WO2015022818A1 - 多層構造体 - Google Patents
多層構造体 Download PDFInfo
- Publication number
- WO2015022818A1 WO2015022818A1 PCT/JP2014/067713 JP2014067713W WO2015022818A1 WO 2015022818 A1 WO2015022818 A1 WO 2015022818A1 JP 2014067713 W JP2014067713 W JP 2014067713W WO 2015022818 A1 WO2015022818 A1 WO 2015022818A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyamide resin
- acid
- layer
- carbon atoms
- nylon
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- 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
- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
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- 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
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, 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
Definitions
- the present invention relates to a multilayer structure having at least two polyamide resin layers, and more particularly to a multilayer structure suitably used for tubular structures such as pipes, hoses and tubes.
- polyamide resins such as nylon 11 and nylon 12 have been used in a wide range of applications due to their high chemical resistance, and are widely used, for example, in structures such as various pipes, hoses and tubes.
- strict exhaust gas regulations have been imposed from the viewpoint of environmental pollution prevention.
- a high barrier property is required to suppress diffusion into the inside.
- Patent Document 1 discloses a multilayer structure including a polyamide layer made of nylon 11 and / or nylon 12 and a barrier layer made of nylon 9T.
- nylon 9T cannot be said to be sufficiently excellent in barrier properties
- the multilayer structure described in Patent Document 1 cannot be said to have sufficient fuel barrier properties, particularly barrier properties against alcohol gasoline.
- polymetaxylylene adipamide (MXD6) is known as a resin having excellent barrier properties, and MXD6 has been studied for use as a barrier layer in various applications.
- MXD6 has low adhesion to nylon 11 and nylon 12, and a multilayer structure in which MXD6 is laminated as a barrier layer on a layer made of nylon 11 or nylon 12 has low interlaminar adhesion and lacks practicality.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a multilayer structure capable of improving interlayer adhesion while improving chemical resistance and barrier properties. It is.
- the present inventors use metaxylylenediamine and an aliphatic carboxylic acid having 4 to 8 carbon atoms as constituent monomers for the polyamide resin layer (A) formed of nylon 11, nylon 12, or the like.
- the polyamide resin layer (B) formed from a mixture of the polyamide resin (B1) and a polyamide resin (B2) having an aliphatic carboxylic acid having 9 to 12 carbon atoms and xylylenediamine as a constituent monomer is laminated.
- the inventors have found that the adhesiveness of these resin layers (A) and (B) can be improved while improving the chemical properties and barrier properties, and have completed the following present invention.
- the present invention relates to the following multilayer structures (1) to (7).
- the polyamide resin layer (B) contains 70 mol% or more of a structural unit derived from metaxylylenediamine as a diamine unit, and 70 mol% or more of a structural unit derived from an aliphatic dicarboxylic acid having 4 to 8 carbon atoms as a dicarboxylic acid unit.
- Polyamide resin (B1) containing, and polyamide containing 70 mol% or more of structural units derived from xylylenediamine as a diamine unit, and 70 mol% or more of structural units derived from aliphatic dicarboxylic acid having 9 to 12 carbon atoms as dicarboxylic acid units A polyamide resin composition (b) containing a resin (B2), A multilayer structure in which the content ratio (B1 / B2) of the polyamide resin (B1) to the polyamide resin (B2) is 55/45 to 85/15 by mass ratio.
- the xylylenediamine constituting the diamine unit in the polyamide resin (B2) is metaxylylenediamine, or a mixture of metaxylylenediamine and paraxylylenediamine, and metaxylylenediamine and paraxylylene.
- the multilayer structure of the present invention has at least a polyamide resin layer (A) and a polyamide resin layer (B) as constituent layers.
- A polyamide resin layer
- B polyamide resin layer
- a polyamide resin layer (A) is comprised from a polyamide resin (A1), or is comprised from the polyamide resin composition (a) containing a polyamide resin (A1).
- the polyamide resin (A1) contains at least one of structural units derived from lactam having 10 to 12 carbon atoms and structural units derived from aminocarboxylic acids having 10 to 12 carbon atoms.
- the polyamide resin layer (A) contains the polyamide resin (A1), so that the chemical resistance, mechanical strength, flexibility and the like of the multilayer structure can be improved.
- the number of carbon atoms of the lactam and / or aminocarboxylic acid is preferably 11 to 12 from the viewpoints of availability, chemical resistance and the like.
- the structural unit derived from a lactam having 10 to 12 carbon atoms and / or an aminocarboxylic acid having 10 to 12 carbon atoms is usually composed of an ⁇ -aminocarboxylic acid unit represented by the following general formula (I).
- p represents an integer of 9 to 11, and preferably 10 to 11.
- lactam having 10 to 12 carbon atoms include decane lactam, undecane lactam, and dodecane lactam.
- aminocarboxylic acid having 10 to 12 carbon atoms include 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
- the polyamide resin (A1) is not limited to those consisting only of structural units derived from lactams having 10 to 12 carbon atoms and / or aminocarboxylic acids having 10 to 12 carbon atoms, as long as these structural units are the main components. Good.
- “main component” means that it does not impede the effects of the present invention, but includes other structural units, and is not particularly limited.
- the structural unit derived from lactam having 10 to 12 carbon atoms and / or aminocarboxylic acid having 10 to 12 carbon atoms is, for example, 60% by mass or more, preferably 80 to 100% by mass, as a monomer. More preferably, it occupies a range of 90 to 100% by mass.
- Examples of other structural units in the polyamide resin (A1) include lactams other than lactams having 10 to 12 carbon atoms, aminocarboxylic acids other than aminocarboxylic acids having 10 to 12 carbon atoms, or nylon salts composed of diamines and dicarboxylic acids.
- lactams other than lactams having 10 to 12 carbon atoms include lactams other than lactams having 10 to 12 carbon atoms, aminocarboxylic acids other than aminocarboxylic acids having 10 to 12 carbon atoms, or nylon salts composed of diamines and dicarboxylic acids.
- lactams other than lactams having 10 to 12 carbon atoms
- aminocarboxylic acids other than aminocarboxylic acids having 10 to 12 carbon atoms
- nylon salts composed of diamines and dicarboxylic acids The structural unit derived from is mentioned.
- lactams other than those having 10 to 12 carbon atoms include lactams having 3 or more members, and specific examples include ⁇ -caprolactam, ⁇ -enantolactam, ⁇ -pyrrolidone, ⁇ -piperidone, and the like.
- aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid and the like.
- the diamine constituting the nylon salt is ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine.
- dicarboxylic acid constituting the nylon salt examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1 Aliphatic dicarboxylic acids such as 1,12-dodecanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,3- or 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid, Mention may be made of aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid.
- the polyamide resin (A1) is mainly composed of a structural unit derived from nylon 11, dodecanlacactam and / or 12-aminododecanoic acid, which is mainly composed of a structural unit derived from undecane lactam and / or 11-aminoundecanoic acid.
- Nylon 12 or a mixture of these nylon 11 and nylon 12 is preferred.
- the polyamide resin layer (A) may be composed of the polyamide resin (A1), but from the polyamide resin composition (a) containing other resin components and / or additives in addition to the polyamide resin (A1). It may be configured.
- the content of the polyamide resin (A1) is preferably 60% by mass or more, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass.
- Polyamide resins other than the polyamide resin (A1) contained in the polyamide resin composition (a) include polycaproamide (nylon 6), polyethylene adipamide (nylon 26), polytetramethylene adipamide (nylon 46). ), Polyhexamethylene adipamide (nylon 66), polyhexamethylene azelamide (nylon 69), polyhexamethylene sebamide (nylon 610), polyhexamethylene undecamide (nylon 611), polyhexamethylene dodecamide (Nylon 612), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene dodecamide (nylon 912), polydecamethylene dodecamide (nylon 1012), polydodecamethylene Do Camide (nylon 1212), polymetaxylylene adipamide (nylon MXD6), polytrimethylhexamethylene terephthalamide (TMHT), polybis (4-aminocyclohex
- the modified resin component contains a modified polyolefin from the viewpoint of impact resistance and adhesion to the resin layer (B).
- the modified polyolefin is a polymer obtained by modifying a copolymer of an olefin selected from ethylene and propylene and an ⁇ -olefin having 3 or more carbon atoms different from the olefin with a carboxyl group-containing monomer and / or a derivative thereof. (C1) is preferably used.
- the modified polyolefin has a functional group that has an affinity for the polyamide resin (A1) and improves adhesion to the resin layer (B) by modification with a carboxyl group-containing monomer and / or derivative thereof. Will be included.
- the carboxyl group-containing monomer and / or derivative thereof is preferably introduced into the main chain or side chain by copolymerization or graft modification, but more preferably introduced into the side chain.
- Examples of the functional group having affinity for the polyamide resin (A1) include a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, and a carboxylic acid amide group.
- carboxyl group-containing monomer and / or derivative thereof containing these functional groups examples 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, italy anhydride Acid
- Examples of the ⁇ -olefin 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, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-
- the modified polyolefin a polymer obtained by modifying a copolymer of ethylene and propylene with a carboxyl group-containing monomer and / or a derivative thereof is preferably used, and among them, maleic anhydride-modified ethylene / propylene copolymer Is more preferable.
- modified polyolefin examples include a copolymer (C2) of an olefin selected from ethylene and propylene and a monomer selected from ⁇ , ⁇ -unsaturated carboxylic acid and unsaturated carboxylic acid ester. It is done.
- ⁇ , ⁇ -unsaturated carboxylic acid monomer used in this case include acrylic acid and methacrylic acid, and examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester monomer include those unsaturated carboxylic acids.
- this copolymer (C2) may be further modified with the above-mentioned carboxyl group-containing monomer and / or a derivative thereof, similarly to the above-described copolymer (C1). This modification is usually carried out by graft modification and these are introduced into the side chain. Copolymers (C1) and (C2) may be used alone or in combination.
- the content of the modified polyolefin is preferably 1 to 45% by mass, more preferably 5 to 30% by mass.
- the polyamide resin composition (a) may contain a thermoplastic resin other than the above-mentioned resins as other resin components.
- the thermoplastic resin include polyolefin resins such as high density polyethylene (HDPE), low density polyethylene (LDPE), ultrahigh molecular weight polyethylene (UHMWPE), isotactic polypropylene, and ethylene propylene copolymer (EPR) resin; Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polyethylene naphthalate (PEN), poly Polyester resins such as butylene naphthalate (PBN) and liquid crystal polyester; Polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO); Polysulfones such as polysulfone (PSF) and polyethersulfone (PES) Resin; Polythioether resins such as rephenylene
- Polynitrile resins polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate, ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC) Polyvinyl chloride (PVC), polyvinyl chloride such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resin such as cellulose acetate and cellulose butyrate; polyfluoride Vinylidene (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexa Fluorine resins such as fluoropropylene copolymer (TFE),
- plasticizers such as benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, hydroxybenzoic acid alkyl esters, carbon black, and the like.
- Conductive fillers exemplified by graphite, metal-containing fillers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, etc. Is mentioned.
- the polyamide resin (A1) can be obtained by polymerizing the above constituent monomers, and is obtained, for example, by ring-opening polymerization of lactam or polycondensation of aminocarboxylic acid.
- the polymerization method is not particularly limited, and known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be employed. These polymerization methods can be used alone or in appropriate combination.
- the production apparatus includes known polyamides such as batch reaction kettles, single tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as uniaxial kneading extruders and biaxial kneading extruders. Manufacturing equipment can be used.
- the polyamide resin (A1) has a relative viscosity of 1.5 to 4.0, preferably 2.0 to 3.5.
- the relative viscosity of the polyamide resin (A1) and the later-described polyamide resin (B1) and polyamide resin (B2) is obtained by dissolving 0.2 g of a sample in 20 mL of 96% by mass sulfuric acid, and the Canon Fenceke type It means the ratio of the drop time (t) measured at 25 ° C. with a viscometer and the drop time (t 0 ) of 96% by mass sulfuric acid itself measured in the same manner, and is represented by the following formula.
- Relative viscosity t / t 0
- the polyamide resin layer (B) is composed of a polyamide resin composition (b) containing a polyamide resin (B1) and a polyamide resin (B2).
- a polyamide resin composition (b) containing a polyamide resin (B1) and a polyamide resin (B2).
- B1 and the polyamide resin (B2) will be described in more detail.
- the polyamide resin (B1) has a diamine unit in which 70 mol% or more is a structural unit derived from metaxylylenediamine and a dicarboxylic acid unit in which 70 mol% or more is a structural unit derived from an aliphatic dicarboxylic acid having 4 to 8 carbon atoms. It consists of In the present invention, the polyamide resin composition (b) constituting the polyamide resin layer (B) contains the polyamide resin (B1), whereby the barrier performance of the multilayer structure can be improved.
- the diamine unit in the polyamide resin (B1) contains 70 mol% or more of a structural unit derived from metaxylylenediamine from the viewpoint of appropriately expressing barrier properties and thermal properties such as glass transition temperature and melting point, preferably It is contained in an amount of 80 to 100 mol%, more preferably 90 to 100 mol%.
- the diamine unit in a polyamide resin (B1) may consist only of a structural unit derived from metaxylylenediamine, it may contain a structural unit derived from diamine other than metaxylylenediamine.
- diamines other than metaxylylenediamine tetramethylenediamine, pentamethylenediamine, 2-methyl-1,5-pentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine
- decamethylene Aliphatic diamines such as diamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine; 1,3- or 1,4-bis (aminomethyl) cyclohexane, 1,3-or Alicyclic diamines such as 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane Bis (4-aminophenyl) A Le, p-phenylenediamine, p-
- Examples of the aliphatic dicarboxylic acid having 4 to 8 carbon atoms in the polyamide resin (B1) include ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 8 carbon atoms.
- Examples of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid. From the viewpoint of barrier properties and availability, adipine Acid is preferred.
- the dicarboxylic acid unit in the polyamide resin (B1) is a structural unit derived from an aliphatic dicarboxylic acid having 4 to 8 carbon atoms from the viewpoint of appropriately expressing barrier properties and thermal properties such as glass transition temperature and melting point. Is contained in an amount of 70 mol% or more, preferably 80 to 100 mol%, more preferably 90 to 100 mol%.
- the dicarboxylic unit in the polyamide resin (B1) may be composed only of a constituent unit derived from an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, but a dicarboxylic acid other than an aliphatic dicarboxylic acid having 4 to 8 carbon atoms. You may contain the structural unit derived from.
- examples of the dicarboxylic acid other than the aliphatic dicarboxylic acid having 4 to 8 carbon atoms include aliphatic dicarboxylic acids having 3 or less carbon atoms such as oxalic acid and malonic acid; azelaic acid, sebacic acid, 1,9 -Aliphatic dicarboxylic acids having 9 or more carbon atoms such as nonanedicarboxylic acid and 1,10-decanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. It is not limited. These can be used alone or in combination of two or more.
- all the diamine units are composed of structural units derived from metaxylylenediamine, and all the dicarboxylic acid units are composed of structural units derived from adipic acid. Most preferred.
- the melting point of the polyamide resin (B1) is preferably in the range of 170 to 270 ° C., more preferably in the range of 175 to 270 ° C., and still more preferably in the range of 180 to 270 ° C., from the viewpoint of heat resistance and melt moldability. Is in the range of 180-260 ° C. Melting
- fusing point is measured using a differential scanning calorimeter according to the method of the Example mentioned later.
- the relative viscosity of the polyamide resin (B1) is preferably 1.7 to 4.0, more preferably 1 from the viewpoints of mechanical strength, moldability and melt-mixability with other resins in the polyamide resin layer (B). It is in the range of .9 to 3.8.
- the polyamide resin (B2) is composed of a diamine unit in which 70 mol% or more is a structural unit derived from xylylenediamine and a dicarboxylic acid unit in which 70 mol% or more is a structural unit derived from an aliphatic dicarboxylic acid having 9 to 12 carbon atoms. It will be.
- the polyamide resin composition (b) constituting the polyamide resin layer (B) contains the above-mentioned polyamide resin (B2), so that the barrier performance of the multilayer structure can be maintained satisfactorily. The adhesiveness of the resin layer (B) to the polyamide resin layer (A) can be improved.
- the carbon number of the aliphatic dicarboxylic acid unit contained in the dicarboxylic acid unit is 70 mol% or more is 8 or less, the adhesiveness cannot be improved, and when the carbon number is 13 or more, the barrier property is not improved.
- metaxylylenediamine constituting the diamine unit of the polyamide resin (B2)
- metaxylylenediamine, paraxylylenediamine or a mixture thereof is preferable, metaxylylenediamine alone, or metaxylylenediamine and paraxylylenediamine It is more preferable to use it as a mixture.
- the xylylenediamine constituting the diamine unit of the polyamide resin (B2) paraxylylenediamine relative to the total amount of metaxylylenediamine and paraxylylenediamine
- the ratio is preferably 90 mol% or less, more preferably 50 mol% or less, still more preferably 35 mol% or less.
- the melting point of the polyamide resin (B2) is preferably close to the melting point of the polyamide resin (B1).
- the diamine unit in the polyamide resin (B2) contains 70 mol% or more of a structural unit derived from xylylenediamine, preferably 80 to 100 mol%, more preferably 90 from the viewpoint of maintaining good barrier performance and adhesiveness. Contains ⁇ 100 mol%.
- the diamine unit in a polyamide resin (B2) may consist only of a structural unit derived from xylylenediamine, it may contain a structural unit derived from diamine other than xylylenediamine.
- polyamide resin (B2) as diamines other than xylylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methyl-1,5-pentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine
- An aliphatic diamine such as decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine; 1,3- or 1,4-bis (aminomethyl) cyclohexane, 1, Fats such as 3- or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane Cyclic diamine; bis (4- Minofeniru) ether, p-phen
- Examples of the aliphatic dicarboxylic acid having 9 to 12 carbon atoms include ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 9 to 12 carbon atoms.
- Examples of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 9 to 12 carbon atoms include azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and the like. Sebacic acid is preferable from the viewpoint of excellent barrier performance and adhesiveness.
- These dicarboxylic acids may be used alone or in combination of two or more.
- the dicarboxylic acid unit in the polyamide resin (B2) preferably contains 70 mol% or more of a structural unit derived from an aliphatic dicarboxylic acid having 9 to 12 carbon atoms from the viewpoint of improving the barrier properties and adhesion. Is contained in an amount of 80 to 100 mol%, more preferably 90 to 100 mol%.
- the dicarboxylic acid unit in the polyamide resin (B2) may be composed only of a structural unit derived from an aliphatic dicarboxylic acid having 9 to 12 carbon atoms, but a dicarboxylic acid other than the aliphatic dicarboxylic acid having 9 to 12 carbon atoms may be used. You may contain the structural unit derived from an acid.
- examples of the dicarboxylic acid other than the aliphatic dicarboxylic acid having 9 to 12 carbon atoms include aliphatic dicarboxylic acids having 8 or less carbon atoms such as succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid; Aliphatic carboxylic acids having 13 or more carbon atoms such as 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid; terephthalic acid, isophthalic acid, Examples include aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, but are not limited thereto.
- the melting point of the polyamide resin (B2) is preferably in the range of 170 to 270 ° C., more preferably in the range of 175 to 270 ° C., and still more preferably in the range of 180 to 270 ° C., from the viewpoint of heat resistance and melt moldability. Is in the range of 180-260 ° C. Melting
- fusing point is measured using a differential scanning calorimeter according to the method of the Example mentioned later.
- the relative viscosity of the polyamide resin (B2) is preferably 1.1 to 3.0, more preferably 1 from the viewpoints of mechanical strength, moldability and melt mixing with other resins in the polyamide resin layer (B). The range is from 3 to 2.9, and more preferably from 1.5 to 2.8.
- the content ratio (B1 / B2) of the polyamide resin (B1) to the polyamide resin (B2) is 55/45 to 85 / It will be 15.
- the mass ratio is preferably 60/40 to 80/20, and more preferably 60/40 to 70/30.
- the polyamide resin composition (b) constituting the polyamide resin layer (B) may consist only of a mixture of the polyamide resin (B1) and the polyamide resin (B2) as a resin component, but the effect of the present invention is impaired. As long as it is not included, a thermoplastic resin other than the polyamide resin (B1) and the polyamide resin (B2) may be contained.
- the total amount of the polyamide resin (B1) and the polyamide resin (B2) with respect to the total amount of the polyamide resin composition (b) constituting the polyamide resin layer (B) is usually 60% by mass or more, preferably 70 to 100% by mass, more preferably Is 80 to 100% by mass, more preferably 90 to 100% by mass. By making the total amount 60% by mass or more, it becomes easy to improve the barrier property and adhesiveness.
- thermoplastic resin other than the polyamide resin (B1) and the polyamide resin (B2) contained in the polyamide resin composition (b) constituting the polyamide resin layer (B) is not particularly limited, but the polyamide resin layer (B) Examples thereof include flexible thermoplastic resins that increase the flexibility of the resin, and specific examples include low elastic modulus polyamides, modified polyolefins, and mixtures thereof.
- Examples of the low elastic modulus polyamide include polyamides having a lower elastic modulus than the polyamide resin (B1) and the polyamide resin (B2).
- nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11, nylon 12, caprolactam-hexamethylene adipamide copolymer (nylon 666) and the like can be exemplified, and these can be used alone or in admixture of two or more.
- nylon 6, nylon 66, and nylon 666 are preferably used because they have a high effect of improving flexibility.
- the modified polyolefin is a polyolefin modified with a carboxyl group-containing monomer.
- polyethylene, polypropylene, or the like can be used, which may be a homopolymer or a copolymer, and among them, polyethylene is preferable from the viewpoint of flexibility, weather resistance, and the like.
- polyethylene low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and the like can be used.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- MDPE medium density polyethylene
- HDPE high density polyethylene
- copolymer a copolymer of ethylene or propylene and a monomer that can be copolymerized with these can be used.
- ⁇ -olefin As a monomer that can be copolymerized with ethylene or propylene, for example, ⁇ -olefin, styrenes, dienes, cyclic compounds, oxygen atom-containing compounds and the like can be mentioned.
- the ⁇ -olefin include 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
- Examples of the styrenes include styrene, 4-methylstyrene, 4-dimethylaminostyrene and the like.
- Examples of the dienes include 1,3-butadiene, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene and the like.
- Examples of the cyclic compound include norbornene and cyclopentene.
- Examples of the oxygen atom-containing compound include hexenol, hexenoic acid, and methyl octenoate. These monomers that can be copolymerized may be used alone or in combination of two or more. Further, it may be a copolymer of ethylene and propylene. The copolymer may be any of alternating copolymerization, random copolymerization, and block copolymerization.
- Examples of the carboxyl group-containing monomer include acrylic acid, maleic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, and the like.
- maleic anhydride is preferable from the viewpoint of melt mixing with other resins.
- maleic anhydride-modified polyethylene is preferable from the viewpoint of elastic modulus.
- the modification is usually performed by copolymerization or graft modification.
- the modification rate of the modified polyolefin is preferably from 0.2 to 5% by mass, more preferably from 0.3 to 3% by mass, from the viewpoint of melt mixing and fluidity with the polyamide resin (B1) and the polyamide resin (B2). More preferably, it is 0.5 to 1.5% by mass.
- the content of the flexible thermoplastic resin with respect to the total amount of the polyamide resin composition (b) constituting the polyamide resin layer (B) is usually 40% by mass or less, preferably 0 to 20% by mass, more preferably 0 to 10% by mass. %.
- the polyamide resin composition (b) may also contain a thermoplastic resin other than the thermoplastic resin exemplified as the flexible thermoplastic resin.
- the polyamide resin constituting the polyamide resin layer (A) You may make it contain suitably selecting from what was enumerated as another thermoplastic resin which may be contained in a composition (a).
- the polyamide resin composition (b) may contain an additive as long as the effects of the present invention are not impaired.
- Additives include fillers, stabilizers, colorants, UV absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, fibrous reinforcements, plasticizers, lubricants, heat resistance Examples include, but are not limited to, agents, matting agents, nucleating agents, anti-coloring agents, and anti-gelling agents.
- at least one polyamide resin layer (A) is directly bonded to at least one polyamide resin layer (B).
- the manufacturing method of a polyamide resin (B1) and a polyamide resin (B2) are obtained by polycondensation of a diamine component and a dicarboxylic acid component.
- the production method is not particularly limited and can be carried out by any method and polymerization conditions.
- a polyamide resin can be produced by a method in which a salt composed of a diamine component and a dicarboxylic acid component is heated in a pressurized state in the presence of water and polymerized in a molten state while removing added water and condensed water. .
- the polyamide resin can also be produced by a method in which a diamine component is directly added to a molten dicarboxylic acid component and polycondensed under normal pressure.
- a diamine component is continuously added to the dicarboxylic acid component, and the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide.
- polycondensation proceeds.
- a small amount of monoamine, monocarboxylic acid or the like may be added as a molecular weight modifier.
- a phosphorus atom-containing compound, an alkali metal compound, Known additives such as alkaline earth metal compounds may be added.
- the polyamide resin composition (b) constituting the polyamide resin layer (B) of the present invention can be obtained by melt-kneading the polyamide resin (B1) and the polyamide resin (B2).
- Examples of the method of melt-kneading the polyamide resin composition (b) include a method of melt-kneading using various commonly used extruders such as a single-screw or twin-screw extruder. Among these, production is also possible. The method using a twin screw extruder is preferable from the viewpoints of properties and versatility.
- the screw of the twin-screw extruder preferably has at least one reverse screw element portion and / or a kneading disk portion, and it is preferable to perform melt kneading while partially retaining the polyamide resin composition in the portion.
- the polyamide resin composition (b) is melt-kneaded, and then extruded as it is together with the polyamide resin composition (a) constituting the polyamide resin layer (A) to form a multilayer structure. It is good also as a multilayer structure with a polyamide resin layer (A) by performing extrusion molding, injection molding, etc. anew.
- the multilayer structure of the present invention comprises a polyamide resin layer (A) (hereinafter sometimes abbreviated as (A) layer) and a polyamide resin layer (B) (hereinafter sometimes abbreviated as (B) layer).
- A polyamide resin layer
- B polyamide resin layer
- Each can have one or more layers. Specifically, the following layer configurations are mentioned, and a layer configuration in which coextrusion is performed with a multilayer die using an extruder is preferable.
- Two-type two-layer configuration specifically, (A) layer / (B) layer, (B) layer / (A) layer, and the like.
- the multilayer structure of the present invention is preferably a hollow structure, and more preferably a cylindrical structure.
- the cylindrical structure for example, a pipe, a hose, a tube or the like having a hollow inside and a liquid or gas can be moved from one side to the other in the hollow portion.
- examples of the hollow structure other than the cylindrical structure include various containers such as a tank and a bottle for storing and storing a liquid or the like inside.
- the hollow structure of the present invention is preferably used for an application in which the liquid that moves inside or is contained in the interior is a fuel oil, and more preferably used in an application in which it is alcohol gasoline. is there.
- the multilayer structure is a hollow structure such as a cylindrical structure, from the viewpoint of barrier properties, weather resistance, chemical resistance, etc.
- the hollow portion of the hollow structure that is, the (B) layer and (A) layer from the inside
- the layer structure may be selected according to the use of the hollow structure, but from the viewpoint of the balance between flexibility and barrier properties and economy, the (B) layer / the (A) layer from the inside are two types and two layers.
- a structure and a two-kind three-layer structure of (A) layer / (B) layer / (A) layer are more preferable.
- the thickness of the multilayer structure may be appropriately set depending on the application, but the total thickness of the laminate is preferably 0.01 to 10 mm from the viewpoint of barrier properties and flexibility. Further, it is more preferably in the range of 0.1 to 5 mm.
- the thickness of the polyamide resin layer (B) when the thickness of the polyamide resin layer (A) of the laminate is 1 is preferably in the range of 0.01 to 2 from the viewpoint of barrier properties and flexibility. More preferably, it is in the range of 1 to 1.2.
- the method for forming the multilayer structure is not particularly limited, and can be manufactured by employing a known technique. For example, each resin composition constituting each layer is melted and kneaded, and each molten resin composition is supplied to a multilayer tube extruder, multilayer film extruder, etc. equipped with a die capable of forming a multilayer structure. What is necessary is just to shape
- a polyamide resin layer (A) is provided, and a structure of (B) layer / (A) layer from the inside may be employed. Further, a multilayer structure of (A) layer / (B) layer is molded by the same method, and the polyamide resin layer (A) is coated on the multilayer structure, and (A) layer / (B) is applied from the inside. A multilayer structure of layer / (A) layer may be used.
- the multilayer structure of the present invention may be provided with an extrudable resin layer as long as the effects of the present invention are not impaired. it can.
- the resin layer include those formed from a thermoplastic resin such as maleic anhydride-modified polyolefin resin, fluororesin, polyimide resin, polyamide resin, polyester resin, polystyrene resin, and vinyl chloride resin. Even when these resin layers are provided, in the multilayer structure, it is preferable that at least one polyamide resin layer (A) and at least one polyamide resin layer (B) are directly bonded.
- the polyamide resin layer (A) contains a structural unit derived from a lactam having 10 to 12 carbon atoms and / or an aminocarboxylic acid having 10 to 12 carbon atoms. Flexibility, mechanical strength, etc. can be increased. Further, the polyamide resin composition (b) constituting the polyamide resin layer (B) bonded to the polyamide resin layer (A) contains a predetermined polyamide resin (B1) and a predetermined polyamide resin (B2). Thus, the interlayer adhesion between the polyamide resin layer (A) and the polyamide resin layer (B) can be improved while improving the barrier performance of the multilayer structure.
- Relative viscosity ( ⁇ r) A 0.2 g sample was precisely weighed and stirred at 20 to 30 ° C. in 20 ml of 96% by mass sulfuric acid to completely dissolve it to prepare a solution. Thereafter, 5 ml of the solution was quickly taken into a Cannon Fenceke viscometer, and allowed to stand in a thermostatic bath at 25 ° C. for 10 minutes, and then the drop time (t) was measured. Further, the dropping time (t 0 ) of 96% by mass sulfuric acid itself was measured in the same manner. The relative viscosity was calculated from t and t 0 according to the following formula.
- Relative viscosity t / t 0 (2) Measurement of melting point (Tm) Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), DSC measurement (differential scanning calorimetry) at a heating rate of 10 ° C./min in a nitrogen stream ) To obtain a melting point (Tm).
- Production Example 1 (Production of polyamide resin (B1-1)) A reaction vessel equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet is charged with 730.8 g of adipic acid, 0.6322 g of sodium hypophosphite monohydrate and 0.4404 g of sodium acetate in a vessel. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 250 ° C., 681.0 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added dropwise thereto, and polymerization was performed for about 2 hours.
- MXDA metaxylylenediamine
- Polymetaxylylene adipamide (polyamide resin) (B1-1) was obtained.
- the obtained polyamide resin (B1-1) had a relative viscosity ( ⁇ r) of 2.1 and a melting point (Tm) of 237.4 ° C.
- Production Example 2 (Production of polyamide resin (B2-1)) A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 800 g of sebacic acid, 0.613 g of sodium hypophosphite monohydrate and 0.427 g of sodium acetate, After sufficiently purging with nitrogen, it was melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 230 ° C., 536 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dropped therein and polymerization was performed for about 2 hours to obtain a polyamide resin (B2-1). The obtained polyamide resin (B2-1) had a relative viscosity ( ⁇ r) of 2.3 and a melting point (Tm) of 191.3 ° C.
- MXDA metaxylylenediamine
- Production Example 3 (Production of polyamide resin (B2-2)) A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 800 g of sebacic acid, 0.613 g of sodium hypophosphite monohydrate and 0.427 g of sodium acetate, After sufficiently purging with nitrogen, it was melted at 170 ° C. while supplying nitrogen gas at 20 ml / min.
- Nylon 12 (Ube Industries, UBESTA3030U, relative viscosity 2.27) is mixed with maleic anhydride-modified ethylene / propylene copolymer (JSR, JSRT7712SP) as a modified polyolefin in advance, and a kneading disk.
- JSR maleic anhydride-modified ethylene / propylene copolymer
- JSR JSRT7712SP
- pellets of a polyamide resin composition (a) comprising 80% by weight of nylon 12 and 20% by weight of modified polyolefin were obtained.
- this polyamide resin composition (a) is referred to as (A1-1) and used in Example 7.
- Nylon 11 Arkema, trade name.
- Rilsan BESN 0 TL relative viscosity 3.0 Nylon 12 (PA12): Arkema, trade name.
- Rilsan AESN 0 TL relative viscosity 2.3
- Nylon 9T PA9T: Kuraray Co., Ltd., trade name.
- Example 1 (Production of polyamide resin composition)
- the polyamide resin (B1-1) produced in Production Example 1 and the polyamide resin (B2-1) produced in Production Example 2 were dry blended at a mass ratio (B1 / B2) of 80/20, and then the kneading disc was used.
- Example 2-7 The same procedure as in Example 1 was conducted except that the polyamide resin and the polyamide resin composition for constituting the resin layers (A) and (B) and the mass ratio (B1 / B2) were changed to those shown in Table 1. did.
- Comparative Example 1 A nylon 12 was used to form a monolayer film at an extrusion temperature of 260 ° C. with a monolayer film molding machine comprising one extruder. The thickness of this single layer film was 200 ⁇ m.
- Comparative Example 2 The same procedure as in Example 1 was performed except that the polyamide resin (B1-1) obtained in Production Example 1 was used in place of the mixture of polyamide resin (B1-1) and polyamide resin (B2-1). .
- Comparative Example 3 The same operation as in Example 2 was performed except that nylon 11 was used instead of the polyamide resin (B2-1).
- Comparative Examples 4 and 5 The same operation as in Example 4 was performed except that the mass ratio (B1 / B2) was as shown in Table 1.
- Nylon 9T is used in place of the polyamide resin (B1-1) and the mixture of the polyamide resin (B2-1), the molding temperature is (A) layer extrusion temperature 260 ° C., and (B) layer extrusion temperature 300 ° C. The same operation as in Example 4 was performed except that the path temperature was changed to 300 ° C.
- the multilayer structures of Examples 1 to 7 have good adhesion of the polyamide resin layer (B) to the polyamide resin layer (A), and further have a small amount of CE10 permeation. The property was also good.
- Comparative Example 1 the single-layer structure formed from nylon 12 alone had poor barrier properties and was not at a practically usable level.
- Comparative Examples 2 and 4 when the polyamide resin layer (B) was molded only from the polyamide resin (B1) or the content of the polyamide resin (B2) was reduced, the barrier performance was improved. However, the adhesiveness of the polyamide resin layer (B) to the polyamide resin layer (A) could not be improved.
- Comparative Example 3 when the polyamide resin layer (B) was molded from a mixture of the polyamide resin (B1) and nylon 11, both the adhesiveness and the barrier property could not be sufficiently improved. Furthermore, as shown in Comparative Example 5, when the content of the polyamide resin (B2) was increased, the adhesiveness could be improved, but the barrier property could not be sufficiently increased. In addition, as shown in Comparative Example 6, when the polyamide resin layer (B) was molded from nylon 9T instead of molding from a mixture of the polyamide resin (B1) and the polyamide resin (B2), the adhesion was improved. However, the barrier property could not be sufficiently increased.
- the multilayer structure of the present invention has excellent chemical resistance and barrier properties, and also has good interlayer adhesion, so it is used for hollow structures such as various tubes, pipes, hoses, tanks, bottles, etc. In particular, it is suitably used for fuel tubes, fuel pipes, and fuel hoses.
Abstract
Description
バリア性を高める手段としては、ナイロン11又はナイロン12からなるポリアミド層に加えて、バリア性に優れるバリア層を設けた多層構造体が提案されている。例えば、特許文献1には、ナイロン11及び/又はナイロン12からなるポリアミド層と、ナイロン9Tからなるバリア層を含む多層構造体が開示されている。
また、バリア性に優れる樹脂としては、ポリメタキシリレンアジパミド(MXD6)が知られており、MXD6は、様々な用途でバリア層として使用されることが検討されている。しかし、MXD6は、ナイロン11及びナイロン12との接着性が低く、ナイロン11又はナイロン12からなる層に、MXD6をバリア層として積層した多層構造体は、層間接着性が低く実用性に欠けるという問題がある。
本発明は、以上の問題点に鑑みてなされたものであり、本発明の課題は、耐薬品性及びバリア性を優れたものとしつつ、層間接着性も良好にできる多層構造体を提供することである。
本発明は、以下の(1)~(7)の多層構造体に関する。
前記ポリアミド樹脂層(A)が、炭素数10~12のラクタム由来の構成単位、及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくともいずれかの構成単位を含むポリアミド樹脂(A1)、又は該ポリアミド樹脂(A1)を含有するポリアミド樹脂組成物(a)から構成され、
前記ポリアミド樹脂層(B)が、ジアミン単位がメタキシリレンジアミン由来の構成単位を70モル%以上含み、ジカルボン酸単位が炭素数4~8の脂肪族ジカルボン酸由来の構成単位を70モル%以上含むポリアミド樹脂(B1)と、ジアミン単位がキシリレンジアミン由来の構成単位を70モル%以上含み、ジカルボン酸単位が炭素数9~12の脂肪族ジカルボン酸由来の構成単位を70モル%以上含むポリアミド樹脂(B2)とを含有するポリアミド樹脂組成物(b)から構成され、
ポリアミド樹脂(B1)のポリアミド樹脂(B2)に対する含有量の割合(B1/B2)が質量比で55/45~85/15である、多層構造体。
(2)前記炭素数4~8の脂肪族ジカルボン酸がアジピン酸である上記(1)に記載の多層構造体。
(3)ポリアミド樹脂(B2)におけるジアミン単位を構成する前記キシリレンジアミンが、メタキシリレンジアミン、パラキシリレンジアミン又はその混合物である上記(1)又は(2)に記載の多層構造体。
(4)ポリアミド樹脂(B2)におけるジアミン単位を構成する前記キシリレンジアミンが、メタキシリレンジアミンであり、或いは、メタキシリレンジアミンとパラキシリレンジアミンの混合物で、かつメタキシリレンジアミン及びパラキシリレンジアミンの総量に対するパラキシリレンジアミンの割合が、90モル%以下である上記(3)に記載の多層構造体。
(5)前記ポリアミド樹脂(A1)が、ナイロン11及びナイロン12の少なくともいずれかである上記(1)~(4)のいずれかに記載の多層構造体。
(6)前記炭素数9~12の脂肪族ジカルボン酸が、セバシン酸である上記(1)~(5)のいずれかに記載の多層構造体。
(7)パイプ、ホース、又はチューブである上記(1)~(6)のいずれかに記載の多層構造体。
本発明の多層構造体は、少なくともポリアミド樹脂層(A)及びポリアミド樹脂層(B)を構成層として有するものである。以下、各層についてより詳細に説明する。
ポリアミド樹脂層(A)は、ポリアミド樹脂(A1)から構成され、又はポリアミド樹脂(A1)を含有するポリアミド樹脂組成物(a)から構成されるものである。
<ポリアミド樹脂(A1)>
ポリアミド樹脂(A1)は、炭素数10~12のラクタム由来の構成単位、及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくともいずれかの構成単位を含むものである。本発明では、ポリアミド樹脂層(A)がポリアミド樹脂(A1)を含むことで、多層構造体の耐薬品性、機械強度、柔軟性等を良好にすることができる。
ラクタム及び/又はアミノカルボン酸の炭素数は、入手容易性、耐薬品性等の観点から11~12が好ましい。
上記炭素数10~12のラクタム及び/又は炭素数10~12のアミノカルボン酸由来の構成単位は、通常、下記一般式(I)で表されるω-アミノカルボン酸単位からなるものである。
炭素数10~12のラクタムとしては、具体的には、デカンラクタム、ウンデカンラクタム、ドデカンラクタムが挙げられる。また、炭素数10~12のアミノカルボン酸としては、10-アミノデカン酸、11-アミノウンデカン酸、12-アミノドデカン酸が挙げられる。
ポリアミド樹脂(A1)における他の構成単位としては、例えば、炭素数10~12のラクタム以外のラクタム、炭素数10~12のアミノカルボン酸以外のアミノカルボン酸、又はジアミンとジカルボン酸からなるナイロン塩由来の構成単位が挙げられる。
変性ポリオレフィンとしては、エチレン及びプロピレンから選択されるオレフィンと、このオレフィンとは異なる炭素数3以上のα-オレフィンとの共重合体をカルボキシル基含有単量体及び/又はその誘導体で変性した重合体(C1)が好ましく使用される。変性ポリオレフィンは、カルボキシル基含有単量体及び/又はその誘導体による変性によって、ポリアミド樹脂(A1)に対して親和性を有し、かつ樹脂層(B)との接着性を向上させる官能基を分子中に含むこととなる。
カルボキシル基含有単量体及び/又はその誘導体は、共重合又はグラフト変性によって、主鎖又は側鎖に導入されることが好ましいが、側鎖に導入されることがより好ましい。
また、この共重合体(C2)は、上記した共重合体(C1)と同様に、上記したカルボキシル基含有単量体及び/又はその誘導体でさらに変性したものであってもよい。なお、この変性は、通常グラフト変性で行われこれらは側鎖に導入される。
共重合体(C1)及び(C2)は、単独で使用されてもよいし、混合して使用されてもよい。
ポリアミド樹脂層(A)において、変性ポリオレフィンの含有量は、好ましくは1~45質量%、より好ましくは5~30質量%である。
なお、本明細書において、ポリアミド樹脂(A1)、並びに後述するポリアミド樹脂(B1)及びポリアミド樹脂(B2)の相対粘度は、試料0.2gを96質量%硫酸20mLに溶解し、キャノンフェンスケ型粘度計にて25℃で測定した落下時間(t)と、同様に測定した96質量%硫酸そのものの落下時間(t0)の比を意味し、次式で示される。
相対粘度=t/t0
ポリアミド樹脂層(B)は、ポリアミド樹脂(B1)と、ポリアミド樹脂(B2)とを含むポリアミド樹脂組成物(b)から構成されるものである。以下、ポリアミド樹脂(B1)と、ポリアミド樹脂(B2)についてさらに詳細に説明する。
ポリアミド樹脂(B1)は、70モル%以上がメタキシリレンジアミン由来の構成単位であるジアミン単位と、70モル%以上が炭素数4~8の脂肪族ジカルボン酸由来の構成単位であるジカルボン酸単位からなるものである。
本発明では、ポリアミド樹脂層(B)を構成するポリアミド樹脂組成物(b)が、ポリアミド樹脂(B1)を含有することで、多層構造体のバリア性能を優れたものとすることができる。
このように、ポリアミド樹脂(B1)におけるジアミン単位は、メタキシリレンジアミン由来の構成単位のみからなってもよいが、メタキシリレンジアミン以外のジアミン由来の構成単位を含有してもよい。ここで、メタキシリレンジアミン以外のジアミンとしては、テトラメチレンジアミン、ペンタメチレンジアミン、2-メチル-1,5-ペンタンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ドデカメチレンジアミン、2,2,4-又は2,4,4-トリメチルヘキサメチレンジアミン等の脂肪族ジアミン;1,3-又は1,4-ビス(アミノメチル)シクロヘキサン、1,3-又は1,4-ジアミノシクロヘキサン、ビス(4-アミノシクロヘキシル)メタン、2,2-ビス(4-アミノシクロヘキシル)プロパン、ビス(アミノメチル)デカリン、ビス(アミノメチル)トリシクロデカン等の脂環族ジアミン;ビス(4-アミノフェニル)エーテル、パラフェニレンジアミン、パラキシリレンジアミン、ビス(アミノメチル)ナフタレン等の芳香環を有するジアミン類等を例示することができるが、これらに限定されるものではない。
このように、ポリアミド樹脂(B1)におけるジカルボン単位は、炭素数4~8の脂肪族ジカルボン酸由来の構成単位のみからなってもよいが、炭素数4~8の脂肪族ジカルボン酸以外のジカルボン酸由来の構成単位を含有してもよい。
ポリアミド樹脂(B1)において、炭素数4~8の脂肪族ジカルボン酸以外のジカルボン酸としては、シュウ酸、マロン酸等の炭素数3以下の脂肪族ジカルボン酸;アゼライン酸、セバシン酸、1,9-ノナンジカルボン酸、1,10-デカンジカルボン酸等の炭素数9以上の脂肪族ジカルボン酸;テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸が例示できるが、これらに限定されるものではない。これらは単独で又は2種以上を組み合わせて用いることができる。
本発明においては、ポリアミド樹脂(B1)としては、全てのジアミン単位がメタキシリレンジアミン由来の構成単位からなり、全てのジカルボン酸単位がアジピン酸由来の構成単位からなるポリメタキシリレンアジパミドが最も好ましい。
ポリアミド樹脂(B1)の相対粘度は、ポリアミド樹脂層(B)における機械的強度、成形性及び他の樹脂との溶融混合性の観点から、好ましくは1.7~4.0、より好ましくは1.9~3.8の範囲である。
ポリアミド樹脂(B2)は、70モル%以上がキシリレンジアミン由来の構成単位であるジアミン単位と、70モル%以上が炭素数9~12の脂肪族ジカルボン酸由来の構成単位であるジカルボン酸単位からなるものである。
本発明では、ポリアミド樹脂層(B)を構成するポリアミド樹脂組成物(b)が、上記のポリアミド樹脂(B2)を含有することで、多層構造体のバリア性能を良好に維持しつつも、ポリアミド樹脂層(B)のポリアミド樹脂層(A)に対する接着性を良好にすることができる。なお、ジカルボン酸単位に70モル%以上含まれる脂肪族ジカルボン酸単位の炭素数が、8以下となると、上記接着性を良好にできなくなり、13以上となると上記バリア性を良好にできなくなる。
パラキシリレンジアミンの割合が90モル%以下であれば、ポリアミド樹脂(B2)の融点が、ポリアミド樹脂(B1)の融点に近接して好ましい。
このように、ポリアミド樹脂(B2)におけるジアミン単位は、キシリレンジアミン由来の構成単位のみからなってもよいが、キシリレンジアミン以外のジアミン由来の構成単位を含有してもよい。
ポリアミド樹脂(B2)において、キシリレンジアミン以外のジアミンとしては、テトラメチレンジアミン、ペンタメチレンジアミン、2-メチル-1,5-ペンタンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ドデカメチレンジアミン、2,2,4-又は2,4,4-トリメチルヘキサメチレンジアミン等の脂肪族ジアミン;1,3-又は1,4-ビス(アミノメチル)シクロヘキサン、1,3-又は1,4-ジアミノシクロヘキサン、ビス(4-アミノシクロヘキシル)メタン、2,2-ビス(4-アミノシクロヘキシル)プロパン、ビス(アミノメチル)デカリン、ビス(アミノメチル)トリシクロデカン等の脂環族ジアミン;ビス(4-アミノフェニル)エーテル、パラフェニレンジアミン、ビス(アミノメチル)ナフタレン等の芳香環を有するジアミン類等を例示することができるが、これらに限定されるものではない。
このように、ポリアミド樹脂(B2)におけるジカルボン酸単位は、炭素数9~12の脂肪族ジカルボン酸由来の構成単位のみからなってもよいが、炭素数9~12の脂肪族ジカルボン酸以外のジカルボン酸由来の構成単位を含有してもよい。
ポリアミド樹脂(B2)において、炭素数9~12の脂肪族ジカルボン酸以外のジカルボン酸としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸等の炭素数8以下の脂肪族ジカルボン酸;1,11-ウンデカンジカルボン酸、1,12-ドデカンジカルボン酸、1,13-トリデカンジカルボン酸、1,14-テトラデカンジカルボン酸等の炭素数13以上の脂肪族カルボン酸;テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸等を例示できるが、これらに限定されるものではない。
ポリアミド樹脂(B2)の相対粘度は、ポリアミド樹脂層(B)における機械的強度、成形性及び他の樹脂との溶融混合性の観点から、好ましくは1.1~3.0、より好ましくは1.3~2.9、さらに好ましくは1.5~2.8の範囲である。
ポリアミド樹脂層(B)において、上記質量比を55/45未満とすると、バリア性が十分に優れたものにできなくなる。また質量比を85/15より大きくすると、ポリアミド樹脂層(B)のポリアミド樹脂層(A)に対する接着性を良好にすることができなくなる。このような観点から、上記質量比は、60/40~80/20であることが好ましく、60/40~70/30であることがより好ましい。
ポリアミド樹脂層(B)を構成するポリアミド樹脂組成物(b)全量に対するポリアミド樹脂(B1)及びポリアミド樹脂(B2)の合計量は、通常60質量%以上、好ましくは70~100質量%、より好ましくは80~100質量%、更に好ましくは90~100質量%である。上記合計量を60質量%以上となることで、バリア性及び接着性を良好にしやすくなる。
ポリオレフィンとしては、ポリエチレン、ポリプロピレン等を用いることができ、単独重合体であっても共重合体であってもよく、中でも柔軟性、耐候性等の観点からポリエチレンが好ましい。
ポリエチレンは、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)、超低密度ポリエチレン(VLDPE)、中密度ポリエチレン(MDPE)、高密度ポリエチレン(HDPE)等を用いることができる。
また、共重合体としては、エチレン又はプロピレンと、これらと共重合することができる単量体との共重合体を用いることができ、エチレン又はプロピレンと共重合することができる単量体として、例えばα-オレフィン、スチレン類、ジエン類、環状化合物、酸素原子含有化合物等が挙げられる。
上記α-オレフィンとしては、1-ブテン、3-メチル-1-ブテン、3-メチル-1-ペンテン、4-メチル-1-ペンテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン等が挙げられる。上記スチレン類としては、スチレン、4-メチルスチレン、4-ジメチルアミノスチレン等が挙げられる。上記ジエン類としては、1,3-ブタジエン、1,5-ヘキサジエン、1,4-ヘキサジエン、1,7-オクタジエン等が挙げられる。上記環状化合物としては、ノルボルネン、シクロペンテン等が挙げられる。酸素原子含有化合物としては、ヘキセノール、ヘキセン酸、オクテン酸メチル等が挙げられる。これら共重合することができる単量体は、単独で使用してもよいし、2種類以上を併用してもよい。また、エチレンとプロピレンとの共重合体であってもよい。
共重合体は、交互共重合、ランダム共重合、ブロック共重合のいずれであってもよい。
変性は、通常、共重合又はグラフト変性によって行われる。変性ポリオレフィンの変性率は、ポリアミド樹脂(B1)及びポリアミド樹脂(B2)との溶融混合性及び流動性の観点から、好ましくは0.2~5質量%、より好ましくは0.3~3質量%、更に好ましくは0.5~1.5質量%である。
なお、ポリアミド樹脂組成物(b)は、上記の柔軟性熱可塑性樹脂として例示した熱可塑性樹脂以外の熱可塑性樹脂も含有してもよく、例えば、上記ポリアミド樹脂層(A)を構成するポリアミド樹脂組成物(a)に含有され得るその他の熱可塑性樹脂として列挙したものから適宜選択して含有させてもよい。
なお、本発明の多層構造体においては、少なくとも1つのポリアミド樹脂層(A)が、少なくとも1つのポリアミド樹脂層(B)に直接接着されることが好ましい。
ポリアミド樹脂(B1)及びポリアミド樹脂(B2)は、ジアミン成分と、ジカルボン酸成分を重縮合して得られるものである。その製造方法は、特に限定されるものではなく、任意の方法、重合条件により行うことができる。例えば、ジアミン成分とジカルボン酸成分とからなる塩を水の存在下に加圧状態で昇温し、加えた水及び縮合水を除きながら溶融状態で重合させる方法によりポリアミド樹脂を製造することができる。また、ジアミン成分を溶融状態のジカルボン酸成分に直接加えて、常圧下で重縮合する方法によってもポリアミド樹脂を製造することができる。この場合、反応系を均一な液状態で保つために、ジアミン成分をジカルボン酸成分に連続的に加え、その間、反応温度が生成するオリゴアミド及びポリアミドの融点よりも下回らないように反応系を昇温しつつ、重縮合が進められる。
また、ポリアミド樹脂(B1)及びポリアミド樹脂(B2)の重縮合時には、分子量調整剤として少量のモノアミン、モノカルボン酸等を加えても良い。
さらに、ポリアミド樹脂(B1)及びポリアミド樹脂(B2)の重縮合時には、アミド化反応を促進する効果や、重縮合時の着色を防止する効果を得るために、リン原子含有化合物、アルカリ金属化合物、アルカリ土類金属化合物等の公知の添加剤を添加してもよい。
本発明のポリアミド樹脂層(B)を構成するポリアミド樹脂組成物(b)は、ポリアミド樹脂(B1)とポリアミド樹脂(B2)とを溶融混練することで得ることができる。
ポリアミド樹脂組成物(b)を溶融混練する方法については、単軸もしくは二軸押出機等の通常用いられる種々の押出機を用いて溶融混練する方法等が挙げられるが、これらのなかでも、生産性、汎用性等の点から二軸押出機を用いる方法が好ましい。
二軸押出機のスクリューは少なくとも1箇所以上の逆目スクリューエレメント部分及び/又はニーディングディスク部分を有し、該部分においてポリアミド樹脂組成物を一部滞留させながら溶融混練を行うことが好ましい。
ポリアミド樹脂組成物(b)は、溶融混練し、その後、そのままポリアミド樹脂層(A)を構成するポリアミド樹脂組成物(a)と共に押出成形し、多層構造体としてもよく、一度ペレットとした後、改めて押出成形、射出成形等を行ってポリアミド樹脂層(A)との多層構造体としてもよい。
また、ポリアミド樹脂組成物(b)に添加剤を添加する場合、ポリアミド樹脂(B1)とポリアミド樹脂(B2)とを溶融混練する際に、添加剤を同時に混練してもよい。
本発明の多層構造体は、ポリアミド樹脂層(A)(以下、(A)層と略記することがある)及びポリアミド樹脂層(B)(以下、(B)層と略記することがある)を、それぞれ1層又は2層以上有することができる。具体的には、以下に示すような層構成が挙げられ、押出機を用いて多層ダイにより共押出する層構成であることが好ましい。
(1)2種2層構成;具体的には、(A)層/(B)層、(B)層/(A)層など。
(2)2種3層構成;具体的には、(A)層/(B)層/(A)層、(B)層/(A)層/(B)層など。
(3)2種4層構成;具体的には、(A)層/(B)層/(A)層/(B)層、(B)層/(A)層/(B)層/(A)層など。
なお、本明細書において、多層構造体が筒状成形体等の中空構造体である場合、例えばX/Y/Zの表記は、断りのない限り内側からX、Y、Zの順に積層していることを示す。また、多層構造体が(A)層を複数層有する場合、複数の(A)層は同一でも異なっていてもよく、(B)層についても同様である。
多層構造体が筒状構造体等の中空構造体である場合、バリア性、耐候性、耐薬品性等の点から、中空構造体の空洞部分、すなわち内側から(B)層及び(A)層の順の層構成を少なくとも有することが好ましい。
層構成は中空構造体の用途に応じ好ましい態様を選択すればよいが、柔軟性とバリア性とのバランス及び経済性の観点から、内側から(B)層/(A)層の2種2層構成及び(A)層/(B)層/(A)層の2種3層構成がより好ましい。
また積層体のポリアミド樹脂層(A)の厚みを1とした際のポリアミド樹脂層(B)の厚みは、バリア性、柔軟性の観点から0.01~2の範囲であることが好ましく、0.1~1.2の範囲であることがより好ましい。
その樹脂層としては、例えば、無水マレイン酸変性ポリオレフィン樹脂、フッ素樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリスチレン樹脂、及び塩化ビニル樹脂等の熱可塑性樹脂から形成されるものが挙げられる。なお、これら樹脂層が設けられる場合でも、多層構造体においては、少なくとも1つのポリアミド樹脂層(A)と、少なくとも1つのポリアミド樹脂層(B)が直接接着されたほうがよい。
試料0.2gを精秤し、96質量%硫酸20mlに20~30℃で撹拌し、完全に溶解させ、溶液を調製した。その後、速やかにキャノンフェンスケ型粘度計に当該溶液5mlを取り、25℃の恒温槽中で10分間放置後、落下時間(t)を測定した。また、96質量%硫酸そのものの落下時間(t0)も同様に測定した。t及びt0から次式により相対粘度を算出した。
相対粘度=t/t0
(2)融点(Tm)の測定
示差走査熱量計((株)島津製作所製、商品名:DSC-60)を用い、昇温速度10℃/分で窒素気流下にDSC測定(示差走査熱量測定)を行い、融点(Tm)を求めた。
JIS K5600-5-6(ISO2409)に準拠し、各実施例、比較例で作製したフィルムの(B)層にカッターで2mm間隔の碁盤の目状に100目の切り込みを入れ、セロハンテープ(登録商標、ニチバン株式会社製)を切り込み部分に貼り付け、5分以内に60度に近い角度で0.5~1.0秒で確実に引き離し、(B)層の剥離状況を確認した。上記100目のうち1目も剥がれなかったものを剥離無しとして表1において“A”とした。また、上記100目のうち1目でも剥がれた場合、剥離有りとして、表1において“C”とした。
(4)バリア性評価
透過断面積11.34cm2のアルミ製のカップにCE10(イソオクタン/トルエン/エタノール=45/45/10容量%)を15ml入れ、各実施例、比較例で作製したフィルムで開口部を封止し、40℃の雰囲気下に静置した。封止後、300時間後のカップの重量変化を測定した。
なお、以下の実施例、比較例におけるバリア性評価において、フィルムが(A)層及び(B)層の2層からなる場合には、(B)層側をカップ側(内側)にして測定した。
(ポリアミド樹脂(B1-1)の製造)
撹拌機、窒素ガス導入口、縮合水排出口を備えた容積約3Lの反応容器にアジピン酸730.8g、次亜リン酸ナトリウム一水和物0.6322g及び酢酸ナトリウム0.4404gを仕込み、容器内を十分窒素置換した後、窒素ガスを20ml/分で供給しながら170℃で溶融させた。250℃まで徐々に昇温しながら、そこへメタキシリレンジアミン(MXDA)(三菱ガス化学(株)製)681.0gを滴下し約2時間重合を行い、ポリメタキシリレンアジパミド(ポリアミド樹脂(B1-1))を得た。得られたポリアミド樹脂(B1-1)の相対粘度(ηr)が2.1、融点(Tm)が237.4℃であった。
(ポリアミド樹脂(B2-1)の製造)
撹拌機、窒素ガス導入口、縮合水排出口を備えた容積約3Lの反応容器にセバシン酸800g、次亜リン酸ナトリウム一水和物0.613g及び酢酸ナトリウム0.427gを仕込み、容器内を十分窒素置換した後、窒素ガスを20ml/分で供給しながら170℃で溶融させた。230℃まで徐々に昇温しながら、そこへメタキシリレンジアミン(MXDA)(三菱ガス化学(株)製)536gを滴下し約2時間重合を行い、ポリアミド樹脂(B2-1)を得た。得られたポリアミド樹脂(B2-1)は、相対粘度(ηr)が2.3、融点(Tm)が191.3℃であった。
(ポリアミド樹脂(B2-2)の製造)
撹拌機、窒素ガス導入口、縮合水排出口を備えた容積約3Lの反応容器にセバシン酸800g、次亜リン酸ナトリウム一水和物0.613g及び酢酸ナトリウム0.427gを仕込み、容器内を十分窒素置換した後、窒素ガスを20ml/分で供給しながら170℃で溶融させた。250℃まで徐々に昇温しながら、そこへメタキシリレンジアミン(MXDA)(三菱ガス化学(株)製)375gと、パラキシリレンジアミン(PXDA)(三菱ガス化学(株)製)161gとの混合液(モル比(MXDA/PXDA=70/30))を滴下し約2時間重合を行い、ポリアミド樹脂(B2-2)を得た。得られたポリアミド樹脂(B2-2)は、相対粘度(ηr)が2.2、融点(Tm)が212.0℃であった。
(ポリアミド樹脂組成物(A1-1)の製造)
ナイロン12(宇部興産(株)製、UBESTA3030U、相対粘度2.27)に、変性ポリオレフィンとして無水マレイン酸変性エチレン/プロピレン共重合体(JSR(株)製、JSRT7712SP)を予め混合し、ニーディングディスクを備えたφ37mmスクリュー径の二軸押出機に供給し、シリンダー温度180~260℃で溶融混練し、溶融樹脂をストランド状に押出した後、これを水槽に導入し、冷却、カット、真空乾燥して、80重量%のナイロン12及び20重量%の変性ポリオレフィンよりなるポリアミド樹脂組成物(a)のペレットを得た。以下、このポリアミド樹脂組成物(a)を(A1-1)といい、実施例7で使用した。
ナイロン11(PA11):アルケマ社製、商品名.リルサンBESN 0 TL、相対粘度3.0
ナイロン12(PA12):アルケマ社製、商品名.リルサンAESN 0 TL、相対粘度2.3
ナイロン9T(PA9T):クラレ社製、商品名.ジェネスタ N1001D
(ポリアミド樹脂組成物の製造)
製造例1で製造したポリアミド樹脂(B1-1)と、製造例2で製造したポリアミド樹脂(B2-1)とを質量比(B1/B2)80/20でドライブレンドした後、ニーディングディスクからなる混練部を有する直径28mmのスクリュー、真空ベントならびにストランドダイを備える二軸押出機にて、シリンダー温度280℃で溶融混練し、ポリアミド樹脂層(B)を形成するためのポリアミド樹脂組成物(b)を得た。
次に、ポリアミド樹脂層(A)を形成するためのナイロン11、及び上記のポリアミド樹脂層(B)を形成するためのポリアミド樹脂組成物(b)を用いて、2台の押し出し機と、2種3層の多層構造体を形成する流路を備えた多層フィルム成形機にて、(A)層押出温260℃、(B)層押出温度260℃、積層後流路温度260℃で、(A)層/(B)層からなる多層構造体(多層フィルム)を形成した。(A)層の厚みは100μm、(B)層の厚みは100μmであった。
樹脂層(A)及び(B)を構成するためのポリアミド樹脂及びポリアミド樹脂組成物、並びに、質量比(B1/B2)を表1に示すものに変更した以外は、実施例1と同様に実施した。
ナイロン12を用い、1台の押出機からなる単層フィルム成形機にて、押出温度260℃で単層フィルムを成形した。この単層フィルムの厚みは、200μmであった。
比較例2
ポリアミド樹脂(B1-1)とポリアミド樹脂(B2-1)の混合物の代わりに、製造例1で得たポリアミド樹脂(B1-1)単体を用いた点を除いて実施例1と同様に実施した。
比較例3
ポリアミド樹脂(B2-1)の代わりに、ナイロン11を使用した点を除いて実施例2と同様に実施した。
比較例4、5
質量比(B1/B2)を表1に示すようにした点を除いて実施例4と同様に実施した。
比較例6
ポリアミド樹脂(B1-1)及びポリアミド樹脂(B2-1)の混合物の代わりにナイロン9Tを用いるとともに、成形温度を(A)層押出温260℃、(B)層押出温度300℃、積層後流路温度300℃に変更した以外は、実施例4と同様に実施した。
一方、比較例1に示すように、ナイロン12単体から成形された単層構造体はバリア性が悪く、実用的に使用できるレベルではなかった。また、比較例2、4に示すように、ポリアミド樹脂層(B)をポリアミド樹脂(B1)のみから成形し、あるいは、ポリアミド樹脂(B2)の含有量を少なくすると、バリア性能が良好となったが、ポリアミド樹脂層(B)のポリアミド樹脂層(A)に対する接着性を良好にできなかった。
また、比較例3に示すように、ポリアミド樹脂層(B)をポリアミド樹脂(B1)及びナイロン11の混合物から成形すると、接着性及びバリア性のいずれも十分に高めることができなった。さらに、比較例5に示すように、ポリアミド樹脂(B2)の含有量を高くすると、接着性は良好にできたが、バリア性は十分に高くすることができなかった。
また、比較例6に示すように、ポリアミド樹脂層(B)を、ポリアミド樹脂(B1)及びポリアミド樹脂(B2)の混合物から成形する代わりに、ナイロン9Tで成形すると、接着性は良好になったが、バリア性を十分に高くすることができなった。
Claims (7)
- ポリアミド樹脂層(A)及びポリアミド樹脂層(B)を有する多層構造体であって、
前記ポリアミド樹脂層(A)が、炭素数10~12のラクタム由来の構成単位、及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくともいずれかの構成単位を含むポリアミド樹脂(A1)、又は該ポリアミド樹脂(A1)を含有するポリアミド樹脂組成物(a)から構成され、
前記ポリアミド樹脂層(B)が、ジアミン単位がメタキシリレンジアミン由来の構成単位を70モル%以上含み、ジカルボン酸単位が炭素数4~8の脂肪族ジカルボン酸由来の構成単位を70モル%以上含むポリアミド樹脂(B1)と、ジアミン単位がキシリレンジアミン由来の構成単位を70モル%以上含み、ジカルボン酸単位が炭素数9~12の脂肪族ジカルボン酸由来の構成単位を70モル%以上含むポリアミド樹脂(B2)とを含有するポリアミド樹脂組成物(b)から構成され、
ポリアミド樹脂(B1)のポリアミド樹脂(B2)に対する含有量の割合(B1/B2)が質量比で55/45~85/15である、多層構造体。 - 前記炭素数4~8の脂肪族ジカルボン酸が、アジピン酸である請求項1に記載の多層構造体。
- ポリアミド樹脂(B2)におけるジアミン単位を構成する前記キシリレンジアミンが、メタキシリレンジアミン、パラキシリレンジアミン又はその混合物である請求項1又は2に記載の多層構造体。
- ポリアミド樹脂(B2)におけるジアミン単位を構成する前記キシリレンジアミンが、メタキシリレンジアミンであり、或いは、メタキシリレンジアミンとパラキシリレンジアミンの混合物で、かつメタキシリレンジアミン及びパラキシリレンジアミンの総量に対するパラキシリレンジアミンの割合が、90モル%以下である請求項1又は2に記載の多層構造体。
- 前記ポリアミド樹脂(A1)が、ナイロン11及びナイロン12の少なくともいずれかである請求項1~4のいずれかに記載の多層構造体。
- 前記炭素数9~12の脂肪族ジカルボン酸が、セバシン酸である請求項1~5のいずれかに記載の多層構造体。
- パイプ、ホース、又はチューブである請求項1~6のいずれかに記載の多層構造体。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017094564A1 (ja) | 2015-11-30 | 2017-06-08 | 三菱瓦斯化学株式会社 | 多層構造体 |
WO2018092623A1 (ja) | 2016-11-18 | 2018-05-24 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品および成形品の製造方法 |
WO2019065232A1 (ja) | 2017-09-29 | 2019-04-04 | 宇部興産株式会社 | 積層チューブ |
JP2021514416A (ja) * | 2018-02-21 | 2021-06-10 | アルケマ フランス | タンク内への燃料輸送を意図とした環状管状構造物 |
CN113165305A (zh) * | 2018-12-04 | 2021-07-23 | 阿科玛法国公司 | 用于运输空调用流体的多层管状结构体 |
JP7124919B1 (ja) | 2021-04-13 | 2022-08-24 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
WO2022219988A1 (ja) * | 2021-04-13 | 2022-10-20 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
JP7318839B1 (ja) * | 2022-03-28 | 2023-08-01 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、および、成形品の製造方法 |
WO2023188549A1 (ja) * | 2022-03-28 | 2023-10-05 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、および、成形品の製造方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6911665B2 (ja) | 2016-11-18 | 2021-07-28 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品および成形品の製造方法 |
EP3406440B1 (en) * | 2017-05-23 | 2022-11-02 | Cooper-Standard Automotive (Deutschland) GmbH | Multilayer tube for guiding fuel fluid and method of manufacturing same |
US11447632B2 (en) | 2017-07-31 | 2022-09-20 | Mitsubishi Gas Chemical Company, Inc. | Easily tearable film, multilayer film, packaging material, and container |
WO2020039967A1 (ja) | 2018-08-24 | 2020-02-27 | 三菱瓦斯化学株式会社 | 多層容器及びその製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006044201A (ja) * | 2004-06-29 | 2006-02-16 | Ube Ind Ltd | 積層構造体 |
JP2006297894A (ja) * | 2005-03-24 | 2006-11-02 | Ube Ind Ltd | ポリアミド積層二軸延伸フィルム |
JP4175942B2 (ja) | 2002-10-29 | 2008-11-05 | 株式会社クラレ | 積層構造体 |
JP2009279927A (ja) * | 2008-04-24 | 2009-12-03 | Mitsubishi Gas Chem Co Inc | バリア性に優れた積層体 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2884518B1 (fr) * | 2005-04-14 | 2007-09-21 | Arkema Sa | Structure barriere a base de polyamide mxd.10 |
FR2909433B1 (fr) * | 2006-11-30 | 2014-01-10 | Arkema France | Utilisation d'une structure multicouche pour la fabrication de conduites de gaz, notamment de methane. |
RU2570453C2 (ru) * | 2010-07-08 | 2015-12-10 | Мицубиси Гэс Кемикал Компани, Инк. | Полиамидные полимерные композиции |
CA2812171C (en) * | 2010-11-26 | 2013-08-27 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resins and processes for molding them |
JP6011531B2 (ja) | 2011-06-27 | 2016-10-19 | 三菱瓦斯化学株式会社 | チューブ状容器 |
-
2014
- 2014-07-02 EP EP14836902.8A patent/EP3034301B1/en active Active
- 2014-07-02 MX MX2016001920A patent/MX2016001920A/es active IP Right Grant
- 2014-07-02 KR KR1020167000470A patent/KR102245023B1/ko active IP Right Grant
- 2014-07-02 JP JP2015531745A patent/JP6409775B2/ja active Active
- 2014-07-02 RU RU2016104787A patent/RU2647030C2/ru active
- 2014-07-02 US US14/911,234 patent/US10016962B2/en active Active
- 2014-07-02 BR BR112016002466A patent/BR112016002466B8/pt active IP Right Grant
- 2014-07-02 CA CA2918146A patent/CA2918146C/en active Active
- 2014-07-02 CN CN201480043076.0A patent/CN105451992B/zh active Active
- 2014-07-02 WO PCT/JP2014/067713 patent/WO2015022818A1/ja active Application Filing
- 2014-08-13 TW TW103127797A patent/TWI658930B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4175942B2 (ja) | 2002-10-29 | 2008-11-05 | 株式会社クラレ | 積層構造体 |
JP2006044201A (ja) * | 2004-06-29 | 2006-02-16 | Ube Ind Ltd | 積層構造体 |
JP2006297894A (ja) * | 2005-03-24 | 2006-11-02 | Ube Ind Ltd | ポリアミド積層二軸延伸フィルム |
JP2009279927A (ja) * | 2008-04-24 | 2009-12-03 | Mitsubishi Gas Chem Co Inc | バリア性に優れた積層体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3034301A4 |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108472943B (zh) * | 2015-11-30 | 2021-04-06 | 三菱瓦斯化学株式会社 | 多层结构体 |
KR20180088371A (ko) | 2015-11-30 | 2018-08-03 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 다층구조체 |
WO2017094564A1 (ja) | 2015-11-30 | 2017-06-08 | 三菱瓦斯化学株式会社 | 多層構造体 |
KR102570894B1 (ko) * | 2015-11-30 | 2023-08-25 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 다층구조체 |
JPWO2017094564A1 (ja) * | 2015-11-30 | 2018-09-13 | 三菱瓦斯化学株式会社 | 多層構造体 |
EP3385074A4 (en) * | 2015-11-30 | 2019-10-30 | Mitsubishi Gas Chemical Company, Inc. | MULTILAYER STRUCTURE |
CN108472943A (zh) * | 2015-11-30 | 2018-08-31 | 三菱瓦斯化学株式会社 | 多层结构体 |
WO2018092623A1 (ja) | 2016-11-18 | 2018-05-24 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品および成形品の製造方法 |
WO2019065232A1 (ja) | 2017-09-29 | 2019-04-04 | 宇部興産株式会社 | 積層チューブ |
US10933615B2 (en) | 2017-09-29 | 2021-03-02 | Ube Industries, Ltd. | Multilayer tubes |
JP2021514416A (ja) * | 2018-02-21 | 2021-06-10 | アルケマ フランス | タンク内への燃料輸送を意図とした環状管状構造物 |
CN113165305A (zh) * | 2018-12-04 | 2021-07-23 | 阿科玛法国公司 | 用于运输空调用流体的多层管状结构体 |
JP7124919B1 (ja) | 2021-04-13 | 2022-08-24 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
WO2022219988A1 (ja) * | 2021-04-13 | 2022-10-20 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
WO2022219989A1 (ja) * | 2021-04-13 | 2022-10-20 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
JP2022162764A (ja) * | 2021-04-13 | 2022-10-25 | 三菱瓦斯化学株式会社 | 燃料用中空構造体 |
WO2023188549A1 (ja) * | 2022-03-28 | 2023-10-05 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、および、成形品の製造方法 |
JP7318839B1 (ja) * | 2022-03-28 | 2023-08-01 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、および、成形品の製造方法 |
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CA2918146C (en) | 2020-09-15 |
KR102245023B1 (ko) | 2021-04-27 |
RU2016104787A (ru) | 2017-09-21 |
TWI658930B (zh) | 2019-05-11 |
EP3034301B1 (en) | 2019-04-24 |
RU2647030C2 (ru) | 2018-03-13 |
KR20160043949A (ko) | 2016-04-22 |
TW201518089A (zh) | 2015-05-16 |
CN105451992B (zh) | 2018-01-05 |
US20160193813A1 (en) | 2016-07-07 |
MX2016001920A (es) | 2016-06-02 |
EP3034301A1 (en) | 2016-06-22 |
EP3034301A4 (en) | 2017-04-26 |
JP6409775B2 (ja) | 2018-10-24 |
CA2918146A1 (en) | 2015-02-19 |
BR112016002466B1 (pt) | 2021-07-13 |
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