WO2004069534A1 - Element forme de resine stratifiee et son procede de production - Google Patents

Element forme de resine stratifiee et son procede de production Download PDF

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Publication number
WO2004069534A1
WO2004069534A1 PCT/JP2004/001387 JP2004001387W WO2004069534A1 WO 2004069534 A1 WO2004069534 A1 WO 2004069534A1 JP 2004001387 W JP2004001387 W JP 2004001387W WO 2004069534 A1 WO2004069534 A1 WO 2004069534A1
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WIPO (PCT)
Prior art keywords
layer
resin molded
laminated resin
fuel
adhesive
Prior art date
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PCT/JP2004/001387
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English (en)
Japanese (ja)
Inventor
Satoshi Inamoto
Takeshi Inaba
Shigehito Sagisaka
Hidenori Ozaki
Original Assignee
Daikin Industries, Ltd.
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Priority to JP2005504915A priority Critical patent/JPWO2004069534A1/ja
Publication of WO2004069534A1 publication Critical patent/WO2004069534A1/fr

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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
    • 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
    • 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
    • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer

Definitions

  • the present invention relates to a laminated resin molded article and a method for producing the same.
  • Fluororesins are used in various applications because of their excellent properties such as heat resistance, chemical resistance, weather resistance, electrical insulation, low friction, and non-adhesion. Nevertheless, fluororesins are expensive and have poor mechanical strength and dimensional stability, so that lamination of fluororesins with other organic or inorganic materials is being studied.
  • fluoropolymers are inherently poor in affinity with other materials due to their non-adhesiveness and chemical resistance, so even if you try to laminate with other materials other than fluororesins by heat fusion, The bonding strength is insufficient, and even if a certain level of bonding strength is obtained, the bonding strength is not reproducible depending on the type of the material to be bonded, and it is difficult to always obtain a stable bonding strength.
  • the bonding strength is insufficient, and even if a certain level of bonding strength is obtained, the bonding strength is not reproducible depending on the type of the material to be bonded, and it is difficult to always obtain a stable bonding strength.
  • the method of bonding fluororesin and other materials other than fluororesin is as follows: (1) The surface of the mating material to be bonded is treated by sand plaster treatment or the like to physically increase the surface area and bond.
  • the methods (1) and (2) each require a processing step, which complicates the process, resulting in poor productivity, and limits the type and shape of the mating material to be bonded. Furthermore, the adhesive strength is insufficient, and the resulting resin laminate tends to have external problems such as coloring and scratches.
  • Examples of the adhesive used in the method (3) include a hydrocarbon-based adhesive.
  • Charcoal As a resin laminate using a hydride-based adhesive, a polyvinylidene fluoride layer or an ethylene / tetrafluoroethylene copolymer layer is used as an inner layer, and an ethylene novyl alcohol copolymer layer is used as an outer layer, and an inner layer is used.
  • a fuel tube using an ethylene-z-ester acrylate copolymer as an adhesive between the outer layer and the outer layer is known (for example, see Japanese Patent Application Laid-Open No. 5-247478).
  • hydrocarbon-based adhesives have insufficient adhesive strength and insufficient heat resistance of the adhesive itself. Coloring etc. occurs, and the resulting resin laminate has insufficient heat resistance, chemical resistance, water resistance, etc. of the adhesive layer, so the adhesive strength is reduced due to usage conditions such as temperature, humidity, and fuel type. In addition, there has been a problem that the adhesive strength is greatly reduced due to a change with time.
  • a resin laminate comprising a layer made of a tetrafluoroethylene copolymer having a carbonate group at the polymer terminal as an inner layer, a layer made of polyethylene having an epoxy group as an intermediate layer, and a layer made of polyethylene as an outer layer. It is disclosed (see, for example, International Publication No. 98858973 pamphlet).
  • a layer composed of an ethylene / butyl acetate copolymer in which the vinyl acetate unit X mol% and the degree of conversion ⁇ % satisfy XY Using a layer composed of an ethylene / butyl acetate copolymer in which the vinyl acetate unit X mol% and the degree of conversion ⁇ % satisfy XY.
  • a layer made of a fluororesin having a hydroxyl group is bonded to a layer made of polyethylene, the adhesive strength does not decrease over time, and such an ethylene-butyl acetate copolymer has relatively low fuel oil resistance. It is described as being excellent (see, for example, International Publication No. 01 / 141,401 pamphlet.).
  • the outermost layer of the fuel tube is a layer made of polyethylene
  • polyethylene has poor creep resistance, so cracks are likely to occur in places where long-term stress is applied, such as connector insertion parts, and the elastic modulus of polyethylene Due to the relatively high ratio, the tube was difficult to bend and the low-temperature impact resistance was poor.
  • the fuel permeation rate of the fluororesin used is too high compared to the fuel permeation rate of the ethylene / butyl alcohol copolymer, and there has been a problem that delamination occurs during long-term use.
  • a fuel tube using a layer made of polyamide 12 with excellent mechanical properties such as tensile strength a layer made of an ethylene / butyl alcohol copolymer is used as an intermediate layer, and a polyamide A structure in which a layer consisting of 6 is used as the innermost layer is disclosed (for example, see Japanese Patent Application Laid-Open No. 3-176683).
  • polyamide-based resin is used for the innermost layer, even if the innermost layer is made thin, long-term use of fuel will cause oligomers, monomers and plasticizers to elute, causing clogging of the filter around the engine. There was a problem of causing.
  • the innermost layer made of polyamide 6 should be made as thin as possible.
  • the layer made of the alcohol copolymer is liable to crack due to the brittleness of the material, resulting in insufficient burst resistance and low-temperature impact resistance required for the fuel tube.
  • no means has been shown to solve this problem.
  • a fuel tube in which a layer made of an ethylenenovinyl alcohol copolymer is the innermost layer is disclosed (for example, see Japanese Patent Application Laid-Open No. 3-177684).
  • Ethylene butyl alcohol copolymer is in contact with fuel, so chemical resistance is insufficient.
  • Ethylene vinyl alcohol copolymer absorbs water in air and fuel due to its water absorption, so chemical permeability is low. There was a problem that it declined.
  • a resin laminate containing a fluororesin and an ethylene butyl alcohol copolymer does not discolor during molding and maintains interlayer adhesion for a long time.
  • it overcomes the problem that cracks are likely to occur in the layer made of ethylene / vinyl alcohol copolymer when the shape is changed. No impact resistance, especially low temperature impact resistance, was obtained.
  • the object of the present invention is that it does not deteriorate during molding processing, and is excellent in fuel oil resistance, non-elution property, creep resistance, heat resistance, low-temperature impact resistance, etc., interlayer adhesive strength ⁇ fuel permeability resistance It is another object of the present invention to provide a laminated resin molded article capable of suppressing the temporal deterioration of low-temperature impact resistance and suppressing the fuel permeability.
  • the present invention provides a laminated resin molded article including a layer (A) made of a polyamide resin, a layer (B) made of a thermoplastic resin having excellent fuel permeability resistance, and a layer (C) made of an adhesive fluororesin. Wherein the layer (A), the layer (B) and the layer (C) are laminated in this order.
  • the laminated resin molded article of the present invention includes a layer (A) composed of a polyamide resin, a layer (B) composed of a thermoplastic resin having excellent fuel permeability, and a layer (C) composed of an adhesive fluororesin.
  • thermoplastic resin having excellent fuel permeation resistance which forms the layer (B) constituting the laminated resin molded article of the present invention, is a resin made of a thermoplastic polymer having excellent fuel permeation resistance.
  • the thermoplastic polymer having excellent fuel permeability resistance is a polymer having relatively large cohesive energy between polymer chains and / or within polymer chains.
  • thermoplastic polymer having excellent fuel permeation resistance a polymer having a high crystallinity or a polymer having a polar functional group and a large intermolecular force is preferable, and has a high crystallinity and a polar functional group. And a polymer having a large intermolecular force.
  • Xmm / m 2 / day More preferably, it is 0.5 (g Xmm / mVd ay) or less.
  • the polar functional group which may be possessed by the thermoplastic polymer having excellent fuel permeation resistance is a functional group having polarity and capable of participating in adhesion to an adhesive fluororesin.
  • the polar functional group may be the same functional group as the adhesive functional group described later as the adhesive fluororesin has, or may be a different functional group.
  • the polar functional group is not particularly limited, and examples thereof include an amino group, a cyano group, a sulfide group, a hydroxy group, and the like, in addition to those described below as the adhesive functional group. Among them, an amino group, a carbonyl group ⁇ / Oxy groups, cyano groups, sulfide groups, and hydroxyl groups are preferred, and hydroxyl groups are more preferred.
  • thermoplastic resin having excellent fuel permeation resistance is not particularly limited, but in terms of excellent gas permeation resistance, a resin composed of an ethylene / vinyl alcohol copolymer; a polyacrylonitrile resin [PAN]; a polyethylene terephthalate resin [P ET], polybutylene terephthalate resin [PBT], polyethylene naphthalate resin [PEN], polybutylene naphthalate resin [PBN], liquid crystal polyester [LC
  • PVF polyvinylidene fluoride resin
  • PVDF polyvinylidene fluoride resin
  • the thermoplastic resin having excellent fuel permeation resistance preferably has low-temperature impact resistance and has an Izod impact strength at 140 ° C of 2.5 kJ / m 2 or more. Preferably, there is. 2. If it is less than 5 k jZm 2, tends to be insufficient cold ⁇ of laminated resins obtained molded article. A more preferred lower limit is 3. a 5 k J Zm 2, still more preferred lower limit is 4. a 5 k J / m 2.
  • the above Izod impact strength depends on the application, but as a normally conceivable application, a value within the above range is required. For example, it may be 20 k jZm 2 or less.
  • the above-mentioned Izod impact strength is a value measured and measured in accordance with ASTM D 256-84.
  • the above-mentioned Izod impact strength is based on a U-F IMP ACT TESTER (manufactured by Ueshima Seisakusho). Set the measurement sample taken out of the thermostat at 40 ° C on the table, immediately shake it down with a hammer with a load of 1.33 kg at a strike speed of 3.4 em / s, and It is a value calculated by converting the impact energy (kgf ⁇ cm) into joules (J) and dividing by the sample cross-sectional area (m 2 ).
  • the resin consisting of an ethylene / vinyl alcohol copolymer is preheated at 220 to 230 ° C. for 20 minutes, and 30 MPa at 3 MPa. After pressurizing for 2 seconds and cooling with water, a pressed sheet with a thickness of 3.2 mm was obtained, cut into a width of 12 mm and a length of 50 mm, and a 2.54 mm deep notch was inserted. Obtained by holding in the tank for 4 hours.
  • the thermoplastic resin having excellent fuel permeation resistance forming the layer (B) in the present invention is a resin composed of an ethylene butyl alcohol copolymer
  • the resin composed of the ethylene / vinyl alcohol copolymer may be a low-temperature resin.
  • the resin comprising an ethylene-vinyl alcohol copolymer having low-temperature impact resistance include a resin to which a plasticizer is added, a resin in which two or more polyamide resins are mixed, a resin in which a hydroxy-functionalized polyetheramine is mixed, and the like.
  • examples of such a resin include, for example, JP-A-8-269260, JP-A-53-88067, JP-A-59-20345, and JP-A-52-141785. And the like.
  • Examples of commercially available resins made of ethylene and vinyl alcohol copolymers having improved low-temperature impact resistance include EVAL XEP505B (manufactured by Kuraray Co., Ltd.).
  • Izod impact strength at of preferably 2. 5 k jZm 2 or more, more preferably 3. 5 k J / m 2 or more, more preferably is used as 4. is 5 k jZm 2 or more, within the above range if the value, and may be for example 20 k J Zni 2 below.
  • thermoplastic resin having excellent fuel permeability which forms the layer (B) constituting the laminated resin molded article of the present invention
  • a resin composed of an ethylene / vinyl alcohol copolymer The alcohol copolymer is obtained by vulcanizing an ethylene / vinyl acetate copolymer obtained from ethylene and vinyl acetate.
  • the blending ratio of ethylene and butyl acetate to be copolymerized is appropriately determined according to the ratio of the number of moles of butyl acetate units defined by the following formula.
  • the ethylene / butyl alcohol copolymer is obtained by curing an ethylene / butyl acetate copolymer having X mol% of vinyl acetate units at a degree of polymerization of ⁇ / 0 .
  • the X mole% of the vinyl acetate unit and the ⁇ % of the degree of conversion satisfy XXY / 100 ⁇ 7. If XX ⁇ 100 or 7, the permeation resistance and the interlaminar adhesive strength may be insufficient.
  • XXYZ10010 is more preferred, and XXY / 100 ⁇ 50 is even more preferred.
  • the value of XXY / 100 is an index of the hydroxyl group content of the ethylene / butyl alcohol copolymer, and the large value of XXYZYZ 100 indicates that the ethylene / butyl alcohol copolymer has a large value. It means that the content of hydroxyl groups is high.
  • the hydroxyl group is a group that can participate in adhesion between the layer made of the thermoplastic resin having excellent fuel permeability resistance and a mating material to be laminated. When the content of the hydroxyl group is high, the obtained laminated resin is obtained. The interlayer adhesion of the molded body is improved.
  • the “partner to be laminated” refers to a material that is laminated in contact.
  • the “vinyl acetate unit X mol%” means that the vinyl acetate unit occupies the total number of moles [N] of the added ethylene and vinyl acetate in the molecule of the ethylenedivinyl alcohol copolymer.
  • Xi (%) (N / N) X 100
  • Means the average value of the molar content Xi represented by The above-mentioned mol acetate unit mol% is a value obtained by measuring using infrared absorption spectroscopy [IR].
  • butyl acetate unit means a part of the molecular structure of the ethylene / vinyl alcohol copolymer, which is derived from the acetate acetate.
  • the above-mentioned butyl acetate unit may be hydrogenated to have a hydroxyl group, or may be one which has not been tested and has an acetoxyl group.
  • degree of degradation is a percentage representing the ratio of the number of hydrogenated vinyl acetate units to the sum of the number of vinylated vinyl acetate units and the number of unpurified vinyl acetate units. It is.
  • the degree of degradation described above is a value obtained by measurement using infrared absorption spectroscopy [IR].
  • the ethylene / vinyl alcohol copolymer preferably has a melt flow rate [MFR] at 200 ° C. of 0.5 to: L 00 g / 10 minutes. Whether it is less than 0.5 g / 10 minutes or more than 100 g / 10 minutes, the melt viscosity of the ethylene / vinyl alcohol copolymer and the adhesive fluororesin forming the layer (C) Since the difference from the melt viscosity of the layer becomes large, the thickness of the layer (C) and / or the thickness of the layer (B) may be uneven during molding, which is not preferable.
  • a preferred lower limit is 1 g / 10 minutes, and a preferred upper limit is 50 gZ10 minutes.
  • MFR is a value obtained by measuring under the conditions of a load of 5 kg, an orifice diameter of 2 mm, and a land length of 8 mm.
  • thermoplastic resin having excellent resistance to fuel permeation may be added in a range not impairing the object of the present invention, for example, various additives such as a stabilizer such as a heat stabilizer, a reinforcing agent, a filler, an ultraviolet absorber, and a pigment.
  • the layer (B) may be formed by using together with an agent. By forming the layer (B) together with such an additive, properties such as thermal stability, hardness, abrasion resistance, chargeability, and weather resistance of the obtained laminated resin molded article can be improved.
  • the adhesive fluororesin that forms the layer (C) constituting the laminated resin molded article of the present invention includes at least an adhesive with the layer (B) made of a thermoplastic resin having excellent fuel permeability resistance. Those having properties are preferred.
  • the above-mentioned adhesive fluororesin for example, by having an adhesive functional group, it is possible to change Z or a site on a molecular structure different from the adhesive functional group into a structure that exhibits adhesiveness by heating. Thus, those having adhesive properties can be mentioned.
  • a resin having an adhesive functional group is preferable from the viewpoint of excellent adhesiveness.
  • the term “adhesive functional group” means a functional group that can participate in adhesion to a thermoplastic resin having excellent fuel permeation resistance.
  • the above-mentioned adhesive functional group is one which can react with the polar functional group of the thermoplastic resin having excellent fuel permeation resistance constituting the above-mentioned layer (B) or capable of performing an intermolecular interaction such as a hydrogen bond.
  • the “J having a carbonyl group” is a concept including a case where the J is a carbonyl group itself. That is, the adhesive functional group may be a carbonyl group.
  • the organic group for R in the above formula is, for example, Ci Cs. C 2 -C 2 having alkyl group, an ether bond.
  • Alkyl group and the like preferably Ci Cs alkyl group, C 2 -C 4 alkyl group having ether binding.
  • the halogenoformyl group is represented by —COY (where Y represents a Group VII atom), and includes, for example, one COF, one COC1, and the like.
  • the number of the above adhesive functional groups depends on the type and shape of the mating material to be laminated, the purpose and application of bonding, the required adhesive strength, the type of tetrafluoroethylene-based copolymer described below, and the bonding method Can be selected as appropriate.
  • the adhesive fluororesin may be composed of a polymer having an adhesive functional group at either a polymer chain terminal or a side chain. It may be composed of a polymer having both side chains. When the polymer has an adhesive functional group at its terminal, it may be present at both ends of the polymer chain, or may be present at only one of the ends.
  • the adhesive fluororesin has the adhesive functional group
  • the fluororesin made of a polymer having an adhesive functional group at the polymer chain end deteriorates heat resistance, mechanical properties, and chemical resistance. It is preferable because it is advantageous in terms of productivity and cost.
  • the adhesive fluororesin is made of a polymer having a monomer unit derived from a fluorine-containing ethylenic monomer.
  • the adhesive fluororesin may be composed of a polymer having a monomer unit derived from a fluorine-containing ethylenic monomer and a fluorine-free ethylenic monomer unit.
  • the “unit” of the polymer constituting the adhesive fluororesin means a part derived from a monomer, which is a part of the molecular structure of the polymer. For example, tetrafurfuryl O b ethylene units, - CF 2 - CF 2 - represented by.
  • the fluorine-containing ethylenic monomer is a butyl group-containing monomer having a fluorine atom and not having an adhesive functional group, for example, tetrafluoroethylene [TFE], vinylidene fluoride [VdF] , Black mouth trifluoroethylene [CTFE], fluorine fluoride / VF [VF], hexafenoleo mouth propylene [HFP], hexafenoleo mouth isobutene, perfluoro (alkyl butyl ether) [PAVE], the following general formula (i ):
  • X 2 represents a hydrogen atom or a fluorine atom
  • X 3 represents a hydrogen atom, a fluorine atom or a chlorine atom
  • n represents an integer of 1 to 10.
  • the fluorine-free ethylenic monomer is a vinyl group-containing monomer having no fluorine atom and no adhesive functional group.
  • examples thereof include ethylene [Et], propylene, 1-butene, 2 —Butene, butyl chloride, vinylidene chloride and the like.
  • the adhesive fluororesin is not particularly limited, but preferably has relatively low crystallinity and the resulting laminated resin molded article has excellent impact resistance.
  • Examples of such an adhesive fluororesin include tetrafluoroethylene-based resins. What consists of a polymer [TFE-type copolymer] is preferable.
  • the TFE-based copolymer is a polymer having a TFE unit.
  • the TFE-based copolymer may include, together with the TFE unit, one or more monomer units derived from other fluorine-containing ethylenic monomers other than TFE, and / or a fluorine-free ethylenic monomer. It may have one or more monomer units derived from.
  • TFE-based copolymer examples include, for example, a TFE / Et / HFP copolymer, a TFE / Et copolymer, a TFE / VdF / HFP copolymer, and a TFE / ⁇ ⁇ E copolymer.
  • TFE / HF P / PAVE copolymer and the like can be suitably used.
  • Polyvinylidene fluoride is generally said to have high crystallinity and poor impact resistance, but can be suitably used by copolymerizing a small amount of a modified monomer with VdF.
  • the adhesive fluororesin is made of a polymer having an adhesive functional group in a side chain
  • the adhesive functional group-containing ethylenic monomer is used in accordance with the intended adhesive fluororesin. It can be obtained by copolymerizing a fluorine-containing ethylenic monomer of a different type and blend with a fluorine-free ethylenic monomer if desired.
  • the term “adhesive functional group-containing ethylenic monomer” means a vinyl group-containing monomer having an adhesive functional group, which may or may not have a fluorine atom. This is a different concept from the above-mentioned “fluorine-containing ethylenic monomer” and “fluorine-free ethylenic monomer” in that it has an adhesive functional group.
  • the adhesive fluororesin has an adhesive functional group at a polymer chain terminal and is composed of a polymer in which the adhesive functional group is a carbonyl group, as described later, peroxycarbonate is used. Can be used as a polymerization initiator.
  • the adhesive fluororesin must have a melt viscosity that allows it to flow at a temperature at which the coextruded material can be melted without being thermally decomposed, for example, when the laminated resin molded article is formed by coextrusion. Is preferred.
  • the temperature range at which the polyamide resin can be suitably heated and melted is about 200 ° C to 300 ° C. It is preferable to have a melt viscosity capable of flowing in the step.
  • the melting point of the adhesive fluororesin is preferably from 150 to 270 ° C. If the temperature is lower than 150 ° C, it may be difficult to keep the fuel permeability low. If the temperature exceeds 270 ° C, the type of the mating material to be laminated may be limited, which is not preferable.
  • the lower limit of the melting point is more preferably 190 ° C.
  • the upper limit is more preferably 250 ° C.
  • the upper limit is more preferably 230 ° C.
  • the melt flow rate [MFR] of the adhesive fluororesin is preferably 1 to 100 gZl0 minutes. Whether it is less than 1 g / 10 min or more than 100 g / 10 min, the melt viscosity of the adhesive fluororesin and the thermoplastic viscosity of the layer (B), which is excellent in fuel permeability, is excellent.
  • the thickness of the layer (C) and the thickness of the layer (C) and the thickness of the layer (B) or the thickness of the layer (B) may be uneven during molding. A more preferred upper limit is 50 g / 10 minutes.
  • the above MFR is a value obtained by measuring at a specific measurement temperature under the conditions of a load of 5 kg, an orifice diameter of 2 mm, and a land length of 8 mm.
  • the above specific measurement temperature has a melting point of 2
  • a high melting point type adhesive fluororesin having a temperature of 00 ° C or more and 270 ° C or less, it is 297 ° C
  • a low melting point type adhesive resin having a melting point of 150 ° C or more and less than 200 ° C.
  • the temperature is 265 ° C.
  • the above-mentioned adhesive fluororesin is a high melting point type having a melting point of not less than 200 ° C and not more than 270 ° C when the fuel permeability of the obtained laminated resin molded article is to be kept low.
  • ⁇ 1 is 0.1 to 100 gZl 0 minutes can be suitably used.
  • the melting point is 150 ° C or more and less than 200 ° C.
  • a low melting point type having an MFR at 265 ° C. of 0.1 to 100 g / l 0 minutes can be suitably used.
  • As the fuel permeation resistance of the adhesive fluororesin it is preferable that the fuel permeation rate at 60 ° C.
  • test pseudo fuel type CE 10 be 20 (g Xmm / mday) or less. More preferably, it is 10 (g Xmm / m 2 / day) or less, even more preferably 2 (g Xmm / m 2 / day) or less.
  • the test pseudo fuel type CE10 is the same as described above.
  • the thermoplastic resin with excellent fuel permeability that forms the layer (B) conforms to the pseudo fuel type CE10 for testing.
  • Ratio of fuel permeation rate [Zb] at 60 ° C [ZcZZb] to fuel permeation rate [Zc] at 60 ° C for test pseudo fuel type CE10 of adhesive fluororesin forming layer (C) [ZcZZb] Is preferably 100 or less.
  • the above Z c / Zb is the same as or equivalent to the thermoplastic resin having excellent fuel permeability that forms the layer (B) and the adhesive fluororesin that forms the layer (C). .
  • Preferred specific examples of the adhesive fluororesin in the present invention include those comprising the following copolymer (I) and those comprising the following copolymer (II).
  • R f 2 represents CF 3 or OR f 1
  • R f 1 represents.
  • the copolymer (I) for example, at least, tetrafurfuryl O b ethylene unit 20-80 mole 0/0, Echiren unit 20-8 0 mole 0/0, and, copolymerizable with these other single And copolymers composed of 0 to 60 mol% of monomer units.
  • the mole% of each monomer unit is based on the above-mentioned adhesive functional group-containing ethylenic monomer in the total number of moles of the monomer units constituting the molecular chain of the copolymer.
  • the number of moles excluding the number of moles of the derived monomer units is defined as 100 mole%, and the ratio of each monomer unit to the 100 mole%.
  • the other monomer units in the copolymer (I) are optional components, and are appropriately subjected to copolymerization according to the intended use of the obtained laminated resin molded article.
  • Examples of the other copolymerizable monomers include hexafluoropropylene, trichlorofluoroethylene, propylene, and the following general formula (iiii):
  • X 1 and X 2 are the same or different and each represent a hydrogen atom or a fluorine atom
  • X 3 represents a hydrogen atom, a fluorine atom or a chlorine atom
  • n is an integer of 1 to 10.
  • R f 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
  • R f 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
  • Adhesive fluororesins made of a copolymer such as the above copolymer (I) are excellent in heat resistance, chemical resistance, weather resistance, electrical insulation, low chemical liquid permeability, and non-adhesiveness. Since the melting point can be lowered relatively easily, co-extrusion with an organic material having a relatively low melting point and no heat resistance becomes possible, which is preferable because a laminated resin molded article can be easily obtained. Above all,
  • (I-1) At least 30 to 70 mol of tetrafluoroethylene units 0 /. , E Ji Ren units 20 to 55 mole 0/0, and a copolymer consisting of monomer units 0-10 mol% represented by the general formula (iii),
  • (1-3) At least 30 to 70 mol of tetrafluoroethylene units 0 /. 20 to 55 mol% of ethylene units, and 0 to 10 mol of monomer units represented by the above general formula (iv). / 0 is preferred.
  • Each of the monomer units represented by the general formula (iV) in (1-3) is an optional component, and is appropriately subjected to copolymerization according to the intended use of the obtained laminated resin molded article.
  • (I 1 -1) at least, tetrafurfuryl O b ethylene units 65-95 mole 0/0, ⁇ Pi, to hexa consisting Full O b propylene unit 5-35 mol% copolymer, the Tet rough Ruo b ethylene units the preferable lower limit of a 75 mole 0/0, a preferred upper limit of Kisafuruo port propylene units into the is 25 mole 0/0,
  • (II -4) at least, Te trouble O b ethylene units 30 to 80 mole 0/0, the sum of the ⁇ beauty, the hexa full O b propylene units and vinylidene fluoride Rai de unit 20 To 70 mol%.
  • the method for producing the adhesive fluororesin in the present invention is not particularly limited, and a known method can be used.
  • an adhesive fluororesin consisting of a polymer having an adhesive functional group on the side chain, the fluorine-containing ethylenic monomer and adhesive functional group of the type and composition appropriate for the target adhesive fluororesin It can be obtained by copolymerizing the containing ethylenic monomer and, if desired, a fluorine-free ethylenic monomer.
  • Suitable adhesive functional group-containing ethylenic monomers include those having a carbonyl group as the adhesive functional group, such as perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1 Monomers containing fluorine, such as trifluormethacrylic acid fluoride and perfluorobutenoic acid; and monomers containing no fluorine, such as acrylic acid, methacrylic / leic acid, acrylic acid chloride, and vinylene carbonate, respectively No.
  • the above-mentioned peroxycarbonates include diisopropylpropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxysop, pinolecarbonate, bis (4-t Xyl) veroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate and the like are preferred.
  • the amount of peroxycarbonate used depends on the type and composition of the desired adhesive fluororesin, the molecular weight, the polymerization conditions, and the type of peroxycarbonate used. The amount is 0.05 to 20 parts by mass relative to 0 parts by mass, a particularly preferred lower limit is 0.1 parts by mass, and a particularly preferred upper limit is 10 parts by mass.
  • the polymerization method for obtaining the adhesive fluororesin is not particularly limited, and includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization.
  • a suspension polymerization in an aqueous medium using peroxycarbonate as a polymerization initiator is preferred.
  • a fluorine-based solvent can be added to water and used.
  • the fluorine-based solvent used in the suspension polymerization CH 3 CC 1 F 2, CH 3 CC 1 2 F, CF 3 CF 2 CC 1 2 H, CF 2 C 1 CF 2 C FHC 1 etc.
  • hydrochloride port Furuoro alkane Chlorofluoroalkanes such as CF 2 C 1 CFC 1 CF 2 CF 3 , CF 3 CFC 1 CFC 1 CF 3 ; CF 3 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF per full O b alkanes such as 3; perf Ruo b Per full O b cycloalkanes cyclobutane like.
  • PA full O b alkanes, par Fluorocycloalkanes are preferred.
  • the use amount of the fluorinated solvent is preferably 10 to 100% by mass based on water from the viewpoint of suspendability and economy.
  • the polymerization temperature is not particularly limited,
  • the polymerization pressure is appropriately determined according to other polymerization conditions such as the type and amount of the solvent to be used, the vapor pressure, the polymerization temperature, and the like, but may be usually from 0 to 9.8 MPaG.
  • a usual chain transfer agent for example, a hydrocarbon such as isopentane, n-pentane, n-hexane, cyclohexane, etc .; Alcohols; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and methyl chloride may be used.
  • the adhesive fluororesin may be used together with various additives such as a stabilizer such as a heat stabilizer, a reinforcing agent, a filler, a UV absorber, and a pigment within a range not impairing the object of the present invention. ) May be formed.
  • a stabilizer such as a heat stabilizer, a reinforcing agent, a filler, a UV absorber, and a pigment within a range not impairing the object of the present invention.
  • the layer made of the adhesive fluororesin in the present invention is composed of the above-mentioned adhesive fluororesin and other components blended as required. If necessary, the layer made of the adhesive fluororesin (C) Can be electrically conductive.
  • the term “conductive” means that flammable volatile organic substances such as fuel and organic solvents come into contact with the insulator for a long time. There is a danger that the static charge will accumulate and ignite, but it means that it has electrical characteristics to such an extent that this static charge does not accumulate. When the layer (C) has conductivity, the possibility of ignition is reduced even when the flammable volatile organic substance comes into contact with an insulator such as an adhesive fluororesin in the layer (C). .
  • the layer (C) is preferably conductive when used in contact with combustible volatile organic substances.
  • the layer (C) made of the adhesive fluororesin is made conductive, it is preferable to mix a conductive material such as carbon black and acetylene black.
  • the compounding amount is preferably 20% by mass or less, more preferably 15% by mass or less of the above-mentioned adhesive fluororesin.
  • the lower limit of the blending amount may be an amount that provides the above-described electrical characteristics to such an extent that the static charge is not accumulated.
  • the layer (A) constituting the laminated resin molded article of the present invention is made of a thermoplastic resin different from the adhesive fluororesin used for the layer (C).
  • the thermoplastic resin used for the layer (A) is not particularly limited, and examples thereof include a polyacetal resin such as a polyurethane resin, a polyester resin, a polyamide resin, a polyaramid resin, a polyamide imide resin, and a polyphenylene oxide resin [PPO].
  • thermoplastic resin acrylic resin, styrene resin, acrylonitrile / butadiene nostyrene resin [ABS], vinyl chloride resin, cellulose resin, polyether ether ketone resin [PEEK], polysulfone resin, polyether sal Examples include a polyethylene resin [PES], a polyetherimide resin, and a polyphenylene sulfide resin, and a vinyl acetate resin may be used as long as the resin is different from the above-mentioned ethylene / butyl alcohol copolymer.
  • the thermoplastic resin used in the layer (A) is excellent in adhesiveness to other materials and mechanical toughness, and polyamide resin is preferable in that the obtained laminated resin molded article can be made flexible. preferable.
  • thermoplastic resins having excellent fuel permeability resistance those used for the layer (B) are not used simultaneously as the thermoplastic resin for the layer (A).
  • the resin used as the thermoplastic resin having excellent heat resistance is selected from the viewpoint of suppressing the fuel permeability to be lower than the resin used as the thermoplastic resin for the layer (A), while the resin used for the layer (A) is used as the thermoplastic resin.
  • the resin is selected from the viewpoint of maintaining the mechanical strength of the laminated resin molded article of the present invention. From these viewpoints, when a polyester resin, a PPS resin, or a resin made of an ethylene Z-Butyl alcohol copolymer is selected as the thermoplastic resin having excellent fuel permeation resistance of the layer (B), the heat of the layer (A) is obtained. It is preferable to select a polyamide resin as the plastic resin.
  • the layer (A) made of the polyamide resin has excellent mechanical properties such as tensile strength, burst resistance, low-temperature impact resistance, and flexibility. It can be.
  • the polyamide-based resin is made of a crystalline polymer having an amide bond [1-NHCO—] as a repeating unit in the molecule.
  • a resin composed of a crystalline polymer in which an amide bond is bonded to an aliphatic structure or an alicyclic structure, a so-called nylon resin.
  • nylon resins include nylon 6, nylon 66, nylon 11, nylon 12, nylon 61, nylon 61, nylon 66, nylon 66/1, nylon 46, and metal.
  • Examples include a silylendiamine / adipic acid copolymer, and at least two kinds of blends thereof.
  • the polyamide resin used as the thermoplastic resin of the layer (A) also preferably has low-temperature impact resistance.
  • Methods for improving the low-temperature impact resistance of the polyamide resin include, for example, impact resistance including a mixture of a general-purpose rubber and a halogenated copolymer of alkyl styrene with isomonoolefin having 4 to 7 carbon atoms.
  • Examples of such a resin include, for example, Japanese Patent Publication No. 11507979, US Pat. No. 4,174,358, Japanese Patent Publication No. 2003-516457, US Pat. No. 5,610,223, and French Patent Invention No. 2640632. And US Patent Application Publication No. 09 / 293,195.
  • polyamide resins having improved low-temperature impact resistance include, for example, UBESTA 3030MI 1 (manufactured by Ube Industries, Ltd.), A4877, and A4878 (both manufactured by Daicel Degussa). .
  • the polyamide resin preferably has an Izod impact strength at ⁇ 40 ° C. of 7 kJ / m 2 or more . When it is less than 7 kJ / m 2 , the low-temperature impact resistance of the obtained laminated resin molded article tends to be insufficient. A more preferred lower limit is 10 kJZm 2 , and a still more preferred lower limit is 35 kJ / m 2 .
  • the Izod impact strength depends on the application, but as a normally conceivable application, it may be, for example, 80 kjZm 2 or less as long as it is within the above range.
  • the Izod impact strength is as described above for the thermoplastic resin having excellent fuel permeation resistance. .
  • a polyamide resin having an Izod impact strength at _40 ° C within the above range is used, and the Izod impact strength at -40 ° C is within the above range.
  • the use of a thermoplastic resin having excellent fuel permeation resistance means that either one of them may be employed, but it is preferable to employ both in terms of enhancing the low-temperature impact resistance.
  • the polyamide resin forming the layer (A) that forms the laminated resin molded article of the present invention has a structure in which an amide bond is not repeated as a repeating unit. It may be made of a high polymer. Examples of such a polyamide resin include polyamide elastomers such as nylon 6-polyester copolymer, nylon 6 / polyether copolymer, nylon 12-polyester copolymer, nylon 12 / polyether copolymer, and the like. Or And the like.
  • polyamide elastomers are obtained by block copolymerization of a nylon oligomer and a polyester oligomer via an ester bond, or block copolymerization of a nylon oligomer and a polyether oligomer via an ether bond. It was obtained by Examples of the polyester oligomer include polycaprolactone and polyethylene adipate. Examples of the polyether oligomer include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the above-mentioned polyamide-based elastomer, a nylon 6Z polytetramethylene dalicol copolymer and a nylon 12Z polytetramethylene glycol copolymer are preferable.
  • nylon 6, nylon 66, nylon 11, nylon 12, nylon 61 can be used because sufficient mechanical strength can be obtained even when the polyamide resin is a thin layer.
  • Nylon 6 6 Z 12, Nylon 6 Polyester copolymer, Nylon 6 / Polyester copolymer, Nylon 12 Z Polyester copolymer, Nylon 1 2 It is preferably at least one selected from the group consisting of a Z polyester copolymer and a blend of at least two of these.
  • the melting point of the polyamide resin is not particularly limited.
  • the polyamide resin when a laminated resin molded article is formed by coextrusion, the polyamide resin is not thermally decomposed at a temperature at which the material to be coextruded can be melted.
  • the temperature may be any of the above.
  • the molecular weight of the polyamide-based resin is not particularly limited as long as the molecular weight is such that the desired mechanical strength can be obtained.
  • the polyamide resin may be used together with various additives such as a stabilizer such as a heat stabilizer, a strengthening agent, a filler, an ultraviolet absorber, and a pigment within a range not impairing the object of the present invention. ) May be formed.
  • a stabilizer such as a heat stabilizer
  • a strengthening agent such as a heat stabilizer
  • a filler such as a heat absorber
  • an ultraviolet absorber such as an ultraviolet absorber
  • a pigment within a range not impairing the object of the present invention.
  • properties such as thermal stability, surface hardness, abrasion resistance, electrification, and weather resistance of the obtained laminated resin molded article can be improved.
  • the laminated resin molded body of this effort has a layer (A) made of polyamide resin, A layer (B) composed of a thermoplastic resin having excellent properties and a layer (C) composed of an adhesive fluororesin are laminated in this order.
  • the laminated resin molded article may be composed of only the layer (A), the layer (B), and the layer (C). Both the layer (A) and the layer (B) may be used.
  • Other layers different from the above-mentioned layer (C) may be laminated with the above-mentioned layer (A), the above-mentioned layer (B) and the above-mentioned layer (C).
  • the “other layer different from the layer (A), the layer (B), and the layer (C)” may be simply referred to as “other layer”.
  • the other layers may be one kind or two or more kinds.
  • the laminated resin molded article of the present invention may be one in which an adhesive layer is adhesively laminated as the other layer between the layer (B) and the layer (C).
  • the layer (B) and the layer (C) can be in contact with each other because of excellent adhesion between the layer (B) and the layer (C) without any intervention.
  • the initial adhesive strength between the layer (B) and the layer (C) is 2 ON, cm or more. Is preferred.
  • the above-mentioned initial adhesive strength is more preferably 25 NZ cm or more in practical use.
  • the laminated resin molded article has the initial adhesive strength of 20 N / cm or more and the adhesive strength after fuel immersion of 20 NZcm, the initial adhesive strength of 25 NZcm or more, and the adhesive strength after fuel immersion. More preferably, the strength is 25 NZ cm.
  • the initial adhesive strength and the adhesive strength after immersion in the fuel are values obtained by measuring by a measuring method described later.
  • the laminated resin molded article of the present invention has a sufficient adhesive force between the layer (A) and the layer (B), but has an adhesive force between the layer (A) and the layer (B).
  • another layer described above may be interposed between the layer (A) and the layer (B) as an adhesive layer (D).
  • the adhesive layer (D) can be used as the layer (A) and the layer (B) without using the same.
  • the adhesive strength of this is sufficient, it is preferable to use it especially when the polyamide resin of the layer (A) is nylon 11 or nylon 12.
  • the adhesive layer (D) is preferably made of nylon 1 in the layer (A).
  • the resin is interposed between the layer (A) and the layer (B).
  • the resin that can be used for the adhesive layer (D) is not particularly limited as long as it has adhesiveness to both the layer (A) and the layer (B).
  • polyolefins such as polyethylene and polypropylene Polyolefin which is modified with maleic anhydride or the like; an adhesive fluororesin which can be used for the layer (C); in this case, an adhesive fluororesin used for the layer (C) and an adhesive used for the layer (D)
  • an adhesive fluororesin which can be used for the layer (C)
  • an adhesive fluororesin used for the layer (C) and an adhesive used for the layer (D)
  • the adhesive layer (D) is preferably an adhesive fluororesin, a polyamide resin, or a mixture of an adhesive fluororesin and a polyamide resin.
  • thermoplastic polymer forming the layer (B) made of a thermoplastic resin having excellent fuel permeability a polymer having a polar functional group and a large intermolecular force is used, so that there are many water-absorbing polymers. Due to the effect of this water absorption, the fuel resistance decreases, and the low-temperature impact resistance decreases. Therefore, shielding the layer (B) from moisture is very effective in suppressing a change with time in the physical properties of the laminated resin molded product. Since the fluororesin has a high barrier property against water, the use of the adhesive fluororesin for the adhesive layer (D) means that the layer (B) is sandwiched between the fluororesin layers, and that the layer (B) can be used over time. This is advantageous in that it has an effect of suppressing excessive water absorption and can suppress a temporal decrease in fuel permeability resistance and low-temperature impact resistance of the laminated resin laminate.
  • the layer (A) preferably has a higher amine value.
  • the laminated resin molded article of the present invention is intended to protect the laminated resin molded article from vibration, impact, etc., on the surface of the layer (A) opposite to the layer (B). In addition, it may have the above-mentioned other layers such as an elastomer layer.
  • the elastomer constituting the above-mentioned elastomer layer may be a thermoplastic elastomer.
  • the laminated resin molded article of the present invention includes a conductive layer (E) as the other layer.
  • the conductive layer (E) is in contact with the surface of the layer (C) made of the adhesive fluororesin opposite to the surface (B) made of the thermoplastic resin having excellent fuel permeability. May be used.
  • the “conductive layer (E)” is a conductive layer made of a fluororesin.
  • the conductive layer (E) is a layer made of a fluororesin, but is conceptually different from the layer (C) as is apparent from one embodiment of the other layers.
  • the fluororesin used for the conductive layer (E) may be an adhesive fluororesin or a fluororesin different from the adhesive fluororesin.
  • the laminated resin molded article containing the conductive layer (E) is particularly preferably a fuel tube, a fuel hose or a fuel tank to be described later. In this case, the conductive layer (E) is used in view of utilizing conductivity. ) Is preferably located at the position in contact with the fuel, usually at the innermost layer.
  • the laminated resin molded article of the present invention is formed by laminating the above-mentioned layer (A), layer (B) and layer (C), it has excellent interlayer adhesion, and also has an adhesive property for forming the layer (C). It has properties such as excellent fuel oil resistance, chemical resistance, heat resistance, weather resistance, electrical insulation, non-adhesiveness, and non-elution properties possessed by the fluoropolymer.
  • the fuel permeability of the laminate was merely the sum of the fuel permeability of each single layer.
  • the layer (A) made of a polyamide-based resin together with the layer (B) made of a thermoplastic resin having excellent fuel permeation resistance, the laminated resin molded article has a The fuel permeability can be kept much lower than the sum of the fuel permeability of each single layer.
  • the thickness of the layer (C) which is usually made of an expensive adhesive fluororesin, can be made relatively thin.
  • the laminated resin molded article is provided with the layer (A) made of the polyamide resin, thereby suppressing the occurrence of cracks and facilitating bending. Shapes and convoluted shapes can be produced, and even when these shapes are used, fuel permeability and the like are kept low and crack resistance is excellent.
  • the laminated resin molded article of the present invention has a low-temperature impact resistance as a polyamide resin constituting the layer (A).
  • a material that has high impact resistance and low-temperature impact resistance as the thermoplastic resin of layer (B) that has excellent fuel permeability, the low-temperature impact resistance of the entire tube is greatly improved. It is possible to improve the thickness of the layer (C) made of the adhesive fluororesin.
  • Thinning the layer (C) made of the adhesive fluororesin is advantageous in terms of cost because it can reduce the amount of fluororesin, which is generally considered expensive, and it is a standard for fuel tubes. Accordingly, when the overall thickness is determined, or when the predetermined thickness is used for an intended use, the layer (B) can be thickened, and the fuel permeation resistance of the entire laminated resin molded article can be improved.
  • the layer (C) made of the adhesive fluororesin is preferably not more than 25% of the total thickness of the laminated resin molded article.
  • the thickness of the entire laminated resin molded article of the present invention is 1 mm , 0.25 mm or less, more preferably 0.15 mm, and still more preferably about 0.1 mm.
  • the layer (B) made of a thermoplastic resin having excellent fuel permeability is used together with the layer (B) made of a thermoplastic resin having excellent fuel permeability.
  • the layer (A) made of a polyamide-based resin, it is possible to improve the fuel permeation resistance of the entire laminated resin molded article.
  • the layer (C) composed of the adhesive fluororesin can be made to be 10% or less of the total thickness of the laminated resin molded article. Even in such a case, the low-temperature impact resistance test described in SAE-J2260 can be used. A laminate that does not crack can be obtained.
  • the overall thickness of the laminated resin molded article of the present invention is lmm
  • the layer (C) made of the adhesive fluororesin is thinned to 0.1 mm
  • the layer (C) made of fluororesin and the layer (B) made of thermoplastic resin having excellent fuel permeability are laminated with a strong adhesive force
  • the above layer (A) is used as the outer layer.
  • a fuel tube is used, a tube that does not crack in the low-temperature impact resistance test described in SAE-J2260 is produced.
  • the laminated resin molded article of the present invention can 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 above film shape, sheet shape, tube shape and hose shape are corrugated. ed) shape or convoluted shape.
  • tubes, hoses and tanks can be suitably used for fuel.
  • the layer (C) is preferably in a position in contact with the fuel, that is, usually the innermost layer.
  • the layer (A) is an outer layer
  • the layer (B) is an intermediate layer
  • the layer (C) has a positional relationship between the layer (A) and the layer (B) with the inner layer.
  • the “outer layer”, “inner layer”, and “intermediate layer” refer to the above-mentioned layers (A), (B), and ⁇ in the shapes having the concept of inside and outside such as tubes, hoses, and tanks.
  • the layer (C) may have another layer on the surface on the side opposite to the layer (B).
  • the above-mentioned laminated resin molded article comprises a layer (A) made of a polyamide resin as an outer layer, a layer (C) made of an adhesive fluororesin as an inner layer, and a thermoplastic resin having excellent fuel permeability resistance. It is preferable that the layer (B) be an intermediate layer.
  • This laminated resin molded article is particularly preferable when used as a fuel tube, a fuel hose, or a fuel tank. It is sometimes referred to as “laminate resin molding for fuel”.) In this case, it is more preferable that the layer (B) and the layer (C) are in contact with each other. In the laminated resin molded article, the layer (B) and the layer (C) are in contact with each other, and are composed of only the layer (A), the layer (B), and the layer (C). You can.
  • the laminated resin molded article is a laminated resin molded article further including an adhesive layer (D).
  • the adhesive layer (D) is different from the layer (A) made of a polyamide resin in heat resistance excellent in fuel permeation resistance. Those present between the layer (B) and the layer made of a plastic resin are more preferable.
  • the laminated resin molded article is a laminated resin molded article including the above layer (A) as an outer layer, the above layer (C) as an inner layer, and the above layer (B) as an intermediate layer. A) and the above layer (B )) And the adhesive layer (D), and is particularly preferable when used as a fuel tube, a fuel hose or a fuel tank.
  • the laminated resin molded article can further improve the adhesive strength between the above-mentioned shunn (A) and the above-mentioned layer (B).
  • the polyamide resin of the layer (A) is nylon 12, as described above, it can be sufficient.
  • the layer (B) and the layer (C) are in contact with each other.
  • the laminated resin molded article is a laminated resin molded article further including the above-mentioned conductive layer (E), wherein the conductive layer (E) is a layer of an adhesive fluororesin (C) which has a resistance to heat resistance.
  • the layer may be in contact with the surface opposite to the layer (B) made of a thermoplastic resin having excellent fuel permeability.
  • This laminated resin molded product is particularly preferable when used as a fuel tube, a fuel hose or a fuel tank.
  • the laminated resin molded article may not include the adhesive layer (D), but preferably has the adhesive layer (D) between the layer (A) and the layer (B). It is preferable that the layer (B) is in contact with the above-mentioned layer (C).
  • the conductive layer (E) is preferably the innermost layer in the laminated resin molded article. Since the laminated resin molded article includes the conductive layer (E), the layer (C) does not need to be conductive, but the layer (C) may be
  • the above-mentioned laminated resin molded article is suitable not only for a fuel that can be suitably used particularly for a fuel tube, a fuel hose or a fuel tank, but also for applications in contact with combustible volatile organic substances other than fuel. Can be used.
  • the method for producing the laminated resin molded article of the present invention is not particularly limited, and is appropriately selected according to the type and properties of the resin forming each layer.
  • Examples of the above method include a method of co-extrusion of the material constituting each layer in a multilayer form, a method of separately molding the material constituting each layer into a sheet or film shape, and then pressing the obtained layers under heating.
  • a method of laminating by heat fusion is exemplified.
  • the die temperature of multi-layer coextrusion the resin Since the temperature is preferably as high as possible within the range not decomposing, the temperature is preferably higher than 225 ° C, more preferably 230 ° C or more. Conventionally, when multi-layer co-extrusion using an ethylene / butyl alcohol copolymer was performed at a die temperature of 250 ° C. or less, in the method for producing a laminated resin molded article of the present invention, 250 ° C. Molding can be performed at a temperature exceeding. When a conductive material is not used for the innermost layer, the die temperature is preferably 240 to 260 ° C.
  • the innermost layer is made of a conductive material
  • molding at a die temperature exceeding 250 ° C is preferable from the viewpoint of suppressing melt fracture and lowering the resistance value, and more preferably at 260 ° C or higher.
  • the upper limit is preferably 300 ° C., more preferably 290 ° C., and even more preferably 280 ° C., from the viewpoint of suppressing the decomposition and deterioration of the thermoplastic resin having excellent fuel permeability.
  • the same die temperature can be used when the above layer (B) is made of ethylene butyl alcohol copolymer.
  • the laminated resin molded article is excellent in fuel oil resistance, solvent resistance, chemical resistance, non-elution property, etc., and can suppress fuel permeability to a low level. Can be used for contacting applications.
  • the fuel is not particularly limited, and includes, for example, a fuel oil such as gasoline, petroleum, light oil, or heavy oil; a pseudo fuel such as Fue 1C; a peroxyside-containing fuel obtained by mixing the above fuel oil, pseudo fuel, or the like with peroxide; An alcohol-containing fuel obtained by mixing a fuel oil, a pseudo fuel, or the like with methanol, ethanol, or the like can be given.
  • the fuel may be a gaseous fuel such as methane, natural gas, and dimethyl ether.
  • the laminated resin molded article can be suitably used for suppressing the permeation of the alcohol-containing fuel.
  • the solvent is not particularly limited as long as it is mainly composed of a solvent usually used as a solvent.
  • the solvent include organic acids such as acetic acid, formic acid, cresol and phenol; alcohols such as methanol and ethanol; ethylenediamine; Amines such as diethylenetriamine and ethanolamine; amides such as dimethylacetamide; esters such as ethyl acetate and butyl acetate; hydrocarbons such as hexane; ketones such as acetone and dimethyl ketone; Of which one or a mixture of two or more And the following.
  • the solvent may be one obtained by dissolving a resin or the like in a solvent generally used as the above solvent, such as a paint.
  • the laminated resin molded article can be suitably used as the solvent, particularly for applications in contact with combustible volatile organic substances.
  • the laminated resin molded body is a layer (a) made of a thermoplastic resin having excellent fuel permeability resistance.
  • the laminated resin molded article can be used for the following applications.
  • the laminated resin molded article has excellent impact resistance, particularly low-temperature impact resistance in addition to non-elution and flexibility, it can be suitably used as a tube or a hose.
  • the laminated resin molded article is excellent in fuel oil resistance and the like, and has low fuel permeability. It can be particularly preferably used as a hose or a fuel hose.
  • a tube that does not crack in the low-temperature impact resistance test described in SAE-J2260 can be provided from the viewpoint of low-temperature impact resistance.
  • the laminated resin molded article has excellent impact resistance, particularly low-temperature impact resistance in addition to non-elution, flexibility, and the like, and thus can be suitably used as a tank.
  • a conventional product in which a resin laminate having a top layer made of polyethylene or the like is joined to form a tank has a problem in that the contents leak from the joint surface where the layers made of polyethylene or the like are adhered due to low adhesion.
  • the layers (C) composed of the adhesive fluororesin are compatible with each other and bonded. Because of its excellent strength, even when used as a tank, the contents are unlikely to leak from the joint surface of the laminated resin molded product.
  • the laminated resin molded article has excellent fuel oil resistance and low fuel permeability
  • the above-mentioned tank can be particularly suitably used as a fuel tank.
  • the above-mentioned laminated resin molded article when the above-mentioned layer (C) has conductivity, or when the above-mentioned conductive layer (E) has excellent fuel permeation resistance among the surfaces of the above-mentioned layer (C).
  • the conductive layer (C) and the conductive layer (E) are preferably the innermost layer in the laminated resin molded article.
  • Such a laminated resin molded body does not accumulate electrostatic charge even when in contact with the above-mentioned flammable volatile organic substance, and has a low possibility of ignition.
  • the surface resistance value of the inner surface of the tube is set to SAE-J2260. According to the test method provided, a laminate having a value of less than ⁇ / sq can be provided.
  • N 500 AW / 8 d f (a)
  • the infrared absorption spectrum analysis was performed 40 times using a Perkin-Elmer FTIR spectrometer 176 OX (manufactured by PerkinElmer Inc.). Based on the obtained IR spectrum, the base line was automatically determined by Perkin-ElmerSpecctrumfoorwindowsVer.1.4C.
  • the melting peak when the temperature was raised at a rate of 10 ° 0 minutes was recorded, and the temperature corresponding to the maximum value was defined as the melting point (Tm).
  • a 1 cm wide test piece was cut from the tubular resin molded article, and a 180 ° peel test was performed at a speed of 25 mmZ on a Tensilon universal testing machine. The maximum 5-point average in the elongation-tensile strength graph was calculated. It was determined as the initial bond strength (NZcm).
  • the resin pellets to be used for each layer of the tube-shaped laminated resin molded product were placed in a mold with a diameter of 120 mm and heated by a press machine (fluorocarbon resin: 260 ° C, other resins other than fluorocarbon resin: 230 ° C ) And melt-pressed at a pressure of about 2.9 MPa to obtain a sheet having a thickness of 0.1 mm.
  • Tables 1 and 2 show the values of the fuel permeation rate of each resin single layer used in the calculation of the fuel permeation rate of the entire laminated resin molded product in Tables 5 and 8.
  • the tube-shaped laminated resin molded product was cut to a length of 40 cm, a SUS 316 reservoir tank with a capacity of 12 Oml was attached with a swage port, and the permeation amount of CE 10 was measured in accordance with SAE J17737.
  • the fuel permeation rate (g Xmm / day / m 2 ) was calculated from the measured thickness of the tubular resin molded article.
  • the calculated value P of the fuel permeation rate of the laminated resin molded article was calculated by the following formula based on the actually measured value of the fuel permeation rate of the single layer measured by the method described above.
  • the mixture was evaporated in a flask, dried for 24 hours in a constant temperature bath at 80 ° C, and the mass of the eluted material was measured.
  • the mass of the eluted material, the surface area of the laminated resin molding in the liquid contact portion, and the mass of the fuel The dissolution rate (g / l 00 ml / m 2 ) was calculated from.
  • Table 2 shows the trade names of the ethylene Z butyl alcohol copolymer used in the experimental examples, the values of X mol% of vinyl acetate units, the degree of oxidation Y%, and XXY / 100.
  • Table 3 shows the physical properties of the fluororesin used in the experimental examples.
  • TFE tetrafluoroethylene
  • Et ethylene
  • VdF vinylidene fluoride
  • HFP hexafluoropropylene
  • HF-P e perfluoro (1,1,5-trihydryl 1-pentene)
  • PMVE perfluoro (methyl vinyl ether).
  • the polyamide resins used in the experimental examples are as follows.
  • PA 12 Vestamid X7297 (manufactured by Degussa AG) and A4878 (manufactured by Daicel Degussa) were used. BESNP40TL (manufactured by Atofina) was used as Polyamide 11 [PA11]. UBE nylon 1018 I (manufactured by Ube Industries) was used as polyamide 6 [PA6].
  • nylon 6 (trade name: UBE nylon 10181, manufactured by Ube Industries) and nylon 1 2 (trade name: UBE STA3030B, manufactured by Ube Industries)
  • the polyethylene resins used in the experimental examples were low-density polyethylene [LDPE] (trade name: Petrocene 292, manufactured by Tosoh Corporation) and maleic anhydride-modified polystyrene [modified PE] (trade name: ADMER NF 528) , Manufactured by Mitsui Chemicals, Inc.).
  • the resins consisting of the ethylene / butyl alcohol copolymer used in the experimental examples were EVAL F101A (Kuraray), Mersen H 6051 (Tosoichi), Technolink K200 (Taoka Chemical). ), And Mersen H6410M (manufactured by Tohso I) and Xepar XEP505B (manufactured by Kuraray).
  • Experimental Example 1 25 Using a four-layer, four-layer tube co-extrusion device equipped with a multi-manifold die, the resins shown in Table 5, Table 6, Table 7, and Table 8 were respectively applied to four extruders. The supplied resin was continuously molded into a tube-shaped laminated resin molded article having an outer diameter of 8 mm and an inner diameter of 6 mm. Table 58 shows the molding conditions and the evaluation results of the obtained tubes.
  • PA12A Vestamid X 7297 (Degusa AG)
  • PA12B A4878 (Daicel Degussa)
  • PA11 BESNP 40 TL (Atofina)
  • PA 6 Nylon 6 (trade name: UBE nylon 101 81, manufactured by Ube Industries)
  • PAmix Nylon 6 (trade name: UBE nylon 1018 1, manufactured by Ube Industries) and nylon 1 2 (trade name: UBESTA 3030 B) (Made by Ube Industries)
  • LDPE Petrocene 292 (manufactured by Toso Corporation)
  • E VOH 1 EVAL F 10 1 A (Kuraray)
  • EVOH3 Techno Link K 200 (Taoka Chemical Co., Ltd.)
  • E VOH4 Mersen H6410M (manufactured by Tohso I)
  • E VOH 5 Evar XE P 505 B (manufactured by Kuraray)
  • Table 5 shows that the interlayer adhesion of the laminated resin molded article of Experimental Example 14 using the XYZ / l 00 ⁇ 7 ethylene / butyl alcohol copolymer for the middle layer and the adhesive fluororesin for the inner layer It was good even after immersion.
  • Experimental Example 23 in which an ethylene-Z-Bier alcohol copolymer of XXYZ100 ⁇ 7 was used for the intermediate layer in Table 7 and a fluororesin having no adhesive functional group was used for the inner layer, no interlayer was bonded at all.
  • Experimental Example 2 in Table 5 and Experimental Example 20 in Table 7 both used EVOH 1 for the intermediate layer and adhesive fluoroplastic FB for the inner layer, and the thickness of each layer was the same, but the outer layer was LDPE.
  • the fuel permeation rate of the whole tube was almost the same as the value calculated from the fuel permeation rate of each single layer.However, when the polyamide resin was used for the outer layer, the fuel permeation rate was particularly low. I understood.
  • Experimental Examples 1 to 11 and 14 in Table 5 using a polyamide resin for the outer layer each single-layer fuel was used regardless of the presence or absence of the adhesive layer and the thickness of each layer. The measured fuel permeation rate was much lower than the calculated value based on the permeation rate.
  • the fuel permeability is suppressed to be much lower than the sum of the fuel permeability of each layer, and the interlayer adhesive strength, fuel oil resistance, non-elution property, and low-temperature impact resistance are started to be used.
  • An excellent laminated resin molded product can be obtained over time and after elapse of time. Since the above-mentioned laminated resin molded article has the above-mentioned excellent characteristics, the fuel tube and the fuel It can be suitably used for applications such as fuel hoses and fuel tanks. ,

Landscapes

  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

La présente invention a trait à un élément formé de résine stratifiée dont la qualité ne se modifie pas lors de sa formation et présentant une excellente résistance aux huiles combustibles, une propriété de non dissolution, une résistance au fluage, une résistance thermique, et une résistance aux chocs à basse température. L'élément formé de résine stratifiée présente une faible perméabilité aux combustibles, et il est possible d'éliminer la détérioration avec le vieillissement de l'adhérence entre les couches, de la résistance à la perméabilité ou de la résistance aux chocs à basse température dans cet éléments formé de résine stratifiée. L'élément formé de résine stratifiée comportant une couche (A) constituée d'une résine polyamide, une couche (B) constituée d'une résine thermoplastique avec une excellente imperméabilité aux combustibles, et une couche (C) constituée d'une résine fluorée adhésive se caractérise en ce que la couche (A), la couche (B) et la couche (C) sont disposées dans cet ordre.
PCT/JP2004/001387 2003-02-10 2004-02-10 Element forme de resine stratifiee et son procede de production WO2004069534A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007118520A (ja) * 2005-10-31 2007-05-17 Kyoraku Co Ltd 多層構造体および多層容器
JP2009006575A (ja) * 2007-06-28 2009-01-15 Nissan Motor Co Ltd 多層ホース
JP2012107244A (ja) * 2004-10-05 2012-06-07 Arkema France 可撓性のある半結晶ポリアミド
KR20200027974A (ko) * 2017-07-12 2020-03-13 다우 글로벌 테크놀로지스 엘엘씨 해충 방지 케이블 자켓팅
EP4032430A4 (fr) * 2019-09-20 2023-11-01 Daikin Industries, Ltd. Copolymère contenant du fluor

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Publication number Priority date Publication date Assignee Title
JPH05247478A (ja) * 1992-03-05 1993-09-24 Nitta Moore Co Ltd 燃料移送用チューブ
WO1999045044A1 (fr) * 1998-03-06 1999-09-10 Daikin Industries, Ltd. Materiau adhesif a base de composes fluores et stratifie fabrique dans ce materiau
WO2001014141A1 (fr) * 1999-08-25 2001-03-01 Daikin Industries, Ltd. Stratifie en polymere fluore

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247478A (ja) * 1992-03-05 1993-09-24 Nitta Moore Co Ltd 燃料移送用チューブ
WO1999045044A1 (fr) * 1998-03-06 1999-09-10 Daikin Industries, Ltd. Materiau adhesif a base de composes fluores et stratifie fabrique dans ce materiau
WO2001014141A1 (fr) * 1999-08-25 2001-03-01 Daikin Industries, Ltd. Stratifie en polymere fluore

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107244A (ja) * 2004-10-05 2012-06-07 Arkema France 可撓性のある半結晶ポリアミド
JP2007118520A (ja) * 2005-10-31 2007-05-17 Kyoraku Co Ltd 多層構造体および多層容器
JP2009006575A (ja) * 2007-06-28 2009-01-15 Nissan Motor Co Ltd 多層ホース
KR20200027974A (ko) * 2017-07-12 2020-03-13 다우 글로벌 테크놀로지스 엘엘씨 해충 방지 케이블 자켓팅
JP2020530644A (ja) * 2017-07-12 2020-10-22 ダウ グローバル テクノロジーズ エルエルシー 害虫耐性ケーブル外被
US11361884B2 (en) 2017-07-12 2022-06-14 Dow Global Technologies Llc Pest-resistant cable jacketing
JP7159283B2 (ja) 2017-07-12 2022-10-24 ダウ グローバル テクノロジーズ エルエルシー 害虫耐性ケーブル外被
KR102590671B1 (ko) * 2017-07-12 2023-10-19 다우 글로벌 테크놀로지스 엘엘씨 해충 방지 케이블 자켓팅
EP4032430A4 (fr) * 2019-09-20 2023-11-01 Daikin Industries, Ltd. Copolymère contenant du fluor

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