WO2007135938A1

WO2007135938A1 - Fuel-barrier material and molded article formed therefrom

Info

Publication number: WO2007135938A1
Application number: PCT/JP2007/060101
Authority: WO
Inventors: Toshiki Ichisaka; Tomihiko Yanagiguchi; Haruhisa Masuda
Original assignee: Daikin Industries, Ltd.
Priority date: 2006-05-24
Filing date: 2007-05-17
Publication date: 2007-11-29

Abstract

A fuel-barrier material which has all of excellent heat resistance, chemical resistance, and oil resistance, is melt-moldable, and is excellent in flexibility and impermeability to fuels. Also provided are a molded article formed from the fuel-barrier material and a fuel tube and fuel hose comprising a layer formed from the fuel-barrier material. The fuel-barrier material comprises 95-20 wt.% fluororesin (A) and 5-80 wt.% crosslinked fluororubber (B), wherein the fluororesin (A) is a copolymer of tetrafluoroethylene and hexafluoropropylene or a copolymer of tetrafluoroethylene, hexafluoropropylene, and a perfluoro(alkyl vinyl ether) and the crosslinked fluororubber (B) has a fluorine concentration of 68 wt.% or higher, at least part of the fluororubber (B) having been crosslinked.

Description

Specification

Fuel barrier material and molded article formed therefrom

Technical field

The present invention relates to a fuel barrier material containing a specific fluorine resin (A), a high fluorine concentration, and a crosslinked fluororubber (B). The present invention also relates to a molded article formed from the fuel barrier material, a fuel tube including a layer formed from the fuel noble material force, and a fuel hose.

Background art

[0002] Due to the recent increase in environmental awareness, legislation has been developed to prevent fuel volatilization. In particular, the automobile industry has become a material with excellent fuel barrier properties, especially in the United States, where there is a significant tendency to suppress fuel volatilization. Needs are growing. As materials with excellent fuel barrier properties, thermoplastic resins such as polyphenylene sulfide resin, ethylene bull alcohol resin, liquid crystal polyester resin, etc. are used. For example, bridge rubber is generally inferior in fuel barrier properties, and when it is used for automobile parts such as fuel hoses, this volatility and transpiration of fuel is required to be improved. Among the cross-linked rubbers, the power of the cross-linked fluororubber is not good. The fuel barrier properties are significantly inferior to the thermoplastic resins listed above, and they are flexible and have excellent fuel barrier properties. Material development is an urgent need.

[0003] Under the circumstances described above, “Dyneon THV” has been developed as a resin that is flexible, has a fuel barrier property, and has melt moldability and recyclability (for example, Modern Fluoropolymers: high performance). polymers for diverse applications, jon yl ey & Sons, Chichster, (1997) Chapterl 3, JP 2000-274562 and JP 2002-276862). However, as the properties of the resin described in these documents, the hardness and elastic modulus increase when trying to increase the fuel barrier property, and the fuel barrier property becomes extremely poor when trying to decrease the hardness and elastic modulus. There is a problem of hesitation S, and there is insufficient balance between flexibility and fuel barrier properties.

[0004] In addition, fluororubber has excellent heat resistance, chemical resistance, compression set, and other properties, and is used in many applications in the automotive, semiconductor, and industrial fields. one On the other hand, fluorinated resin has excellent properties such as slidability, heat resistance, chemical resistance, weather resistance, and electrical properties, and is used in a wide range of fields such as automobiles, industrial machinery, office automation equipment, and electrical and electronic equipment. . For the purpose of further improving the heat resistance of fluororubber, or for the purpose of imparting flexibility to fluorocarbon resin, polymer alloys of fluororubber and fluorocarbon resin have been studied (for example, JP-A-61-57641). The polymer alloy is attracting attention in the vicinity of fuel such as fuel tube material, which requires both fuel permeation resistance and flexibility.

[0005] However, in such a polymer alloy of fluororubber and fluorine resin, it is necessary to increase the fluorine resin component in order to improve fuel permeation resistance. However, if the fluorine resin component is increased, There is a problem that flexibility is impaired. On the other hand, in order to improve flexibility, it is necessary to increase the amount of the fluoro rubber component, but it becomes more difficult to uniformly disperse the rubber in the resin that becomes the continuous phase (sea component). As a result, the rubber of the dispersed phase (island component) forms a co-continuous phase, and there is a problem that sufficient properties of the resin cannot be obtained.

[0006] In addition, a composition of a thermoplastic elastomer having a fluorocarbon and fluororubber strength having a tetrafluoroethylene / hexafluoropropylene copolymer (FEP) force having excellent fuel permeation resistance is also known. (For example, see Japanese Patent Laid-Open Nos. 10-101880 and 10-219062). However, in the thermoplastic elastomer compositions disclosed in JP-A-10-101880 and JP-A-10-219062, there are more rubber components than the resin components, so that the obtained alloy has a low fuel barrier property and a high fuel barrier property. It has the problem that it is not suitable for applications that require

[0007] Therefore, a polymer alloy that has both fluororesin and fluororubber power with both fuel permeation resistance and flexibility! There is nothing yet!

Disclosure of the invention

[0008] An object of the present invention is to provide a fuel barrier material that has excellent heat resistance, chemical resistance, and oil resistance, is melt-moldable, and has excellent flexibility and fuel barrier properties. is there. Another object of the present invention is to provide a molded article formed from the fuel barrier material, a fuel tube including a layer formed from the fuel noble material force, and a fuel hose. [0009] Namely, the present invention provides a fuel barrier material comprising 80 to 5 wt% fluorine榭脂(A) 95 to 20 weight ^_0/0 and crosslinked fluororubber (B),

Fluorine resin (A) Force Copolymer with tetrafluoroethylene and hexafluoropropylene strength or Copolymer with Tetrafluoroethylene, Hexafluoropropylene and Perfluoro (alkyl vinyl ether) And

The crosslinked fluororubber (B) has a fluorine concentration of 68% by weight or more, and at least a part of the crosslinked fluororubber is crosslinked.

The present invention relates to a fuel barrier material.

[0010] The cross-linked fluororubber (B) is dynamically added to the fluororubber (b) together with the cross-linking agent (C) under the melting condition of the fluorocobalt (A) in the presence of the fluorocobalt (A). It is preferable that it is cross-linked.

[0011] It is preferable that the molded article formed with a fuel barrier material force has a fuel permeability coefficient force of 0 (g'mm) / (m ² -day) or less and a tensile elastic modulus of 600 MPa or less.

[0012] The melting point of the fluorinated resin (A) is preferably 150 ° C to 330 ° C.

[0013] Fluoro rubber (b) 1S Bilidene fluoride Z Tetrafluoroethylene Z Hexafluoropropylene fluororubber is preferred.

[0014] Cross-linking agent (C) force It is preferable that it is a polyhydroxyl compound.

[0015] The present invention also relates to a molded article formed from the fuel barrier material.

[0016] Further, the present invention relates to a fuel tube and a fuel hose including a layer in which the fuel barrier material force is formed.

In the present specification, the “fluorine concentration” is a value obtained by calculating the weight ratio of fluorine atoms in the fluororubber polymer.

[0018] In addition, the term "fuel" in this specification refers to a substance used for obtaining energy in the automobile field, industrial field, and industrial field such as gasoline, kerosene, light oil (diesel oil), and heavy oil. The concept includes bio-derived alcohol and bio-diesel, mixed fuel of bio-alcohol and gasoline, and mixed fuel of bio-diesel and light oil (diesel oil).

BEST MODE FOR CARRYING OUT THE INVENTION [0019] The present invention provides a fuel barrier material containing fluorine榭脂(A) 95 to 20 weight ^_0/0 and crosslinked fluororubber (B) 80 to 5 weight ^_0/0,

Fluororesin (A) Force Tetrafluoroethylene (hereinafter referred to as TFE) and Hexafluoropropylene (hereinafter referred to as HFP) copolymer or TFE, HFP and Perfluoro (alkyl butyl ether) (hereinafter referred to as “HFP”) PAVE) is a copolymer that also has power,

The present invention relates to a fuel barrier material.

In the present invention, an excellent fuel barrier property can be obtained by using a copolymer of TFE and HFP or a copolymer of TFE, HFP and PAVE force as the fluorine resin (A). It is possible to obtain a certain fuel barrier material.

[0021] TFE and as a copolymer consisting of HFP, but are not limited to, TFE units 70-99 molar%, HFP units 1 to 30 mol ^_0/0 a copolymer is it is preferred instrument TFE units 80-95 mole ^_0/0 and HFP units 5 to 20 mol ^_0/0 and more preferably a force styrenesulfonate! /,. 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.

[0022] The type of the copolymer comprising TFE and HFP is not limited as long as it can be copolymerized with TFE and HFP as the third component which may contain the third component.ヽ (except PAVE). For example, black trifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (hereinafter referred to as VdF), fluorinated bulu, general formula (1) :

CH = CX ¹ (CF) X ² (1)

2 2 n

(Wherein, X ¹ is a hydrogen atom or a fluorine atom, X ² is a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10)

Fluororefine etc. indicated by

[0023] TFE, HFP, Examples of the third component monomer force styrenesulfonate, Do limited !, force TFE units 67 to 98.9 mole ^_0/0, HFP units 1 to 30 mol ^_0/0, the Third component monomer unit 0.1 to 3 mol% Powerful copolymer is preferred TFE unit 78.5 to 54.5 Le ^_0/0, HFP units 5 to 20 mol ^_0/0, the third component monomer units from 0.3 to 1.5 mol ^_0/0 and more preferably a Chikararana Ru copolymer. If the TFE unit is less than 67 mol%, the mechanical properties tend to decrease, and if it exceeds 98.9 mol%, the moldability tends to decrease.

[0024] TFE, HFP, as the copolymer consisting of PAVE, limited Do, but, TFE unit 6 from 7 to 98.9 mole ^_0/0, HFP units 1 to 30 mol ^_0/0, PAVE units 0. 1-3 mole ^_0/0 a copolymer is it is preferred instrument TFE units 78.5 to 94.5 mole ^_0/0, HFP units 5 to 20 mol%, PAVE units from 0.3 to 1.5 and more preferably a copolymer consisting mol ^_0/0. If the TFE unit is less than 67 mol%, the mechanical properties tend to decrease, and if it exceeds 98.9 mol%, the melting point becomes too high and the moldability tends to decrease.

Here, examples of PAVE include PAVE having an alkyl group having 1 to 5 carbon atoms such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl butyl ether).

[0026] Further, the melting point of the fluorinated resin (A) is preferably 150 to 330 ° C, more preferably 150 to 310 ° C, and further preferably 150 to 290 ° C. It is particularly preferably 170 to 270 ° C. If the melting point of fluorine resin (A) is less than 150 ° C, the heat resistance of the resulting fuel noble material tends to decrease, and if it exceeds 330 ° C, it will be in the presence of fluorine resin (A). When the rubber (b) is dynamically cross-linked under the melting condition of the fluorine resin (A), it is necessary to set the melting temperature above the melting point of the fluorine resin (A). Rubber (b) tends to heat deteriorate.

[0027] The crosslinked fluororubber (B) used in the present invention is not particularly limited as long as it is a fluororubber having a fluorine concentration of 68% by weight or more and at least a part of which is crosslinked. Absent.

[0028] The fluorine concentration of the crosslinked fluororubber (B) is 68 wt% or more, preferably 68 to 75 wt%, more preferably 69 to 74 wt%, 70 to 73 wt%. % Is more preferable. When the fluorine concentration is less than 68% by weight, the mechanical properties of the obtained fuel barrier material tend to be lowered.

[0029] The cross-linked fluororubber (B) is dynamically added to the fluororubber (b) together with the cross-linking agent (C) under the melting condition of the fluorocobalt (A) in the presence of the fluorocobalt (A). It is obtained that it has been cross-linked The fuel barrier material that has good moldability and improved mechanical properties is preferred. Here, the dynamic cross-linking treatment means that the fluororubber (b) is dynamically cross-linked simultaneously with melt kneading using a Banbury mixer, pressurizer / extruder, extruder or the like. Among these, it is preferable to use an extruder such as a twin screw extruder because a high shear force can be applied. By dynamically performing the crosslinking treatment, the phase structure of the fluorocarbon resin (A) and the crosslinked fluororubber (B) and the dispersion of the crosslinked fluororubber (B) can be controlled.

[0030] Examples of the fluororubber (b) include perfluorofluororubber (bl) and non-perfluorofluororubber (b2).

[0031] Examples of the perfluoro fluorine rubber (bl) include a TFEZPAVE copolymer and a TFEZHFPZ PAVE copolymer.

[0032] Examples of the non-perfluorofluororubber (b2) include VdF-based polymers and TFEZ-propylene-based copolymers, which are used alone or in a range that does not impair the effects of the present invention. Any combination can be used.

[0033] The examples of the perfluoro fluororubber (bl) and the non-perfluorofluororubber (b2) are the constitution of the main monomer, and those obtained by copolymerizing a crosslinking monomer, a modified monomer, etc. are also suitable. Can be used. As the crosslinking monomer or modifying monomer, a known crosslinking monomer such as an iodine atom, bromine atom or double bond-containing monomer, a transfer agent, a modified monomer such as a known ethylenically unsaturated compound, or the like can be used. .

[0034] Specific examples of the VdF polymer include a VdFZHFP copolymer, a VdF / TFE ZHFP copolymer, a VdFZTFEZ propylene copolymer, a VdFZ ethylene ZHFP copolymer, and a VdFZTFEZPAVE copolymer. Examples thereof include VdFZPAVE copolymer, VdF ZCTFE copolymer and the like. More specifically, it is preferably a fluorine-containing copolymer comprising 25 to 85 mol% of VdF and 75 to 15 mol% of at least one other monomer copolymerizable with VdF.

Here, as at least one other monomer copolymerizable with VdF, for example, TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, penta Fluorinated monomers such as fluoropropylene, trifluorobutene, tetrafluoroisobutene, PAVE, fluorinated bur, ethylene, propylene, alkyl butyl ether Non-fluorine monomers such as These can be used alone or in any combination.

[0036] Among the fluororubbers, a fluororubber containing a VdF unit and an HFP unit is preferred from the viewpoint of heat resistance, compression set, workability, and cost. It is more preferable.

[0037] From the viewpoint of good compression set, VdFZTFEZHFP is preferably at least one rubber selected from the group consisting of VdFZHFP fluororubber, VdFZTFEZ HFP fluororubber, and TFEZ propylene fluororubber. More preferred is fluororubber.

[0038] The fluororubber (b) used in the present invention can be produced by a usual emulsion polymerization method. Polymerization conditions such as temperature and time during polymerization may be appropriately determined depending on the type of monomer and the target elastomer.

[0039] The crosslinking agent (C) used in the present invention can be appropriately selected according to the type of the fluororubber (b) to be crosslinked and the melt-kneading conditions.

[0040] When the fluororubber (b) contains a crosslinkable group (cure site), the cross-linking system used in the present invention is appropriately selected depending on the type of the cure site or the use of the molded product to be obtained. That's fine. As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

[0041] Here, cross-linking by a polyol cross-linking system is preferable in that it has a carbon-oxygen bond at the cross-linking point, and has a feature of being excellent in moldability with a small compression set.

[0042] In the case of crosslinking by an organic peroxide crosslinking system, since it has a carbon-carbon bond at the crosslinking point, a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine crosslinking system having a carbon-nitrogen double bond. Compared to the above, it is characterized by excellent chemical resistance and steam resistance.

[0043] When cross-linked by polyamine cross-linking, it has a carbon-nitrogen double bond at the cross-linking point and is characterized by excellent dynamic mechanical properties. However, compared with the case of crosslinking using a polyol crosslinking system or an organic peroxide crosslinking system, the compression permanent There is a tendency for distortion to increase.

[0044] Therefore, in the present invention, it is more preferable to use a polyol crosslinking system or an organic peroxide crosslinking system. It is more preferable to use a polyol crosslinking system.

[0045] As the crosslinking agent (C) in the present invention, a polyamine-based, polyol-based or organic peroxide-based crosslinking agent can be used.

[0046] Examples of the polyamine crosslinking agent include hexamethylenediamine carbamate, N, N, 1-disinnamylidene 1, 6 hexamethylenediamine, 4, 4'-bis (aminocyclohexenole) methane power rubamate. And polyamine compounds. Of these, N, N'-dicinnamylidene 1, 6 hexamethylenediamine is preferred!

[0047] As the polyol cross-linking agent, a compound conventionally known as a fluororubber cross-linking agent can be used. For example, a polyhydroxy compound, particularly, a polyhydroxy aromatic compound having excellent heat resistance. A compound is preferably used.

[0048] The polyhydroxy aromatic compound is not particularly limited. For example, 2, 2 bis (4 hydroxyphenol) propane (hereinafter referred to as bisphenol A), 2, 2 bis (4 hydroxyphenol). ) Perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3 dihydroxybenzene, 1,7 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 4,4'-dihydroxydiphenyl 4, 4 'dihydroxystilbene, 2, 6 dihydroxyanthracene, hydroquinone, catechol, 2, 2-bis (4-hydroxyphenol) butane (hereinafter referred to as bisphenol B), 4, 4-bis (4— Hydroxyphenol) Valeric acid, 2, 2 Bis (4 hydroxyphenol) Tetrafluorodiclopropane Propane, 4, 4, Dihydroxydiph Ninoles norephone, 4, 4, -dihydroxydiphenyl ketone, tri (4-hydroxyphenol) methane, 3, 3 ', 5, 5, monotetrachlorobisphenol A, 3, 3', 5, 5, One tetrabromobisphenol A. These polyhydroxy aromatic compounds may be alkali metal salts, alkaline earth metal salts, and the like, but it is preferable that the above metal salts are not used when the copolymer is prayed using an acid. ,.

[0049] The organic peroxide crosslinking type crosslinking agent may be any organic peroxide compound that can easily generate a peroxide radical in the presence of heat or a redox system. , 1 Bis (t-butylperoxy)-3, 5, 5 Trimethylcyclohexane, 2, 5 Dimethyl Hexane 2, 5 Dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, a, α-bis (t-butyl peroxide) —p diisopropylbenzene, 2, 5 dimethyl-2,5 di ( t-butyl peroxide) hexane, 2,5 dimethyl-2,5 di (t-butylperoxy) monohexene-3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t —Butyl peroxyisopropyl carbonate and the like can be mentioned. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferred.

[0050] Among these, polyhydroxy aromatic compounds are preferred because polyhydroxy compounds are excellent in heat resistance because they are excellent in moldability with small compression set such as molded articles to be obtained. Bisphenol AF is more preferred.

[0051] In the polyol crosslinking system, a crosslinking accelerator (D) is usually used in combination with the polyol crosslinking agent. When the crosslinking accelerator (D) is used, the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

[0052] As the cross-linking accelerator (D) of the polyol cross-linking system, an organic compound is generally used. Ammonium compounds are not particularly limited. For example, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, monofunctional compounds Amine compounds are preferred, and among these, quaternary ammonium salts and quaternary phospho- um salts are preferred.

[0053] The quaternary ammonium salt is not particularly limited. For example, 8-methyl 1,8 diazabicyclo [5, 4, 0] -7 undecese-um chloride, 8-methyl-1,8 diazabicyclo [ 5, 4, 0] — 7 Hundesaceum iodide, 8—Methyl-1, 8 diazabicyclo [5, 4, 0] — 7 Hundesse-um hydroxide, 8-methyl 1,8 diazabicyclo [5,

4, 0] —7undecem methylsulfate, 8 ethyl 1,8 diazabicyclo [

5, 4, 0] —7 Undecem-bromide, 8 Propyl 1,8 Diazabicyclo [5, 4, 0] —7 Undecem-bromide, 8 Dodecyl 1,8 Diazabicyclo [5, 4, 0]-7 —Undece- Um chloride, 8 dodecyl 1, 8 diazabicyclo [5, 4, 0] — 7 ung Dece-um hydroxide, 8 eicosyl-1,8 diazabicyclo [5,4,0] -7-undece-um chloride, 8-tetracosyl1,8 diazabicyclo [5,4,0] —7undece -Um chloride, 8 benzyl-1,1,8 diazabicyclo [5,4,0] —7 undese-um chloride (hereinafter referred to as DBU—B), 8 benzyl-1,1,8 diazabicyclo [5, 4, 0] 7 undese Muhydroxide, 8 Phenethyl- 1,8 Diazabicyclo [5, 4, 0] — 7 Undece-um chloride, 8-— (3-Felpropyl) — 1, 8 Diazabi-sic mouth [5, 4, 0] — 7 Undense- Um chloride. Among these, DBU-B is preferable from the viewpoint of the crosslinkability and the physical properties of the cross-linked product.

[0054] The quaternary phospho-um salt is not particularly limited, and examples thereof include tetrabutyl phospho-um chloride, benzyl triphenyl phospho-um chloride (hereinafter referred to as BTPPC), benzyl trimethyl phospho-um chloride, Examples thereof include benzyltributylphosphomethylene chloride, tributylarylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, and benzylphenol (dimethylamino) phosphonium chloride. Among these, crosslinkability and physical properties of the crosslinked product From the above, benzyltrif-phosphoro-um chloride (BTPPC) is preferred.

[0055] Further, as a crosslinking accelerator (D), a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, chlorine disclosed in JP-A-11-147891 Free bridge accelerators can also be used.

[0056] Examples of the crosslinking accelerator (D) for organic peroxides include triaryl cyanurate, triaryl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N, -m— Phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triaryl isocyanate (2, 3, 3 卜! ; Funore age P 2 P P peninole) 1, 3, 5— Triazine— 2, 4, 6 Trione), Tris (Dialylamine) — S Triazine, Triaryl phosphite, N, N diallyacrylamide, 1, 6 Divinyldodecafluor hexane, hexaryl phosphoramide, N, N, Ν ', Ν, monotetraallyl phthalamide, Ν, Ν, Ν', Ν, 1 tetraallyl malonami , Tri Bulle iso Xia isocyanurate, 2,4,6 Bulle methyltrimethoxysilane siloxane, tri (5-norbornene one 2-methylene) Shianureto, triallyl phosphite can give. Among these, triallyl isocyanurate HTAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

[0057] The amount of the crosslinking agent (C) to be added is preferably 0.1 to: LO parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the fluororubber (b). Part. If the cross-linking agent (C) is less than 0.1 parts by weight, the cross-linking of the fluororubber (b) does not proceed sufficiently, and the resulting fuel barrier material tends to decrease the heat resistance and oil resistance. If the amount exceeds 10 parts by weight, the moldability of the resulting fuel barrier material tends to decrease.

[0058] The addition amount of the crosslinking agent (C) and the crosslinking accelerator (D) was adjusted so that 90% vulcanization time T90 at the temperature during dynamic crosslinking treatment was 2 to 6 minutes. 90% completion time is more preferably the amount adjusted so that the T90 is 3-5 minutes. If the optimum vulcanization time T90 is less than 2 minutes, the dispersion of the crosslinked rubber tends to be uneven and coarse, and if it exceeds 6 minutes, it takes a long time for the rubber to crosslink. And there is a tendency not to completely crosslink.

[0059] Here, vulcanization 90% completion time T90 is the temperature at the time of dynamic vulcanization using JSR type chilastometer Π type and V type at the time of primary press vulcanization of fluoro rubber (b). Obtain the vulcanization curve, and the time to reach 90% of the maximum torque value is the 90% completion time (T90).

[0060] The melting condition means a temperature at which the fluororesin (A) and the fluororubber (b) are melted. The melting temperature varies depending on the glass transition temperature and the Z or melting point of fluorocarbon resin (A) and fluororubber (b), respectively, but is preferably 120-330 ° C. More preferably. If the temperature is less than 120 ° C, the dispersion between the fluorocarbon resin (A) and the fluororubber (b) tends to become coarse, and if it exceeds 330 ° C, the rubber (b) will be thermally deteriorated. There is a tendency to.

[0061] The obtained fuel barrier material has a structure in which the fluorine resin (A) forms a continuous phase and the crosslinked fluorine rubber (B) forms a dispersed phase, or the fluorine resin (A) and the crosslinked fluorine. The rubber (B) can have a structure that forms a co-continuity, and among them, the fluorocarbon resin (A) forms a continuous phase and the cross-linked fluororubber (B) has a structure that forms a dispersed phase. I prefer that.

[0062] Even when the fluororubber (b) forms a matrix at the beginning of dispersion! /, The melt viscosity is increased by the fluororubber (b) becoming the cross-linked fluororubber (B) as the crosslinking reaction proceeds. Rise and bridge The silicon rubber (B) becomes a dispersed phase or forms a co-continuous phase with the fluorine resin (A).

[0063] When such a structure is formed, the fuel barrier material of the present invention exhibits excellent heat resistance, chemical resistance, and oil resistance, and also has excellent fuel permeation resistance and flexibility. At that time, the average dispersed particle size of the crosslinked fluororubber (B) is preferably 0.01 to 30 / ζ πι. If the average dispersed particle size is less than 0.01 m, the fluidity tends to decrease, and if it exceeds 30 m, the strength of the resulting fuel barrier material tends to decrease.

[0064] In addition, the fuel barrier material of the present invention is preferred and / or the form of the fluorocarbon resin (A) forms a continuous phase, and the crosslinked fluororubber (B) forms a dispersed phase. A part of the structure may include a co-continuous structure of fluorine resin (A) and crosslinked fluororubber (B).

[0065] Further, the fuel barrier material of the present invention, fluorine榭脂(A) 95 to 20 wt%, crosslinking fluororubber (B) preferably be composed of 5 to 80 weight ^_0/0 device fluorine榭脂( A) 92-30 weight ^_0/0, crosslinked fluororubber (B) 8 to 70 weight ^_0/0 also more preferably comprising power tool fluorine榭脂(A) 90 to 60 wt%, crosslinking fluororubber (B) 10 more preferably consisting of 40 wt ^_0/0. The fuel barrier material obtained when the fluorine resin (A) is less than 20% by weight tends to have poor fluidity and the molding processability tends to deteriorate. The fuel barrier property obtained when it exceeds 95% by weight The balance between material flexibility and fuel barrier properties tends to be poor.

[0066] The fuel permeability material strength of the present invention The fuel permeability coefficient of the formed article is preferably 40 (g'mm) / (m ² .day) or less, and 30 (g · mm) / ( m ² .day) or less is more preferable 20 (g 'mm) Z (m ² * day) or less is more preferable 5 (g-mm) / (m ² -day) It is particularly preferred that The lower limit value of the fuel permeability coefficient is not particularly limited, and the lower the value, the better. If the fuel permeation coefficient exceeds 40 (g-mm) / (m ² -day), the fuel permeation resistance is low, so it is necessary to increase the thickness of the molded product to suppress the fuel permeation amount. Economically unfavorable. Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability, and conversely, when the fuel permeation coefficient is large, the fuel permeates, so that it is suitable as a molded product such as a fuel tube.

[0067] The fuel permeability coefficient was measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test specified in JIS Z 0208. This is a test method that measures the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, put 18 mL of simulated fuel CE10 (toluene Z isooctane Z ethanol = 45 Z45 Z10 vol%) into a SUS container (open area 1.26 X 10 " ³ m ² ) with a volume of 20 mL. Then, set the sheet-like test piece in the open part of the container and seal it to make a test piece.Place the test piece in a constant temperature device (60 ° C), measure the weight of the test piece, and measure the weight per unit time. When the weight loss becomes constant, the fuel permeability is obtained by the following formula.

[0068] [Equation 1] Fuel permeation coefficient (g. Mm / m ² -day) =

[: Reduced weight)] X [Sheet thickness (mm)]

[Opening area ^{1. 2 6 X 1 0- 3} (m 2)] X [Measurement interval (day)]

[0069] The tensile modulus of the molded article formed from the fuel barrier material of the present invention is preferably 600 MPa or less, more preferably 550 MPa or less, and more preferably 500 MPa or less. Is more preferable. The lower limit value of the tensile modulus is not particularly limited. The force is preferably 5 MPa or more, more preferably lOMPa or more. If the tensile modulus exceeds 600 MPa, it tends to be unsuitable for molded products that require flexibility.

[0070] The fuel barrier material of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate and the like. Inorganic fillers, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softeners, etc. It can be added as long as it does not affect the effect.

[0071] The fuel barrier material of the present invention can be molded using a general molding method or molding apparatus. As a molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding and the like can be adopted, and the fuel barrier material of the present invention is used for the purpose of use. Correspondingly, it is formed into a molded body of any shape. [0072] Further, the present invention relates to a molded article obtained by using the fuel barrier material of the present invention, and the molded article includes a molded article of a sheet or a film, and the present invention. It includes a laminated structure having a layer with a clear fuel barrier material force and a layer with another material force.

[0073] In the laminated structure of at least one layer that also has the fuel barrier material force of the present invention and at least one layer that has the other material force, the other material has the required characteristics and intended use. What is necessary is just to select an appropriate thing according to the way. Examples of the other materials include polyolefin (eg, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene propylene copolymer, polypropylene, etc.), nylon, polyester, butyl chloride. Thermoplastic polymers such as fat (PVC), salt vinylidene resin (PVDC), cross-linked rubber such as ethylene propylene gen rubber (EPDM), butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, polypropylene / EPDM composite, etc. Examples thereof include thermoplastic elastomers, metals, glass, wood, and ceramics.

[0074] In the molded article having the laminated structure, an adhesive layer may be interposed between the layer made of the fuel barrier material of the present invention and the base material layer made of another material. By interposing the adhesive layer, the layer having the fuel barrier material force of the present invention and the base material layer having another material force can be firmly joined and integrated. Examples of adhesives used in the adhesive layer include acid anhydride-modified products of gen-based polymers; acid anhydride-modified products of polyolefins; polymer polyols (for example, glycol compounds such as ethylene glycol and propylene glycol, and adipic acid). Polyester polyols obtained by polycondensation of dibasic acids such as; partial saponified products of copolymers of acetic acid vinyl and salt and butyl and polyisocyanate compounds (for example, 2, 4 tolylene diisocyanate, etc. (for example, a reaction product with a molar ratio of glycol compound such as 1, 6 hexamethylene glycol and diisocyanate compound such as 2, 4 tolylene diisocyanate, etc. 1: 2) A molar ratio of a trioylol compound such as trimethylolpropane to a diisocyanate compound such as 2,4 tolylene diisocyanate is 1 to 3. Response product, etc.); or the like can be used. For forming the laminated structure, a known method such as co-extrusion, co-injection, or extrusion coating can be used.

[0075] The present invention includes a fuel hose or fuel comprising a single layer of the fuel barrier material of the present invention. A container is included. The use of the fuel hose is not particularly limited, and examples thereof include a filler hose for automobiles, an evaporative hose, and a breather hose. The use of the fuel container is not particularly limited, and examples thereof include a fuel container for automobiles, a fuel container for motorcycles, a fuel container for small generators, and a fuel container for lawn mowers.

[0076] Further, the present invention includes a multilayer fuel hose or a multilayer fuel container including a layer made of the fuel barrier material of the present invention. The multi-layer fuel hose or multi-layer fuel container is composed of the layer having the fuel barrier material force of the present invention and at least one layer having the other material force, and these layers do not interpose the adhesive layer or intervene. And are adhered to each other.

[0077] Examples of other material strength layers include layers made of rubber other than the fuel barrier material of the present invention and layers made of thermoplastic resin.

[0078] From the viewpoint of chemical resistance and flexibility, the rubber includes acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, vinyl fluoride, epoxy rubber. Acrylonitrile monobutadiene rubber or hydrogenated rubber thereof, which is preferably at least one kind of rubber selected from the group consisting of chlorohydrin rubber, EPDM and acrylic rubber, blend rubber of acrylonitrile monobutadiene rubber and polyvinyl chloride, More preferably, it is made of at least one rubber selected from the group consisting of fluororubber and epichlorohydrin rubber.

[0079] In addition, as a fuel barrier material, from the viewpoint of fuel barrier properties, fluorine resin, polyamide-based resin, polyolefin resin, polyester-based resin, polyvinyl alcohol-based resin, polyvinyl chloride resin Fluorine resin, polyamide-based resin, polybulle alcohol-based resin, poly-phenylene sulfide-based resin, which is preferably selected from the group consisting of rubber-based resin and polyphenylene sulfide-based resin. More preferred is a thermoplastic rosin that is at least one selected from the group consisting of fats.

[0080] The fuel hose or the fuel container including the layer made of the fuel barrier material obtained by the present invention and the layer made of other rubber or other thermoplastic resin is particularly limited. For example, fuel hoses such as filler hose, evaporative hose, breather hose for automobiles; fuel containers for automobiles, fuel containers for motorcycles, small generators And a fuel container such as a lawn mower fuel container.

[0081] Among these, as a fuel hose comprising a layer made of the fuel barrier material of the present invention and a layer made of other rubber, acrylonitrile monobutadiene rubber or its hydrogenated rubber, acrylo-tolyl monobutadiene rubber and A fuel hose that also has a three-layer force of an outer layer that also has a rubber strength blended with polychlorinated bur or epichlorohydrin rubber, an intermediate layer that also has the fuel barrier material strength of the present invention, and an inner layer that also has a fluorine rubber strength, or acrylonitrile monobutadiene rubber or its hydrogen A fuel hose composed of two layers: an additive rubber, an outer layer of acrylonitrile monobutadiene rubber and polysalt rubber, or an outer layer also having an epichlorohydrin rubber force, and an inner layer of the fuel barrier material of the present invention. Excellent fuel barrier properties' Preferable for its flexibility and chemical resistance Masashi.

[0082] Further, when a laminated structure having a layer made of the fuel barrier material of the present invention and a layer made of another material is produced, the surface of the fuel barrier material of the present invention is surfaced as necessary. Processing may be performed. The surface treatment is not particularly limited as long as it is a treatment method that enables adhesion. For example, discharge treatment such as plasma discharge treatment or corona discharge treatment, wet metal sodium Z naphthalene solution Processing. A primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When the primer treatment is applied, the surface treatment can be performed to treat the surface of the fluorine resin, but the fuel barrier properties are pre-treated with plasma discharge treatment, corona discharge treatment, metal sodium Z naphthalene solution treatment, etc. It is more effective to further prime the surface of the material.

[0083] The fuel barrier material of the present invention and a molded article comprising the composition can be suitably used in the following fields.

[0084] In semiconductor-related fields such as semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma addressed liquid crystal panels, field emission display panels, solar cell substrates, etc., o (square) rings, packings, sealing materials, tubes Rolls, coatings, linings, gaskets, diaphragms, hoses, etc., which are CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation equipment, exhaust equipment , Used for chemical piping and gas piping Can do. Specifically, as a gate valve O-ring, as a sealing material, a quartz window o-ring, as a sealing material, as a chamber o-ring, as a sealing material, as a gate o-ring, as a sealing material, as a bell jar o-ring, as a seal O ring for coupling as material, o ring for pump as seal material, seal material, diaphragm, o ring for semiconductor gas control device, o ring for resist developer and stripper as seal material As a sealing material, as a wafer cleaning solution hose, as a tube, as a wafer transfer roll, as a resist developer bath, as a lining for a stripping solution bath, as a coating, as a lining, coating or as a wet etching bath for a wafer cleaning solution bath It can be used as a lining or coating. In addition, sealing materials' sealing agent, optical fiber quartz coating material, electronic parts for insulation, vibration proofing, waterproofing, moisture proofing, circuit board potting, coating, adhesive seals, gaskets for magnetic storage devices, It is used as a modifier for sealing materials such as epoxy, sealant for clean rooms and clean rooms.

[0085] In the automotive field, gaskets, shaft seals, valve stem seals, sealing materials and hoses can be used for engines and peripheral devices, and hoses and sealing materials can be used for AT devices. Rings, tubes, packings, valve cores, hoses, seals and diaphragms can be used in fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, hold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, Ettater packing, fuel pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston packing, cylinder liner seal, knob stem seal, automatic transmission front pump seal, rear axle On seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas re-burner sheath, bearing Nore, EGR tubes, twin key bush tube for sensors Daiafuramu carburetor, rubber vibration isolator (engine mount, exhaust part, etc.), afterburner for hose can be used as an oxygen sensor bush.

[0086] In the aircraft field, rocket field, and ship field, diaphragms, O (square) rings, Such as a tube, a tube, a knock, a hose, and a sealing material, which can be used for a fuel system. Specifically, in the aircraft field, it is used for jet engine valve stem seals, fuel supply hoses, gaskets and o-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. Used for propeller shaft stern seals, intake / exhaust valve stem seals for diesel engines, valve seals for notary valves, and shaft seals for butterfly valves.

[0087] In the field of chemicals such as plants, linings, valves, knocks, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, chemical-resistant coatings, etc. are available. It can be used in the production process of chemicals such as agricultural chemicals, paints, and fats. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packings for sulfuric acid production equipment, pesticide sprayers, seals for pesticide transfer pumps, gas pipe seals, plating solutions Seals, high-temperature vacuum dryer packing, paper belt roller seals, fuel cell seals, wind tunnel joint seals, trichlene-resistant rolls (for textile dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH It can be used as a packing for a tube connection part of a meter, a chlorine gas transfer hose, a benzene, a rainwater drain hose for a toluene storage tank, an analytical instrument, a seal for a scientific instrument, a tube, a diaphragm, a valve part, and the like.

[0088] In the pharmaceutical field such as pharmaceuticals, it can be used as a medicine stopper or the like.

[0089] In the photographic field such as a developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, rolls and the like can be mentioned, which are respectively used for a film developing machine, a tangential film developing machine, a printing roll and a coating roll be able to. Specifically, as a developing roll of a film developing machine / coiled film image forming machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating tool, and a magnetic tape manufacturing coating It can be used as a line guide roll, various coating rolls, and the like. Furthermore, dry copying machine seals, printing equipment printing rolls, scrapers, tubes, valve parts, coating, coating equipment coating rolls, scrapers, tubes, valve parts, printer ink tubes, rolls, belts, dry copying machine belts It can be used as a roll, a roll for a printing press, a belt, or the like.

[0090] The tube can also be used in the field of analysis and science machines. [0091] In the field of food plant equipment, linings, valves, knockers, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, belts, and the like can be mentioned and used for food production processes. Specifically, it can be used as a plate-type heat exchanger seal, a solenoid valve seal of a vending machine, or the like.

[0092] In the field of nuclear plant equipment, packing, O-rings, hoses, sealing materials, diaphragms

, Nozzles, rolls, tubes, etc.

[0093] In the steel field such as iron plate processing equipment, there are rolls and the like, which can be used for iron plate processing rolls and the like.

[0094] In the general industrial field, packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, rolls for PPC copiers, Examples include roll blades and belts. Specifically, oil pressure, lubrication machine seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seal (vacuum) valves, automatic packaging machine seals It is used for diaphragms (pollution measuring devices) for analysis of sulfur dioxide and chlorine gas in the air, printing press rolls, belts, pickling squeeze rolls, and so on.

In the electric field, specifically, it is used as an insulating oil cap for Shinkansen, a ventilator seal for a liquid ring transformer, a jacket for an oil well cable, and the like.

[0096] In the fuel cell field, specifically, a sealant between electrodes and separators is used as a seal for hydrogen 'oxygen' product water piping.

[0097] In the field of electronic components, specifically, it is used as a heat-dissipating material raw material, an electromagnetic shielding material raw material, a modified material for printed wiring board pre-preda resin such as epoxy, an anti-scattering material such as a light bulb, and a hard disk drive gasket of a computer. Used.

[0098] There are no particular limitations on what can be used for on-site molding, such as metal gasket coatings for automobile engines, gaskets for engine oil pans, rolls for copiers, printers, Architectural sealant, gasket for magnetic recording device, sealant for clean room filter unit, coating agent for printed circuit board, electrical 'electronic component fixing agent, insulation moisture-proof treatment of electrical equipment lead wire terminal, electric furnace, etc. Examples include oven seals, end treatment of sheathed heaters, microwave oven window frame seals, adhesion of CRT wedges and necks, adhesion of automotive electrical components, joint seals for kitchens, bathrooms, and washrooms.

[0099] The molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable as a fuel peripheral part. In addition, the molded article of the present invention is particularly useful as a sealing material, knock, roller, tube or hose.

Example

[0100] Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

[0101] <Vulcanization characteristics>

Obtain the vulcanization curves at 170 ° C and 260 ° C using the JSR type kilastometer type II, and determine the minimum viscosity (ML), vulcanization degree (MH), induction time (T10) and optimum Find the sulfur time (T90). If no change in torque is observed after 30 minutes in the heated state, the vulcanization reaction is considered not to have progressed.

[0102] <Preparation of sheet specimen>

After setting the fuel barrier material produced in Examples and Comparative Examples in a mold and holding it at 290 ° C. for 15 to 30 minutes with a heat press machine to bring the dynamic cross-linking composition into a molten state, A 3MPa load is applied for 1 minute and compression molded to produce a sheet-shaped test piece of the specified thickness.

[0103] <Measurement of tensile strength at break, tensile elongation at break and tensile modulus>

Prepare a 2mm thick sheet-shaped test piece by the above method, and punch out a dumbbell-shaped test piece with a distance between marked lines of 3.18mm using ASTM V type dumbbell. Using the obtained dumbbell-shaped test piece, using an autograph (AGS—J 5kN, manufactured by Shimadzu Corporation), in accordance with ASTM D638, under the condition of 50 mmZ, the tensile elongation at break at 25 ° C Measure the tensile strength at break and tensile modulus.

[0104] Fuel permeability>

A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. Put 18mL of a simulated fuel CE10 (toluene Z Isoota Tan Z ethanol = 45Z45Z10 capacity ^_0/0) to SU S steel container (opening area 1. 26 X 10 "V) with 20mL of volume, the sheet-like test A piece Set to the open part of the vessel and seal to make the specimen. The test specimen was placed in a thermostatic device (60 ° C), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following formula.

[0105] [Equation 2] Fuel permeation coefficient ((g, mm) / (m ² · day))

[Reduced weight-(g)] X-[Sheet thickness (mm)]

[Open part area 1.2 6 X 10 " ³ ( ^ms )] X [Measurement interval (da _y )]

[0106] <Liquidity>

Using the pellets of the fuel barrier material produced in the examples and comparative examples, the melt flow rate (under the conditions of 297 ° C, 5 kg load or 10 kg load) was measured with a melt flow measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd.). MFR) was measured.

[0107] <Adhesion evaluation test>

Using the pellets of the fuel barrier material produced in the examples, a sheet-like test piece having a thickness of 0.5 mm was produced by the above method. This sheet test piece, or the sheet treated with the surface of this sheet test piece and the rubber composition are set in a stacking die, and a 3MPa load is applied for 15 to 30 minutes at 170 ° C with a heat press machine. A rubber-fuel barrier material laminate was molded. Each of the vulcanized rubber-fuel barrier material laminates was cut into strips of 1. Ocm width x 10 cm to prepare test specimens for adhesion test. These test specimens were then JIS-K6256 (vulcanized rubber In accordance with the method described in Adhesion Test Method), a peel test was conducted at 25 ° C at a tensile speed of 50 mmZmin.

[0108] <Atmospheric pressure plasma treatment>

The surface of the sheet of fuel barrier material is set to 3 mm between the high and low voltage electrodes using an atmospheric pressure plasma treatment machine, an AC power supply with a frequency of 5 kHz is used, a voltage of 2 kV is applied, and ArZHe ( The plasma treatment was performed under the following conditions: vol) ratio = 50Z50, hydrogen concentration 2 ((vol)%), plasma energy density 2 α / cm ² ) t ヽぅ.

[0109] <Corona discharge treatment>

The discharge electrode (30 cm width) of the corona treatment device was covered with a container made of acrylic resin, and air was allowed to flow for 10 LZ at atmospheric pressure. Tantec's HV05—Type 2 power supply, corona output 25 The sheet surface of the fuel barrier material was treated with OW at a moving speed of ImmZ.

[0110] Metal sodium Z naphthalene treatment>

The sheet of the fuel barrier material was immersed in a metal sodium / naphthalene solution (Tetraetch, manufactured by Junye Co., Ltd.) for 5 seconds. The treated film was thoroughly washed with ethyl alcohol and water and then dried in an oven at 80 ° C.

[0111] In the examples and comparative examples, the following fluorinated resin (A), fluororubber (b), crosslinking agent (C) and crosslinking accelerator (D) were used.

[0112] Fluororesin (Al)>

TFE, consisting HFP copolymer (TFE: HFP = 91.7: 8.3 mol ^_0/0, mp 260 ° C) [0113] Ku fluorine榭脂(A2)>

TFE, HFP and Pafuruoro (propyl Bulle ether) force becomes copolymer (TF E: HFP: Pafuruoro (propyl Bulle ether) = 90.5: 9.1: 0.4 mole ^_0/0, mp 255 ° C)

[0114] <Fluoro rubber (bl— 1)>

VdF, 3-way based rubber consisting of TFE and HFP (VdF: TFE: HFP = 50:20: 30 Monore ^_0/0, the fluorine concentration = 71 wt%)

[0115] <Fluoro rubber (bl-2)>

VdF, 3-way based rubber consisting of TFE and HFP (VdF: TFE: HFP = 30:40: 30 Monore ^_0/0, the fluorine concentration = 73 wt%)

[0116] <Fluoro rubber (bl-3)>

Binary rubber consisting of VdF and HFP (VdF: HFP = 78: 22 Monore ^_0/0, the fluorine concentration = 6 6 wt%)

[0117] Crosslinking agent (C)>

Polyol-based cross-linking agent: 2, 2-bis (4-hydroxyphenol) perfluoropropane (Daikin Industries, Ltd. “Bisphenol AF”)

[0118] <Crosslinking accelerator (D)>

Benzyltriphenylphospho-um chloride (BTPPC, manufactured by Hokuko Chemical Co., Ltd.) [0119] Production Example 1 (Preparation of fluororubber composition (b2-1)) As shown in Table 1, fluororubber (bl— 1) in 100.0 parts by weight, cross-linking agent (C) 2.0 parts by weight, cross-linking accelerator (D) 1 part by weight, magnesium oxide (kiyoヮ 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight were added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b2-1).

[0120] Production Example 2 (Preparation of fluororubber composition (b2-2))

As shown in Table 1, fluororubber (bl-2) in 100.0 parts by weight, cross-linking agent (C) 2.0 parts by weight, cross-linking accelerator (D) l. 0 parts by weight, magnesium oxide (kiyoヮ 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight were added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b2-2).

[0121] Production Example 3 (Preparation of fluororubber composition (b2-3))

As shown in Table 1, fluororubber (bl-3) in 100.0 parts by weight, cross-linking agent (C) 2.17 parts by weight, cross-linking accelerator (D) 0.11 parts by weight, magnesium oxide (kiyoヮ 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight were added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b2-3).

[0122] [Table 1] Table 1

Examples 1-12

After pre-mixing the compound of the above-mentioned fluoro resin (A1 or A2) and fluororubber composition (b2-1, b2-2) in the ratio shown in Table 2 or Table 3, it is supplied to the twin screw extruder. The Then, they were melt-kneaded under conditions of a cylinder temperature of 290 ° C. and a screw rotation speed of 500 rpm to produce pellets of a fuel barrier material. Using the obtained pellets of fuel barrier material, a sheet-like test piece is prepared by the above-described method, and the hardness, tensile breaking strength, tensile breaking elongation, tensile elastic modulus, fuel permeability coefficient and melt flow rate are measured. The results are shown in Table 2 or Table 3.

[0124] Comparative Examples 1 to 3

Using the same method as in Examples 1 to 12, except that the fluororubber thread and composition (b2-3) was used instead of the fluororubber thread composition (b2-1 or b2-2), Barrier material pellets were prepared, and various measurements were performed using the sheet-like test pieces. Table 3 shows the measurement results.

[0125] Comparative Example 4

Table 3 shows the results of measurements of hardness, tensile strength at break, tensile elongation at break, tensile elastic modulus, fuel permeability coefficient and melt flow rate using the Dyneon “THV 200G” pellets by the methods described above.

[0126] Comparative Example 5

Table 3 shows the results of measurement of hardness, tensile strength at break, tensile elongation at break, tensile modulus, fuel permeability coefficient and melt flow rate using the Dyneon “THV 500G” pellets by the methods described above.

[0127] Comparative Example 6

Table 3 shows the results of measurement of hardness, tensile strength at break, tensile elongation at break, tensile modulus, fuel permeability coefficient and melt flow rate using the Dyneon “THV 815G” pellets by the methods described above.

[0128] The fuel barrier material obtained in Examples 1 to 12 was obtained by observing the morphology with a scanning electron microscope (manufactured by JEOL Ltd.), and the fluororesin (A) formed a continuous phase and crosslinked. It was found that the fluororubber (B) has a structure forming a dispersed phase. In Examples 1 to 12, the dispersed particle size of the crosslinked fluororubber (B) was 20 m or less.

[0129] Production Example 4 (Preparation of fluororubber composition (b2-4))

Fluoro rubber (bl— 1) 100.0 parts by weight, cross-linking agent (C) 2.0 parts by weight, cross-linking accelerator (D) 0 5 parts by weight, magnesium oxide (Kiyo Izuma Mag 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight, calcium hydroxide (Caldic 2000, Omi Chemical Co., Ltd.) 6.0 parts by weight Then, the mixture was kneaded using an 8-inch open roll to prepare a fluororubber composition (b2-4).

[0130] Production Example 5 (Preparation of epichlorohydrin rubber composition)

Epoxychlorohydrin rubber (Epichromer CG, Daiso Co., Ltd.) 100.0 parts by weight, Carbon black (N-550, Cancarb Ltd.) 80 parts by weight, Plasticizer (ADK cizer RS-107, Asahi Denka Kogyo Co., Ltd.) 5. 0 parts by weight, Lubricant (Splender R—300) 2. 0 parts by weight, anti-aging agent (NOCRACK NBC, Ouchi Shinsei Chemical Co., Ltd.) 2. 0 parts by weight, synthetic, Ido mouth talcite (DHT — 4A, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight, Magnesium Oxide (Kyoichi Tsumugi 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight, DBU phenol succinate (P— 1 52) 1. 5 parts by weight, 6-methylquinoxaline-2,3-dithiocarbonate (Daisonette XL-21S, Daiso Co., Ltd.) 1. Add 5 parts by weight and knead using an 8-inch open roll. A hydrin rubber composition was prepared.

[0131] The sheet of fuel barrier material obtained in Example 2 and the fluororubber composition (b2-4) obtained by the production method shown in Production Example 4 or obtained by the production method shown in Production Example 5 The adhesion evaluation test with the epichlorohydrin rubber composition was carried out by the above method. The peel strength is 10 NZcm when a fluororubber composition is used, and 8 NZcm when an epichlorohydrin rubber composition is used. Regardless of the type of rubber composition used, the fuel barrier material and vulcanization are used. The rubber sheet interface was peeled off.

[0132] The surface of the sheet of the fuel barrier material obtained in Example 2 was subjected to atmospheric pressure plasma treatment, and the surface treated, and the fluororubber composition obtained by the production method shown in Production Example 4 (b) 2-4) Or, an adhesion evaluation test with the epichlorohydrin rubber composition obtained by the production method shown in Production Example 5 was conducted by the above method. Regardless of the type of rubber composition used, it was found that the vulcanized rubber sheet part failed and the peel strength was 30 NZcm or more.

[0133] The surface of the sheet of fuel barrier material obtained in Example 2 was subjected to corona discharge treatment, and the surface-treated sheet and the fluororubber composition obtained by the production method shown in Production Example 4 (b2- 4) or an epichlorohydrin rubber composition obtained by the production method shown in Production Example 5 The adhesion evaluation test was conducted by the above method. Regardless of the type of rubber composition used, it was found that the vulcanized rubber sheet part was destroyed and its peel strength was 30 NZcm or more.

[0134] The surface of the sheet of the fuel barrier material obtained in Example 2 was treated with a metal sodium Z naphthalene solution, and the surface was treated, and the fluororubber composition obtained by the production method shown in Production Example 4 ( The adhesiveness evaluation test with the epichlorohydrin rubber composition obtained by the production method shown in b2-4) or Production Example 5 was conducted by the above method. Regardless of the type of rubber composition used, it was found that the vulcanized rubber sheet part failed and the peel strength was 30 NZcm or more.

[0135] [Table 2]

Table 2

Table 3

The fuel barrier material of the present invention contains a specific fluorine resin (A) and a high fluorine concentration crosslinked fluororubber (B), and thus has excellent heat resistance, chemical resistance, and oil resistance, and is melted. It can be formed and has excellent flexibility and fuel barrier properties.

Claims

The scope of the claims

[1] A fuel barrier material containing fluorine榭脂(A) 95 to 20 weight ^_0/0 and crosslinked fluororubber (B) 80 to 5 weight ^_0/0,

Fuel barrier material.

[2] The cross-linked fluororubber (B) is dynamically added to the fluororubber (b) together with the cross-linking agent (C) under the melting condition of the fluorocobalt (A) in the presence of the fluororesin (A). 2. The fuel barrier material according to claim 1, which has been subjected to a crosslinking treatment.

[3] A molded article that also has a fuel barrier material strength has a fuel permeability coefficient of 40 (g · mm) / (m ² · day) or less and a tensile modulus of 600 MPa or less. The fuel barrier material according to Item 2 or Item 2.

[4] The fuel barrier material according to any one of claims 1 to 3, wherein the melting point of the fluororesin (A) is 150 ° C to 330 ° C.

[5] Fluororubber (b) force Berylidene fluoride Z Tetrafluoroethylene Z Hexafluoride The fuel barrier material according to any one of claims 1 to 4, which is a propylene-based fluororubber .

[6] The fuel barrier material according to any one of claims 2 to 5, wherein the crosslinking agent (C) is a polyhydroxy compound.

[7] A molded article formed with the fuel barrier material force according to any one of claims 1 to 6.

[8] A fuel tube comprising a layer formed with the fuel barrier material force according to any one of claims 1 to 6.

[9] A fuel hose including a layer formed with the fuel barrier material force according to any one of claims 1 to 6.