JP2006282950A - Polyamide resin composition and molded product made of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide 11 and/or 12 resin composition which shows good extrusion moldability and yields a molded product excellent in creep property and impact property, and the molded product made of the same. <P>SOLUTION: The polyamide resin composition is obtained by compounding (B) 0.05-1.0 pt.wt N, N'-carbonyl bislactam of formula (I) [wherein Rs are each an alkyl group and may be identical to or different from each other] with (A) 100 pts.wt. polyundecaneamide (polyamide 11) and/or polydodecaneamide (polyamide 12) having a terminal amide group concentration of ≥15 (μeq/1 g polymer) and has relative viscosity measured according to JIS K-6920 in 96% sulfuric acid with a polymer concentration of 10 g/dm<SP>3</SP>at 25°C of 2.3-3.0. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyamide resin composition and a molded body comprising the same, and more specifically, polyamide 11 having a high molecular weight by melt mixing, good extrusion moldability, and excellent molded and excellent impact characteristics. And / or 12 resin compositions and molded articles comprising the same.

  Polyamide 11 or 12 is excellent in strength, toughness, chemical resistance, flexibility, and dimensional stability, and is used in various industrial fields as a material for injection molded products and materials for extruded products such as tubes, sheets and films. ing. In recent years, the development of applications in the field of extruded products such as automobiles, various industrial tubes, hoses and the like using polyamide 11 or 12 has progressed, and in particular, the demands in this field are becoming increasingly sophisticated and diversified.

  Especially in the field of extruded products, in the field of pipes for transportation of infrastructure such as gas and water that are buried underground, substitution of materials from metal to resin has progressed due to problems of rusting and resistance to earthquakes. It's getting on. In particular, as a metal substitute material, there is an increasing expectation for polyamide 11 or 12 having excellent creep strength and other strength, impact properties, flexibility, wear resistance, and chemical resistance, and the creation of a material that can be used in the field. Is required. Furthermore, in the molding of thick extruded products such as these pipes for transporting infrastructure, if the melt viscosity of the material is low, self-weight deformation called drawdown becomes a problem, and there is less uneven thickness and a uniform thickness distribution. And securing a sufficient thickness may be difficult. Therefore, there is a demand for polyamide 11 or 12 that is excellent in extrudability and can provide a molded product having good dimensional accuracy. In addition, in molded articles such as pipes for infrastructure transportation, creep characteristics and impact characteristics are one of the physical properties that are particularly important in terms of performance, extrudability is good, and creep characteristics and impact characteristics are excellent. There is an increasing demand for excellent polyamide 11 or 12.

  In general, it is said that the higher the molecular weight of a polymer, the better the properties related to durability such as creep properties and impact properties. Regarding the method of increasing the molecular weight of the polyamide, for example, after mixing a relatively low molecular weight polyamide with a phosphorus compound in a molten state, it is shaped into pellets, powder, etc., and then increased in molecular weight by a solid phase polymerization method. A method is disclosed (see Patent Document 1). However, the solid-phase polymerization method requires a long time to obtain a desired molecular weight and requires new equipment, resulting in an increase in production cost.

  On the other hand, a method of obtaining a high molecular weight polyamide by melting and mixing bislactam with a polyamide having a relatively low molecular weight is disclosed (see Patent Document 2). However, in this document, there is no description regarding polyamide 11 or 12, and further, technical description and suggestion regarding molded products using the resin composition, particularly thick extrusion molded products, hollow molded products, and laminated hollow molded products. Has not been made.

Japanese Patent Laid-Open No. 3-97732 JP-T-2001-521576

  An object of the present invention is to provide a polyamide 11 and / or 12 resin composition having a good extrusion moldability and having excellent creep characteristics and impact characteristics, and a molded body comprising the same.

  As a result of intensive studies to achieve the above object, the present inventor has blended polyamide 11 and / or polyamide 12 having a specific terminal amide group concentration with N, N′-carbonylbislactam. However, it has been found that the extrusion moldability is good, and the molded body made of the resin composition is excellent in creep characteristics and impact characteristics.

That is, the present invention
(B) with respect to 100 parts by weight of polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) having a terminal amide group concentration of 15 (μeq / g polymer) or more, (B) the following general formula (I) N, N′-carbonylbislactam represented by the formula: JIS K-6920 relative viscosity (in 96% sulfuric acid, polymer concentration 10 g / dm ³ , 25 ° C.) It is related with the polyamide resin composition characterized by being 2.3-3.0, and a molded object consisting thereof.

［式中、Ｒは、アルキル基であり、それぞれ同一であっても、異なっていてもよい。］

[Wherein, R is an alkyl group, which may be the same or different. ]

  Further, the molded body comprising the polyamide 11 and / or 12 resin composition relates to a hollow molded body selected from the group consisting of tubes, hoses, pipes, bottles, tanks, ducts, and further the polyamide 11 and / or 12 resin. The present invention relates to a laminated hollow molded article including a layer made of a composition and a layer made of a chemical liquid permeation preventive resin.

  The resin composition obtained by blending polyamide 11 and / or polyamide 12 having a specific terminal amide group concentration with N, N′-carbonylbislactam has good extrusion moldability, and the resulting molded product has creep characteristics. Excellent impact characteristics. Therefore, the polyamide 11 and / or 12 resin composition is preferably used as a hollow molded article such as a tube, a hose, a pipe, a bottle, a tank, or a duct, particularly as a thick hollow molded article. Furthermore, the resin composition makes it possible to produce a laminated hollow molded article at a high molding processing temperature, which has been difficult in the past, due to an increase in melt viscosity. It is excellent in properties such as properties, and is expected to be expanded in the future.

The present invention is described in detail below.
The polyundecanamide (polyamide 11) used in the present invention is a polyamide represented by the following formula (—CO— (CH ₂ ) ₁₀ —NH—) _n having an acid amide bond (—CONH—): It is representative and can be obtained by polymerizing 11-aminoundecanoic acid or undecane lactam. The polydodecanamide (polyamide 12) is typically a polyamide having an acid amide bond (—CONH—) represented by the following formula: (—CO— (CH ₂ ) ₁₁ —NH—) _n , It can be obtained by polymerizing 12-aminododecanoic acid or dodecane lactam.

  (A) Polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) may be a copolymer containing the above monomer as a main component (60% by weight or more). Examples of the copolymer component include lactam, aminocarboxylic acid, or nylon salt composed of diamine and dicarboxylic acid.

  Examples of lactams include pyrrolidone, piperidone, caprolactam, enantolactam, capryl lactam, undecane lactam (excluding polyamide 11), dodecane lactam (excluding polyamide 12), and aminocarboxylic acids include 6-aminocaproic acid and 7-aminoheptane. Examples include acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid (excluding polyamide 11), 12-aminododecanoic acid (excluding polyamide 12), and the like. These can use 1 type (s) or 2 or more types.

  Examples of the diamine constituting the nylon salt include ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8- Octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecane Diamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2 / 3-methyl-1,5- Pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4 / 2 , 4-trimethyl-1,6-hexanediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, Bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2, 2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethyl Alicyclic diamines such as amines, paraphenylenedia Emissions, meta-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, aromatic diamines such as 4,4'-diaminodiphenyl ether. These can use 1 type (s) or 2 or more types.

  The dicarboxylic acids constituting the nylon salt include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid dicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecane Dicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid, dimethylmalonic acid, 2-methyladipic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, trimethyladipic acid, etc. Aliphatic carboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3 / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid, and the like, Isof Phosphoric acid, terephthalic acid, 1,4 / 2,6 / 2,7-naphthalenedicarboxylic acid, 1,3 / 1,4-phenylenedioxydiacetic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4 Examples include aromatic dicarboxylic acids such as' -dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-diphenyldicarboxylic acid. These can use 1 type (s) or 2 or more types.

  In addition, (A) polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) used in the present invention may be a homopolymer, or a mixture with the copolymer described above. Alternatively, it may be a mixture with other polyamide resin. The content of polyamide 11 and / or polyamide 12 in the mixture is preferably 60% by weight or more, and more preferably 80% by weight or more.

  Other polyamide resins include polycaproamide (polyamide 6), polyundecanamide (polyamide 11) (excluding polyamide 11), polydodecanamide (polyamide 12) (excluding polyamide 12), polyethylene adipamide (polyamide) 26), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), azelamide polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexa Methylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polynonamethylene azide Amide (polyamide 96), azeramido polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), polynonamethylene undecamide (polyamide 911), polynonamethylene dodecamide (polyamide 912), Polynonamethylene terephthalamide (polyamide 9T), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), Polynonamethylenenaphthalamide (polyamide 9N), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecameti Dodecamide (polyamide 1012), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide ( Polyamide 10N), polyundecamethylene undecamide (polyamide 1111), polyundecamethylene dodecamide (polyamide 1112), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I) , Polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene adipamide (polyamide 126), poly Decamethylene azelamide (polyamide 129), polydodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I) ), Polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene beramide (polyamide MXD8), Polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene tele Phthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methane Terephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide ( Polyamide IPD6), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI) and these polyamide raw materials monomers A copolymer using several kinds of the like. These can use 1 type (s) or 2 or more types.

  (A) Polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) is a batch type reaction kettle, a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, It is produced using a known polyamide production apparatus such as a kneading reaction extruder such as a biaxial kneading extruder. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

The relative viscosity of polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) measured in accordance with JIS K-6920 (in 96% sulfuric acid, polymer concentration 10 g / dm ³ , 25 ° C. ) Is preferably 1.8 to 2.8, and more preferably 1.9 to 2.7. If the relative viscosity is less than the above value, the mechanical properties of the obtained molded product may be insufficient, and if the relative viscosity exceeds the above value, the extrusion pressure or torque becomes too high, and the molded product is produced. May be difficult.

The terminal amide group concentration of (A) polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) used in the present invention is the reaction with (B) N, N′-carbonylbislactam described later. Considering the properties, it is necessary to be 15 μeq / g of polymer or more. The terminal amino group concentration is preferably 20 μeq / g polymer or more, more preferably 30 μeq / g polymer 1 g or more. Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like material, it is more preferably 80 μeq / g of polymer.
The terminal amino group concentration can be measured by dissolving the polyamide in a phenol / methanol mixed solution and titrating with 0.05N hydrochloric acid.

  Usually, polyamide is often added in combination of one or more of monoamine, diamine, monocarboxylic acid and dicarboxylic acid in order to adjust the molecular weight and stabilize the melt during molding. In (A) polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) used in the present invention, the amount of the molecular weight regulator used depends on the terminal amide group concentration and relative viscosity defined above. It is decided appropriately.

  In (A) polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12), it is preferable to add diamine at the stage of polymerization in order to satisfy the condition of terminal amino group concentration. Specific examples of the diamine include ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2 / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2, 4 / 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonane Aliphatic diamines such as amines, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis ( 3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3 , 3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine, and other alicyclic diamines, paraphenylenediamine, metaphenylenediamine, paraxylylenediamine Metaxylylene range Emissions, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and aromatic diamines such as 4,4'-diaminodiphenyl ether. These can use 1 type (s) or 2 or more types. Among the above diamines, aliphatic diamines and / or alicyclic diamines are more preferable from the viewpoint of suppressing gel generation.

  The amount of the diamine added is appropriately determined by a known method in consideration of the terminal amino group concentration of the polyamide to be produced and the relative viscosity. Usually, it is preferable that the addition amount of a diamine is 0.5-20 meq / mol, respectively with respect to a polyamide raw material (monomer or monomer unit which comprises a repeating unit), and 1.0-10 meq / mol. More preferably (the equivalent of amino group is defined as 1 equivalent of the amount of amino group that reacts 1: 1 with a carboxyl group to form an amide group). When the addition amount exceeds the above value, it may be difficult to produce a polyamide having a desired viscosity.

  (B) N, N′-carbonylbislactam used in the present invention is a compound represented by the following formula (I).

  In the formula, R is an alkyl group, which may be the same or different. The number of carbon atoms forming the ring including the carbon of R is more preferably 4-16, and further more preferably 5-12. Preferable specific examples of R include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and the like.

(B) N, N′-carbonylbislactam represented by the general formula (I) is produced by reacting lactam with phosgene (COCl ₂ ) in benzene in the presence of a tertiary alkylamine as a catalyst. can do. It is not limited to these methods, and other methods can be used as appropriate.

  (B) The addition amount of N, N'-carbonylbislactam is 0.05 to 1.0 part by weight with respect to 100 parts by weight of (A) polyamide 11 and / or polyamide 12. The amount is preferably 0.1 to 0.75 parts by weight, and more preferably 0.15 to 0.5 parts by weight. When the addition amount is less than 0.05 parts by weight, the obtained invention effect is small, and when the blending amount exceeds 1.0 part by weight, the effect of the present invention corresponding to the addition amount is not manifested economically. Disadvantageous.

Therefore, (B) with respect to 100 parts by weight of polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) having a terminal amide group concentration of 15 (μeq / 1 g of polymer) or more according to the present invention. Polyamide 11 and / or 12 resin composition comprising 0.05 to 1.0 parts by weight of N, N′-carbonylbislactam is a relative viscosity measured according to JIS K-6920 (polymer concentration 10 g in 96% sulfuric acid). / Dm ³ , 25 ° C.) is 2.3 to 3.0. When the relative viscosity is within the above range, as described later, it is possible to obtain a molded article having good extrusion moldability and excellent creep characteristics and impact characteristics. The relative viscosity of the resin composition is preferably 2.35 to 2.9, and more preferably 2.4 to 2.8. If it is less than the above value, the excellent effect of the present invention cannot be obtained, and if it exceeds the above value, the extrusion pressure and torque become too high, making it difficult to produce a molded product. The melt flow rate measured at 250 ° C. and a load of 5000 g is preferably 0.1 to 19 g / 10 minutes, more preferably 0.2 to 15 g / 10 minutes, and 0.3 to 10 g. More preferably, it is / 10 minutes. Further, the melt flow rate measured at 250 ° C. under a load of 5000 g and the relative viscosity are expressed by the formula (1).

（ここで、ηｒは相対粘度、ＭＦＲはメルトフローレートである。）

(Where ηr is the relative viscosity and MFR is the melt flow rate)

It is particularly preferable that By satisfying the above formula, the raw material (A) polyamide 11 and / or 12 is effectively extended with (B) N, N′-carbonylbislactam with almost no crosslinking structure. Show.

  In the production of the polyamide 11 and / or 12 resin composition of the present invention, a predetermined amount of (A) polyamide 11 and / or polyamide 12 and (B) N, N′-carbonylbislactam in a pellet state or powder state is usually used. Pre-blended at room temperature using a high-speed rotary mixer such as a Henschel mixer or a low-speed rotary mixer such as a corn blender or tumbler used for mixing, and the mixture is further mixed with a Banbury mixer, a super mixer, a mixing roll, Using a melt-kneading method in which a mixture such as a twin-screw continuous mixer, Brabender plastograph, kneader, single-screw extruder, twin-screw extruder is used, and the mixture melts and kneads at a temperature at which the melting proceeds sufficiently and does not decompose. Generally done. In addition, (B) N, N′-carbonylbislactam having a high concentration is kneaded in advance into (A) polyamide 11 and / or polyamide 12 using a single-screw or twin-screw extruder, and this is diluted during molding. The so-called master batch method used in the above may be adopted. Moreover, at the time of melt kneading, it is preferable to volatilize and remove the generated water under an inert gas flow or under reduced pressure.

  Furthermore, in the polyamide 11 and / or 12 resin composition of the present invention, if necessary, an antioxidant such as phenol, thioether, phosphite, amine, isocyanurate, organotin, copper, etc. Heat stabilizers, resorcinol-based, salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, triazine-based, metal complex-based UV absorbers and hindered amine-based light stabilizers, benzenesulfonic acid alkylamide Plasticizers such as hydroxybenzoic acid alkyl esters and polyhydric alcohols, fatty acid metal salts, lubricants such as bisamide compounds, glass fibers, carbon fibers, carbon black, carbon nanotubes, graphite, wollastonite, zeolite, kaolin, mica , Clay, bentonite, montmorillonite , Talc, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, zinc oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, hydroxide Fillers such as aluminum, zinc, lead, nickel, aluminum, copper, iron, stainless steel, alkylamine, alkylamide, alkyl ether, alkylphenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate, Antistatic agents such as alkyl phosphates, quaternary ammonium salts, alkyl betaines, red phosphorus, tin oxide, zirconium hydroxide, aluminum hydroxide, magnesium hydroxide Flame retardants, inorganic fillers, fatty acids such as hydramines such as halogen, phosphate esters such as ammonium phosphate, ammonium polyphosphate, melamine or cyanuric acid such as melamine cyanurate and ethylene dimelamine dicyanurate Organic crystal nucleating agents such as metal salts, low molecular weight polyamides, higher fatty acids, higher fatty acid esters, higher aliphatic alcohols and other crystallization accelerators, polyolefin compounds, silicone compounds, long chain aliphatic ester compounds, Release agents such as long-chain aliphatic amide compounds, ethylene / α-olefin copolymers, ethylene / α, β-unsaturated carboxylic acid copolymers, ethylene / α, β-unsaturated carboxylic acid esters Copolymers, ionomer polymers, unhydrogenated or hydrogenated aromatic vinyl compounds / conjugated diene compound block copolymers, and these Impact modifiers such as modified products, foaming agents, perylene, perinone, heterocyclic, disazo, monoazo, naphtholazo, azo lake, azomethine, phthalocyanine, selenium, dye lake, quinacridone , Dioxazine, diketopyrrolopyrrole, anthraquinone, anthrapyridine, ansanthrone, isoindolinone, indanthrone, flavanthrone, indigo, thioindigo, quinophthalone, quinoline, benzimidazo Examples of the colorant include rhon, triphenyl methane, chromate molybdate, sulfide / selenide, ferrocyanide, bismuth panadate, calcium carbonate, carbon black, titanium oxide, and yellow titanium.

  In the polyamide 11 and / or 12 resin composition of the present invention, it is also possible to add (C) cyclic imino ether represented by the following general formula (II).

  In the formula, R1 is a divalent organic group selected from the group consisting of ethylene, substituted ethylene, trimethylene and substituted trimethylene, and the ring structure is a 5-membered ring or a 6-membered ring. R2 is a divalent organic group selected from the group consisting of an alkylene group, a cycloalkylene group, and an arylene group. N in the formula is 0 or 1.

  R1 in the general formula (II) is a divalent organic group selected from the group consisting of ethylene, substituted ethylene, trimethylene and substituted trimethylene, and the substituted ethylene or substituted trimethylene has an alkyl group having 1 to 10 carbon atoms. , An aryl group having 6 to 15 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl, nonyl, decyl and the like, and examples of the aryl group include phenyl, naphthyl, diphenyl, and the following general formula (III An aryl group represented by

(Where R3 is —O—, —CO—, —S—, —SO ₂ —, —CH ₂ —, —CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —, etc.). Examples of the cycloalkyl group include cyclohexyl. Of these, R5 is more preferably ethylene or trimethylene.

  R2 in the general formula (II) is a divalent organic group selected from the group consisting of an alkylene group, a cycloalkylene group, and an arylene group. For example, R1 is an alkylene group having 1 to 10 carbon atoms and 6 to 15 carbon atoms. Examples thereof include an arylene group, a cycloalkylene group having 5 to 12 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms. Specific examples of the alkylene group include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and dimethylmethylene, and the arylene group includes phenylene, naphthylene, and diphenylene. And an arylene group represented by the following general formula (IV):

(Where R4 is —O—, —CO—, —S—, —SO ₂ —, —CH ₂ —, —CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —, etc.). Examples of the cycloalkylene group include cyclohexylene.

  In the (C) cyclic imino ether represented by the general formula (II), a 5-membered ring is a compound called bisoxazoline, and a 6-membered ring is a compound called bisoxazine. Specifically, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2 , 2'-bis (4,4'-dimethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl-2-) Oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline) 2,2′-bis (4-phenyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2, 2'-m-phenylenebis (2-oxazoline), 2,2 '-P-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-o-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2, 2'-tetramethylene bis (2-oxazoline), 2,2'-hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-decamethylene bis (2 -Oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-9,9 Bisoxazolines such as' -diphenoxyethanebis (4,4'-dimethyl-2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline) Compounds, and 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 '-Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylenebis ( 5, 6 Dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis (5,6-dihydro) -4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5,6-dihydro-4H- 1,3-oxazine) and 2,2′-p, p′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like. These can use 1 type (s) or 2 or more types.

  Among these compounds, 2,2′-bis (2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2′-m-phenylenebis (2-oxazoline), 2, 2'-bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 ' -M-Phenylenebis (5,6-dihydro-4H-1,3-oxazine) is preferred.

  These compounds can be easily synthesized by a method of ring closure by reacting the corresponding bisamide alcohol with a dehydrating agent such as concentrated sulfuric acid or thionyl chloride, or a method of ringing by reacting the corresponding bisamide halide with an alkali. It is not limited to this method, Other methods can also be used suitably.

  The amount of (C) cyclic iminoether added is preferably 0.1 to 1.0 part by weight, and 0.2 to 0.75, relative to 100 parts by weight of (A) polyamide 11 and / or polyamide 12. More preferably, it is part by weight.

  The polyamide 11 and / or 12 resin composition of the present invention is obtained by a known molding method, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, melt spinning, etc. Films, sheets, tubes, hoses, pipes, bottles, tanks, ducts, and other various shapes can be produced. Furthermore, since the polyamide 11 and / or 12 resin composition has good extrudability and is excellent in creep characteristics and impact characteristics, hollow molded articles such as tubes, hoses, pipes, bottles, tanks, ducts, etc. It is preferable to be used as

  Tubes, hoses, or pipes are manufactured using an extruder, melt-extruded, extruded into a cylindrical shape through an annular die, shaped through a sizing foamer that controls the dimensions, cooled in a water tank, etc., and then wound up by a take-up machine Is done. At that time, by using the polyamide 11 and / or 12 resin composition of the present invention, the extruded molten resin does not hang down between the die and the sizing foamer, and has a uniform thickness with little uneven thickness. It has a distribution and can secure a sufficient thickness.

  The production of bottles, tanks or ducts is made by extruding a resin from an extruder into a die having a circular flow path to make a parison, and expanding the parison by gas pressure and bringing it into close contact with a mold. Done. At that time, by using the polyamide 11 and / or 12 resin composition of the present invention, when forming a parison to be blown, there is little self-weight deformation called drawdown, and a blow hollow molded product is punctured. It has a strength that can be stretched without being, and has a uniform thickness distribution with little uneven thickness, and a sufficient thickness can be ensured.

  The polyamide 11 and / or 12 resin composition of the present invention has good extrudability and is excellent in creep characteristics and impact characteristics, and has a high utility value by itself. By laminating, it is possible to add more characteristics.

  In particular, automobile piping hoses are transported with alcohol-containing gasoline blended with alcohols such as ethanol from the viewpoint of saving gasoline consumption and improving performance. In recent years, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through piping hose partition walls have been implemented. For such strict regulations, the single layer hose that uses polyamide 11 or polyamide 12 alone, which has been used in the past and has excellent strength, toughness, chemical resistance, and flexibility, has sufficient anti-permeability properties for alcohol-containing gasoline. Rather, as a method for solving this problem, a laminated hose in which a resin with good chemical solution permeation prevention properties (sometimes referred to as a chemical solution permeation prevention resin) has been proposed has been proposed. Are polymetaxylylene adipamide (polyamide MXD6), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene naphthalamide (polyamide 9N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene naphthalamide (Polyamide 12N), polybutylene naphthalate (PBN), liquid crystal polyester (LCP), polyphenylene sulfide (PPS), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP) , FEP), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene, / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoro Ethylene / tetrafluoroethylene / ethylene copolymer (CTFE / TFE / Et), chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer (CTFE / TFE / HFP) , Chlorotrifluoroethylene / tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (CTFE / TFE / PAVE), and the like. At this time, if necessary, an adhesive layer may be provided between the polyamide 11 and / or 12 resin composition of the present invention and the layer made of the chemical liquid permeation preventive resin, or the polyamide 11 and / or the present invention. You may use the chemical | medical solution permeation-proof resin which has a functional group which can adhere | attach with 12 resin composition.

  The chemical solution permeation-preventing resin has a higher molding processing temperature than the generally used polyamide 11 or polyamide 12 or the like. In addition, the static electricity generated by the internal friction of the chemical circulating in the pipe or friction with the pipe wall accumulates, and there is a risk of explosion by igniting the chemical. In the resin composition containing the hose, the hose is manufactured at an extremely severe molding processing temperature in order to ensure fluidity. Furthermore, since it has impact absorbability and ease of attachment, a molded body having a corrugated region is manufactured. The molding processing temperature at the time of manufacturing the molded body having the corrugated region is usually 10 to 20 ° C. higher than the molding processing temperature of the molded body not having the corrugated region in order to facilitate molding. The polyamide 11 and / or 12 resin composition of the present invention enables production of a laminated molded body at a high molding processing temperature, which has been difficult in the past, due to an increase in melt viscosity. is there.

  In the present invention, the laminated molded body is preferably a laminated hollow molded body such as a tube, a hose, a pipe, a bottle, a tank, or a duct. As a method for producing a laminated hollow molded body, melt extrusion is performed using an extruder corresponding to the number of layers or the number of materials, and the melt is extruded and supplied into a die. Lamination method (co-extrusion method), or once a single-layer hollow molded body or a laminated hollow molded body manufactured by the above-mentioned method is manufactured in advance, and an adhesive is sequentially applied to the outside as necessary. And a method (coating method) in which the resins are integrated and laminated. The laminated hollow molded body of the present invention is manufactured by a co-extrusion method in which various materials are co-extruded in a molten state, and both are thermally fused (melt-bonded) to produce a laminated molded hollow molded body in one step. Is preferred.

  In addition, when the obtained laminated hollow molded body has a complicated shape, or when it is subjected to heat bending after molding to form a molded product, the above-described laminated hollow molded body is used to remove residual distortion of the molded product. After the formation, it is possible to obtain a desired molded product by heat treatment for 0.01 to 10 hours at a temperature lower than the lowest melting point among the melting points of the resin constituting the hollow molded body.

  A laminated hollow molded body may have a corrugated region as described above. The waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region is not limited to having the entire length of the laminated hose, but may be partially provided in an appropriate region on the way. The corrugated region can be easily formed by first molding a straight tubular hollow molded body and then molding it to obtain a predetermined corrugated shape or the like. Furthermore, for example, necessary parts such as a connector can be added, or an L shape or a U shape can be formed by bending.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
In addition, the physical-property measurement in an Example and a comparative example was performed as follows.

The properties of polyamide 11 and / or 12 were measured by the following method.
[Relative viscosity]
According to JIS K-6920, the measurement was performed in 96% sulfuric acid under the conditions of a polyamide concentration of 1% and a temperature of 25 ° C.

[Terminal carboxyl group concentration]
A predetermined amount of polyamide sample is placed in a three-necked pear-shaped flask, 40 mL of benzyl alcohol is added, and then immersed in an oil bath set at 180 ° C. under a nitrogen stream. The mixture was stirred and dissolved by a stirring motor attached to the upper part, and titrated with an N / 20 sodium hydroxide solution using phenolphthalein as an indicator to determine the terminal carboxyl group concentration.

[Terminal amino group concentration]
Put a predetermined amount of polyamide sample in a conical flask with a stopcock, add 40 mL of a pre-adjusted solvent phenol / methanol (volume ratio 9/1), stir and dissolve with a magnetic stirrer, and use thymol blue as an indicator Then, titration with N / 20 hydrochloric acid was performed to determine the terminal amino group concentration.

The characteristics of the fluorine-containing polymer were measured by the following method.
[Composition of fluorinated polymer]
It was measured by melt NMR analysis and fluorine content analysis.

[Number of terminal carbonate groups in fluorine-containing polymer]
As for the number of terminal carbonate groups in the fluorine-containing polymer, the peak to which the carbonyl group of the carbonate group (—OC (═O) O—) belongs appears at the absorption wavelength of 1809 cm ⁻¹ by the infrared absorption spectrum analysis. absorbance was measured to calculate the number of main chain carbonate groups to the number ¹⁰⁶ carbons in the fluorine-containing polymer by the following equation.
[Number of carbonate groups relative to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer] = 500 AW / εdf
A: Absorbance at peak of carbonate group (—OC (═O) O—) ε: Molar absorbance coefficient [cm ⁻¹ · mol ⁻¹ ] of carbonate group (—OC (═O) O—). Ε = 170 from the model compound.
W: Composition average molecular weight calculated from the monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm]

(Evaluation of the physical properties)
[Creep characteristics]
Both ends of the ASTM No. 3 tensile test piece were cut off to prepare a test piece having a central parallel part of 190 mm. Using a creep tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), a test piece was sandwiched between 110 mm chucks, and a creep test was performed under conditions of a test temperature of 80 ° C. and a load of 46 kg. The value of creep strain (%) was obtained from the difference between the distance between chucks at the start of the test and the distance between chucks after 100 hours of testing. The smaller the creep strain value, the better the creep characteristics.

[Charpy impact strength with notch]
The notched Charpy impact strength at 0 ° C. was measured by a method based on ISO 179 / 1eA.

(Alcohol-containing gasoline permeation prevention)
One end of a hose cut to 200 mm was sealed, and alcohol-containing gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio was placed inside, and the remaining end was also sealed. Thereafter, the entire weight was measured, and then the test hose was placed in an oven at 60 ° C., and the change in weight was measured every day. The change in weight per day was divided by the surface area per meter of hose to calculate the alcohol-containing gasoline permeation amount (g / m ² · day).

(Interlayer adhesion)
The hose cut to 200 mm was further cut in half in the longitudinal direction to create a test piece. Using a Tensilon universal testing machine, a 180 ° peel test was performed at a tensile speed of 50 mm / min. The peel strength was read from the maximum point of the SS curve, and the interlayer adhesion was evaluated.

[Materials Used in Examples and Comparative Examples]
(A1) Polyamide 11 and / or polyamide 12 resin composition (A-1) Manufacture of polyamide 12 In a 70 liter autoclave, 20 kg of dodecane lactam and 1 kg of water were charged, the inside of the polymerization tank was replaced with nitrogen, and then heated to 100 ° C. At this temperature, the reaction system was stirred so as to be in a uniform state. Next, the temperature in the polymerization tank was raised to 260 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 3.5 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellet was dried under reduced pressure. The relative viscosity of the polymer was 2.42, the terminal amino group concentration was 28 μeq / g, the carboxyl group concentration was 34 μeq / g, and the melt flow rate measured at 250 ° C. under a load of 5000 g was 5.5 g / 10 minutes (hereinafter referred to as the following). The polyamide 12 is referred to as (A-1)).

(A-2) Manufacture of polyamide 11 In a 70 liter autoclave, 20 kg of 11-aminoundecanoic acid and 1 kg of water were charged, the inside of the polymerization tank was replaced with nitrogen, and then heated to 100 ° C., and the reaction system was uniformly at this temperature. It stirred so that it might become a state. Next, the temperature in the polymerization tank was raised to 260 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 0.4 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellet was dried under reduced pressure. The polymer had a relative viscosity of 2.40, a terminal amino group concentration of 30 μeq / g, a carboxyl group concentration of 32 μeq / g, a melt flow rate measured at 250 ° C. under a load of 5000 g, and 8.5 g / 10 minutes (hereinafter referred to as “following”). The polyamide 11 is referred to as (A-2)).

(A-3) Manufacture of polyamide 11 (A-2) In the manufacture of polyamide 11, pellets were produced in the same manner as in the manufacture of (A-2) polyamide 11 except that 0.087 kg of 30% phosphoric acid aqueous solution was further charged. Got. The pellets are supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt kneaded at a cylinder temperature of 180 to 260 ° C., and water is removed from the vent by volatilization under reduced pressure. After extrusion into a strand, this was introduced into a water bath, cooled, cut and vacuum dried. The relative viscosity of the polymer was 2.75, the terminal amino group concentration was 0 μeq / g, the carboxyl group concentration was 107 μeq / g, and the melt flow rate measured at 250 ° C. under a load of 5000 g was 6.5 g / 10 minutes (hereinafter referred to as the following). The polyamide 11 is referred to as (A-3)).

(A1-1) Manufacture of polyamide 12 resin composition (B-1) N, N'-carbonylbiscaprolactam (CBC) (manufactured by DSM Co., Ltd., ALLINCO-CBC) is mixed in advance with the (A-1) polyamide 12 And supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, Ltd., model: TEX44). Polyamide 1299 is melt-kneaded at a cylinder temperature of 180 to 260 ° C., volatilized and removed from the vent under reduced pressure, and the molten resin is extruded into a strand shape, which is then introduced into a water bath, cooled, cut and vacuum dried. A pellet of polyamide 12 resin composition consisting of 0.5% by weight and 0.5% by weight of N, N′-carbonylbiscaprolactam was obtained. The relative viscosity of the resin composition was 2.58, 250 ° C., and the melt flow rate measured at a load of 5000 g was 1.9 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-1)). .

(A1-2) Manufacture of polyamide 12 resin composition (A1-1) In the manufacture of polyamide 12 resin composition, the blending ratio of (A) polyamide 12 and (B) N, N′-carbonylbiscaprolactam (CBC) Except having changed into the ratio shown in Table 1, the pellet of the polyamide 12 resin composition was obtained by the method similar to manufacture of the (A1-1) polyamide 12 resin composition. The resin composition had a relative viscosity of 2.63, a melt flow rate of 1.5 g / 10 minutes measured at 250 ° C. and a load of 5000 g (hereinafter, this polyamide resin composition is referred to as (A1-2)). .

(A1-3) Production of polyamide 12 resin composition (A1-1) In production of polyamide 12 resin composition, (A) polyamide 12 and (B) N, N′-carbonylbiscaprolactam (CBC) Except having changed into the ratio shown in Table 1, the pellet of the polyamide 12 resin composition was obtained by the method similar to manufacture of the (A1-1) polyamide 12 resin composition. The relative viscosity of the resin composition was 2.50, 250 ° C., and the melt flow rate measured at a load of 5000 g was 2.8 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-3)). .

(A1-4) Production of polyamide 12 resin composition (A1-1) In production of polyamide 12 resin composition, (A) polyamide 12 and (B) N, N'-carbonylbiscaprolactam (CBC) Except having changed into the ratio shown in Table 1, the pellet of the polyamide 12 resin composition was obtained by the method similar to manufacture of the (A1-1) polyamide 12 resin composition. The relative viscosity of the resin composition was 2.43, and the melt flow rate measured at 250 ° C. and a load of 5000 g was 4.1 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-4)). .

(A1-5) Manufacture of a polyamide 11 resin composition (A1-1) In the manufacture of a polyamide 12 resin composition, (A1) except that the polyamide 12 was changed to (A-2) polyamide 11 (A1- 1) Polyamide 11 resin composition pellets were obtained in the same manner as in the production of the polyamide 12 resin composition. The relative viscosity of the resin composition was 2.56, 250 ° C., and the melt flow rate measured at a load of 5000 g was 3.8 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-5)). .

(A1-6) Production of polyamide 12 resin composition (A1-1) In production of polyamide 12 resin composition, (A-1) polyamide 12, (B) N, N′-carbonylbiscaprolactam (CBC) (DSM (C) 2,2′-m-phenylenebis (2-oxazoline) (1,3-PBO) (manufactured by Mikuni Pharmaceutical Co., Ltd., CP resin A component 1) , 3-PBO), except that (A1-1) Polyamide 12 99.0 wt%, N, N′-carbonylbiscaprolactam 0.5 wt. %, 2,2′-m-phenylenebis (2-oxazoline) 0.5 wt% polyamide 12 resin composition pellets were obtained. The relative viscosity of the resin composition was 2.48, 250 ° C., and the melt flow rate measured at a load of 5000 g was 1.7 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-6)). .

(A1-7) Manufacture of Polyamide 12 Resin Composition (A-1) Polyamide 12 (B) N, N′-carbonylbiscaprolactam (CBC) (DSM Co., Ltd., ALLINCO-CBC), improved impact While a maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Co., Ltd., JSR T7712SP) is mixed in advance as a material and supplied to a biaxial melt kneader (manufactured by Nippon Steel Works, Ltd., model: TEX44), From the middle of the cylinder of the biaxial melt kneader, benzenesulfonic acid butyramide is injected as a plasticizer with a metering pump, melt-kneaded at a cylinder temperature of 180 to 260 ° C., and the molten resin is extruded into a strand shape. Introduced into water tank, cooled, cut and vacuum dried, polyamide 12 resin 84.5 wt%, N, N'-carbonylbiscaprola Pellets of polyamide 12 resin composition comprising 0.5% by weight of cutam, 10% by weight of impact modifier, and 5% by weight of plasticizer were obtained. The melt flow rate of the resin composition measured at 250 ° C. and a load of 5000 g was 1.0 g / 10 minutes (hereinafter, this polyamide resin composition is referred to as (A1-7)).

Fluorine-containing polymer (chemical solution permeation prevention resin)
(E-1) Production of fluorinated polymer An autoclave with a stirrer having an internal volume of 174 liters was degassed, and 51 kg of ion-exchanged water, 35 kg of perfluorocyclobutane, perfluoro (methyl vinyl ether) (CF2 = CFOCF3) [PMVE 10.4 kg was charged, and the inside of the autoclave was kept at 35 ° C. Next, tetrafluoroethylene [TFE] was injected to 0.8 MPa, and then 0.38 kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was added to initiate polymerization. A monomer mixed gas having a molar ratio of TFE / PMVE = 87/13 was continuously charged so that the pressure was kept constant during the polymerization. 20 hours after the start of polymerization, the autoclave internal temperature was cooled to room temperature and the pressure in the polymerization layer was purged to normal pressure. The obtained slurry-like fluorine-containing polymer was washed with water and dried to obtain 20 kg of a fluorine-containing polymer powder. This powder was melted at 180 to 285 ° C. using a short screw extruder to prepare a fluorine-containing polymer pellet, and then heated and dried at 150 ° C. (hereinafter, this fluorine-containing polymer was (E-1).)

  The composition of the fluorine-containing polymer is 87.3 / 12.7 in terms of a molar ratio of polymerized units based on TFE / polymerized units based on PMVE, and the carbonate end groups derived from the polymerization initiator of the fluorine-containing polymer. The number was 230. The melting point was 225 ° C.

  (E-1) 100 parts by weight of a fluorine-containing polymer and 13 parts by weight of carbon black (manufactured by Electrochemical Co., Ltd.) were mixed in advance, and a biaxial melt kneader (manufactured by Toshiba Machine Co., Ltd., model: TEM-) 48SS), melt-kneaded at a cylinder temperature of 240-300 ° C, extrude the molten resin into a strand, introduce it into a water tank, cool the discharged strand with water, cut the strand with a pelletizer, and remove moisture Therefore, it was dried for 10 hours with a dryer at 120 ° C. to obtain conductive fluorine-containing polymer pellets (hereinafter, this conductive fluorine-containing polymer is referred to as (E-2)).

Example 1
A test piece was molded by an injection molding method using the polyamide 12 resin composition (A1-1), and the creep characteristics and Charpy impact strength were measured. The results are shown in Table 1.

Example 2
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1 except that the polyamide 12 resin composition (A1-1) was changed to (A1-2) in Example 1. The results are shown in Table 1.

Example 3
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1, except that the polyamide 12 resin composition (A1-1) was changed to (A1-3) in Example 1. The results are shown in Table 1.

Example 4
In Example 1, except that the polyamide 12 resin composition (A1-1) was changed to the polyamide 11 resin composition (A1-5), the creep characteristics and Charpy impact strength were measured in the same manner as in Example 1. did. The results are shown in Table 1.

Example 5
In Example 1, except that the polyamide 12 resin composition (A1-1) was changed to the polyamide 12 resin composition (A1-6), the creep characteristics and Charpy impact strength were measured in the same manner as in Example 1. did. The results are shown in Table 1.

Comparative Example 1
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1 except that the polyamide 12 resin composition (A1-1) was changed to polyamide 12 (A-1) in Example 1. The results are shown in Table 1.

Comparative Example 2
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1 except that the polyamide 12 resin composition (A1-1) was changed to polyamide 11 (A-2) in Example 1. The results are shown in Table 1.

Comparative Example 3
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1, except that the polyamide 12 resin composition (A1-1) was changed to polyamide 11 (A-3) in Example 1. The results are shown in Table 1.

Comparative Example 4
Creep characteristics and Charpy impact strength were measured in the same manner as in Example 1, except that the polyamide 12 resin composition (A1-1) was changed to (A1-4) in Example 1. The results are shown in Table 1.

Example 6
Polyamide 12 resin composition (A1-1) is supplied by a Piper (Plastic Engineering Laboratory Co., Ltd.) pipe molding machine equipped with a straight die and sizing former, melted at an extrusion temperature of 220 ° C., and discharged. The molten resin thus formed was molded, cooled, and taken out to obtain a pipe having an inner diameter of 137.5 mm and an outer diameter of 168 mm. There was little uneven thickness and it had a uniform thickness distribution.

Comparative Example 5
In Example 6, except that the polyamide 12 resin composition (A1-1) was changed to polyamide 11 (A-3), a pipe having an inner diameter of 137.5 mm and an outer diameter of 168 mm was obtained in the same manner as in Example 6. Although it tried to obtain, the uneven thickness was large and it did not have a uniform thickness distribution.

Example 7
Using the above-mentioned (A) polyamide 12 resin composition (A1-7), (E) fluorine-containing polymer (E-1), and conductive fluorine-containing polymer (E-2), (A) at an extrusion temperature of 250 ° C., (E-1) at an extrusion temperature of 260 ° C., and (E-2) at an extrusion temperature of 300 ° C. The melted resin was melted separately, and the discharged molten resin was joined by an adapter, and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die that controls dimensions and taken up, and (A) a layer (outermost layer) composed of a polyamide 12 resin composition (A1-7), (E) a fluorine-containing polymer (E- (E) layer (intermediate layer) consisting of 1), (E) (e ') layer (innermost layer) consisting of a conductive fluorine-containing polymer (E-2), the layer structure is (a) A laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm at /(e)/(e′)=0.75/0.15/0.10 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 2. Moreover, when the electroconductivity of the said laminated hose was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square, and it confirmed that it was excellent in static electricity removal performance. Further, in a Plabor (Plastics Engineering Laboratory Co., Ltd.) three-layer hose molding machine, (A) is an extrusion temperature of 260 ° C., (E-1) is an extrusion temperature of 280 ° C., and (E-2) is an extrusion temperature of 320. Melted separately at ℃, extruded straight pipe laminated hose, introduced into vacuum type corrugated hose molding machine, outer diameter 32mm, length 100mm of both ends smooth part, outer diameter 36mm of bellows part, length 300mm, The layer structure was (a) / (e) / (e ′) = 0.90 / 0.20 / 0.10 mm, a total thickness of 1.2 mm, and a total length of 500 mm to obtain a laminated corrugated hose. It was confirmed that even the bellows portion had strong interlayer adhesion.

Comparative Example 6
In Example 7, except that the polyamide 12 resin composition (A1-7) was changed to polyamide 11 (A-3), an attempt was made to obtain a laminated corrugated hose by the same method as in Example 7. Since the temperature was very high, the surface smoothness of the straight tube laminated hose was poor, and furthermore, the lack of interlayer adhesion at the bellows portion, which was thought to be due to the difference in melt viscosity of each material, was confirmed.

Claims (6)

(B) with respect to 100 parts by weight of polyundecanamide (polyamide 11) and / or polydodecanamide (polyamide 12) having a terminal amide group concentration of 15 (μeq / g polymer) or more, (B) the following general formula (I) Relative viscosity measured in accordance with JIS K-6920 (in 96% sulfuric acid, polymer concentration 10 g / dm ³ , 25 ° C.) is 2.3 to 3.0.

[Wherein, R is an alkyl group, which may be the same or different. ] The polyamide resin composition according to claim 1, wherein the (B) N, N'-carbonylbislactam is either carbonylbiscaprolactam or carbonylbisdodecalactam. The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin composition further comprises (C) a cyclic imino ether. The molded object formed by shape | molding the polyamide resin composition in any one of Claim 1 to 3. The molded article according to claim 4, wherein the molded article is a hollow molded article selected from the group consisting of a tube, a hose, a pipe, a bottle, a tank, and a duct. A laminated hollow molded body comprising a layer made of the polyamide resin composition according to any one of claims 1 to 3 and a layer made of a chemical liquid permeation preventive resin.