with hydrogen at a pressure of 20 MPa or more, and is a hollow molded product that comes into contact with hydrogen of 30 MPa or more. It is preferably used depending on the application. On the other hand, it is preferably used for hollow molded products that come into contact with hydrogen at a pressure of 200 MPa or less, preferably used for hollow molded products that come into contact with hydrogen of 150 MPa or less, and more preferably used for hollow molded products that come into contact with hydrogen of 100 MPa or less. Examples of the hollow molded product that comes into contact with high-pressure hydrogen include a tank for high-pressure hydrogen, a tank liner for high-pressure hydrogen, a pipe for high-pressure hydrogen, a pump for high-pressure hydrogen, and a tube for high-pressure hydrogen. Above all, it can be preferably used for high-pressure hydrogen containers such as high-pressure hydrogen tanks and high-pressure hydrogen tank liners.

The high-pressure hydrogen tank liner preferably has a body of a high-pressure hydrogen tank liner at six locations in the longitudinal direction and a standard deviation σ of the thickness measured at equal intervals of 0.3 or less. If the standard deviation σ of the thickness measured at 6 locations at regular intervals is greater than 0.3, the wall thickness of the tank liner for high-pressure hydrogen is non-uniform, and stress concentration occurs when high-pressure hydrogen is repeatedly filled and released. Since it becomes large, defects and cracks are likely to occur.

Here, the thickness of the body of the high-pressure hydrogen tank liner is measured at the center of each arc using a point micrometer. The standard deviation σ of the thickness can be calculated by the following formula using the _{obtained thickness x k.}
Equation 1) x = (1/6) Σx _k (k = 1-6)
Equation 2) V = (1/6) Σ (x _k −x) ² (k = 1-6)
Equation 3) σ = √V
x: Average thickness at 6 locations x _k : Thickness at each location (mm)
V: Thickness dispersion σ: Standard deviation of thickness.

The thickness of the hollow molded product in which the standard deviation σ of the thickness measured at six locations in the longitudinal direction of the high-pressure hydrogen tank liner at equal intervals is 0.3 or less is not particularly limited, but is in the range of 0.5 mm to 5 mm. Is preferable.

In order to set the standard deviation σ of the thickness of the body of the high-pressure hydrogen tank liner at six locations in the longitudinal direction at equal intervals to 0.3 or less, for example, the method of molding by the above-mentioned press blow molding method can be mentioned. ..

Hereinafter, the effects of the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. The evaluation in each Example and Comparative Example was performed by the following method.

(1) Repeated filling and discharging characteristics of high-pressure hydrogen (defect points)
The hollow molded products obtained in Examples 1 to 6 and Comparative Examples 5 to 8 were subjected to X-ray CT analysis, and the presence or absence of defective points was observed. After putting the hollow molded product having no defects into the autoclave, hydrogen gas was injected into the autoclave up to 20 MPa over 5 minutes, held for 1 hour, and then depressurized over 5 minutes until the pressure became normal. This was set as one cycle and repeated for 100 cycles. After repeating 100 cycles, X-ray CT analysis was performed on the test piece using TDM1000-IS manufactured by Yamato Scientific Co., Ltd., and the presence or absence of defect points of 10 μm or more was observed. , Those with defective points were regarded as "Yes".

(2) Tensile elongation (toughness)
A test cut out from the body of the hollow molded product (thickness of about 2 mm) obtained in Examples 1 to 6 and Comparative Examples 5 to 8 with a height of 100 mm and a width of 3 mm so that the longitudinal direction is the length direction of the tank. After adjusting the humidity of the five pieces for 30 minutes under the conditions of a temperature of 23 ° C. and a humidity of 50%, a tensile test was carried out at a speed between chucks of 50 mm and 10 mm / min to evaluate the tensile elongation. The average value of 5 measurements was taken as the tensile elongation. The tensile elongation of the hollow molded product being 50% or more indicates that the toughness is maintained and the thermal stability is high even after receiving the heat applied during blow molding.

(3) Melt tension The pellets obtained in each Example and Comparative Example were subjected to a test temperature using Capillograph 1C (cylinder inner diameter 9.55 mm, orifice length 10.0 mm, inner diameter 1.0 mm) manufactured by Toyo Seiki Seisakusho. The polyamide resin composition is filled in a cylinder set at 260 ° C. and melted by compacting and holding for 20 minutes, and then the molten resin at 260 ° C. is extruded from an orifice in a strand shape at a piston speed of 10 mm / min. .. This strand was taken up at a take-up speed of 10 m / min by passing through the circular guide of the lower tension detection pulley, and the detected tension was defined as the melt tension.

(4) Pick-up speed at break The pellets obtained in each Example and Comparative Example were tested using Capillograph 1C (cylinder inner diameter 9.55 mm, orifice length 10.0 mm, inner diameter 1.0 mm) manufactured by Toyo Seiki Seisakusho. The polyamide resin composition is filled in a cylinder whose temperature is set to 260 ° C. and melted by compacting and holding for 20 minutes, and then the molten resin at 260 ° C. is stranded from the orifice at a piston speed of 10 mm / min. Extrude. The strand was wound at a take-up speed of 10 m / min through the circular guide of the lower tension detection pulley to stabilize the detected tension. After it became stable, it was ^{wound while accelerating the take-up speed at an acceleration of 400 m / min 2} , and the take-up speed at the time when the strand broke was set to the take-up speed at the time of breakage.

(5) Standard deviation of thickness measured at equal intervals at 6 points in the longitudinal direction of the body of the hollow molded product (standard deviation of thickness)
With respect to the hollow molded products obtained in Examples 1 to 6 and Comparative Examples 5 to 8, the center of the arc was measured at 6 locations in the longitudinal direction at equal intervals using a point micrometer, and the obtained thickness x _{From k} , the average thickness was calculated by Equation 1. Further, the standard deviation σ of the thickness was calculated by the following formula 3.
Equation 1) x = (1/6) Σx _k (k = 1-6)
Equation 2) V = (1/6) Σ (x _k −x) ² (k = 1-6)
Equation 3) σ = √V
x: Average thickness at 6 locations x _k : Thickness at each location (mm)
V: Thickness dispersion σ: Standard deviation of thickness.

The raw materials and abbreviations used in each Example and Comparative Example are shown below.

(Raw material and abbreviation for polyamide 6 resin (A))
PA6 (ηr2.7): Polyamide 6 resin (relative viscosity 2.70 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA6 (ηr3.0): Polyamide 6 resin (relative viscosity 3.00 at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml)
PA6 (ηr3.4): Polyamide 6 resin (relative viscosity 3.40 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA6 (ηr4.4): Polyamide 6 resin (relative viscosity 4.40 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA6 (ηr6.3): Polyamide 6 resin (relative viscosity 6.30 at 25 ° C. in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml)
PA6 / PA66 copolymer: Polyamide 6 / polyamide 66 copolymer (relative viscosity 4.20 at 25 ° C. in a 98% concentrated sulfuric acid solution having a melting point of 190 ° C. and a resin concentration of 0.01 g / ml).

(Raw material and abbreviation for impact resistant material (B))
Impact-resistant material 1: Ethylene / 1-butene copolymer (MFR (190 ° C., 2160 g load) 0.5 g / 10 minutes, density 0.862 g / cm ³ ).

Impact resistant material 2: MFR (190 ° C., 2160 g load) 0.5 g / 10 minutes, density 0.862 g / cm ³ , 100 parts by weight of ethylene / 1-butene copolymer, 1.05 maleic anhydride 0.04 parts by weight and 0.04 part by weight of peroxide (manufactured by Nichiyu Co., Ltd., trade name Perhexin 25B) were mixed and melt-extruded at a cylinder temperature of 230 ° C. using a twin-screw extruder to obtain an impact resistant material 2. .. The obtained impact resistant material 2 is an ethylene / 1-butene copolymer modified with maleic anhydride, and the amount of modification with respect to 100 parts by weight of the ethylene / 1-butene copolymer is 1.0 part by weight. Specifically, when a part of the side chain is modified with maleic anhydride and the weight of the ethylene / 1-butene copolymer into which the unsaturated carboxylic acid is introduced is 100 parts by weight, the introduced unsaturated carboxylic acid The weight of the modified portion is 1.0 part by weight.

For the measurement of each part by weight, 100 parts by weight of the ethylene / 1-butene copolymer and 1.05 parts by weight of maleic anhydride were melt-kneaded, and the obtained unsaturated carboxylic acid was introduced into the ethylene / 1-butene. Weigh the pellets of the copolymer. The weight of the unsaturated carboxylic acid-modified portion is as follows: unsaturated carboxylic acid is dissolved in xylene at 130 ° C., a 0.02 mol / L ethanol solution of potassium hydroxide (manufactured by Aldrich) is used as the titrator, and the indicator is A 1% phenolphthalein ethanol solution is prepared and the molar concentration of unsaturated carboxylic acid obtained by titration is converted to mass. Then, the weight of the unsaturated carboxylic acid-modified ethylene / 1-butene copolymer was converted per 100 parts by weight and used as "the weight of the introduced unsaturated carboxylic acid-modified part".

Impact resistant material 3: Maleic anhydride 2.1 based on 100 parts by weight of an ethylene / 1-butene copolymer having an MFR (190 ° C., 2160 g load) of 0.5 g / 10 minutes and a density of 0.862 g / cm ^3. 0.1 parts by weight and 0.1 part by weight of peroxide (manufactured by Nichiyu Co., Ltd., trade name Perhexin 25B) were mixed and melt-extruded at a cylinder temperature of 230 ° C. using a twin-screw extruder to obtain an impact resistant material 3. .. The obtained impact resistant material 3 is an ethylene / 1-butene copolymer modified with maleic anhydride, and the amount of modification with respect to 100 parts by weight of the ethylene / 1-butene copolymer is 2.0 parts by weight. Specifically, when a part of the side chain is modified with maleic anhydride and the weight of the ethylene / 1-butene copolymer into which the unsaturated carboxylic acid has been introduced is 100 parts by weight, the introduced unsaturated carboxylic acid The weight of the modified portion is 2.0 parts by weight.

Impact resistant material 4: MFR (190 ° C., 2160 g load) 0.5 g / 10 minutes, density 0.862 g / cm ³ , 100 parts by weight of ethylene / 1-butene copolymer, 3.32 maleic anhydride 0.25 parts by weight and 0.25 parts by weight of peroxide (manufactured by Nichiyu Co., Ltd., trade name Perhexin 25B) were mixed and melt-extruded at a cylinder temperature of 230 ° C. using a twin-screw extruder to obtain an impact resistant material 4. .. The obtained impact-resistant material 4 is a maleic anhydride-modified ethylene / 1-butene copolymer, and the amount of modification with respect to 100 parts by weight of the ethylene / 1-butene copolymer is 3.2 parts by weight. Specifically, when a part of the side chain is modified with maleic anhydride and the weight of the ethylene / 1-butene copolymer into which the unsaturated carboxylic acid has been introduced is 100 parts by weight, the introduced unsaturated carboxylic acid The weight of the modified portion is 3.2 parts by weight.

(Raw material and abbreviation for metal halide (C))
Metal halide 1: Copper iodide (I) (manufactured by Wako Pure Chemical Industries, Ltd.)
Metal halide 2: Potassium iodide (manufactured by Wako Pure Chemical Industries, Ltd.).

[Examples 1 to 6, Comparative Examples 5 and 6]
Each of the raw materials shown in Tables 1 and 2 has a screw arrangement in which the cylinder temperature is set to 240 ° C. and one kneading zone is provided, and the screw rotation speed is 150 rpm. -7V) (L / D = 45 (where L is the length from the raw material supply port to the discharge port and D is the diameter of the screw)) and melt-kneaded. The gut discharged from the die at a speed of 20 kg / h was rapidly cooled by passing it through a cooling bath filled with water whose temperature was adjusted to 10 ° C. for 10 seconds, and then pelletized with a strand cutter to obtain pellets. .. The obtained pellets were vacuum dried at a temperature of 80 ° C. for 12 hours in a vacuum dryer to obtain pellets after drying. From the obtained pellets, a hollow molded product having a length of 200 mm and a diameter of φ100 mm was obtained under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. using a press blow molding machine (manufactured by OSSBERGER). The results of evaluation by the above-mentioned method using the hollow molded product are shown in Tables 1 and 2.

In Example 1, as the polyamide 6 resin (A), PA6 (ηr = 3.4) is kneaded with 85 parts by weight, the impact resistant material 2 is kneaded with 15 parts by weight, and the metal halide 1 is kneaded with 0.1 parts by weight. bottom. The resin temperature during melt-kneading was 260 ° C. The melt tension of the obtained pellets was 40 mN, and the take-up speed at break was> 200 m / min, which was good. The hollow molded product had no defects, and the standard deviation of the thickness was 0.206, which was within a problem-free range.

Example 2 was the same as that of Example 1 except that the polyamide 6 resin (A) of Example 1 was changed to PA6 (ηr = 4.4). The resin temperature during melt-kneading was 265 ° C. The average dispersion diameter of the impact-resistant material 2 of the obtained pellets was 0.13 μm, which was finely dispersed. The melt tension of the obtained pellets was 70 mN, and the take-up speed at break was 150 m / min, which were good. The hollow molded product had no defects and had a good standard deviation of thickness of 0.082.

Example 3 was the same as that of Example 1 except that the polyamide 6 resin (A) of Example 1 was changed to PA6 (ηr = 6.3). The resin temperature during melt-kneading was 287 ° C. The melt tension of the obtained pellets was 115 mN, and the take-up speed at break was 130 m / min, which was good. The hollow molded product had no defects and had a good standard deviation of 0.111 in thickness.

Example 4 was the same as that of Example 2 except that the impact resistant material 2 of Example 2 was changed to the impact resistant material 3. The resin temperature during melt-kneading was 272 ° C. The melt tension of the obtained pellets was 85 mN, and the take-up speed at break was 107 m / min, which were good. The hollow molded product had no defects and had a good standard deviation of thickness of 0.073.

Example 5 was the same as in Example 2 except that the metal halide was changed. The resin temperature during melt-kneading was 267 ° C. The melt tension of the obtained pellets was 73 mN, and the take-up speed at break was 165 m / min, which was good. The hollow molded product had no defects and had a good standard deviation of thickness of 0.065.

Example 6 was the same as that of Example 2 except that the ratio of PA6 and the impact resistant material 2 was changed. The resin temperature during melt-kneading was 258 ° C. The melt tension of the obtained pellets was 31 mN, and the take-up speed at break exceeded 200 m / min, which was good. The hollow molded product had no defects, and the standard deviation of the thickness was 0.177, which was within a problem-free range.

On the other hand, in Comparative Example 5, although there was no metal halide (C) and there were no defects in the hollow molded product, burning occurred. In Comparative Example 6, PA6 (ηr = 3.0), PA6 / PA66 copolymer (ηr = 4.2), and impact-resistant material 2 were used, and their respective ratios were changed. The melt tension of the obtained pellets was as small as 18 mN, and the take-up speed at break was 180 m / min. Defects occurred in the hollow molded product, and the standard deviation of the thickness was 0.380.

[Comparative Examples 1 to 3]
Each raw material shown in Table 2 has a screw arrangement in which the cylinder temperature is set to 240 ° C. and one kneading zone is provided, and the screw rotation speed is 150 rpm. ) (L / D = 45 (where L is the length from the raw material supply port to the discharge port and D is the diameter of the screw)) and melt-kneaded. The gut discharged from the die at a speed of 20 kg / h was rapidly cooled by passing it through a cooling bath filled with water whose temperature was adjusted to 10 ° C. for 10 seconds, and then pelletized with a strand cutter to obtain pellets. .. The obtained pellets were vacuum dried at a temperature of 80 ° C. for 12 hours in a vacuum dryer to obtain pellets after drying. From the obtained pellets, press blow molding was performed using a press blow molding machine (manufactured by OSSBERGER) under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. I couldn't get it.

In Comparative Examples 1 and 2, PA6 (ηr = 2.7) was used. The melt tension of the obtained pellets was as small as 9 mN in Comparative Example 1 and 14 mN in Comparative Example 2, and the take-up speed at break exceeded 200 m / min. In Comparative Example 3, an impact resistant material 1 (without unsaturated carboxylic acid modification) was used. The melt tension of the obtained pellets was as small as 18 mN, and the take-up speed at break was as low as 25 m / min.

[Comparative Example 4]
For each raw material shown in Table 2, a twin-screw extruder (TEX30α-35BW-7V manufactured by JSW) having a cylinder temperature of 240 ° C., a screw arrangement with one kneading zone, and a screw rotation speed of 150 rpm. ) (L / D = 45 (where L is the length from the raw material supply port to the discharge port and D is the diameter of the screw)) and melt-kneaded. The gut discharged from the die at a speed of 20 kg / h was rapidly cooled by passing it through a cooling bath filled with water whose temperature was adjusted to 10 ° C. for 10 seconds, and then pelletized with a strand cutter to obtain pellets. .. The obtained pellets were vacuum dried at a temperature of 80 ° C. for 12 hours in a vacuum dryer to obtain pellets after drying. From the obtained pellets, press blow molding was performed using a press blow molding machine (manufactured by OSSBERGER) under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. It was torn and a hollow molded product could not be obtained.

In Comparative Example 4, an impact resistant material 4 (unsaturated carboxylic acid modification amount of 3.2 parts by weight) was used. The melt tension of the obtained pellets was 92 mN, but the take-up speed at break was as low as 38 m / min.

[Comparative Example 7]
For each raw material shown in Table 2, a twin-screw extruder (TEX30α-35BW-7V manufactured by JSW) having a cylinder temperature of 225 ° C., a screw arrangement with one kneading zone, and a screw rotation speed of 100 rpm. ) (L / D = 45 (where L is the length from the raw material supply port to the discharge port and D is the diameter of the screw)) and melt-kneaded. The gut discharged from the die at a speed of 20 kg / h was rapidly cooled by passing it through a cooling bath filled with water whose temperature was adjusted to 10 ° C. for 10 seconds, and then pelletized with a strand cutter to obtain pellets. .. The obtained pellets were vacuum dried at a temperature of 80 ° C. for 12 hours in a vacuum dryer to obtain pellets after drying. From the obtained pellets, a hollow molded product having a length of 200 mm and a diameter of φ100 mm was obtained under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. using a press blow molding machine (manufactured by OSSBERGER). Table 2 shows the results of evaluation by the above-mentioned method using a hollow molded product.

In Comparative Example 7, the resin composition was the same as that of Example 2, but the resin temperature at the time of melting was as low as 232 ° C. The average dispersion diameter of the impact-resistant material 2 of the obtained pellets was coarsely dispersed as 0.62 μm, the melt tension of the obtained pellets was as low as 19 mN, and the take-up speed at break was 65 m / min. Defect points were generated in the hollow molded product, and the standard deviation of the thickness was 0.320, which was a large variation.

[Comparative Example 8]
Each raw material shown in Table 2 is a twin-screw extruder (TEX30α-35BW-7V manufactured by JSW) in which the cylinder temperature is set to 300 ° C., the screw arrangement is provided with three kneading zones, and the screw rotation speed is 300 rpm. ) (L / D = 45 (where L is the length from the raw material supply port to the discharge port and D is the diameter of the screw)) and melt-kneaded. The gut discharged from the die at a speed of 20 kg / h was rapidly cooled by passing it through a cooling bath filled with water whose temperature was adjusted to 10 ° C. for 10 seconds, and then pelletized with a strand cutter to obtain pellets. .. The obtained pellets were vacuum dried at a temperature of 80 ° C. for 12 hours in a vacuum dryer to obtain pellets after drying. From the obtained pellets, a hollow molded product having a length of 200 mm and a diameter of φ100 mm was obtained under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. using a press blow molding machine (manufactured by OSSBERGER). Table 2 shows the results of evaluation by the above-mentioned method using a hollow molded product.

In Comparative Example 8, the resin composition was the same as that of Example 2, but the resin temperature at the time of melting was as high as 340 ° C. The melt tension of the obtained pellets was as low as 19 mN, and the take-up speed at break was 72 m / min. Defect points were generated in the hollow molded product, and the standard deviation of the thickness was 0.310, which was a large variation.

From the above results, it is a polyamide resin composition comprising a polyamide 6 resin (A), an impact resistant material (B) and a metal halide (C), and is measured at 260 ° C. of the polyamide resin composition. Filling with high-pressure hydrogen by forming a hollow molded product by a press blow molding method using a polyamide resin composition having a melt tension of 20 mN and a take-back speed at break of 50 m / min when measured at 260 ° C. It was also found that a hollow molded product in which the occurrence of defect points and cracks is suppressed and the retention stability is excellent can be obtained for the first time even if the pressure is released repeatedly.

The production method of the present invention is extremely useful because a hollow molded product that comes into contact with high-pressure hydrogen can be obtained, which can suppress the occurrence of defect points and cracks even when the high-pressure hydrogen is repeatedly filled and released.

Claims (5)

A method for producing a hollow molded product, which comprises a step of forming a hollow molded product by a press blow molding method using a polyamide resin composition, wherein the polyamide resin composition comprises 70 to 99 parts by weight of the polyamide 6 resin (A). A polyamide resin composition obtained by blending 0.005 to 1 part by weight of a metal halide (C) with a total of 100 parts by weight of 1 to 30 parts by weight of the impact resistant material (B). Manufacture of a hollow molded product that comes into contact with high-pressure hydrogen, characterized in that the melt tension measured at 260 ° C. is 20 mN or more and the take-back speed at break when measured at 260 ° C. is 50 m / min or more. Method. The above-mentioned polyamide 6 resin (A) is characterized in that the relative viscosity (ηr) of a 98% sulfuric acid solution having a resin concentration of 0.01 g / ml at a temperature of 25 ° C. is 3.3 to 7.0. 1. The method for producing a hollow molded product that comes into contact with high-pressure hydrogen according to 1. Production of a hollow molded product in contact with high-pressure hydrogen according to claim 1 or 2, wherein the impact-resistant material (B) contains an ethylene / α-olefin copolymer modified with an unsaturated carboxylic acid and / or a derivative thereof. Method. The ethylene / α-olefin copolymer modified with the unsaturated carboxylic acid and / or a derivative thereof was introduced from the modification with respect to 100 parts by weight of the ethylene / α-olefin copolymer. The method for producing a hollow molded product that comes into contact with high-pressure hydrogen according to claim 3, wherein the acid and / or a derivative portion thereof is 0.1 to 2.5 parts by weight. The method for producing a hollow molded product that comes into contact with high-pressure hydrogen according to any one of claims 1 to 4, wherein the metal halide (C) contains an alkali metal halide and / or copper iodide.