WO2006004013A1 - Procédé servant à produire un corps multicouche et corps multicouche - Google Patents

Procédé servant à produire un corps multicouche et corps multicouche Download PDF

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Publication number
WO2006004013A1
WO2006004013A1 PCT/JP2005/012122 JP2005012122W WO2006004013A1 WO 2006004013 A1 WO2006004013 A1 WO 2006004013A1 JP 2005012122 W JP2005012122 W JP 2005012122W WO 2006004013 A1 WO2006004013 A1 WO 2006004013A1
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WIPO (PCT)
Prior art keywords
polyamide
layer
polycondensate
laminate
fluororesin
Prior art date
Application number
PCT/JP2005/012122
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English (en)
Japanese (ja)
Inventor
Satoshi Inamoto
Tsuyoshi Miyamori
Takeshi Inaba
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2006004013A1 publication Critical patent/WO2006004013A1/fr

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Classifications

    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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

Definitions

  • the present invention relates to a laminate manufacturing method and a laminate.
  • a laminate comprising a polyamide layer made of polyamide-based resin and a fluorine resin layer made of fluorine-based resin has attracted attention because it is excellent in fuel permeation resistance and is suitable for a fuel tube of an automobile.
  • the regulations on emission regulations have tended to be expanded to include, for example, underground underground tubes in gas stations and the transfer of oil from subsea oil fields.
  • laminates containing polyamide layers and fluororesin layers have begun to be used in various applications.
  • the polyamide layer and the fluorine resin layer are generally formed by extrusion molding.
  • extrusion molding examples include simultaneous coextrusion molding in which a molten body is supplied to a die by a simultaneous coextrusion method to form two or more layers to form a laminate, a tube shape, and a sheet shape
  • extrusion lamination that extrudes molten resin on a preform such as, and laminates a new layer.
  • a laminated tube extruded from a tube die is cooled while being drawn so that its outer wall is in contact with the sizing plate and transferred.
  • This sizing ensures that the outer wall of the laminated tube is flat. Force that can be smoothly smoothed
  • the inner wall has a problem of unevenness due to unevenness in thickness that can be seen as unevenness in extrusion.
  • the sizing performed after the die force is also extruded may be used not only in the tube extrusion, but also in the profile extrusion such as L-shape, U-shape, etc.
  • the profile extrusion such as L-shape, U-shape, etc.
  • Patent Document 1 Pamphlet of International Publication No. 01Z70485 (Claim 1)
  • Patent Document 2 Pamphlet of International Publication No. 01Z58685
  • An object of the present invention is to improve the moldability of a polyamide-based polycondensate in view of the above-mentioned current situation,
  • the present invention provides a method for producing a laminate having excellent interlayer adhesion and a laminate having excellent interlayer adhesion.
  • the present invention is a laminate production method for producing a laminate comprising a polyamide-based polycondensate layer (1) and a fluorine resin layer (2) in contact with the polyamide-based polycondensate layer (1).
  • a polyamide-based polycondensate composition comprising a polyamide-based polycondensate and a fluorine resin (Q) having a melting point of 170 ° C. or higher is subjected to extrusion molding, whereby the polyamide-based polycondensate layer ( Forming 1)
  • a laminate manufacturing method comprising an extrusion molding step.
  • the present invention is a laminate comprising a polyamide-based polycondensate layer (la) having a melting point of 200 ° C or higher and also having a polyamide-based polycondensate force, and a fluororesin layer (2),
  • the laminate is characterized in that the adhesive strength between the polyamide polycondensate layer (la) and the fluororesin layer (2) is 20 NZcm or more.
  • the laminate production method of the present invention comprises a laminate comprising a polyamide-based polycondensate layer (1) and a fluororesin layer (2) in contact with the polyamide-based polycondensate layer (1) (hereinafter referred to as “ This may be referred to as a “fluororesin layer-containing laminate”.
  • the polyamide-based polycondensate layer (1) is a polyamide-based polycondensate composition composed of a polyamide-based polycondensate and a fluorine resin (Q) having a melting point of 170 ° C or higher. It is formed by subjecting it to extrusion molding.
  • polyamide-based polycondensate a so-called nylon rosin having a polymer force in which an amide bond in a molecule is bonded to an aliphatic structure or an alicyclic structure, or an amide bond in a molecule is bonded to an aromatic structure.
  • aramid resin made of a polymer.
  • the nylon resin is not particularly limited.
  • nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6,66, nylon 66, 12, nylon 46, MXD6 Polyester such as nylon, metaxylylenediamine Z adipic acid copolymer
  • the marker can also be used, and two or more of these may be used in combination.
  • the aramid resin is not particularly limited, and examples thereof include polyparaphenylene terephthalamide, polymetaphenylene-isophthalamide, and the like.
  • the polyamide-based polycondensate may be a polymer having a structure in which a structure having no amide bond as a repeating unit is block-copolymerized or graft-copolymerized in a part of the molecule.
  • nylon-based copolymer power such as nylon 6Z polyester copolymer, nylon 6Z polyether copolymer, nylon 12Z polyester copolymer, nylon 12Z polyether copolymer, etc. And so on.
  • the polyamide-based copolymer is obtained by block copolymerization of a nylon oligomer and a polyester oligomer via an ester bond, or a block copolymer of a nylon oligomer and a polyether oligomer via an ether bond. It was obtained by doing.
  • polyester oligomer examples include poly-strength prolatatone and polyethylene adipate
  • polyether oligomer examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
  • nylon 6Z polytetramethylene glycol copolymer and nylon 12Z polytetramethylene glycol copolymer are preferable.
  • nylon 6 nylon 66, nylon 46, nylon 11, Nylon 12, nylon 610, nylon 612, nylon 6,66, nylon 66,12, nylon 6Z polyester copolymer, nylon 6Z polyether copolymer, nylon 12Z polyester copolymer, nylon 12Z polyether copolymer, etc. You can use a combination of two or more of these.
  • Preferred examples of the polyamide-based polycondensate include those having a melting point of 200 ° C or higher, such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 6,66 and the like. .
  • the fluorine resin (Q) is a fluorine resin having a melting point of 170 ° C or higher. Since the melting point of the fluororesin is 170 ° C. or higher, it can act as a processing aid at the processing temperature during extrusion molding described later, that is, the temperature at which the polyamide polycondensate is melted. Monkey.
  • the melting point of the fluororesin (Q) is preferably 200 ° C or more, more preferably 240 ° C or more, in that the effect of the present invention can be effectively exhibited. . If it is in the said range, it is preferable that it is 330 degrees C or less.
  • the fluororesin (Q) also has a fluoropolymer power.
  • the fluorine-containing polymer is a polymer in which fluorine atoms are bonded to all or part of carbon atoms constituting the main chain of the polymer.
  • fluoropolymer examples include one or more perfluoromonomers such as tetrafluoroethylene [TFE], hexafluoropropylene [HFP], and perfluoro (alkyl butyl ether) [PAVE].
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • PAVE perfluoro (alkyl butyl ether)
  • examples thereof include polymers obtained by polymerization using the polymer.
  • the perfluoromonomer is a monomer in which the main chain is composed of carbon atoms and fluorine atoms and, optionally, oxygen atoms, and the hydrogen atoms are not bonded to the carbon atoms of the main chain.
  • Perfluorovinyl monomers such as TFE and HFP; and PAVE monomers such as perfluoro (propyl ether) [PPVE].
  • the oxygen atom is usually ether oxygen.
  • the fluorine-containing polymer is, for example, a perfluoropolymer such as polytetrafluoroethylene [PTFE], TFEZHFP copolymer [FEP], TFEZPAVE copolymer [PFA].
  • a perfluoropolymer such as polytetrafluoroethylene [PTFE], TFEZHFP copolymer [FEP], TFEZPAVE copolymer [PFA].
  • PTFE polytetrafluoroethylene
  • FEP TFEZHFP copolymer
  • PFA TFEZPAVE copolymer
  • fluorine-containing polymer includes those in which the repeating unit is only the perfluoromonomer and has a structural unit derived from an initiator, a chain transfer agent, or the like at the terminal.
  • the PTFE is a low molecular weight PTFE having a weight average molecular weight of usually 1,000,000 or less, preferably 100,000 or less, and, for example, JP-A-4-154842 And PTFE having a core-shell structure as described in JP-A-5-279579.
  • the fluorine-containing polymer is obtained by copolymerizing a small amount of one or two or more kinds of optional comonomers other than the essential (co) monomer together with the essential (co) monomer for the copolymer. It may be.
  • the optional comonomer is not particularly limited, and includes, for example, a butyl monomer not containing fluorine such as ethylene [Et] and propylene [Pr]; a black fluorocarbon monomer such as black trifluoroethylene [CTFE]; Other fluorine-containing vinyl monomers other than the above-mentioned perfluoro monomers such as vinylidene fluoride [VdF], fluorine fluoride, trifluoroethylene, etc .; having functional groups such as hydroxyl groups and carbonyl groups Examples thereof include monomers and monomers having a cyclic structure.
  • the cyclic structure is not particularly limited, and examples thereof include cyclic ether structures such as a cyclic acetal structure. Preferably, at least two carbon atoms constituting the cyclic ether structure are the main chain of the fluoropolymer. It is a part of
  • the optional comonomer for copolymerizing the above small amount is preferably 5% by mass or less of the obtained fluoropolymer, more preferably 1% by mass or less, and more preferably 0.5% by mass or less. More preferably. If it exceeds 5% by mass, the desired properties of the copolymer may not be obtained.
  • the fluorine-containing polymer may have a polar functional group having reactivity with a polyamide-based polycondensate at the main chain end and Z or side chain.
  • the polar functional group having reactivity with the polyamide-based polycondensate is not particularly limited, and examples thereof include a group having a carbonyl group.
  • 1 20 1 10 2 20 Indicates an alkyl group or the like.
  • Preferred examples include OCH CH CH OCH CH and the like.
  • the haloformyl group is represented by COY (Y is a Group VII atom), and includes -COF, mono-COC1, and the like.
  • the fluoropolymer is substantially free of polar functional groups having reactivity with the polyamide polycondensate.
  • the phrase “substantially having no polar functional group” means that even if the polar functional group is slightly present at the main chain end and Z or side chain, it does not function as the polar functional group. It means that it is not involved in the reaction with the polyamide polycondensate.
  • the number of polar functional groups that the fluoropolymer may have per million carbon atoms is preferably 50 or less, more preferably 30 or less, and even more preferably 10 or less.
  • the number of the polar functional groups possessed by the fluoropolymer can be determined, for example, by the method described in US Pat. No. 5,132,368.
  • the fluorine-containing polymer does not substantially have a polar functional group, so that the polyamide can be used in, for example, a mold, die surface, nozzle, screw surface, barrel inner wall of an extrusion molding machine or an injection molding machine.
  • a polar functional group for example, a mold, die surface, nozzle, screw surface, barrel inner wall of an extrusion molding machine or an injection molding machine.
  • the fluorine-containing polymer is synthesized by polymerizing the monomer components using conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and gas phase polymerization. It can be done.
  • a known chain transfer agent can be suitably used.
  • a polymer having a functional group at the chain end is obtained. This polymer is treated with, for example, steam treatment, fluorine gas [F] treatment, ammonia treatment, etc. to stabilize the chain end.
  • a polymer in the case of suspension polymerization, a polymer can be obtained without substantially having the polar functional group without performing these treatments.
  • the fluororesin (Q) the above-mentioned perfluoropolymer, which is a melt-formable fluororesin, is more preferable to FEP and PFA. Is preferable.
  • the fluorine resin (Q) may be the same type as the fluorine resin (P) described later, or may be a different type.
  • the melting point of the fluororesin (Q) is that the fluororesin (Q) is melted at a temperature at which the polyamide polycondensate melts in a molding machine. From a preferable point, it is preferable that the temperature is not higher than the processing temperature of the polyamide-based polycondensate, for example, not higher than 320 ° C. The temperature is not higher than the melting point of the polyamide-based polycondensate to be used, for example, not higher than 265 ° C. More preferably.
  • the combination of the polyamide polycondensate and the fluorine resin (Q) is not particularly limited in the polyamide polycondensate composition, but the polyamide polycondensation having a melting point of 200 ° C. or higher is not particularly limited.
  • nylon 6, nylon 66, nylon 610, nylon 612, nylon 6Z66, and nylon 66Z12 A combination of FEP and at least one selected from the group forces consisting of nylon 6, nylon 66 and nylon 612, which is preferably a combination of FEP and Z or PFA, and at least one selected from the group force of FEP and Z or PFA is more preferable.
  • the fluorine resin (Q) is 0.005 to 2% by mass of the total of the polyamide-based polycondensate and the fluorine resin (Q).
  • the amount of the above-mentioned fluorine resin (Q) is less than 0.005% by mass, the effect as a desired processing aid may not be obtained.
  • the polycondensate layer (1) may become opaque or cloudy, and the effect corresponding to the amount added is not so great It cannot be obtained and it becomes uneconomical.
  • the amount of addition of the above fluorocoagulant (Q) has a preferable lower limit of 0.01 mass%, a more preferable lower limit of 0.1 mass%, a preferable upper limit of 1.0 mass%, and a more preferable upper limit of 0.7 mass%. %.
  • the polyamide-based polycondensate composition may be blended with other components, if necessary, together with the fluorine-based resin (Q) and the polyamide-based polycondensate.
  • the other components are not particularly limited, for example, whiskers such as potassium titanate, glass fibers, asbestos fibers, carbon fibers, other high-strength fibers, reinforcing materials such as glass powders; stabilizers such as minerals and flakes; Lubricants such as silicone oil and molybdenum disulfide; pigments; conductive agents such as carbon black; impact resistance improvers such as rubber; plasticizers; other additives can be used.
  • whiskers such as potassium titanate, glass fibers, asbestos fibers, carbon fibers, other high-strength fibers, reinforcing materials such as glass powders; stabilizers such as minerals and flakes; Lubricants such as silicone oil and molybdenum disulfide; pigments; conductive agents such as carbon black; impact resistance improvers such as rubber; plasticizers; other additives can be used.
  • the method for preparing the polyamide-based polycondensate composition is not particularly limited, and for example, a conventionally known method can be used.
  • the fluorine-based resin (Q) and the polyamide-based polycondensation can be used.
  • a method of preparing the body by blending it at an appropriate ratio so as to have the above-mentioned mass ratio, adding and mixing the above-mentioned other components as desired, and melt-kneading the mixture under heating as necessary. Etc.
  • the other components may be added when the fluorinated resin (Q) and the polyamide polycondensate are blended, and prior to the blending, the fluorinated resin (Q) and Z or the above polyamide polycondensate may be added in advance and mixed.
  • the fluorinated resin (Q) and the polyamide-based polycondensate may be in a mass ratio within the above range when extrusion molding is performed using the polyamide-based polycondensate composition.
  • the blending is not particularly limited.
  • the blending is performed so that the fluorine resin (Q) and the polyamide polycondensate have a mass ratio within the above range from the beginning, or
  • the ratio of the polyamide polycondensate to the fluorine resin (Q) is within the above range.
  • the polyamide polycondensate is added to the composition (1) to prepare the composition (2) The method etc. which mix
  • the composition (1) is sometimes referred to as a concentrate or a master batch.
  • the fluorine resin (Q) in the composition (1) exceeds 0.005% by mass of the total of the mass of the polyamide-based polycondensate and the mass of the fluorine resin (Q), and 40
  • a more preferable lower limit is 1% by mass, and a more preferable lower limit is 2% by mass, and a more preferable upper limit is 20% by mass.
  • composition (2) may be referred to as a premix.
  • the composition (2) is the composition (1) described above (the polyamide-based polycondensate constituting the composition (1) may hereinafter be referred to as “polyamide-based polycondensate (A)”).
  • a polyamide polycondensate to be added (this polyamide polycondensate to be added may hereinafter be referred to as “polyamide polycondensate (B)”), preferably, fluorine ⁇ (Q) is the fluorine ⁇ (Q), the polyamide-based polycondensate (a) and those which are 0.005 to 2 mass 0/0 of the total of the polyamide-based polycondensate (B) It is.
  • the polyamide-based polycondensate and the fluorine-containing resin (Q) may be powder, granules, pellets, etc., respectively, but the fluorine-containing resin (Q) is used in the polyamide-based polycondensate composition. It is preferable to supply the polyamide-based polycondensate to the extrusion in the form of pellets so that it can be efficiently and uniformly present on the surface.
  • the fluororesin (Q) is extruded in the form of pellets or powder. It is preferable to supply for molding.
  • the fluororesin layer-containing laminate includes a fluorine-resin layer (2) in addition to the polyamide polycondensate layer (1).
  • the fluorine resin layer (2) is a fluorine resin layer having a fluorine resin (P) force.
  • the fluororesin layer (2) can be formed by subjecting a fluororesin (P) composition having a fluororesin (P) force to extrusion molding described later.
  • the fluorine resin (P) is not particularly limited.
  • a fluoropolymer other than the perfluoropolymer hereinafter referred to as "non-perfluoropolymer”. It may be referred to as “fluoropolymer”.
  • the non-perfluoropolymer include ethylene Z tetrafluoroethylene copolymer [ETFE], ethylene Z tetrafluoroethylene Z hexafluoropropylene copolymer [EFEP], and vinyl fluoride.
  • the fluororesin layer (2) is formed by extrusion molding as described later (A) by coextrusion molding, or (B) on an already molded body in extrusion lamination.
  • melt-processable fluorine resin such as FEP and PFA that can be used in these forming methods is more preferable.
  • the fluorine resin (P) preferably has the above-mentioned polar functional group in a ratio of 3 to: LOOO per 1 million carbon atoms from the viewpoint of improving interlayer adhesion. If it is less than 3, the interlayer adhesion to the polyamide polycondensate layer (1) may be insufficient. If the number exceeds 1,000, the gas generated at the bonding interface is adversely affected by the chemical change of the adhesive functional group, and the adhesive strength with the polyamide polycondensate layer (1) is reduced. There is a case. As the number of the above-mentioned adhesive functional groups, a more preferable lower limit is 10 per 1 million carbon atoms, and a more preferable upper limit is 500.
  • the fluorinated resin (P) composition may be composed only of fluorinated resin (P)! /, And if necessary, fluorinated resin (Q), or It may also contain the additives described above for the polyamide-based polycondensate composition containing fluorine resin (Q).
  • fluorine resin (P) composition includes only the above-mentioned fluorine resin (P).
  • the above-mentioned fluorocow (P) composition can be formed by, for example, conventionally known melt-kneading after dry blending the components of the fluorocow (P) composition in advance as desired. Monkey.
  • the method for producing a laminate of the present invention comprises, for extrusion molding, a polyamide-based polycondensate composition comprising the above-mentioned polyamide-based polycondensate and a fluorine resin (Q) having a melting point of 170 ° C or higher.
  • a polyamide-based polycondensate composition comprising the above-mentioned polyamide-based polycondensate and a fluorine resin (Q) having a melting point of 170 ° C or higher.
  • extrusion molding is generally considered as extrusion molding.
  • a resin or a resin composition that will form two or more layers is introduced into a plurality of extruders in a co-extrusion apparatus for each layer, melted, and supplied to a die.
  • Examples thereof include coextrusion molding for forming a laminate, and
  • extrusion lamination for extruding molten resin on a preform to be a layer in the laminate to laminate a new layer.
  • (A) Coextrusion molding is preferred.
  • the method of (A) coextrusion molding is not particularly limited, and for example, the method described in International Publication No. 01Z70485 pamphlet can be used.
  • various conditions relating to the molding machine are not particularly limited, and can be performed under conventionally known conditions.
  • the die temperature and the cylinder temperature for melting the polyamide-based polycondensate composition are usually not less than the melting point of the polyamide-based polycondensate composition to be used. It is a temperature lower than the lower one of the decomposition temperature of the fat (Q) and the decomposition temperature of the polyamide-based polycondensate, preferably 180 ° C or higher and lower than 320 ° C, more preferably 200 ° C. As mentioned above, it is less than 290 ° C.
  • the laminate production method of the present invention includes a polyamide polycondensate layer in contact with the fluorine resin layer (2) by subjecting the polyamide polycondensate composition containing fluorine resin (Q) to extrusion molding. (1) is formed, it is possible to produce a laminate with good ejection stability in the above-described extrusion molding, and the resulting laminate does not cause unevenness in thickness, and the strength of the polyamide-based polycondensate is also high. A laminate in which the layer (1) and the fluororesin layer (2) are well bonded can be obtained.
  • the laminate produced by the extrusion molding step is subsequently sized so that the laminate is cooled while regulating the size and shape.
  • Many processes are performed, but the surface that is in contact with the sizing jig, such as a sizing plate, is not affected by the smoothing of the surface, and the uneven thickness comes from the surface that does not contact the sizing jig.
  • the sizing jig such as a sizing plate
  • the laminate produced by the above extrusion molding process continues sheet winding, but among the laminated sheets newly extruded with a die force, a sheet that comes into contact with the already wound sheet roll
  • the surface is not affected by the fact that the surface is smoothened by contact with the roll, and unevenness due to uneven thickness does not occur on the opposite sheet surface.
  • the surface in contact with the pre-formed body of the layer newly formed by extruding the molten resin is the pre-formed body. Unevenness due to uneven thickness does not occur on the opposite surface without being affected by surface smoothing by extruding upward.
  • the laminate produced by the extrusion molding process is excellent in interlayer adhesion in addition to causing no thickness unevenness.
  • the laminate produced by the above extrusion process has excellent interlayer adhesion! /, The mechanism is not clear, but the fluorine resin (Q) bleeds on the surface of the polyamide polycondensate layer (1). It is surmised that it contributes to adhesion with the adjacent fluorine resin layer (2).
  • the fluoropolymer (P) and the fluorocobalt (Q) are both perfluorinated polymers or non-perfluoropolymers, but one is a perfluoropolymer and the other is a perfluoropolymer. Even when non-perfluoropolymer is used, the interlaminar adhesion between the polyamide polycondensate layer (1) and the fluororesin layer (2) is excellent.
  • the fluororesin layer-containing laminate includes a polyamide-based polycondensate layer (1), a fluororesin layer (2), and If it contains, it may further contain one layer or other layers of two or more layers.
  • the “other layer” is not particularly limited, and examples thereof include a fluorine resin layer having a fluorine resin (R) force, a non-fluorinated or low fluorinated thermoplastic polymer force having a non-fluorinated or low fluorinated layer. Etc.
  • the fluorine resin (R) constituting the other layers is not particularly limited, and examples thereof include those described for the fluorine resin (Q) and the fluorine resin (P) described above.
  • the fluorine resin (R) constituting the other layers may be of the same type as the fluorine resin (P) constituting the fluorine resin layer (2), or different! / Yo! /
  • non-fluorinated or low-fluorinated thermoplastic polymer is a thermoplastic polymer in which the number of CF bonds is less than 3% of the number of CH bonds constituting the polymer. is there.
  • non-fluorinated or low-fluorinated thermoplastic polymer examples include non-fluorinated or low-fluorinated thermoplastic resins, non-fluorinated or low-fluorinated thermoplastic elastomers, and the like.
  • non-fluorinated or low-fluorinated thermoplastic resins include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate [PET] and polybutylene terephthalate [PBT]; polycarbonate resins; Examples thereof include salt and bulge resin, and these modified oils and Z or a mixture of two or more of these may also be used.
  • the non-fluorinated or low-fluorinated thermoplastic elastomer has rubber elasticity at room temperature and is plasticized at a high temperature so that it can be molded into a desired shape.
  • thermoplastic elastomers are excellent in adhesiveness with the polyamide-based polycondensates described later, so that styrene / butadiene-based elastomers, polyolefin-based elastomers, polyester-based elastomers, It is preferable that at least one selected from the group consisting of a polyurethane elastomer, a polychlorinated bur elastomer and a polyamide elastomer is selected.
  • the fluorinated resin (R) and Z, or the non-fluorinated or low-fluorinated thermoplastic polymer is a filler, a plasticizer, an impact resistant material, a pigment, an inorganic substance, etc. within the range not impairing the object of the present invention
  • additives may be added together with other resins and rubbers other than the above-mentioned non-fluorinated or low-fluorinated thermoplastic polymers.
  • a conductive material such as carbon black or acetylene black
  • the fluororesin layer-containing laminate of the present invention at least one of the layers constituting the laminate may be conductive as required.
  • conductive means that, for example, when a flammable fluid such as gasoline continuously contacts an insulator such as grease, there is a possibility that static charge will accumulate and ignite. However, it has electrical characteristics that do not accumulate this static charge. For example, SAE J 2260 specifies that the surface resistance is 10 6 ⁇ or less.
  • the blending ratio of the conductive material in the case where any layer constituting the fluororesin layer-containing laminate in the present invention is conductive is determined by the polymer constituting the layer and the other blended as necessary. It is preferably 20% by mass or less of the total of the above components, and more preferably 15% by mass or less.
  • the lower limit may be an amount that can provide the above-described surface resistance value.
  • the fluororesin layer-containing laminate includes one or more other layers in addition to the polyamide-based polycondensate layer (1) and the fluororesin layer (2).
  • the laminating method for producing the fluororesin layer-containing laminate as long as it includes forming the polyamide polycondensate layer (1) by extrusion molding.
  • the combination of (iii) is not particularly limited.
  • the above (A) two or more layers melted by coextrusion molding are formed on a single layer molded body or a laminate of two or more layers produced by extrusion molding.
  • (B) A method of laminating by extrusion lamination is exemplified.
  • the polyamide polycondensate layer (1) preferably has a thickness of 0.5 to 50 mm.
  • the thickness of the fluorine resin layer (2) is the polyamide polycondensate layer ( It is preferably 1/3 or less of the thickness of 1), more preferably 1/5 or less, and even more preferably 1/10 or less. As long as the thickness of the fluorine resin layer (2) is within the above range, it may be more than 1 / 40th of the thickness of the polyamide polycondensate layer (1).
  • the fluororesin layer-containing laminate has a non-fluorinated or low-fluorinated layer made of a non-fluorinated or low-fluorinated thermoplastic polymer as the other layer, it is not particularly limited, but from the viewpoint of transparency.
  • the thickness of the non-fluorinated or low-fluorinated layer is preferably less than 0.5 mm. Even if the non-fluorinated or low-fluorinated layer has a thickness of, for example, about 0.03 mm, it can exhibit chemical resistance, barrier properties, bacteria resistance, and the like.
  • the fluororesin layer-containing laminate may have various shapes such as a film shape, a sheet shape, a tube shape, a hose shape, a bottle shape, and a tank shape.
  • the film shape, sheet shape, tube shape and hose shape may be a corrugated shape or a convoluted shape.
  • the said fluororesin layer containing laminated body is a hose or a tube as a multilayer molded article.
  • the fluororesin layer-containing laminate includes a polyamide-based polycondensate layer (la) made of a polyamide-based polycondensate having a melting point of 200 ° C or higher, and the above-described fluorine-resin layer (2). It may be a laminate including
  • the polyamide polycondensate constituting the polyamide polycondensate layer (la) is a polyamide polycondensate constituting the polyamide polycondensate layer (1) having a melting point of 200 ° C or higher. Yes.
  • the laminate containing the fluororesin layer preferably has a bond strength between the polyamide polycondensate layer (la) and the fluororesin layer (2) of 20 NZcm or more, preferably 30 NZcm or more. Is more preferable.
  • the adhesive strength is 5 cm long and 1 cm wide test pieces cut from the laminate, and subjected to a 180 ° peel test at a speed of 25 mmZ using a Tensilon universal tester. It is calculated as the maximum of 5 points in the graph.
  • the fluororesin layer-containing laminate is excellent in interlayer adhesion because it is obtained by the laminate production method of the present invention, and can be used for, for example, the following various applications.
  • the fluorine-containing resin layer-containing laminate can also enhance the commercial value in the following various applications from the viewpoint of excellent appearance such as no unevenness in thickness.
  • Tubes' Hoses Automotive fuel tubes, automotive fuel hoses, underground buried tubes for gas stations, oil drilling hoses, gas drilling hoses, natural gas line hoses, gas tubes, gas hoses, chemical liquid tubes, chemical liquid hoses, Water hose, drain hose, brake hose, hydraulic hose, air pressure hose, air compression hose, etc.
  • Films and sheets Sliding members and belt conveyors that require high chemical resistance, such as diaphragms of diaphragm pumps and various packings.
  • Tanks Car radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, gasoline tanks, etc.
  • the fluororesin layer (2) is used as an inner layer, and the polyamide polycondensate layer (1)
  • the laminate When the above-mentioned fluororesin layer-containing laminate is used as a tube hose, the laminate has ETFE or EFEP as the inner layer, nylon 66 or nylon 6 as the intermediate layer, and FEP, ETFE or EFEP as the outer layer, ETFE Preferably, it is a laminate having EFEP or vinylidene fluoride copolymer as an inner layer, nylon 66 or nylon 6 as an intermediate layer, and polyethylene as an outer layer.
  • ETFE Preferably, it is a laminate having EFEP or vinylidene fluoride copolymer as an inner layer, nylon 66 or nylon 6 as an intermediate layer, and polyethylene as an outer layer.
  • the laminate production method of the present invention has the above-described configuration, it is possible to improve the moldability of the polyamide polycondensate and produce a laminate excellent in interlayer adhesion. Since the laminate obtained by the above-mentioned laminate production method is excellent in interlayer adhesion, it can be suitably used as a fuel tube, a chemical solution tube and the like. BEST MODE FOR CARRYING OUT THE INVENTION
  • the melting peak when the temperature was raised at a rate of 10 ° CZ was recorded, and the temperature corresponding to the maximum value was defined as the melting point (Tm).
  • the obtained multilayer tube is cut so that the cross-sectional shape becomes a semicircular shape, and the inner surface of the multilayer tube is observed visually or with a 50 ⁇ stereomicroscope, and the occurrence of surface roughness, foaming, etc. was determined according to the following criteria.
  • N 500AW / ⁇ df (1)
  • the infrared absorption spectrum analysis was performed by scanning 40 times using a Perkin-Elmer FTIR ⁇ Spectrometer 1760 X (manufactured by Perkin Elmer Co., Ltd.).
  • the resulting IR ⁇ vector Perkin- Elmer Spectrum for Ver. Determines baseline automatically using 1.4c, the absorbance was measured of the peaks of 1809cm _1.
  • the film thickness was measured with a micrometer.
  • TFE is tetrafluoroethylene
  • Et is ethylene
  • HFP is hexafluoropropylene
  • VdF is vinylidene fluoride
  • PMVE is perfluoromethyl vinyl.
  • Ether, HF—Pe represents perfluoro (1, 1, 5 trihydro-1 pentene).
  • the outer layer is formed of a polyamide-based polycondensate
  • the inner layer is formed of a fluorine resin.
  • a multilayer tube having a body layer of 0.8 mm and a fluorine resin layer of 0.2 mm was continuously formed at a tube take-up speed of 6 mZ.
  • a multilayer tube was molded in the same manner as in Example 1 except that the grease and molding conditions shown in Table 2 for Examples 2-7 and Table 3 for Comparative Examples 1-4 were used.
  • PA-A is Zytel Nylon66 ETE8073NC010A (DuPont)
  • PA-B is Zytel Nylon6 7335F (DuPont)
  • PA-C is Zytel Nylon612 158L (DuPont) Represents.
  • the laminate production method of the present invention has the above-described configuration, it is possible to improve the moldability of the polyamide polycondensate and produce a laminate excellent in interlayer adhesion. Since the laminate obtained by the above laminate production method is excellent in interlayer adhesion, it can be suitably used as a fuel tube, a chemical solution tube, and the like.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

Il est exposé un procédé servant à produire un corps multicouche ayant une excellente adhérence entre les couches en améliorant l'aptitude à former une résine de polyamide. Il est également exposé un corps multicouche ayant une excellente adhérence entre les couches. Il est précisément exposé un procédé servant à produire un corps multicouche comprenant une couche de produit de polycondensation de polyamide (1) et une couche de résine fluorée (2) laquelle est en contact avec la couche de produit de polycondensation de polyamide (1). Ce procédé est caractérisé en ce qu'il comprend une étape de moulage par extrusion servant à former la couche de produit de polycondensation de polyamide (1) en extrudant une composition de produit de polycondensation de polyamide composée d'un produit de polycondensation de polyamide et d'une résine fluorée (Q) ayant un point de fusion qui n'est pas inférieur à 170°C.
PCT/JP2005/012122 2004-06-30 2005-06-30 Procédé servant à produire un corps multicouche et corps multicouche WO2006004013A1 (fr)

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JP2004-194516 2004-06-30

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WO2019130975A1 (fr) * 2017-12-26 2019-07-04 ダイキン アメリカ インコーポレイティッド Fil électrique, procédé de production de fil électrique et lot maître
JP7041386B1 (ja) 2020-09-30 2022-03-24 ダイキン工業株式会社 フッ素樹脂、積層体、チューブおよびチューブの製造方法
JP7041385B1 (ja) 2020-09-30 2022-03-24 ダイキン工業株式会社 部分フッ素化樹脂、積層体、チューブおよびチューブの製造方法

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WO2001018142A1 (fr) * 1999-09-08 2001-03-15 Daikin Industries, Ltd. Matiere adhesive fluorochimique et produit stratifie obtenu au moyen de celle-ci
WO2001023795A1 (fr) * 1999-09-30 2001-04-05 Asahi Glass Company, Limited Tuyau souple de carburant
JP2002357285A (ja) * 2000-04-24 2002-12-13 Asahi Glass Co Ltd 燃料用ホース

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JPH04224939A (ja) * 1990-12-26 1992-08-14 Tokai Rubber Ind Ltd 燃料配管用樹脂チューブ
WO2001018142A1 (fr) * 1999-09-08 2001-03-15 Daikin Industries, Ltd. Matiere adhesive fluorochimique et produit stratifie obtenu au moyen de celle-ci
WO2001023795A1 (fr) * 1999-09-30 2001-04-05 Asahi Glass Company, Limited Tuyau souple de carburant
JP2002357285A (ja) * 2000-04-24 2002-12-13 Asahi Glass Co Ltd 燃料用ホース

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JP7181228B2 (ja) 2017-12-26 2022-11-30 ダイキン アメリカ インコーポレイティッド 電線、電線の製造方法及びマスターバッチ
CN111465997A (zh) * 2017-12-26 2020-07-28 大金美国股份有限公司 电线、电线的制造方法和母料
JPWO2019130975A1 (ja) * 2017-12-26 2020-10-22 ダイキン アメリカ インコーポレイティッドＤａｉｋｉｎ Ａｍｅｒｉｃａ，Ｉｎｃ． 電線、電線の製造方法及びマスターバッチ
AU2018394478B2 (en) * 2017-12-26 2021-04-08 Daikin America, Inc. Electric wire, method for producing electric wire and master batch
EP3678148A4 (fr) * 2017-12-26 2021-05-19 Daikin America, Inc. Fil électrique, procédé de production de fil électrique et lot maître
CN111465997B (zh) * 2017-12-26 2023-02-17 大金美国股份有限公司 电线、电线的制造方法和母料
WO2019130975A1 (fr) * 2017-12-26 2019-07-04 ダイキン アメリカ インコーポレイティッド Fil électrique, procédé de production de fil électrique et lot maître
JP7041385B1 (ja) 2020-09-30 2022-03-24 ダイキン工業株式会社 部分フッ素化樹脂、積層体、チューブおよびチューブの製造方法
WO2022071529A1 (fr) * 2020-09-30 2022-04-07 ダイキン工業株式会社 Résine fluorée, stratifié, et tube ainsi que procédé de fabrication de celui-ci
JP2022058286A (ja) * 2020-09-30 2022-04-11 ダイキン工業株式会社 フッ素樹脂、積層体、チューブおよびチューブの製造方法
JP2022058285A (ja) * 2020-09-30 2022-04-11 ダイキン工業株式会社 部分フッ素化樹脂、積層体、チューブおよびチューブの製造方法
WO2022071528A1 (fr) * 2020-09-30 2022-04-07 ダイキン工業株式会社 Résine partiellement fluorée, stratifié, et tube ainsi que procédé de fabrication de celui-ci
JP7041386B1 (ja) 2020-09-30 2022-03-24 ダイキン工業株式会社 フッ素樹脂、積層体、チューブおよびチューブの製造方法
CN116234698A (zh) * 2020-09-30 2023-06-06 大金工业株式会社 氟树脂、层积体、管和管的制造方法

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