JP2009255071A - Member for biogenic fuel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible member having good resistance to a biogenic fuel and including layers having a fluororesin composition. <P>SOLUTION: The member such as a pipe or a container for a biogenic fuel has layers of a resin composition comprising a fluororesin (A) and at least partially-crosslinked fluororubber (B). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to various members for biogenic fuels having a resin composition layer of a fluororesin and a cross-linked fluororubber.

  Fluorine-based resins and rubbers are used as materials for various members that come into contact with such fossil fuels because they have heat resistance and resistance to gasoline fuel and diesel fuel.

  Since the fluororesin forms a dense layer, it has relatively good fuel impermeability and mechanical strength, but is not suitable for applications requiring flexibility because of its high elastic modulus. On the other hand, although fluororubber is flexible, its fuel impermeability and mechanical strength are not as good as those of resin.

  By the way, in recent years, changes to so-called biogenic fuels originating from plants such as corn and soybeans have been promoted in consideration of the environment.

  Such biogenic fuels change the quality of various components that come into contact with biogenic fuels under the severe conditions in which petrochemical fuels are used. May deteriorate.

  In order to make it suitable for such a biogenic fuel, Patent Document 1 proposes to use a material in which hydrotalcite is dispersed in a fluoroelastomer.

  However, in order to sufficiently suppress the swelling caused by the biogenic fuel using the material described in Patent Document 1, it is necessary to make the thickness of the material layer considerably thicker than that of the conventional layer. And so on.

JP-T-2006-513304

  An object of this invention is to provide the member which has a layer which consists of a fluororesin composition which is flexible and has the outstanding tolerance with respect to the fuel of biological origin.

  That is, the present invention relates to a biogenic fuel member having a layer of a resin composition comprising a fluororesin (A) and a crosslinked fluororubber (B) that is at least partially crosslinked.

  Examples of the fluororesin (A) include tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoropropyl vinyl ether copolymer, and tetrafluoroethylene-per Including at least one fluororesin selected from the group consisting of fluoropropyl vinyl ether copolymers is preferable from the viewpoint of good resistance to biogenic fuels.

  Examples of the crosslinked fluororubber (B) include vinylidene fluoride-hexafluoropropylene copolymer rubber, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer rubber, tetrafluoroethylene-propylene copolymer rubber, tetrafluoroethylene. -Containing at least one cross-linked fluororubber selected from the group consisting of a hexafluoroethylene-propylene copolymer rubber and a tetrafluoroethylene-perfluoropropyl vinyl ether copolymer rubber; It is preferable from the viewpoint of good solubility.

  Moreover, it is preferable that the cross-linked fluororubber (B) is obtained by dynamic cross-linking from the viewpoint of good resistance to biogenic fuel.

  The mass ratio of the fluororesin (A) and the crosslinked fluororubber (B) is preferably 99: 1 to 10:90 from the viewpoint of good moldability.

  In the present invention, “biological fuel” refers to a fuel made from biomass, for example, bioalcohols such as biomethanol and bioethanol; biomixed gasoline obtained by mixing these bioalcohols and gasoline; ETBE mixed gasoline in which ethyl tertiary butyl ether (ETBE), which is a reaction product with isobutene, and gasoline are mixed; liquid fuel such as biodiesel is called. In addition to the fuel used for these power sources, fuel for heating and the like is also included. Moreover, the combined use of petrochemical fuel is not excluded.

  In addition, the “member for biogenic fuel” refers to a member that may come into contact with fuel regardless of gas or liquid, such as storage, supply, metering supply, and control of exhaust gas of fuel.

  Industrial fields include a wide range of fields such as automobiles, ships, chemical plants, air conditioning systems, aerospace, and semiconductors.

  For example, in the automobile industry, fuel storage members such as fuel tanks, filler hoses and fuel tank cap seals; fuel line hoses or tubes, fuel supply members such as fuel oil hoses for supplying fuel tanks; valves, Examples include fuel supply / distribution members such as diaphragms and fuel injectors; fuel / exhaust seal members such as O-rings, exhaust gas control seals, intake manifolds / gaskets, shaft seals, solenoids / armatures, and the like.

  In particular, it is useful as a biogenic fuel pipe and container provided with the biogenic fuel member of the present invention.

  According to the biogenic fuel member of the present invention, it is possible to provide a member that is flexible and has excellent resistance to biogenic fuel.

  The present invention relates to a member for biogenic fuel having a resin composition layer comprising a fluororesin (A) and a crosslinked fluororubber (B) at least partially crosslinked.

  Although it does not specifically limit as a fluororesin (A), It is preferable that it is a fluororesin containing at least 1 type of fluorine-containing ethylenic polymer. The fluorinated ethylenic polymer preferably has a structural unit derived from at least one fluorinated ethylenic monomer. When having a structural unit derived from a fluorine-containing ethylenic monomer, heat resistance, chemical resistance, electrical properties, etc. are improved.

As the fluorine-containing ethylenic monomer, tetrafluoroethylene (TFE), formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ and / or —OR _f ² ; R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms) Perfluoroolefin; chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (VdF), vinyl fluoride, formula:
^{_{CH 2 = CX 2 (CF 2}} ) n X 3
(Wherein X ² is a hydrogen atom or a fluorine atom; X ³ is a hydrogen atom, a fluorine atom or a chlorine atom; n is an integer of 1 to 10), and the like.

  The fluorine-containing ethylenic polymer may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Non-fluorinated ethylenic monomers other than fluoroolefins can be mentioned. The selection of the non-fluorine ethylenic monomer may be performed according to the application in consideration of the characteristics and functions that can be imparted to each non-fluorine ethylenic monomer well known to those skilled in the art.

  Specific examples of the non-fluorine ethylenic monomer include olefins such as ethylene and propylene; alkyl vinyl ethers and the like. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

  Among these, the following (1) to (6) are used as the fluorinated ethylenic polymer from the viewpoint that the obtained fluororesin composition is excellent in heat resistance, chemical resistance and oil resistance and easy to process. ) Is particularly preferable, but is not limited thereto, and may be used according to the intended purpose.

(1) An ethylene-TFE copolymer composed of TFE and ethylene (hereinafter also referred to as ETFE).
In the case of ETFE, mechanical properties, fuel barrier properties, ease of crosslinking, etc. are preferred. The content molar ratio of the TFE unit and the ethylene unit is preferably (20 to 90) / (80 to 10), more preferably (37 to 85) / (63 to 15), and (38 to 80) / (62 to 20). Is particularly preferred. Moreover, the 3rd component may be contained and the kind will not be limited as long as it can copolymerize with TFE and ethylene as a 3rd component. As the third component, usually the formula:
CH ₂ = CX ⁴ R _f ³ , CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ , CH ₂ = C (R _f ³ ) ₂
(Wherein, X ⁴ is a hydrogen atom or a fluorine atom; R _f ³ is a fluoroalkyl group that may contain an etheric oxygen atom), and among these, CH ₂ = CX ⁴ R more preferably a fluorine-containing vinyl monomer represented by _f ^3, the number of carbon atoms in R _f ³ is a monomer of 1-8 is particularly preferred.

Specific examples of the fluorine-containing vinyl monomer represented by the above formula include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,5-trihydroperfluoropentene-1. 1,1,7-trihydroperfluoroheptene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1,2,2,3 3,4,4,5,5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluorobutene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene (CH ₂ = CFCF ₂ CF ₂ CF ₂ H).

  The content of the third component is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, particularly preferably from 0.2 to 4 mol%, based on the fluorine-containing ethylenic polymer.

(2) TFE, ethylene and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ and / or —OR _f ² ; R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms) Ethylene-TFE-perfluoroethylenically unsaturated compound copolymers such as TFE-HFP copolymer and ethylene-TFE-perfluoro (alkyl vinyl ether) (PAVE) copolymer

(3) Polyvinylidene fluoride (PVdF)

(4) Ethylene-CTFE copolymer consisting of CTFE and ethylene (hereinafter also referred to as ECTFE)

(5) TFE-PAVE copolymer (PFA) or TFE-HFP copolymer (FEP) comprising TFE and the perfluoroethylenically unsaturated compound represented by the formula (1)
In the case of PFA or FEP, heat resistance is particularly excellent in the above-described effects, and in addition to the above-described effects, fuel barrier properties, chemical resistance, and electrical characteristics are preferable. Although not particularly limited, it is preferably a copolymer composed of 70 to 99 mol% of TFE units and 1 to 30 mol% of perfluoroethylenically unsaturated compound units represented by formula (1), and 80 to 97 TFE units. More preferably, it is a copolymer composed of 3 to 20 mol% of perfluoroethylenically unsaturated compound units represented by mol% and formula (1). If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease. In addition, the fluorine-containing ethylenic polymer composed of TFE and the perfluoroethylenically unsaturated compound represented by the formula (1) may contain a third component. As the third component, TFE and the formula (1 The kind is not limited as long as it can be copolymerized with the perfluoroethylenically unsaturated compound represented by ().

(6) CTFE, TFE, and if necessary, a CTFE-TFE-perfluoroethylenically unsaturated compound copolymer comprising a perfluoroethylenically unsaturated compound represented by the formula (1) CTFE-TFE copolymer In this case, the molar ratio of the CTFE unit and the TFE unit is preferably CTFE / TFE = (2-98) / (98-2), and preferably (5-90) / (95-10). More preferred. If the CTFE unit is less than 2 mol%, the liquid impermeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate. In addition, it is preferable to copolymerize a perfluoroethylenically unsaturated compound, and the perfluoroethylenically unsaturated compound unit is 0.1 to 10 mol% based on the total of the CTFE unit and the TFE unit, and the CTFE unit and TFE units are preferably 90 to 99.9 mol% in total. If the perfluoroethylenically unsaturated compound unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, mechanical properties. It tends to be inferior in characteristics and productivity.

  Of these, TFE-ethylene copolymer, TFE-HFP copolymer, TFE-HFP-PAVE copolymer, TFE- are particularly advantageous in terms of resistance to biogenic fuels, mechanical properties, and cost. PAVE copolymers are preferred.

  The number average molecular weight varies depending on the application and the like, but for example, those having a mechanical property and molding processability in the range of 1,000 to 1,000,000, more preferably 5,000 to 500,000 are preferable.

  As the fluororubber constituting the cross-linked fluororubber (B), a fluororubber which can give appropriate elasticity and flexibility (flexibility) to the composition with the fluororesin and can be cross-linked is particularly preferable. It is not limited.

Suitable fluororubbers include, for example, tetrafluoroethylene, vinylidene fluoride, and formula (1):
CF ₂ = CF-R _f ¹ (1)
Wherein R _f ¹ is selected from the group consisting of perfluoroethylenically unsaturated compounds represented by —CF ₃ or —OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group). The inclusion of a structural unit derived from at least one monomer is preferred from the viewpoint of obtaining particles having properties as a rubber elastic body.

  As the fluoro rubber, non-perfluoro fluoro rubber and perfluoro fluoro rubber are preferable.

  Non-perfluorofluororubbers include vinylidene fluoride (VdF) fluororubber, tetrafluoroethylene (TFE) / propylene fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluororubber, ethylene / Hexafluoropropylene (HFP) fluorine rubber, Ethylene / Hexafluoropropylene (HFP) / Vinylidene fluoride (VdF) fluorine rubber, Ethylene / Hexafluoropropylene (HFP) / Tetrafluoroethylene (TFE) fluorine rubber, Fluoro Examples thereof include silicone-based fluororubber, fluorophosphazene-based fluororubber, and the like, which can be used alone or in any combination as long as the effects of the present invention are not impaired. Among these, VdF-HFP copolymer rubber, VdF-HFP-TFE copolymer rubber, TFE-propylene copolymer rubber, TFE-HFP-propylene copolymer rubber, and TFE-PAVE copolymer rubber are heat resistant. And the compatibility with the fluororesin is more preferable.

  Specifically, the VdF rubber (VdF-HFP copolymer rubber, VdF-HFP-TFE copolymer rubber, etc.) has a VdF repeating unit derived from a VdF repeating unit and other comonomers. 20 mol% or more and 90 mol% or less of the total number of moles with the unit is preferable, and 40 mol% or more and 85 mol% or less is more preferable. A more preferred lower limit is 45 mol%, a particularly preferred lower limit is 50 mol%, and a more preferred upper limit is 80 mol%.

  The other monomer in the VdF rubber is not particularly limited as long as it is copolymerizable with VdF. For example, TFE, HFP, PAVE, CTFE, trifluoroethylene, trifluoropropylene, tetrafluoropropylene, penta Fluorine-containing monomers such as fluoropropylene, trifluorobutene, tetrafluoroisobutene, vinyl fluoride, iodine-containing fluorinated vinyl ether; fluorine-free monomers such as ethylene (Et), propylene (Pr), and alkyl vinyl ether These fluorine-containing monomers and non-fluorine-containing monomers can be used alone or in combination of two or more. As the PAVE, perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether) are preferable, and perfluoro (methyl vinyl ether) is particularly preferable.

  Examples of the VdF rubber include VdF / HFP copolymer, VdF / HFP / TFE copolymer, VdF / CTFE copolymer, VdF / CTFE / TFE copolymer, VdF / PAVE copolymer, VdF / TFE copolymer, PAVE copolymer, VdF / HFP / PAVE copolymer, VdF / HFP / TFE / PAVE copolymer, VdF / TFE / Pr copolymer, or VdF / Et / HFP copolymer are preferred, and other More preferably, the monomer has TFE, HFP, and / or PAVE, in particular, VdF / HFP copolymer, VdF / HFP / TFE copolymer, VdF / PAVE copolymer, VdF. / TFE / PAVE copolymer, VdF / HFP / PAVE copolymer, or VdF / HFP / TFE / PAVE copolymer are preferred There.

  The VdF / HFP copolymer preferably has a VdF / HFP composition of (45 to 85) / (55 to 15) (mol%), more preferably (50 to 80) / (50 to 20). (Mol%), and more preferably (60-80) / (40-20) (mol%).

  The VdF / HFP / TFE copolymer preferably has a VdF / HFP / TFE composition of (30-80) / (10-35) / (4-35) (mol%).

  As the VdF / PAVE copolymer, a VdF / PAVE composition having a composition of (65 to 90) / (35 to 10) (mol%) is preferable.

  As the VdF / TFE / PAVE copolymer, a VdF / TFE / PAVE composition having a composition of (40-80) / (3-40) / (15-35) (mol%) is preferable.

  As VdF / HFP / TFE / PAVE copolymerization, the composition of VdF / HFP / TFE / PAVE is (40-90) / (0-25) / (0-40) / (3-35) (mol%). The thing of (40-80) / (3-25) / (3-40) / (3-25) (mol%) is more preferable.

  The TFE / propylene-based fluororubber is a fluorine-containing copolymer composed of TFE 45 to 70 mol% and propylene 55 to 30 mol%. In addition to these two components, 0 to 40 mol% of a specific third component (for example, PAVE) may be contained.

  Examples of the perfluorofluororubber include those made of TFE / PAVE. The composition of TFE / PAVE is preferably (50 to 90) / (50 to 10) (mol%), more preferably (50 to 80) / (50 to 20) (mol%), More preferably, it is (55 to 75) / (45 to 25) (mol%).

  Examples of PAVE in this case include perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), and these can be used alone or in any combination.

  The fluororubber preferably has a number average molecular weight of 1000 to 1200000, more preferably 5000 to 900000. If the molecular weight is less than 1000, the crosslinking does not proceed efficiently, and the mechanical properties of the composition with the resulting fluororesin tend to be inferior. If the molecular weight is 1200000 or more, it is economical due to the problem of fluororubber productivity. Inferior.

  The non-perfluorofluororubber and perfluorofluororubber described above can be produced by conventional methods such as emulsion polymerization, suspension polymerization, and solution polymerization. In particular, according to a polymerization method using an iodine compound known as iodine (bromine) transfer polymerization, a fluororubber having a narrow molecular weight distribution can be produced.

  Although the crosslinking of the fluororubber is not particularly limited, it is possible to carry out by a method of crosslinking simultaneously with the kneading with the fluororesin by a so-called dynamic crosslinking method, because it does not include complicated steps, has good productivity, and is low in cost. preferable.

  The cross-linking system that cross-links the fluoro rubber particles is a type of cross-linkable group when the fluoro rubber contains a cross-linkable group (iodine atom, bromine atom, amino group, cyano group, carboxyl group, alkoxycarbonyl group, hydroxyl group, etc.). Or according to the use of the composition with the fluororesin. Examples of the crosslinking system include a polyamine crosslinking system, a polyol crosslinking system, a peroxide crosslinking system, an imidazole crosslinking system, a triazine crosslinking system, an oxazole crosslinking system, and a thiazole crosslinking system. From the viewpoint of properties, a polyamine crosslinking system, a polyol crosslinking system, and a peroxide crosslinking system are preferable.

  As the crosslinking agent, any of a polyol crosslinking agent, a peroxide crosslinking agent, a polyamine crosslinking agent, an imidazole crosslinking agent, a triazine crosslinking agent, an oxazole crosslinking agent, and a thiazole crosslinking agent can be employed. These crosslinking agents may be used alone or in combination.

  When bisphenol AF is used as a crosslinking agent in the case of polyol-based crosslinking, a quaternary ammonium salt or quaternary phosphonium salt is used as a crosslinking accelerator, and when this crosslinking accelerator and bisphenol AF are used in the form of a solid solution, The dispersibility to rubber becomes good, which is preferable. In addition, the use of a crosslinking accelerator that does not contain chlorine atoms as the crosslinking accelerator can improve the rubber crosslinking characteristics (scorch stability) and productivity (deteriorating substances adhering to the screw cylinder in the extruder). From the point of improving resistance to the material of the extruder.

  Among these, it is preferable to use a solid solution (containing no chlorine atom) of benzyltriphenylphosphonium and bisphenol AF, which is a crosslinking aid. In the case of this combination, the mass ratio of the solid solution of benzyltriphenylphosphonium and bisphenol AF is such that when the uncrosslinked fluororubber and the solid solution are kneaded, the melting point of the solid solution is close to the kneading temperature because the dispersibility of the solid solution is good. It is preferable that the temperature be in the range of 2: 1 to 4: 1 that is a melting point near the kneading temperature.

  The amount of solid solution added (for example, in the case of a solid solution having a ratio of benzyltriphenylphosphonium and bisphenol AF of 4: 1 by mass) makes it easy to adjust the crosslinking density and crosslinking rate of the rubber, and the rubber reagent is dispersed in the rubber. It is preferable to mix | blend 0.1-2.0 mass parts with respect to 100 mass parts of uncrosslinked fluororubber from a point with favorable property. In addition, when mix | blending acid acceptors, such as metal oxides, such as magnesium oxide and a hydrotalcite, about 1-20 weight part may be sufficient with respect to 100 mass parts of uncrosslinked fluororubbers.

  Further, bisphenol AF may be additionally used for the purpose of adjusting the crosslinking rate. The amount of bisphenol AF used additionally is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of uncrosslinked fluororubber.

  The average particle diameter of the cross-linked fluororubber particles is not particularly limited, but is preferably 0.01 to 100 μm from the viewpoint of improving the composite dispersibility with the fluororesin and improving the physical properties. More preferably, it is 30 μm or less, and particularly preferably 10 μm or less.

  Preparation of the resin composition of the fluororesin (A) and the crosslinked fluororubber (B) constituting the biogenic fuel member is a method of crosslinking while kneading the fluororesin and the uncrosslinked fluororubber (dynamic crosslinking method). ) Is preferably employed. In addition, a method of simply kneading the cross-linked fluororubber particles and the fluororesin (dry blend method) may be used, or a mixture of the fluororesin dispersion and the cross-linked fluororubber dispersion may be mixed and dried (dispersion mix method). Good.

  The dynamic cross-linking method is a method in which a fluororesin and a fluororubber are mixed and the fluororubber is cross-linked while kneading at a temperature at which the fluororesin and the fluororubber melt. The melt-kneading temperature varies depending on the glass transition temperature and / or melting point of the fluororesin and fluororubber, respectively, but is preferably 120 to 330 ° C, more preferably 130 to 320 ° C. When the melt kneading temperature is less than 120 ° C., the dispersion between the fluororesin and the fluoro rubber tends to be coarsened, and when it exceeds 330 ° C., the fluoro rubber tends to be thermally deteriorated.

  The obtained fluororesin composition may have a structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber particles form a dispersed phase, or a structure in which the fluororesin and the cross-linked fluororubber form a co-continuity. Of these, the fluororesin preferably has a structure in which a continuous phase is formed and the crosslinked fluororubber particles form a dispersed phase.

  Even when the fluororubber has formed a continuous phase at the beginning of dispersion, as the cross-linking reaction proceeds, the fluororubber becomes a cross-linked fluoro rubber, the melt viscosity increases, and the cross-linked fluoro rubber becomes a disperse phase, or It forms a co-continuous phase with the fluororesin. Further, a part of the structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber particles form a dispersed phase may include a co-continuous structure of the fluororesin and the cross-linked fluororubber.

  When forming such a continuous phase and dispersed phase structure, the fluororesin composition exhibits excellent resistance to biogenic fuels, excellent heat resistance, chemical resistance and oil resistance, and good flexibility ( (Flexibility) and moldability. At that time, the average particle size of the crosslinked fluororubber particles in the dispersed phase is preferably 0.01 to 30 μm, and more preferably 0.1 to 10 μm from the viewpoint of good fluidity.

  In the present invention, the average particle diameter of the crosslinked fluororubber particles in the fluororesin composition can be confirmed by using any one of AFM, SEM, and TEM, or a combination thereof. For example, when using AFM, the difference obtained from the surface information of the fluororesin in the continuous phase and the cross-linked fluororubber particles in the dispersed phase is obtained as a light / dark image, and binarization is possible by dividing the light and dark into gradations. Become. The binarization position is set to the center level divided by gradation, whereby an image with a clear contrast can be obtained, and the crosslinked rubber particle diameter of the dispersed phase can be read. When SEM is used, the AFM can be obtained by enhancing contrast or adjusting brightness or darkness to the image so that the cross-linked fluororubber particles in the dispersed phase are clear from the image obtained by the reflected electron image. Similarly, the cross-linked fluororubber particle size of the dispersed phase can be read. In the case of TEM, the cross-linked rubber particle diameter of the dispersed phase can be read as in AFM and SEM by adjusting the contrast of the obtained image and / or adjusting the brightness and darkness as in SEM.

  The composition ratio in the fluororesin composition constituting the biogenic fuel member of the present invention can be appropriately selected depending on the types, uses, required characteristics, manifestation physical properties, etc. of the fluororesin (A) and the cross-linked fluororubber (B). Well, for example, it can be selected in a wide range of 99/1 to 10/90 as fluororesin (A) / crosslinked fluororubber (B) (mass ratio). Preferably, (A) / (B) is 90/10 to 30/70, more preferably 80/20 to 50/50. When the proportion of the crosslinked fluororubber particles is too small, the flexibility tends to be insufficient, and when too large, the mechanical strength tends to decrease.

  The melt flow rate (MFR) of the fluororesin composition constituting the biogenic fuel member of the present invention is preferably 0.5 to 30 g / 10 min from the viewpoint of good fluidity and molding processability. 1 to 25 g / 10 min is more preferable. The MFR is measured using a melt flow rate measuring device manufactured by Toyo Seiki Seisakusho Co., Ltd., for example, under conditions of 297 ° C. and a load of 5000 g.

  In the present invention, when preparing the fluororesin composition, usual additives such as fillers, processing aids, plasticizers, colorants and the like can be blended as necessary.

  For processing of the obtained fluororesin composition, conventionally known processing methods such as extrusion molding, injection molding, blow molding, press molding, powder coating and the like can be adopted according to the type and shape of the member.

  Further, since the resin composition of the present invention is excellent in processability, it is laminated with a layer (base material) of another material to form a laminate, or coated on the surface of the base material to form a coating layer, sheet It is also possible to use a laminate material having a shape member attached thereto.

  For example, when a fuel hose is manufactured, it can be supplied to an extrusion molding machine to form a laminated hose not only with a single layer hose, but also with other rubber such as fluorine rubber, nitrile rubber, hydrin rubber, acrylic rubber and the like.

  Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to such examples.

  The apparatus and measurement conditions used for property evaluation are as follows.

(1) Mechanical properties (tensile strength, Young's modulus, tensile elongation)
Using the fluororesin compositions obtained in Examples or Comparative Examples, a film having a thickness of 125 μm is prepared by the method shown in Examples or Comparative Examples. This film is punched into test specimens using ASTM micro dumbbells. Using the obtained dumbbell-shaped test piece, using an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation), a tensile test was performed at a tensile speed of 50 mm / min at room temperature in accordance with ASTM D638. Measure tensile strength, Young's modulus, and tensile elongation.

(2) MFR
Using a melt indexer (manufactured by Toyo Seiki Seisakusho), the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 5 kg mainly at 297 ° C. .

(3) Mass change The mass of the sample before dipping in the fuel is measured, and after the sample taken out from the fuel after dipping is dried at room temperature for 24 hours, the oil on the surface is wiped off and the change in mass is examined.

Example 1
100 parts by weight of a VdF rubber (VdF / TFE / HFP = 50/20/30 molar ratio, Mooney viscosity at 100 ° C. 87), 2.0 parts by weight of a crosslinking agent bisphenol AF (manufactured by Daikin Industries, Ltd.), acceleration of crosslinking BTPPC (made by Hokuko Chemical Co., Ltd.) 1.0 part by mass and magnesium oxide (Kyowa Mag 150, produced by Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass are kneaded using an 18-inch open roll, and VdF type A full compound of rubber was obtained.

  10 parts by mass of the above-mentioned VdF rubber full compound was added to 90 parts by mass of ETFE (ethylene / TFE = 35/65 molar ratio, melting point 220 ° C., MFR (297 ° C.) 30.0 g / 10 min). Name: KZW15TW-60MG-NH (-700)) (caliber 15 mm, L / D60) (Technobel Co., Ltd.), melt-kneaded under conditions of cylinder temperature 260 ° C. and screw rotation speed 300 rpm, fluororesin A pellet of the composition was produced.

  With respect to the obtained fluororesin composition, the average particle diameter, MFR, and mechanical properties of the crosslinked fluororubber particles were examined. The average particle diameter of the crosslinked fluororubber particles was 1.1 μm, and the MFR (297 ° C.) was 12.3 g / 10 minutes.

  The pellets of the fluororesin composition were supplied to a T-die extruder (caliber 30 mm, L / D38) (manufactured by Souken Co., Ltd.) and extruded under the conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 10 rpm, and a thickness of 125 μm. A sheet of was prepared.

  After immersing this sample in SME (soybean oil ME) fuel (NEXSOL BD-0100 BIODISEL manufactured by PETER CREMER) at 125 ° C for 250 hours, 500 hours and 1000 hours, the mass change was obtained, and the tensile test was performed in the same manner. went. The test fuel was subjected to liquid exchange every 250 hours. In addition, when the acid value of SME at the time of completion | finish of a test was measured (JISK-2501), it was 1.1-1.8 (mgKOH / g). Young elastic modulus, tensile strength and tensile elongation before immersion, change rate of Young's elastic modulus after immersion (%), change rate of tensile strength (%), change rate of tensile elongation (%) and mass change rate (% ) Is shown in Table 1.

Examples 2-3
The pellets of the fluororesin composition were the same as in Example 1 except that the blending ratio of ETFE and VdF rubber was 70/30 (mass ratio: Example 2) and 50/50 (mass ratio: Example 3). Fabrication and sample sheet fabrication were performed, and mechanical properties and mass change before and after immersion were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 4
100 parts by mass of VdF rubber (VdF / TFE / HFP = 50/20/30 molar ratio, Mooney viscosity 87 at 100 ° C.), 0.8 parts by mass of cross-linking agent bisphenol AF (produced by Daikin Industries), bisphenol AF And 1.5 parts by mass of a solid solution (HW-41, manufactured by Honeywell Specialty Chemicals) of magnesium and a crosslinking accelerator containing no chlorine atom (benzyltriphenylphosphonium), magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) 0 part by mass was kneaded using an 18-inch open roll to obtain a full compound of VdF rubber (B).

  Except for using this full compound, a fluororesin composition pellet and a sample sheet were prepared in the same manner as in Example 1, and the mechanical properties and mass change before and after immersion were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
Example 1 A fluororesin composition pellet and a sample sheet were prepared in the same manner as in Example 1 except that ETFE and uncrosslinked VdF rubber were blended at a ratio of 70/30 (mass ratio). In the same manner, the mechanical properties and mass change before and after immersion were examined. The results are shown in Table 1.

Comparative Example 2
100 parts by mass of VdF rubber (VdF / HFP = 78/22 molar ratio, Mooney viscosity 60 at 100 ° C.), 3 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.), calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Industry Co., Ltd.) 6 parts by mass, MT-C (Thermax, N990) were kneaded using a 6-inch open roll to obtain a full compound of VdF rubber, and then heat-pressed. A sample sheet of crosslinked VdF rubber was prepared, and the mechanical properties before and after immersion and the mass change were examined in the same manner as in Example 1. The results are shown in Table 1.

  Thus, the fluororesin composition in which the cross-linked fluororubber is combined with the fluororesin is a fluororesin composition (Comparative Example 1) or cross-linked fluororubber combined with the uncrosslinked rubber before and after being immersed in the biogenic fuel. Compared with the single substance (Comparative Example 2), the rate of change in mechanical properties and the rate of change in weight were small, indicating significance.

Example 5
Using the sample sheets prepared in Examples 2 and 4 and Comparative Examples 1 and 2, respectively, the following immersion test was performed on SME (soybean oil ME) fuel to which 1% by mass of water was added.

  That is, after immersing a sample at 125 ° C. for 250 hours, 500 hours, and 1000 hours in a mixed solution obtained by adding 1% by mass of water to SME (soybean oil ME) fuel (NEXSOL BD-0100 BIODISEL manufactured by PETER CREMER), the mass Changes were determined and a tensile test was performed in the same manner. The test fuel was subjected to liquid exchange every 250 hours. In addition, when the acid value of SME at the time of completion | finish of a test was measured (JISK-2501), it was 7.5-17.9 (mgKOH / g). Young elastic modulus, tensile strength and tensile elongation before immersion, change rate of Young elastic modulus after immersion (%), change rate of tensile strength (%), change rate of tensile elongation (%) and mass change rate (% ) Is shown in Table 2.

  From Table 2, the fluororesin composition in which the cross-linked fluororubber is combined with the fluororesin, as in the system to which water is not added, is the fluororesin combined with the uncrosslinked rubber before and after being immersed in the biogenic fuel. Compared to the composition (Comparative Example 1) and the crosslinked fluororubber alone (Comparative Example 2), the rate of change in mechanical properties and the rate of change in weight were small, showing significance. In particular, it can be seen that the cross-linked fluororubber alone has a very large weight change rate and poor resistance.

Claims (7)

A biogenic fuel member having a layer of a resin composition comprising a fluororesin (A) and a crosslinked fluororubber (B) at least partially crosslinked. The fluororesin (A) is a tetrafluoroethylene-ethylene copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-hexafluoropropylene-perfluoropropyl vinyl ether copolymer, and a tetrafluoroethylene-perfluoro. The member for biogenic fuel according to claim 1, comprising at least one fluororesin selected from the group consisting of propyl vinyl ether copolymers. The crosslinked fluororubber (B) is vinylidene fluoride-hexafluoropropylene copolymer rubber, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer rubber, tetrafluoroethylene-propylene copolymer rubber, tetrafluoroethylene- The member for biogenic fuel according to claim 1 or 2, comprising at least one crosslinked fluororubber selected from the group consisting of hexafluoroethylene-propylene copolymer rubber and tetrafluoroethylene-perfluoropropyl vinyl ether copolymer rubber. . The member for biogenic fuel according to any one of claims 1 to 3, wherein the crosslinked fluororubber (B) is obtained by dynamic crosslinking. The biofuel fuel member according to any one of claims 1 to 4, wherein the mass ratio of the fluororesin (A) and the cross-linked fluororubber (B) is 99: 1 to 10:90. A biogenic fuel pipe comprising the biogenic fuel member according to any one of claims 1 to 5. A biogenic fuel container comprising the biogenic fuel member according to claim 1.