Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/435—Sulfonamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0038—Plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2023/00—Tubular articles
  • B29L2023/22—Tubes or pipes, i.e. rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/18—Applications used for pipes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics

Definitions

• the present invention relates to a polyamide resin composition for a single-layer hollow molded body and a single-layer hollow molded body.
• Chemical liquid and/or gas transport tubes for automobile piping including hydraulic tubes for power transmission in general industries and pneumatic tubes for automobile air brakes, are designed from the viewpoints of weight reduction and workability (assembleability).
• metal is being replaced as the main material by lightweight resin with excellent rust prevention properties.
• polyamide 11 or polyamide 12 which has excellent strength, toughness, chemical resistance, flexibility, blow moldability, etc., is used as a material for the chemical liquid and/or gas transport tube.
• Patent Document 1 discloses that polyamide 6/12 is used as a substitute for polyamide 12, and by adding a specific amount of plasticizer and modified polyolefin to this, it has the same flexibility as polyamide 12 and can be molded. It is disclosed that a polyamide resin composition with good properties can be obtained.
• Patent Document 2 discloses a polyamide resin composition containing a polyamide resin such as polyamide 6, an impact reinforcing material, a nylon plasticizer, etc. in a predetermined ratio, and it is said that it can be applied to an automobile fuel tube system. It is shown. In the examples, the physical properties, appearance, etc. of the injection molded products are evaluated.
• Patent Document 3 discloses a laminated tube consisting of at least four layers, in which the (b) layer contains a polyamide 6 composition (B1) and the like. Compared to polyamide 12, polyamide 6 is not suitable for producing hollow molded bodies by extrusion molding, and is usually not used in a single layer. Used in multilayer hollow molded bodies in combination with oriented resin layers.
• polyamide resin compositions for single-layer blow molded bodies in which the amounts of polyamide 11 and polyamide 12 are reduced or are not used at all.
• polyamide 6/12 of Patent Document 1 does not use polyamide 12, it has a high proportion of the monomer laurolactam or aminododecanoic acid, and a polyamide with a lower or no proportion of laurolactam or aminododecanoic acid is desired.
• the molded products in the examples were molded by injection molding suitable for polyamide 6, and there were no examples of hollow molded products by extrusion molding, but single-layer hollow molded products by extrusion molding.
• Patent Document 3 merely discloses the use of a layer of a composition containing polyamide 6 in one layer of a laminated tube consisting of at least four layers, and the description is pronounced of a single-layer hollow molded product. There is nothing.
• the present invention is a polyamide resin composition for a single-layer blow-molded body, which does not substantially use polyamide 11 and polyamide 12 and mainly contains polyamide 6, and has characteristics equivalent to those of a multi-layer blow-molded body. It is an object of the present invention to provide a composition that has excellent extrusion moldability into a hollow molded body, and the resulting molded body has excellent flexibility, impact resistance, and durability.
• a polyamide resin composition containing a predetermined polyamide 6, a polyolefin having a functional group, and a plasticizer can form a hollow molded body even when formed into a single layer. It was discovered that the extrusion moldability is excellent, and the resulting molded product is excellent in flexibility, impact resistance, and durability, leading to the present invention.
• a polyamide resin composition for extrusion molding for producing a single-layer blow molded body containing polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c); JIS K 6920 1 g of the polyamide 6 (a) is dissolved in 100 ml of 96% sulfuric acid, and the relative viscosity of the polyamide 6 (a) measured at 25° C.
• polyamide resin composition 100% by mass, containing 60 to 90% by mass of the polyamide 6 (a), 3 to 25% by mass of the polyolefin (b) having the functional group, and 3 to 20% by mass of the plasticizer (c);
• a polyamide resin composition for extrusion molding for producing a single-layer blow molded body containing polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c); JIS K 6920 1 g of the polyamide 6 (a) is dissolved in 100 ml of 96% sulfuric acid, and the relative viscosity of the polyamide 6 (a) measured at 25° C.
• polyamide resin composition 100% by mass, containing 66 to 89% by mass of the polyamide 6 (a), 3 to 25% by mass of the polyolefin (b) having the functional group, and 3 to 20% by mass of the plasticizer (c);
• the functional group-containing polyolefin (b) has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride; ethylene and carbon; A polyamide resin composition which is a copolymer with an ⁇ -olefin having a number of 3 or more.
• the polyolefin (b) having a functional group is an ethylene/1-butene copolymer having a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride; [ The polyamide resin composition according to any one of [1] to [3].
• the plasticizer (c) is at least one selected from the group consisting of benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters, [1] to [4] ]
• the polyamide resin composition according to [6] wherein the thermoplastic resin (d) is an aliphatic copolymerized polyamide resin.
• the aliphatic copolymerized polyamide resin is made of polyamide 6/12, polyamide 6/66/12, polyamide 6/11, polyamide 6/66/11, polyamide 6/610/12, and polyamide 6/612/12.
• [10] 0.25 to 20.0 mass of monomer units derived from laurolactam, aminododecanoic acid, undecanelactam, and aminoundecanoic acid in a total of 100 mass% of polyamide 6(a) and aliphatic copolymerized polyamide resin %, the polyamide resin composition according to any one of [7] to [9].
• [11] Contains 0.25 to 20.0% by mass of monomer units derived from adipic acid and hexamethylene diamine in a total of 100% by mass of polyamide 6(a) and aliphatic copolymerized polyamide resin, [7] ⁇ The polyamide resin composition according to any one of [10].
• a single-layer hollow molded article comprising the polyamide resin composition according to any one of [1] to [11].
• the single-layer hollow molded article according to [12] which is at least one member selected from the group consisting of pipes, tubes, hoses, and tanks.
• a polyamide resin composition for use in a single-layer blow molded body which does not substantially use polyamide 11 and polyamide 12 and contains polyamide 6 as a main component, and does not need to be made into a multilayer blow molded body.
• a composition which has properties equivalent to those of a multilayer hollow molded body, excellent extrusion moldability of the hollow molded body, and excellent flexibility, impact resistance, and durability of the obtained molded body.
• the name of polyamide resin is based on JIS K 6920-1. Furthermore, when a plurality of substances corresponding to each component are present in the composition, the content of each component means the total amount of the plurality of substances, unless otherwise specified.
• substantially not used means not intentionally used as a raw material.
• the polyamide resin composition preferably does not substantially contain polyamide 11 and polyamide 12.
• “not substantially used” and “substantially not included” mean that the total content of polyamide 11 and polyamide 12 in 100% by mass of the polyamide resin composition is less than 0.1% by mass. , preferably less than 0.05% by weight, more preferably less than 0.01% by weight.
• the term "substantially free" used in relation to ethylene-vinyl acetate means that the content of ethylene-vinyl acetate in 100% by mass of the polyamide resin composition is less than 0.1% by mass. preferably less than 0.05% by weight, more preferably less than 0.01% by weight.
• a first aspect of the present invention is a polyamide resin composition for extrusion molding for producing a single-layer blow molded body, comprising polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c).
• polyamide 6 (a) a polyolefin having a functional group
• plasticizer (c) a plasticizer
• 1 g of the polyamide 6(a) is dissolved in 100 ml of 96% sulfuric acid, and the relative viscosity of the polyamide 6(a) measured at 25°C is 3.0 to 4.5. Yes; in 100% by mass of the polyamide resin composition, 60 to 90% by mass of the polyamide 6(a), 3 to 25% by mass of the polyolefin (b) having the functional group, and 3% of the plasticizer (c).
• the polyolefin (b) having a functional group has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride; - A polyamide resin composition that is a copolymer with an olefin.
• Polyamide 6(a) has a relative viscosity of 3.0 to 4.5, a content of 60 to 90% by mass, and component (b) is selected from the group consisting of maleic anhydride and itaconic anhydride.
• polyamide 11 and polyamide 12 are substantially not used, even when a single layer is formed. It is possible to obtain a polyamide resin composition that has excellent extrusion moldability into a hollow molded product, and the resulting molded product has excellent flexibility, impact resistance, and durability.
• a second aspect of the present invention is a polyamide resin composition for extrusion molding for producing a single-layer blow molded body, which comprises polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c).
• polyamide 6 (a) a polyamide resin composition for extrusion molding for producing a single-layer blow molded body
• polyamide 6 (a) polyamide 6 (a)
• polyolefin having a functional group (b) a polyolefin having a functional group
• c plasticizer
• the polyamide resin composition in 100% by mass of the polyamide resin composition, 66 to 89% by mass of the polyamide 6(a), 3 to 25% by mass of the polyolefin (b) having the functional group, and 3% of the plasticizer (c) Contains ⁇ 20% by mass; the polyolefin (b) having a functional group has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride; - A polyamide resin composition that is a copolymer with an olefin.
• Polyamide 6(a) has a relative viscosity of 3.0 to 4.5, a content of 66 to 89% by mass, and component (b) selected from the group consisting of maleic anhydride and itaconic anhydride.
• component (b) selected from the group consisting of maleic anhydride and itaconic anhydride.
• a third aspect of the present invention is a single-layer hollow molded article containing polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c), and substantially free of ethylene-vinyl acetate.
• a polyamide resin composition for extrusion molding for manufacturing in accordance with JIS K 6920, 1 g of the polyamide 6 (a) is dissolved in 100 ml of 96% sulfuric acid, and the polyamide 6 (a) is measured at 25 ° C. has a relative viscosity of 3.0 to 4.5; in 100% by mass of the polyamide resin composition, 60 to 90% by mass of the polyamide 6(a) and 3 to 25% of the polyolefin (b) having the functional group are contained.
• the polyolefin (b) having the functional group is a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride.
• This is a polyamide resin composition which is a copolymer of ethylene and an ⁇ -olefin having 3 or more carbon atoms.
• Polyamide 6(a) has a relative viscosity of 3.0 to 4.5, a content of 60 to 90% by mass, and component (b) is selected from the group consisting of maleic anhydride and itaconic anhydride.
• polyamide 11 and polyamide 12 are substantially not used, even when a single layer is formed. It is possible to obtain a polyamide resin composition that has excellent extrusion moldability into a hollow molded product, and the resulting molded product has excellent flexibility, impact resistance, and durability. Further, even if the polyamide resin composition does not substantially contain ethylene-vinyl acetate, it is possible to obtain a hollow molded article having no microprotrusions and having a good appearance, and the polyamide resin composition does not substantially contain ethylene-vinyl acetate. Accordingly, a hollow molded body having good heat resistance can be obtained.
• the present invention also relates to a single-layer hollow molded article containing the polyamide resin composition of the first to third aspects.
• the single-layer hollow molded article containing the polyamide resin composition of the first embodiment is as follows: polyamide 6 (a), a polyolefin having a functional group (b), and a plasticizer (c). It is a single-layer hollow molded body containing a polyamide resin composition containing; in accordance with JIS K 6920, 1 g of the polyamide 6(a) is dissolved in 100 ml of 96% sulfuric acid, and the polyamide 6 is measured at 25°C.
• the polyolefin (b) having the functional group contains at least one selected from the group consisting of maleic anhydride and itaconic anhydride.
• a single-layer hollow molded product which is a copolymer of ethylene and an ⁇ -olefin having 4 or more carbon atoms, and which has a group derived from the above. The same applies to the single-layer hollow molded articles containing the polyamide resin compositions of the second and third embodiments.
• the present invention further relates to a method for producing a single-layer hollow molded body, which includes a step of extrusion molding the polyamide resin compositions of the first to third aspects.
• the manufacturing method according to the first aspect of the polyamide resin composition is specifically as follows: A method for manufacturing a single-layer hollow molded body, which includes a step of extrusion molding a polyamide resin composition;
• the polyamide resin composition includes polyamide 6(a), a polyolefin having a functional group (b), and a plasticizer (c); in accordance with JIS K 6920, 1 g of the polyamide 6(a) is dissolved in 100 ml of 96% sulfuric acid.
• Polyamide 6(a) has a relative viscosity of 3.0 to 4.5 when dissolved and measured at 25°C; 60 to 90% by mass of polyamide 6(a) in 100% by mass of the polyamide resin composition. , 3 to 25% by mass of the polyolefin (b) having the functional group and 3 to 20% by mass of the plasticizer (c); the polyolefin (b) having the functional group contains maleic anhydride and itaconic anhydride.
• a method for producing a copolymer of ethylene and an ⁇ -olefin having 4 or more carbon atoms which has a group derived from at least one group selected from the group consisting of: The same applies to the method for producing a single-layer blow molded body of the polyamide resin composition of the second and third embodiments.
• the present invention further relates to the use and method of using the polyamide resin compositions of the first to third aspects for producing a single-layer hollow molded body by extrusion molding.
• the use and method of using the polyamide resin composition of the first embodiment are specifically as follows: Use and method of using the polyamide resin composition for producing a single-layer hollow molded body by extrusion molding.
• the polyamide resin composition contains polyamide 6(a), a polyolefin having a functional group (b), and a plasticizer (c); According to JIS K 6920, 1 g of the polyamide 6(a) is 96% Polyamide 6(a) has a relative viscosity of 3.0 to 4.5 when dissolved in 100 ml of sulfuric acid and measured at 25°C; 90% by mass, 3 to 25% by mass of the polyolefin (b) having the functional group, and 3 to 20% by mass of the plasticizer (c); Uses and methods of using a copolymer of ethylene and an ⁇ -olefin having 4 or more carbon atoms, which has a group derived from at least one selected from the group consisting of itaconic anhydride. The same applies to the use and method of using the polyamide resin compositions of the second and third embodiments.
• Polyamide 6(a) is a polyamide resin consisting of structural units selected from the group consisting of ⁇ -caprolactam and ⁇ -aminocaproic acid. Polyamide 6(a) may be used alone or in combination of two or more. Regarding polyamide 6(a), in accordance with JIS K 6920, 1 g of polyamide 6(a) is dissolved in 100 ml of 96% sulfuric acid, and the relative viscosity measured at 25° C. is 3.0 to 4.5. By setting the relative viscosity within the above range, the extrusion moldability of the hollow molded body when formed into a single layer can be improved, and the rigidity and durability of the obtained molded body can be improved.
• the relative viscosity of polyamide 6(a) is 3.0 to 4.5, preferably 3.2 to 4.4, particularly preferably 3.4 to 4.2.
• the relative viscosity of polyamide 6(a) is preferably measured by the method described above, but the relative viscosity of each polyamide resin component and When the mixing ratio is known, the relative viscosity of polyamide 6(a) may be the average value calculated by summing the values obtained by multiplying each relative viscosity by the mixing ratio.
• Polyamide 6(a) is produced by polymerizing or copolymerizing the polyamide raw material by a known method such as melt polymerization, solution polymerization, solid phase polymerization, etc. During polymerization, a catalyst such as amines may be used. Further, after polymerization, the obtained resin may be melt-kneaded. The catalyst can be added at any stage during polymerization or at any stage during melt-kneading after polymerization, but it is preferably added at any stage during polymerization.
• the content of polyamide 6(a) in 100% by mass of the polyamide resin composition is 60 to 90% by mass, preferably 60 to 88% by mass, more preferably 65 to 85% by mass, It is more preferably 66 to 84% by weight, particularly preferably 67 to 84% by weight.
• the content of polyamide 6(a) in 100% by mass of the polyamide resin composition is 60 to 90% by mass, preferably 60 to 88% by mass, and preferably 65 to 88% by mass. It is more preferably 85% by mass, even more preferably 66-84% by mass, and particularly preferably 67-84% by mass. Further, the content of polyamide 6(a) in 100% by mass of the polyamide resin composition can also be 66 to 89% by mass. In the second embodiment, the content of polyamide 6(a) in 100% by mass of the polyamide resin composition is 66 to 89% by mass, preferably 66 to 86% by mass, and 66 to 84% by mass. It is more preferable that the amount is 67 to 84% by mass.
• the polyamide resin composition contains a polyolefin (b) having a functional group.
• the polyolefin (b) having a functional group is a component that imparts flexibility and impact resistance to the obtained molded article. Since the polyolefin (b) contains a functional group in its molecule that has an affinity for polyamide 6 (a), the reactivity and bonding properties between the amino groups of polyamide 6 and the functional groups of the polyolefin (for example, It is presumed that the impact resistance of the polyamide resin composition is improved when molded products are formed from the polyamide resin composition.
• the polyolefin (b) having a functional group may be used alone or in combination of two or more.
• Examples of the functional group of the polyolefin (b) having a functional group include a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. It is believed that at least a portion of the amino groups of polyamide 6(a) and these functional groups react. Among these, from the viewpoint of improving impact resistance, at least one selected from the group consisting of a carboxyl group, a carboxylic acid ester group, and a carboxylic acid anhydride group is preferable, and a carboxylic acid anhydride group is more preferable. preferable.
• Methods for introducing these functional groups into polyolefin include (i) a method of copolymerizing a copolymerizable monomer having a functional group during polymerization of polyolefin, (ii) a method of using a polymerization initiator, a chain transfer agent, etc. (iii) a method of introducing a functional group into the molecular chain or molecular end of a polyolefin, and (iii) a method of grafting a compound (graft compound) having a functional group that can be grafted with the above-mentioned functional group to a polyolefin. These introduction methods can be used alone or in combination as appropriate.
• copolymerizable monomers having these functional groups and the graft compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate , maleic anhydride, itaconic anhydride, cit
• maleic anhydride, itaconic anhydride or citraconic anhydride are preferred, maleic anhydride or itaconic anhydride is more preferred, and maleic anhydride is particularly preferred.
• the content of functional groups in polyolefin (b) having functional groups is calculated as follows: number of moles of functional groups (mmol)/mass of (b) ( kg) is preferably 25 mmol/kg or more and less than 200 mmol/kg, more preferably 35 mmol/kg or more and less than 150 mmol/kg, particularly preferably 40 mmol/kg or more and 120 mmol/kg or less.
• the content of functional groups in polyolefin (b) having functional groups can be determined, for example, when the polyolefin (b) has carboxyl groups, acid anhydride groups, or carboxylic acid ester groups, using a sample solution prepared using toluene and ethanol, It is measured by neutralization titration with a 0.1 mol/L KOH ethanol solution using phenolphthalein as an indicator.
• the polyolefin in the functional group-containing polyolefin (b) is preferably an (ethylene and/or propylene)/ ⁇ -olefin copolymer.
• the polyolefin (b) having a functional group includes the above-mentioned (ethylene and/or propylene)/ ⁇ -olefin copolymer having the above-mentioned functional group, and (having or not having the above-mentioned functional group) Examples include ethylene and/or propylene)/( ⁇ , ⁇ -unsaturated carboxylic acid and/or ⁇ , ⁇ -unsaturated carboxylic acid ester) copolymers, and these can be used alone or in combination of two or more. .
• the above (ethylene and/or propylene)/ ⁇ -olefin copolymer is a polymer obtained by copolymerizing ethylene and an ⁇ -olefin having 3 or more carbon atoms, and/or a polymer obtained by copolymerizing propylene with an ⁇ -olefin having 4 or more carbon atoms. It is a copolymerized polymer. From the viewpoint of flexibility and impact resistance of the resulting molded product, the upper limit of the number of carbon atoms in the ⁇ -olefin is preferably 20, more preferably 10.
• Examples of ⁇ -olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene.
• ethylene/ ⁇ -olefin copolymers having 3 or more carbon atoms are preferred, and ethylene/propylene copolymers or An ethylene/1-butene copolymer is more preferable, and an ethylene/1-butene copolymer is particularly preferable.
• (ethylene and/or propylene)/ ⁇ -olefin copolymers include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6 -Octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7 -nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2- norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropen
• the number of carbon atoms in the total 100 mol% of the ethylene monomer and the ⁇ -olefin monomer having 3 or more carbon atoms constituting the copolymer is preferably more than 5 mol% and 90 mol% or less, more preferably 7 to 87 mol%, and even more preferably 10 to 85 mol%. preferable.
• (ethylene and/or propylene)/( ⁇ , ⁇ -unsaturated carboxylic acid and/or ⁇ , ⁇ -unsaturated carboxylic acid ester) copolymer is ethylene and/or propylene and ⁇ , ⁇ -unsaturated carboxylic acid. and/or a copolymer with an ⁇ , ⁇ -unsaturated carboxylic acid ester monomer.
• the ⁇ , ⁇ -unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid.
• Examples of ⁇ , ⁇ -unsaturated carboxylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and acrylic acid.
• the functional group-containing polyolefin (b) is a polyolefin having a carbon number equal to ethylene and having a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride.
• a copolymer with three or more ⁇ -olefins is more preferable, and an ethylene/propylene copolymer or an ethylene/1-butene copolymer having a group derived from maleic anhydride is even more preferable, having a group derived from maleic anhydride.
• Particularly preferred are ethylene/1-butene copolymers containing groups.
• the functional group-containing polyolefin (b) includes ethylene and ⁇ having 4 or more carbon atoms, which has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride.
• the polyolefin (b) having a functional group has ethylene and a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride, and has 3 carbon atoms.
• a copolymer of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms which has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride. It is preferably a copolymer of ethylene and an ⁇ -olefin having 4 to 20 carbon atoms, which has a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride. More preferably, it is a combination.
• the polyolefin (b) having a functional group is an ethylene/propylene copolymer or an ethylene/1-butene copolymer having a group derived from at least one selected from the group consisting of maleic anhydride and itaconic anhydride.
• ethylene/propylene copolymers or ethylene/1-butene copolymers with groups derived from maleic anhydride are more preferred; /1-butene copolymers are particularly preferred.
• the polyolefin (b) having a functional group may contain a polyolefin having no functional group as long as the functions and characteristics of the polyamide resin composition are not impaired.
• the content of polyolefin (b) having a functional group in 100% by mass of the polyamide resin composition is preferably 3 to 25% by mass, more preferably 7 to 23% by mass, and 10 to 20% by mass. More preferably, the amount is 10 to 15% by mass.
• the polyamide resin composition contains a plasticizer (c).
• a plasticizer (c) By containing the plasticizer (c), flexibility can be imparted to the obtained molded article.
• the plasticizer (c) is preferably at least one selected from the group consisting of benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.
• benzenesulfonic acid alkylamides examples include benzenesulfonic acid propylamide, benzenesulfonic acid butylamide, benzenesulfonic acid 2-ethylhexylamide, and the like.
• toluenesulfonic acid alkylamides examples include N-ethyl-o-toluenesulfonic acid butylamide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, N-ethyl-p -Toluenesulfonic acid 2-ethylhexylamide and the like.
• hydroxybenzoic acid alkyl esters examples include ethylhexyl o-hydroxybenzoate, ethylhexyl p-hydroxybenzoate, hexyldecyl o-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, ethyldecyl o-hydroxybenzoate, and p-hydroxybenzoate.
• benzenesulfonic acid alkylamides such as benzenesulfonic acid butylamide and benzenesulfonic acid 2-ethylhexylamide; N-ethyl-p-toluenesulfonic acid butylamide, N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide, etc.
• toluenesulfonic acid alkylamides and hydroxybenzoic acid alkyl esters such as ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, and ethyldecyl p-hydroxybenzoate; More preferred are ethylhexyl acid and hexyldecyl p-hydroxybenzoate.
• the content of the plasticizer (c) in 100% by mass of the polyamide resin composition is preferably 3 to 20% by mass, more preferably 7 to 14% by mass, and 8 to 13% by mass. is particularly preferred.
• the polyamide resin composition may further include polyamide 6 (a) and a thermoplastic resin (d) other than the polyolefin having a functional group (b). preferable.
• the content of the thermoplastic resin (d) in 100% by mass of the polyamide resin composition is preferably 20% by mass or less, more preferably 5 to 15% by mass, and 7 to 13% by mass. is even more preferable.
• the total content of polyamide 6 (a), polyolefin having a functional group (b), and plasticizer (c) in 100% by mass of the polyamide resin composition is , preferably 80 to 98% by mass, more preferably 85 to 95% by mass, and even more preferably 87 to 93% by mass.
• the content of polyamide 6(a) in 100% by mass of the polyamide resin composition is preferably 60 to 85% by mass, more preferably 60 to 80% by mass, and 60 to 75% by mass.
• the content of polyolefin (b) having a functional group in 100% by mass of the polyamide resin composition is preferably 3 to 25% by mass, more preferably 7 to 23% by mass, and 10 to 15% by mass. It is more preferable that The content of the plasticizer (c) in 100% by mass of the polyamide resin composition is preferably 3 to 20% by mass, more preferably 7 to 14% by mass, and 8 to 13% by mass. is even more preferable.
• thermoplastic resin (d) high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene ( Polyolefin resins such as PP), polybutene (PB), and polymethylpentene (TPX); polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate/styrene copolymer (MS), methyl methacrylate/styrene /Polystyrene resins such as butadiene copolymer (MBS); polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly(ethylene terephthalate/ethylene isophthalate) copolymer (PET/PEI) ), polytrimethylene terephthalate (PTT), polycyclohexane dim
• Polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA); polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride Copolymers, polyvinyl resins such as vinylidene chloride/methyl acrylate copolymers; cellulose resins such as cellulose acetate and cellulose butyrate; polycarbonate resins such as polycarbonate (PC); thermoplastic polyimide (TPI), polyetherimide Polyimide resins such as , polyesterimide, polyamideimide (PAI), polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester elastomers, polyamide resins other than polyamide 6, etc., and in some cases, polyfluoride resins.
• PMMA polymethyl methacrylate
• PEMA polyethyl meth
• thermoplastic resin (d) is preferably a polyamide resin other than polyamide 6.
• polyamide resins other than polyamide 6 include homopolyamide resins other than polyamide 6 and copolyamide resins. Among these, aliphatic homopolyamide resins other than polyamide 6 and aliphatic copolyamide resins are preferred, and aliphatic copolyamide resins are more preferred, from the viewpoint of fluidity and extrusion moldability of the blow molded body. These may be used alone or in combination of two or more.
• Aliphatic homopolyamide resin is a polyamide resin consisting of one type of structural unit derived from an aliphatic monomer.
• the aliphatic homopolyamide resin may be made of at least one of one type of lactam and an aminocarboxylic acid that is a hydrolyzate of the lactam, or may be made of a combination of one type of diamine and one type of dicarboxylic acid. It may be something.
• the combination of diamine and dicarboxylic acid is considered to be one type of monomer unit.
• lactam examples include enantlactam, ⁇ -pyrrolidone, ⁇ -piperidone, ⁇ -octalactam, ⁇ -nonalactam, and ⁇ -decalactam.
• aminocarboxylic acid examples include 7-aminoheptanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, and the like.
• diamines examples include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, Tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, 2,2,4/2,4,4-trimethylhexamethylene Aliphatic diamines such as diamine; 1,3-/1,4-cyclohexyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexy
• dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid.
• aliphatic dicarboxylic acids such as pentadecanedioic acid, hexadecanedionic acid, octadecanedioic acid, eicosanedioic acid; 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornane
• aliphatic dicarboxylic acids such as pentadecanedioic acid, hexadecanedionic acid, octadecanedioic acid, eicosanedioic acid; 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornane
• Examples include alicyclic dicarboxylic acids such as dicarboxylic acids.
• the aliphatic homopolyamide resins include polyamide 4, polyamide 7, polyamide 9, polyamide 10, polyamide 44, polyamide 45, polyamide 46, polyamide 48, polyamide 49, polyamide 54, polyamide 55, polyamide 56, polyamide 66, Polyamide 410, Polyamide 412, Polyamide 58, Polyamide 59, Polyamide 510, Polyamide 512, Polyamide 64, Polyamide 65, Polyamide 68, Polyamide 69, Polyamide 610, Polyamide 612, Polyamide 96, Polyamide 98, Polyamide 99, Polyamide 105, Polyamide 616 , polyamide 618, polyamide 910, polyamide 912, polyamide 106, polyamide 108, polyamide 109, polyamide 1010, polyamide 1012, polyamide 125, polyamide 126, polyamide 129, polyamide 1210, polyamide 1212, polyamide 122, and the like.
• These aliphatic homopolyamide resins can be used alone or as a mixture of two or more.
• polyamide 66 is
• Aliphatic copolymerized polyamide resin is a polyamide resin composed of two or more types of structural units derived from aliphatic monomers.
• the constituent units of the aliphatic copolyamide resin are derived from monomers selected from the group consisting of combinations of diamines and dicarboxylic acids, lactams, and aminocarboxylic acids.
• the combination of diamine and dicarboxylic acid is considered to be one type of monomer unit.
• the same ones as those exemplified as raw materials for the aliphatic homopolyamide resin can be mentioned.
• dicarboxylic acid the same ones as those exemplified as raw materials for the aliphatic homopolyamide resin can be mentioned.
• lactam examples include the same lactams as those exemplified as raw materials for the aliphatic homopolyamide resin. Furthermore, ⁇ -caprolactam, ⁇ -undecanelactam and dodecanelactam ( ⁇ -laurolactam) can be used. Moreover, as the aminocarboxylic acid, the same ones as those exemplified as raw materials for the aliphatic homopolyamide resin can be mentioned. Furthermore, ⁇ -aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid can be used. These diamines, dicarboxylic acids, lactams and aminocarboxylic acids may be used alone or in combination of two or more.
• aliphatic copolyamide resins include copolymers obtained by combining two or more monomers that form polyamides exemplified as aliphatic homopolyamide resins, and more specifically, polyamide 4 /6, polyamide 6/66, polyamide 6/69, polyamide 6/610, polyamide 6/611, polyamide 6/612, polyamide 6/10, polyamide 6/11, polyamide 6/12, polyamide 6/66/12, Examples include polyamide 6/66/11, polyamide 6/66/610, polyamide 6/66/612, polyamide 6/610/12, polyamide 6/612/12, and the like. These aliphatic copolymer polyamide resins can be used alone or as a mixture of two or more.
• the aliphatic copolymerized polyamide resins include polyamide 6/12, polyamide 6/66/12, polyamide 6/11, and polyamide 6. /66/11, polyamide 6/610/12 and polyamide 6/612/12, preferably at least one selected from the group consisting of polyamide 6/12 and polyamide 6/66/12. It is more preferable that it is at least one type of polyamide, and particularly preferable that it is polyamide 6/66/12.
• the relative viscosity of the polyamide resin is determined by dissolving 1 g of the resin in 100 ml of 96% sulfuric acid at 25°C in accordance with JIS K 6920.
• it should be 2.5 or more and 5.0 or less. It is preferably 3.0 or more and 4.5 or less.
• Polyamide resins other than polyamide 6 are produced by polymerizing or copolymerizing the polyamide raw materials using known methods such as melt polymerization, solution polymerization, and solid phase polymerization. During polymerization, a catalyst such as amines may be used. Further, after polymerization, the obtained resin may be melt-kneaded. The catalyst can be added at any stage during polymerization or at any stage during melt-kneading after polymerization, but it is preferably added at any stage during polymerization.
• the polyamide resin composition may further contain a conductive filler.
• Conductivity means that, for example, if a flammable fluid such as gasoline comes into continuous contact with an insulator such as resin, static electricity may accumulate and cause a fire. It means to have electrical properties. This makes it possible to prevent explosions due to static electricity generated during transport of fluid such as fuel.
• the conductive filler includes all fillers added to impart conductivity to the resin, and includes granular, flake, and fibrous fillers.
• particulate fillers include carbon black and graphite.
• flaky filler examples include aluminum flakes, nickel flakes, and nickel coated mica.
• fibrous filler examples include metal fibers such as carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and stainless steel fibers. These can be used alone or in combination of two or more. Among these, carbon nanotubes and carbon black are preferred.
• Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of many essentially continuous layers of regularly arranged carbon atoms and an inner hollow region, with each layer and the hollow region are substantially concentrically disposed about the cylindrical axis of the fibril. Furthermore, it is preferable that the regularly arranged carbon atoms in the outer region are graphitic, and the diameter of the hollow region is 2 nm or more and 20 nm or less.
• the outer diameter of the carbon nanotube is preferably 3.5 nm or more and 70 nm or less, and 4 nm or more and 60 nm or less, from the viewpoint of providing sufficient dispersibility in the resin and good conductivity of the resulting resin molded body. It is more preferable.
• the aspect ratio (length/outer diameter ratio) of the carbon nanotubes is preferably 5 or more, more preferably 100 or more, and even more preferably 500 or more. By satisfying this aspect ratio, it is easy to form a conductive network, and excellent conductivity can be exhibited even when a small amount is added.
• Carbon black includes all carbon blacks that are generally used for imparting electrical conductivity.
• Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and acetylene black obtained by incomplete combustion in a furnace using crude oil as a raw material. Examples include, but are not limited to, furnace black such as Ketjen black produced by Kotchen Black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, and disk black. These can be used alone or in combination of two or more. Among these, acetylene black and furnace black are more preferred.
• the carbon black is preferable to have a good chain structure and a high agglomeration density. It is not preferable to incorporate a large amount of carbon black from the viewpoint of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, and preferably 5 nm or more and 100 nm or less. More preferably, it is 10 nm or more and 70 nm or less.
• the surface area is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more, and even more preferably 50 m 2 /g or more.
• the DBP (dibutyl phthalate) oil absorption amount is preferably 50 ml/100 g or more, more preferably 100 ml/100 g, and even more preferably 150 ml/100 g or more.
• the ash content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.
• the DBP oil absorption amount herein is a value measured by the method specified in ASTM D-2414.
• the volatile content of carbon black is preferably less than 1% by mass.
• the content of the conductive filler varies depending on the type of conductive filler used, so it cannot be unconditionally specified, but from the viewpoint of balance with conductivity, fluidity, mechanical strength, etc., the content should be 100 parts by mass of the polyamide resin composition. On the other hand, it is generally preferable that the amount is 3 parts by mass or more and 30 parts by mass or less.
• the surface resistivity value of the melt extrudate is preferably 10 8 ⁇ /square or less, more preferably 10 6 ⁇ /square or less. preferable.
• addition of the conductive filler tends to cause deterioration in strength and fluidity. Therefore, it is desirable that the content of the conductive filler be as small as possible if the target conductivity level can be obtained.
• the polyamide resin composition may contain antioxidants such as phenolic and phosphorus, heat stabilizers, ultraviolet absorbers, light stabilizers, additive impregnation agents, lubricants, inorganic fillers, electrostatic charges, etc., as necessary. It may also contain inhibitors, flame retardants, crystallization promoters, colorants, and the like. Each of these can be used alone or in combination of two or more. Note that the polyamide resin composition preferably does not contain a polyamide resin thickener.
• the polyamide resin composition has an MFR (temperature of 235°C and load of 2.16 kg) of 0. It is preferably 1 g/10 minutes or more and 20 g/10 minutes or less, more preferably 0.15 g/10 minutes or more and 15 g/10 minutes or less, and 0.18 g/10 minutes or more and 10 g/10 minutes or less. is more preferable, and particularly preferably 0.5 g/10 minutes or more and 10 g/10 minutes or less.
• thermoplastic resin (d) is an aliphatic copolyamide resin
• polyamide 6(a) and an aliphatic copolyamide resin are used.
• the content of monomer units derived from caprolactam and aminohexanoic acid (hereinafter also referred to as monomer units It is more preferably 99.3% by mass, even more preferably 80.0 to 99.0% by mass, and particularly preferably 96.0 to 98.0% by mass.
• thermoplastic resin (d) is an aliphatic copolyamide resin, laurolactam in the total 100% by mass of polyamide 6(a) and aliphatic copolyamide resin
• the content of monomer units derived from aminododecanoic acid, undecane lactam, and aminoundecanoic acid (hereinafter also referred to as monomer units Z) is preferably 0.25 to 20.0% by mass, and 0.35 to 15% by mass. It is more preferably 0.0% by weight, even more preferably 0.50 to 10.0% by weight, and particularly preferably 1.0 to 3.5% by weight.
• thermoplastic resin (d) is an aliphatic copolyamide resin, polyamide 6(a) and aliphatic copolyamide resin
• the content of monomer units derived from adipic acid and hexamethylene diamine (hereinafter also referred to as monomer units Y) in the total 100% by mass is preferably 0.25 to 20.0% by mass, and 0.35% by mass. It is more preferably from 15.0% by weight, even more preferably from 0.50 to 10.0% by weight, and particularly preferably from 1.0 to 3.5% by weight.
• thermoplastic resin (d) is an aliphatic copolymerized polyamide resin
• polyamide 6 The ratio (mass ratio) of the content of monomer units X to Z in the total of 100% by mass of (a) and aliphatic copolymerized polyamide resin is 60.0 to 99.5:0.25 to 20.0:0.
• .25 to 20.0 is preferable, 70.0 to 99.3: 0.35 to 17.5: 0.35 to 17.5 is more preferable, 80.0 to 99.0: 0.50 to 15.0: more preferably 0.50 to 15.0, particularly 93.0 to 98.0: 1.00 to 3.50: 1.00 to 3.50 preferable.
• the method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
• a method for mixing polyamide 6 (a), a polyolefin having a functional group (b) and a plasticizer (c), and an optional thermoplastic resin (d) and other components is to mix the polyamide 6 (a) using a tumbler and/or mixer.
• polyamide 6(a) a method of uniformly dry blending pellets of polyolefin (b) having a functional group and any optional components, and a liquid component such as a plasticizer (c) at the above-mentioned mixing ratio; polyamide 6( a) A method of dry blending the polyolefin (b) having a functional group, a plasticizer (c) and any optional components in advance at the concentration used during molding and melt-kneading; After blending some of the components, melt-kneading. , a method of further blending the remaining components and melt-kneading; or a method of blending some of the components and then mixing the remaining components using a side feeder during melt-kneading.
• a masterbatch in which each component is mixed with the thermoplastic resin (d) can also be used as pellets.
• Melt-kneading can be performed using a kneading machine such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.
• Polyamide resin compositions have excellent extrusion moldability for hollow molded bodies even when formed into a single layer, and the resulting molded bodies have excellent flexibility, impact resistance, and durability, so they are suitable for single-layer hollow molded bodies. Can be used.
• a single-layer hollow molded body can be manufactured by extrusion molding a polyamide resin composition into a tube shape, a hose shape, and various other shapes using an extrusion molding machine or the like.
• extrusion molding may be carried out by extruding the molten resin using an ordinary extrusion molding machine and then passing it through a die.
• the resin temperature during extrusion molding is 10 to 70° C. higher than the melting point of the polyamide resin composition.
• the outer surface, inner surface, etc. of the single-layer hollow molded body may be painted, coated, etc. within a range that does not impede the object of the present invention.
• Examples of single-layer hollow molded bodies include tanks, tubes, pipes, hoses, ducts, and housings. Among these, at least one selected from the group consisting of pipes, tubes, hoses, and tanks is preferable.
• the hollow molded product substantially does not use polyamide 11 and polyamide 12, and has properties equivalent to multilayer hollow molded products using these materials, and has excellent barrier properties against chemicals and gases, tensile strength, etc. Therefore, it has excellent economic efficiency and production stability.
• Single-layer hollow molded bodies can be used for automotive parts such as spoilers, air intake ducts, resonators, fuel tanks, gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and various other hoses, tubes, and tanks, and for electric vehicles.
• automotive parts such as spoilers, air intake ducts, resonators, fuel tanks, gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and various other hoses, tubes, and tanks, and for electric vehicles.
• Examples include mechanical parts such as tool housings and pipes, electrical and electronic parts such as tanks, tubes, and hoses, household and office supplies, building material-related parts, and furniture parts.
• the physical properties of the polyamide resin composition and raw materials were measured using the following methods.
• MFR Fluidity
• test pieces were prepared using an injection molding machine SE100D-C160S manufactured by Sumitomo Heavy Industries, Ltd. in accordance with ISO 294-1.
• a hollow molded body was produced by the following method, and its physical properties were measured.
• the extrusion temperature was set from 220°C to 260°C using a PAL32 (manufactured by Milfer) single-layer tube extrusion molding machine, and a tubular body was formed with an outer diameter of 8 mm and a thickness of 1 mm as target values. (also called a tube).
• Polyamide 6(a) Manufactured by UBE Co., Ltd., relative viscosity 4.08 Polyolefin (b) having a functional group: Tafmer (registered trademark) MH5020 (manufactured by Mitsui Chemicals, Inc., maleic anhydride-modified ethylene/1-butene copolymer, acid anhydride concentration: 100 mmol/kg) Plasticizer (c): Proviplast (registered trademark) 024 (manufactured by Proviron, benzenesulfonic acid butylamide)
• Thermoplastic resin (d-2): The mass ratio (X:Z) of monomer units X derived from caprolactam and aminohexanoic acid and monomer units Z derived from laurolactam and aminododecanoic acid is X:Z 80: Polyamide 6/12 (manufactured by UBE Co., Ltd., relative viscosity 4.08)
• Antioxidant triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan, IRGANOX® 245) and tris(2,4- 9:1 mixture of di-t-butylphenyl) phosphite (BASF Japan, IRGAFOS® 168)
• Example 1 Production of polyamide resin composition (A-1) Polyamide 6 (a) is mixed in advance with polyolefin (b) having a functional group and an antioxidant, and mixed in a twin-screw melt kneader (manufactured by Coperion Co., Ltd., model: ZSK). ), while plasticizer (c) was injected from the middle of the cylinder of the twin-screw melt-kneading machine from a metering pump, melt-kneaded at a cylinder temperature of 230°C to 250°C, and extruded the molten resin into a strand. .
• Example 2 Production of polyamide resin composition (A-2) Polyamide 6 (a), polyolefin (b) having a functional group, thermoplastic resin (d-1) and antioxidant were mixed in advance, and the mixture was mixed in a twin-screw melt kneader ( While supplying the plasticizer (c) to a machine (manufactured by Coperion Co., Ltd., model: ZSK), plasticizer (c) was injected from the middle of the cylinder of the twin-screw melt-kneading machine from a metering pump, and melt-kneaded at a cylinder temperature of 230°C to 250°C. , the molten resin was extruded into a strand.
• a machine manufactured by Coperion Co., Ltd., model: ZSK
• the monomer unit X derived from caprolactam and aminohexanoic acid is 97.14% by mass in the total of 100% by mass of polyamide 6 (a) and thermoplastic resin (d-1),
• the monomer unit Y derived from adipic acid and hexamethylene diamine was 1.43% by mass
• the monomer unit Z derived from laurolactam and aminododecanoic acid was 1.43% by mass.
• Example 8 Production of polyamide resin composition (A-8)
• thermoplastic resin (d-1) was changed to thermoplastic resin (d-2).
• Polyamide 6 (a)/polyolefin having a functional group (b)/plasticizer (c)/thermoplastic resin (d-2)/antioxidant 67.0/12.0/10.0/10.
• Pellets of a polyamide resin composition (A-8) having a mass ratio of 0/1.0 were obtained.
• the monomer unit X derived from caprolactam and aminohexanoic acid is 97.40% by mass in the total of 100% by mass of polyamide 6 (a) and thermoplastic resin (d-2),
• the monomer unit Z derived from laurolactam and aminododecanoic acid was 2.60% by mass.
• the monomer unit X derived from caprolactam and aminohexanoic acid is 97.48% by mass in the total of 100% by mass of polyamide 6 (a) and thermoplastic resin (d-1),
• the monomer unit Y derived from adipic acid and hexamethylene diamine was 1.26% by mass
• the monomer unit Z derived from laurolactam and aminododecanoic acid was 1.26% by mass.
• Table 1 shows the formulations of Examples 1 to 8 and Comparative Examples 1 to 3, and the evaluation results of these pellets and molded products obtained from the pellets.
• Comparative Example 1 the molding stability of the tube was poor and the tube could not be molded, so it was not possible to evaluate the tensile elongation at break, the appearance, and the presence or absence of fine protrusions of the tube.
• polyamide 6 (a) having a relative viscosity of 3.0 to 4.5, polyolefin (b) having a functional group, and plasticizer (c) are included in 100% by mass of the polyamide resin composition.
• Compositions of Examples 1 to 8 containing 60 to 90% by mass of polyamide 6 (a), 3 to 25% by mass of the polyolefin (b) having the functional group, and 3 to 20% by mass of the plasticizer (c) It can be seen that when the product is made into a single-layer hollow molded product by extrusion molding, the resin pressure is low, the tube molding stability and appearance are excellent, and the molded product has excellent flexibility, impact resistance, and durability.
• thermoplastic resin (d) caprolactam and The monomer unit X derived from aminohexanoic acid is 97.14% by mass, the monomer unit Y derived from adipic acid and hexamethylenediamine is 1.43% by mass, and the monomer unit Z derived from laurolactam and aminododecanoic acid is 1.
• the composition of Example 2 containing .43% by mass) has an extremely high tensile elongation at break when formed into a single-layer hollow molded article, and is excellent in durability.
• the composition of Comparative Example 1 which uses polyamide 6 (a) but does not contain polyolefin (b) having a functional group and plasticizer (c), had high resin pressure during tube molding and had poor tube molding stability. Moreover, the flexibility and impact resistance of the molded product were poor.
• the composition of Comparative Example 3 in which the thermoplastic resin (d-1) was blended instead of the plasticizer (c) was inferior in the fluidity of the composition and the flexibility and durability of the molded product.
• the polyamide resin composition of the present invention can be suitably used for producing a single-layer blow molded article.

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