WO1995011940A1 - Composition de resine thermoplastique et stratifie a base de cette composition - Google Patents
Composition de resine thermoplastique et stratifie a base de cette composition Download PDFInfo
- Publication number
- WO1995011940A1 WO1995011940A1 PCT/JP1994/001806 JP9401806W WO9511940A1 WO 1995011940 A1 WO1995011940 A1 WO 1995011940A1 JP 9401806 W JP9401806 W JP 9401806W WO 9511940 A1 WO9511940 A1 WO 9511940A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fluororesin
- layer
- polyamide resin
- thermoplastic resin
- fluorine
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
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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
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
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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
- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the present invention relates to a thermoplastic resin composition and a laminate thereof, and more particularly, to a structure having excellent chemical resistance and impermeability to gasoline, alcohol, acid, and the like, such as hoses, tubes, pipes, seals, and gaskets.
- hoses, tubes, pipes, seals, and gaskets Materials for forming single layers or laminates with fluororesin and / or polyamide resin when molding paper, packing, sheets, films, rollers, bottles, tanks, containers (eg, plates, pots), etc. About.
- fluororesins are used in many fields that take advantage of their features such as heat resistance, oil resistance, and chemical resistance.However, utilizing their low fuel permeability, they are being actively studied as fuel piping materials for automobiles. It became so.
- the fluororesins especially ethylene / fluorinated olefin copolymers have low fuel permeability, flexibility, It has excellent low-temperature impact resistance and heat resistance, and is relatively lightweight as a fluororesin. It is inexpensive and has good workability.It is an ideal material for automotive parts, especially fuel pipes and tubes. Because they are more expensive than ordinary hydrocarbon resins and have a higher specific gravity, further cost reduction and weight reduction are desired.
- Polyamide resins have high strength, high toughness, light weight, and excellent workability.
- Particularly flexible polyamide resins for example, polyamide 11, 12, 6 10 etc.
- polyamide 11, 12, 6 10 etc. are widely used in hoses, tubes, and pipes. It is widely used in automotive parts, taking advantage of its excellent gasoline resistance.
- polyamide resin pipes and tubes have the advantages of light weight and low stiffness
- gasoline mixed with methanol or the like has a high fuel permeability, and has a small amount of moisture and There is a problem with deterioration of materials such as increased fuel permeability and reduced strength of deteriorated gasoline (sour gasoline) associated with electronic fuel injection devices.
- laminating fluororesin and polyamide resin is a way to minimize the amount of relatively expensive fluororesin used in the resin while minimizing the use of such properties as chemical resistance and low fuel permeability. Although it can be said to be an effective means, it is difficult to achieve interlayer adhesion in the laminate, especially with a highly non-adhesive fluororesin. Accordingly, the above-mentioned publication (that is, Japanese Patent Application Laid-Open No. Hei 4-140588) discloses that a blend of a fluorine resin and a polyamide resin is laminated with the polyamide resin. Lamination with the resin itself is not described.
- a method for producing a laminate having a fluororesin layer and a polyamide resin layer by using an adhesive layer has also been proposed (Japanese Patent Application Laid-Open Nos. 412,439, 1993, 516-163). No. 04 and Japanese Unexamined Patent Publication No. Hei 5-193022) disclose a fluororesin component, ie, polyfluorinated resin, specifically studied as a constituent material of the inner fluororesin layer or the adhesive layer in these publications.
- Vinylidene-ethylene-chloro trifluoroethylene copolymer has a favorable processing temperature for co-extrusion with polyamide resin and has low fuel permeability, but has a high modulus of elasticity. It is difficult to satisfy flexibility and low temperature impact resistance.
- ethylene-tetrafluoroethylene-based copolymer is a fluororesin that has low fuel permeability, flexibility and low-temperature impact resistance required for fuel piping materials for automobiles. Because the temperature is higher than the molding temperature of the polyamide resin by nearly 10 o ° c, the thermal properties of the composition and polyamide resin during kneading of the adhesive layer composition and co-extrusion with the fluororesin layer and polyamide resin are reduced. There is a problem of deterioration accompanied by deterioration. Therefore, even in these publications, no specific proposal has been made on lamination by co-extrusion with an ethylene / tetrafluoroethylene copolymer. Summary of the Invention
- thermoplastic resin composition comprising a polyamide resin, a fluororesin and a fluororubber, and a laminate using the thermoplastic resin composition have been developed. It is useful as a material with excellent chemical resistance and impermeability to gasoline, alcohol, acid, etc., when used as molded products, such as hoses, tubes, pipes, seals, gaskets, packings, sheets and films. It was found to be effective and completed the present invention.
- the present invention provides: (i) a polyimide resin of 5 to 80% by weight,
- thermoplastic resin composition comprising 1 to 80 fluororubbers having a tensile modulus at room temperature of 500 kg / cm 2 or less.
- the present invention also provides a molded article in which at least one of the constituent layers is made of the thermoplastic resin composition.
- the composition of the present invention contains fluororubber (iii), it is excellent in flexibility and has good dispersibility of each component constituting the composition. Therefore, a hose, a pipe, a tube, a seal, a gasket can be used alone. It can be used as a material having excellent chemical resistance and impermeability to gasoline, alcohol, acid, etc., such as sheets, films and sheets.
- composition of the present invention can also be used by laminating it with a polyamide resin in order to increase the strength and reduce the weight and cost of the laminate.
- a polyamide resin in order to increase the strength and reduce the weight and cost of the laminate.
- a fluororesin in order to further improve chemical resistance and impermeability, it can be used by laminating with a fluororesin.
- the composition of the present invention can be used as an adhesive layer material in a laminate including a polyamide resin layer and a fluororesin layer.
- any known polyamide resin may be used irrespective of aliphatic type or aromatic type, and a lactam polymer, a diamine and a dicarboxylic acid may be used. It can be appropriately selected and used from condensates, amino acid polymers, copolymers thereof, and blends thereof.
- polyamide resin (i) examples include polyamide 6, 66, 46, 11, 12, 12, 610, 612 and the like.
- a plasticizer component may be added to the polyamide resin for the purpose of improving flexibility. It is also possible to use a polyamide thermoplastic elastomer known as polyetheresteramide.
- the average molecular weight of the polyamide resin (i) is usually from 50,000 to 500,000.
- the polyamides 11, 12, and 6 1 are characterized in that the composition of the present invention has characteristics required as materials for tubes, hoses and pipes mainly used. 0 is preferred.
- the melt viscosity at 250 ° C. under a shear rate of 10 Osec- 1 is 100 ° C. from the viewpoint of adjusting the melt viscosity of the composition. It is preferable to select a polyamide resin having a viscosity of 0.000 poise.
- the fluororesin (ii) used in the composition of the present invention is not particularly limited as long as it is a fluororesin that can be melted and processed.
- fluororesin (ii) examples are, for example, tetrafluoroethylene / fluoroalkylvinyl ether copolymer (hereinafter, referred to as PFA), tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter, referred to as FEP), ethylene Z tetrafluoroethylene Examples include ethylene copolymer (hereinafter referred to as ETFE), polyvinylidene fluoride (hereinafter referred to as PVDF), and polychlorinated trifluoroethylene (hereinafter referred to as PCTFE).
- the average molecular weight of the fluororesin (ii) is usually from 2,0.00 to 1,000,000.
- the PFA preferably comprises 99 to 92% by weight of tetrafluoroethylene and 1 to 8% by weight of fluoroalkyl vinyl ether.
- the FEP preferably consists of 96 to 87% by weight of tetrafluoroethylene and 4 to 13% by weight of hexafluoropropylene.
- the ETFE preferably comprises 90-74% by weight of tetrafluoroethylene and 10-26% by weight of ethylene.
- the fluororesin (ii) may contain one or more other monomers as long as the essential properties are not impaired.
- Other monomers include tetrafluoroethylene (however, excluding PFA and FEP), hesakifluoropropylene (however, excluding FEP), fluoroalkyl vinyl ether (however, excluding PFA), and vinyli'denfluoryl (Excluding PVDF), black trifluoroethylene (except PCTFE), perfluoroalkyl (1 to 10 carbon atoms) ethylene, perfluoroalkyl (1 to 10 carbon atoms) aryl ether, And the formula:
- CF 2 CF [OCF 2 CFX (CF 2 ) m ] felicitOCF 2 (CF 2 ) P Y [Wherein, X is a fluorine or trifluoromethyl group, Y is a halogen, m is a number of 0 or 1 (however, when m is 1, X is limited to fluorine), n is a number of 0 to 5, p is Represents a number from 0 to 2]
- fluororesins when synthesizing a composition by melting and kneading with a polyamide resin and a fluororubber, a vinylidene fluoride polymer or ethylene-Z-containing fluorine-containing copolymer having a relatively low melting point is used. Coalescence is illustrated as being preferred.
- Vinylidene fluoride polymers are polyvinylidene fluoride (PVDF) and resinous copolymers composed of vinylidene fluoride (VDF) and at least one type of fluorine-containing monomer copolymerizable with it. is there.
- tetrafluoroethylene TF E :
- HF P hexafluoropropylene
- CTF E trifluoromethyl ethylene
- pentafluoropropylene trifluoroethylene
- vinylfluoride-based polymer the amount of vinylidene fluoride is at least 80 mol% or more.
- the ethylene / fluorinated olefin copolymer is a resinous polymer having a molar composition ratio of ethylene (TFE and / or CTFE) of 1 ⁇ ⁇ , and a third copolymer that can be copolymerized with them. It contains 0 to 15 mol% of fluorine monomer based on the total amount of ethylene and TFE and / or CTFE.
- the melt viscosity at 250 ° C under a shear rate of 10 Osecr 1 is 10 to 100, a Echiren'no containing fluorine Orefin copolymer having a viscosity of 00 Opoise.
- the molar ratio of ethylene to TFE is from 10/90 to 38/62 in that the amount of the relatively expensive third fluorine-containing monomer can be reduced without impairing the properties of the ethylene Z fluorine-containing olefin copolymer.
- the fluorororubber (iii) used in the composition of the present invention include elastomers such as a vinylidene fluoride copolymer, an ethylene-containing fluorine-containing copolymer, and a tetrafluoroethylene / propylene copolymer. It is a state copolymer.
- the fluoroelastomer (iii) has a tensile modulus at room temperature (23.C) of 500 K gZcm 2 or less, preferably 30 OKgZcm 2 or less, more preferably 10 OKgZcm 2 or less, and most preferably 5 to 5 OKgZcm 2 . It is.
- vinylidene fluoride-based elastomeric copolymer is defined as vinylidene fluoride (VDF) and at least one kind of fluorine-containing monomer copolymerizable therewith [tetrafluoroethylene (TFE :), Perfluoropropylene (HFP), Trifluoroethylene (CTFE :), Hexafluoroisobutylene, Hexafluoroacetone, Pentafluoropropylen, Trifluoroethylene, Vinyl Fluoride, Fluoro And the like).
- VDF vinylidene fluoride
- TFE tetrafluoroethylene
- HFP Perfluoropropylene
- CTFE Trifluoroethylene
- Hexafluoroisobutylene Hexafluoacetone
- Pentafluoropropylen Trifluoroethylene
- Vinyl Fluoride Fluoro And the like
- VDFZHFP copolymer examples include VDFZHFP copolymer, VDFZCTF E copolymer, and terpolymer of VDFZTF E / (HFP or CTFE).
- VDFZHFP copolymer VDF is preferably 40 to 80 mol%, and HFP is preferably 20 to 60 mol%.
- VDFZCTFE copolymer VDF is preferably 40 to 80 mol%, and CTFE is preferably 20 to 60 mol%.
- VDF is 39 to 80 mol%
- that of HFP or CTFE is 10 to 60 mol%
- that of HFP or CTFE is 10 to 60 mol%.
- Ethylene A fluorine-containing olefin-based elastomer copolymer is, for example, about 30 to 90 mol% (preferably about 40 to 80 mol%) of ethylene, about 0.1 to 20 mol% of TFE and / or CTFE, Fluorine-containing molybdenum It is an elastomeric copolymer having a composition of about 10 to 60 mol% of a nomer.
- CH 2 CZ (CF 2 ) wZ
- CF 2 CZ (CF 2) W Z
- CF 2 CFO (CF 2) w Z
- Z is a hydrogen atom or a fluorine atom, or an integer of 1 to 8
- Tetrafluoroethylene / propylene-based elastomer-like copolymer is a tetrafluorene-containing ethylene-propylene molar composition ratio of 95 to 5 to 30/70, and a third fluorine-containing copolymerizable with them. It is an elastomeric copolymer containing 0 to 15 mol% of monomer based on the total amount of tetrafluoroethylene and propylene.
- the fluoroelastomer (iii) is composed of a fluorinated elastomeric polymer single-chain segment (A) and a fluorinated non-elastomeric polymer segment (B). It is also preferable to select a fluorinated segmented polymer of the formula:
- a typical example of such a fluorinated segmented polymer is a polymer having at least two kinds of monomers having radically polymerizable unsaturated bonds in the presence of a radical source and an iodide compound having iodine bonded to carbon.
- the fluorinated segmented polymer is preferably an iodide compound which is a perhalohydrocarbon having 1 to 16 carbon atoms, wherein at least one of the halogen atoms is an iodine atom, and the other halogen atom is a fluorine atom.
- Atom or a group consisting of a fluorine atom and a chlorine atom (however, if chlorine atoms are present, the number is not greater than the number of fluorine atoms, and more than one chlorine atom is present on one carbon atom) Is present), and the weight ratio of the segment (B) to the Z segment (A) is 595 to 60/40, which is a linear block copolymer.
- Such a fluorinated segmented polymer has excellent properties as a thermoplastic elastomer while maintaining flexibility due to high blocking efficiency, and does not contain a thermally unstable structure. It also has sufficient heat resistance during melt-kneading with an ethylene / fluorinated olefin copolymer or simultaneous multilayer extrusion.
- Preferred as the polymer constituting the fluorinated elastomeric polymer chain segment (A) is vinylidene fluoride Z hexafluoropropylene or a copolymer of pentafluoropropylene / tetrafluoroethylene.
- Vinylidenefluoride hexafluoropropylene or pentafluoropropylene copolymer, vinylidenefluoride / chlorotrifluoroethylene copolymer, perfluoroalkylvinylether Z tetrafluoroethylene and / or vinylidenefluoride Is a copolymer of Particularly preferred is a copolymer of vinylidene fluoride / ⁇ hexafluoropropylene or pentafluoropropene Z tetrafluoroethylene (molar ratio: 45 to 90 to 500 to 350).
- perfluoroalkyl (C 1-3) vinyl ether tetrafluoroethylene / vinylidene fluoride copolymer (molar ratio 15-75 / 0-85 / 0-85) It is an elastomeric copolymer having a molecular weight of 30,000-1, 1,000,000.
- the fluorine-containing non-elastomeric polymer chain segment ( ⁇ ) is a vinylidene fluoride copolymer or an ethylene fluorine-containing copolymer, and a kneading blend with a polyamide resin.
- a vinylidene fluoride copolymer or an ethylene fluorine-containing copolymer and a kneading blend with a polyamide resin.
- 250 ° C under a shear rate of 10 Ose 1 Is a vinylidene fluoride copolymer having a molecular weight of 3,000 to 400,000 and an ethylene / fluorine-containing olefin copolymer having a viscosity of 10 to 10,000 L.
- the fluorinated non-elastomeric polymer chain segment (B) in such a fluorinated segmented polymer has the same composition as the fluororesin used in the composition and Z or the fluororesin laminated with the composition.
- the components have the same composition in order to improve the dispersibility of the composition and the interlayer adhesion at the time of lamination with the fluororesin.
- the molar composition ratio of ethylene to TFE is 10Z90-38 / 62
- the third fluorinated monomer copolymerizable therewith is contained in an amount of about 0.1 to 5 mol% based on the total amount of ethylene and TFE.
- Ethylene tetrafluoroethylene copolymer and melt When kneading, kneading or laminating, a fluorine-containing segmented polymer composed of an ethylene Z tetrafluoroethylene-based copolymer containing a third fluorine-containing monomer as a fluorine-containing non-elastomer polymer chain segment [ 1984-33313].
- the amount of the polyamide resin (i) ranges from 5 to 80% by weight. If it is less than 5% by weight, the mechanical strength is poor, and the cost and specific gravity are insufficient.
- the amount of the fluororesin (ii) is 15 to 90% by weight. If the amount is less than 15% by weight, chemical resistance, fuel oil resistance, and fuel permeability are poor. If the content is more than 90% by weight, the mechanical strength is inferior, and the cost and specific gravity become insufficient. In the case of laminating by co-extrusion with a polyamide resin and / or a fluororesin, 45 to 90% by weight is preferable since sufficient interlayer adhesion can be obtained.
- the amount of fluororubber (iii) is from 1 to 80% by weight. If the amount is less than 1% by weight, the compatibility between the component (i) and the component (ii) is insufficient, and the strength is poor. If the content is more than 80% by weight, the cost is high and the heat resistance is inferior. In the case of laminating by co-extrusion with a polyamide resin and / or a fluororesin, 1 to 50% by weight is preferable because sufficient interlayer adhesion can be obtained.
- polymer component containing monomer having epoxy group or carboxylic acid (anhydride) group Is from 1,000 to 200,000, the molecular weight of the (meth) acrylic polymer component is from 1,000 to 200,000, and a block or graft copolymer.
- the molecular weight of is from 2,000 to 400,000.
- the proportion of the monomer having an epoxy group or a carboxylic acid (anhydrous) group in the block or graft copolymer is 1 to 30% by weight.
- a known mixing method is usually employed.For example, after premixing each component with a mixer such as a V-type blender, a tumbler, and a Hensile mixer, the mixture is subjected to twin-screw extrusion.
- the mixture can be pelletized using a melt mixing device such as a mixer.
- the composition of the present invention may be a fibrous reinforcing material such as a glass fiber, a carbon fiber, a ceramic fiber, a potassium titanate fiber, an aramide fiber, a calcium carbonate, a talc, or a myric fiber within a range not to impair the object of the present invention.
- Inorganic fillers such as clay, clay powder, graphite powder, graphite, glass beads, etc., heat-resistant resins such as polyimide, coloring agents, flame retardants and other commonly used inorganic or organic fillers.
- the amount is usually 1 to 70% by weight of the composition.
- conductive powder such as carbon powder is blended to provide an antistatic function.
- An antistatic function is provided as a layer that comes into contact with fuel inside the laminate using the fluororesin that has been applied as the fluororesin layer in this three-layer structure, or a fluororesin layer that does not have an antistatic function. It is also preferable to form a laminated body having a four-layer structure in which a fluorine resin layer is disposed.
- the thickness of the polyimide resin layer in the laminate was 0.01 to 10 mm, and the composition was The thickness of the layer is preferably 0.0 l to lmm, and the thickness of the fluororesin layer is preferably 0.0 l to 5 mm.
- PA1 Polyamide 12 Molecular weight 15,000 No plasticizer 1 0 3
- Tensile modulus A tensile test was performed according to ASTM D 638, and the tensile modulus was measured.
- FE2 and FE3 are polymers in which the fluorinated elastomeric polymer chain segment (A) is a VDFZTFEZHFP copolymer and the fluorinated non-elastomeric polymer chain segment (B) is an ethyleneno TFEZHFP copolymer.
- Reseda GP 300 A graft polymer composed of epoxy-modified polystyrene (trunk) and polymethyl methacrylate (branch).
- the mixture was injected into a twin-screw extruder with a cylinder temperature set at 220 to 240 ° C to obtain pellets.
- compositions A F1 to AF18 are compression molded at 240 to form a composition sheet, which is sandwiched between a separately molded polyamide resin sheet and a fluororesin sheet as an intermediate layer at 240 ° C. After preheating for 3 minutes, a pressure was applied at 2 OKgZcm 2 to form a three-layer sheet (thickness of polyamide resin layer, composition layer and fluororesin layer: 5 mm, 0.5 mm and 0.5 mm, respectively). The polyamide resin layer and the fluororesin layer of the three-layer sheet were grasped, and the adhesion between the layers was observed. The results are shown in Tables II and III.
- test piece with a length of 5 mm was taken from each tube, and the adhesion strength between the layers was measured by a 180 ° peel test at room temperature.
- Inner layer Middle layer (Kg / 5raiD) 0.2 0.5 0.5> 1 0.1
- gasoline for example, gasoline, methanol mixed gasoline, synthetic oil Materials that have excellent chemical resistance to oil, alcohol, acid, etc., and low fuel permeability, such as hoses, tubes, pipes, seals, gaskets, packings, sheets, and films can be provided.
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/633,830 US5891538A (en) | 1993-10-29 | 1994-10-27 | Thermoplastic resin composition and laminate comprising the same |
DE69422417T DE69422417T2 (de) | 1993-10-29 | 1994-10-27 | Thermoplastische harzzusammensetzung und daraus hergestelltes laminat |
EP94931170A EP0726293B1 (en) | 1993-10-29 | 1994-10-27 | Thermoplastic resin composition and laminate made therefrom |
KR1019960702218A KR960705881A (ko) | 1993-10-29 | 1994-10-27 | 열가소성 수지 조성물 및 그의 적층체(thermoplastic resin composition and laminate made therefrom) |
JP51251795A JP3324118B2 (ja) | 1993-10-29 | 1994-10-27 | 熱可塑性樹脂組成物およびその積層体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5/272233 | 1993-10-29 | ||
JP27223393 | 1993-10-29 |
Publications (1)
Publication Number | Publication Date |
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WO1995011940A1 true WO1995011940A1 (fr) | 1995-05-04 |
Family
ID=17510982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1994/001806 WO1995011940A1 (fr) | 1993-10-29 | 1994-10-27 | Composition de resine thermoplastique et stratifie a base de cette composition |
Country Status (7)
Country | Link |
---|---|
US (1) | US5891538A (ja) |
EP (1) | EP0726293B1 (ja) |
JP (1) | JP3324118B2 (ja) |
KR (1) | KR960705881A (ja) |
CN (1) | CN1134164A (ja) |
DE (1) | DE69422417T2 (ja) |
WO (1) | WO1995011940A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023570A1 (fr) * | 1995-12-22 | 1997-07-03 | Elf Atochem S.A. | Composition comprenant un fluoroelastomere et un polyamide thermoplastique et film obtenu |
EP0912330A4 (en) * | 1996-05-23 | 2001-06-13 | Eagle Picher Ind Inc | LAMINATED FUEL AND STEAM RETURN PIPES |
WO2002020024A1 (en) * | 2000-09-08 | 2002-03-14 | Cv Therapeutics, Inc. | Purine ribosides as antiarrhythmics |
JP2009534511A (ja) * | 2006-04-25 | 2009-09-24 | ソルヴェイ・ソレクシス・エッセ・ピ・ア | 熱可塑性フルオロポリマー組成物 |
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- 1994-10-27 KR KR1019960702218A patent/KR960705881A/ko active IP Right Grant
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Cited By (9)
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WO1997023570A1 (fr) * | 1995-12-22 | 1997-07-03 | Elf Atochem S.A. | Composition comprenant un fluoroelastomere et un polyamide thermoplastique et film obtenu |
US5986005A (en) * | 1995-12-22 | 1999-11-16 | Elf Atochem S.A. | Composition including a fluoroelastomer and a thermoplastic polyamide and resulting film |
CN1102616C (zh) * | 1995-12-22 | 2003-03-05 | 埃勒夫阿托化学有限公司 | 改进剂组合物及其与待加工塑料的组合物及含该改性剂组合物的塑料薄膜 |
EP0912330A4 (en) * | 1996-05-23 | 2001-06-13 | Eagle Picher Ind Inc | LAMINATED FUEL AND STEAM RETURN PIPES |
WO2002020024A1 (en) * | 2000-09-08 | 2002-03-14 | Cv Therapeutics, Inc. | Purine ribosides as antiarrhythmics |
US9771588B2 (en) | 2002-02-20 | 2017-09-26 | Sirna Therapeutics, Inc. | RNA interference mediated inhibition of gene expression using chemically modified short interfering nucleic acid (siNA) |
JP2009534511A (ja) * | 2006-04-25 | 2009-09-24 | ソルヴェイ・ソレクシス・エッセ・ピ・ア | 熱可塑性フルオロポリマー組成物 |
CN102079815A (zh) * | 2009-11-26 | 2011-06-01 | 三星电机株式会社 | 制作基板用组合物和用该组合物制作的预浸料坯和基板 |
CN109233158A (zh) * | 2018-10-11 | 2019-01-18 | 安徽中鼎胶管制品有限公司 | 一种耐高温高承压的氟橡胶油管 |
Also Published As
Publication number | Publication date |
---|---|
KR960705881A (ko) | 1996-11-08 |
EP0726293B1 (en) | 1999-12-29 |
CN1134164A (zh) | 1996-10-23 |
EP0726293A1 (en) | 1996-08-14 |
EP0726293A4 (en) | 1998-06-10 |
DE69422417D1 (de) | 2000-02-03 |
DE69422417T2 (de) | 2000-07-13 |
US5891538A (en) | 1999-04-06 |
JP3324118B2 (ja) | 2002-09-17 |
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