WO2018066399A1

WO2018066399A1 - Composition and molding

Info

Publication number: WO2018066399A1
Application number: PCT/JP2017/034518
Authority: WO
Inventors: 祐己桑嶋; 剛志稲葉
Original assignee: ダイキン工業株式会社
Priority date: 2016-10-05
Filing date: 2017-09-25
Publication date: 2018-04-12

Abstract

The purpose of the present invention is to provide a composition with which it is possible to form a molding such as a fuel piping tube that exhibits superior fuel barrier properties and low-temperature impact resistance, and at the same time, has high flexibility. The present invention pertains to a composition characterized by comprising: a fluorine resin containing a chlorotrifluoroethylene unit; and an uncrosslinked fluororubber.

Description

Composition and molded article

The present invention relates to a composition and a molded article.

With the recent increase in environmental awareness, the development of laws to prevent fuel volatilization has progressed. Especially in the automobile industry, there is a significant tendency to suppress fuel volatilization, especially in the United States, and the need for materials with excellent fuel barrier properties is increasing. is there. Thermoplastic resins such as polyphenylene sulfide resins, ethylene vinyl alcohol resins, and liquid crystal polyester resins are used as materials with excellent fuel barrier properties. On the other hand, flexible rubber materials such as crosslinked rubber are generally used. The fuel barrier property is inferior, and when used for automobile parts such as a fuel hose, the volatilization and transpiration of fuel is large, and this improvement is required. Among cross-linked rubbers, cross-linked fluoro rubber has good fuel barrier properties, but it is significantly inferior to fuel barrier properties compared to the thermoplastic resins listed above, and it is flexible and has excellent fuel barrier properties. Is an urgent need.

Therefore, in Patent Document 1, as a thermoplastic polymer composition that is flexible, has high fuel barrier properties, and can be melt-molded, at least partly crosslinks with a fluororesin containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit. A thermoplastic polymer composition comprising the crosslinked fluororubber (B) thus formed has been proposed.

International Publication No. 2007/116876

When high-pressure fuel is transferred using a fuel pipe, the fuel pipe may vibrate vigorously and noise may be generated. To reduce noise, the fuel pipe must be flexible. preferable.

Therefore, the subject of this invention is providing the composition which can form molded articles, such as a fuel piping tube which has the high flexibility while having the outstanding fuel barrier property and low temperature impact resistance.

The present invention is a composition comprising a fluororesin containing a chlorotrifluoroethylene unit and an uncrosslinked fluororubber.

It is preferable that the composition of the present invention does not contain a crosslinking agent, a crosslinking aid and a crosslinking accelerator.

The composition of the present invention preferably further contains a conductive material.

The fluororesin is preferably at least one selected from the group consisting of polychlorotrifluoroethylene and chlorotrifluoroethylene copolymer.

The fluororesin preferably further contains a tetrafluoroethylene unit.

The present invention is also a molded article comprising a layer formed from the composition described above.

The molded article of the present invention preferably further comprises a polyamide resin layer or a rubber layer.

The molded article of the present invention is preferably a fuel piping tube or a hose.

Since the composition of this invention has the said structure, it can form molded articles, such as a fuel piping tube etc. which have the high flexibility at the same time it has the outstanding fuel barrier property and low temperature impact resistance.

Since the molded article of the present invention has the above-described configuration, it has excellent fuel barrier properties and low temperature impact resistance, and at the same time has high flexibility.

Hereinafter, the present invention will be specifically described.

The composition of the present invention is characterized by containing a fluororesin containing chlorotrifluoroethylene (CTFE) units and uncrosslinked fluororubber.

The mass ratio of the fluororesin to the uncrosslinked fluororubber (fluororesin / uncrosslinked fluororubber) is preferably 95/5 to 5/95, and more preferably 95/5 to 50/50. 95/5 to 60/40 is more preferable, and 90/10 to 70/30 is most preferable. If the amount of the uncrosslinked fluororubber is too large, the permeation of the fuel may not be sufficiently suppressed or the low-temperature impact resistance may be deteriorated. If the amount of the uncrosslinked fluororubber is too small, the flexibility of the molded product may be increased. May be inferior.

The fluororesin contains CTFE units. The fluororesin preferably has 1 to 100 mol% of CTFE units, more preferably 10 to 100 mol%, based on all monomer units.

The fluororesin is preferably a melt processable fluororesin. Melt processability means that the polymer can be melted and processed using conventional processing equipment such as extruders and injection molding machines. Therefore, the melt processable fluororesin usually has a melt flow rate of 0.01 to 500 g / 10 min.

The fluororesin preferably has a melt flow rate (MFR) of 1 to 500 g / 10 minutes. MFR is a method in accordance with ASTM D1238, using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a measurement temperature (for example, 297 ° C.) and a load (for example, 5 kg) determined by the type of fluororesin. It is the mass (g / 10 minutes) of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm.

The fluororesin preferably has a melting point of 100 to 323 ° C., more preferably 140 to 323 ° C. The melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

The fluororesin is preferably at least one selected from the group consisting of polychlorotrifluoroethylene [PCTFE] and CTFE copolymers, and selected from the group consisting of PCTFE and CTFE / tetrafluoroethylene (TFE) copolymers. More preferred is at least one selected from the group consisting of CTFE / TFE copolymers. That is, it is preferable that the said fluororesin contains a CTFE unit and also contains a TFE unit.

The CTFE copolymer includes CTFE units, TFE, hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), vinylidene fluoride (VdF), vinyl fluoride, hexafluoroisobutene, formula: CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10), ethylene, And a unit derived from at least one monomer selected from the group consisting of propylene, 1-butene, 2-butene, vinyl chloride, and vinylidene chloride.

The CTFE copolymer is at least selected from the group consisting of a copolymer comprising CTFE units and units derived from at least one monomer selected from the group consisting of TFE, HFP and PAVE. One type is more preferable.

The CTFE copolymer preferably has 10 to 90 mol% of CTFE units based on all monomer units.

As said CTFE copolymer, what contains the monomer ((alpha)) unit derived from a CTFE unit, a TFE unit, and the monomer ((alpha)) copolymerizable with these is especially preferable.

The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and ethylene (Et), vinylidene fluoride (VdF), CF ₂ = CF—ORf ¹ (formula Wherein Rf ¹ is a perfluoro (alkyl vinyl ether) (PAVE) represented by a C 1-8 perfluoroalkyl group, CX ³ X ⁴ = CX ⁵ (CF ₂ ) _n X ⁶ (wherein X ³ , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ⁶ is a hydrogen atom, a fluorine atom or a chlorine atom; n is an integer of 1 to 10), An alkyl perfluorovinyl ether derivative represented by CF ₂ ═CF—OCH ₂ —Rf ² (wherein Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) is exemplified. Preferably, it is at least one selected from the group consisting of AVE, the above vinyl monomer, and an alkyl perfluorovinyl ether derivative, more preferably at least one selected from the group consisting of PAVE and HFP. .

The PAVE is preferably perfluoro (alkyl vinyl ether) represented by CF ₂ ═CF—ORf ⁴ (wherein Rf ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). Fluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), etc., among them, the group consisting of PMVE, PEVE and PPVE More preferably, it is at least one selected from more.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ ═CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

In the CTFE copolymer, the ratio of CTFE units to TFE units is 85 to 10 mol% of TFE units relative to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol of CTFE units. %, And the TFE unit is 80 to 10 mol%. Further, those composed of 15 to 25 mol% of CTFE units and 85 to 75 mol% of TFE units are more preferable.

The CTFE copolymer preferably has a total of CTFE units and TFE units of 90 to 99.9 mol% and monomer (α) units of 0.1 to 10 mol%. If the monomer (α) unit is less than 0.1 mol%, the moldability, the environmental stress crack resistance and the fuel crack resistance tend to be inferior, and if it exceeds 10 mol%, the fuel barrier property, heat resistance, machine It tends to be inferior in properties.

The PAVE unit is preferably 0.5 mol% or more of the total monomer units, and preferably 5 mol% or less.

The content of each monomer unit in the fluororesin and copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The fluororesin is one in which at least one reactive functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a heterocyclic group, and an amino group is introduced into the main chain terminal and / or side chain of the polymer. There may be.

In the present specification, the “carbonyl group” is a carbon divalent group composed of a carbon-oxygen double bond, and is represented by —C (═O) —. The reactive functional group containing the carbonyl group is not particularly limited. For example, a carbonate group, a carboxylic acid halide group (halogenoformyl group), a formyl group, a carboxyl group, an ester bond (—C (═O) O—), an acid Anhydride bond (—C (═O) O—C (═O) —), isocyanate group, amide group, imide group (—C (═O) —NH—C (═O) —), urethane bond (— NH—C (═O) O—), carbamoyl group (NH ₂ —C (═O) —), carbamoyloxy group (NH ₂ —C (═O) O—), ureido group (NH ₂ —C (= O) —NH—), oxamoyl group (NH ₂ —C (═O) —C (═O) —), and the like include those containing a carbonyl group as a part of the chemical structure.

In the amide group, imide group, urethane bond, carbamoyl group, carbamoyloxy group, ureido group, oxamoyl group, etc., the hydrogen atom bonded to the nitrogen atom may be substituted with a hydrocarbon group such as an alkyl group, for example. .

From the point that the reactive functional group is easy to introduce, and the fluororesin has appropriate heat resistance and good adhesion at a relatively low temperature, an amide group, a carbamoyl group, a hydroxyl group, a carboxyl group, A carbonate group, a carboxylic acid halide group, and an acid anhydride bond are preferable, and an amide group, a carbamoyl group, a hydroxyl group, a carbonate group, a carboxylic acid halide group, and an acid anhydride bond are more preferable.

Among these, those having a carbonate group and / or a carboxylic acid halide group described in WO99 / 45044 are particularly preferable.

The fluororesin may be made of a polymer having a reactive functional group at either the main chain terminal or the side chain of the polymer, or has a reactive functional group at both the main chain terminal and the side chain. It may consist of a polymer. When having a reactive functional group at the end of the main chain, it may be present at both ends of the main chain or only at one of the ends. When the reactive functional group also has an ether bond, it may further have the reactive functional group in the main chain.

The fluororesin is preferably composed of a polymer having a reactive functional group at the end of the main chain because it does not significantly reduce mechanical properties and chemical resistance, or because it is advantageous in terms of productivity and cost.

The number of the reactive functional groups may be appropriately selected depending on the type and shape of the rubber layer to be laminated, the purpose and application of adhesion, the required adhesive force and the adhesion method between the adjacent layers, and the like.

The number of reactive functional groups at the main chain end and / or side chain end is preferably 3 to 800 per 1 × 10 ⁶ main chain carbon atoms. Adhesiveness may fall that it is less than 3 per 1 × 10 ⁶ main chain carbon atoms. A more preferred lower limit is 15, a further preferred lower limit is 30, and a particularly preferred lower limit is 120. The upper limit of the number of reactive functional groups at the terminal is more preferably, for example, 200 from the viewpoint of productivity.

The number of reactive functional groups at the terminal is a film sheet having a thickness of 0.25 to 0.30 mm obtained by compression molding the fluororesin powder at a molding temperature of 50 ° C. higher than its melting point and a molding pressure of 5 MPa. The infrared absorption spectrum is analyzed using an infrared spectrophotometer, and the type of characteristic absorption of the reactive functional group is determined by comparison with the infrared absorption spectrum of a known film. It is the number to do.

Number of terminal groups (per 1 × 10 ⁶ carbon atoms in the main chain) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows correction coefficients for the terminal reactive functional groups.

The correction coefficient in Table 1 is a value determined from the infrared absorption spectrum of the model compound in order to calculate the terminal group per 1 × 10 ⁶ main chain carbon atoms.

As a method for introducing the reactive functional group into the terminal of the main chain and / or side chain, a method of introducing the reactive functional group-containing monomer (β) by copolymerization, having a reactive functional group, or A method of using the resulting compound as a polymerization initiator, a method of using a reactive functional group or a generated compound as a chain transfer agent, a method of introducing a reactive functional group into a fluoropolymer by a polymer reaction, a method of using these methods in combination Etc. can be exemplified.

When the reactive functional group is introduced by copolymerization, the reactive functional group-containing monomer (β) is a monomer copolymerizable with the monomer that gives the fluororesin. If it has, it will not be restrict | limited in particular. Specifically, for example, the following can be exemplified.

Examples of the first monomer (β) include aliphatic unsaturated carboxylic acids described in International Publication No. 2005/100420. Unsaturated carboxylic acids have at least one polymerizable carbon-carbon unsaturated bond in one molecule and at least one carbonyloxy group (—C (═O) —O—) in one molecule. What has is preferable.

The aliphatic unsaturated carboxylic acid may be an aliphatic unsaturated monocarboxylic acid or an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups. Examples of the aliphatic unsaturated monocarboxylic acid include unsaturated aliphatic monocarboxylic acids having 3 to 6 carbon atoms such as (meth) acrylic acid and crotonic acid.

Examples of the aliphatic unsaturated polycarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid, maleic anhydride, itaconic anhydride or citraconic anhydride. 6 unsaturated aliphatic polycarboxylic acids.

The second monomer (β) has the formula:
CX ⁷ ₂ = CY ^1- (Rf ⁴ ) _n -Z ¹
(Wherein Z ¹ is the reactive functional group; X ⁷ and Y ¹ are the same or different and are a hydrogen atom or a fluorine atom; Rf ⁴ is an alkylene group having 1 to 40 carbon atoms; A fluorine-containing oxyalkylene group having 2 to 40 carbon atoms having an ether bond or a fluorine-containing oxyalkylene group having 2 to 40 carbon atoms having an ether bond; n is 0 or 1) Saturated compounds.

The content of the reactive functional group-containing monomer (β) unit introduced by copolymerization is preferably 0.05 mol% or more, and more preferably 0.1 mol% or more. If the amount is too large, gelation or vulcanization reaction is likely to occur during heating and melting, so the upper limit of the functional group-containing monomer is preferably 5 mol%, more preferably 3 mol%, and particularly preferably 2 mol%.

The fluororesin may have a heterocyclic group or an amino group at the main chain end or side chain end of the polymer.

The heterocyclic group is a group having a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring of the heterocyclic portion, and may be a saturated ring or an unsaturated ring. It may be a single ring or a condensed ring. Among the heterocyclic groups, an oxazolyl group is preferable.

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. As an amino group, the formula:
-NR ⁴ R ⁵
(Wherein R ⁴ and R ⁵ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). Specific examples of the amino group include —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , —NH (C ₆ H ₅ ).

The fluororesin can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. In the polymerization, each condition such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of the fluororesin.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP); Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Of these, di-n-propyl peroxydicarbonate (NPP) is preferable.

As the chain transfer agent, a water-soluble alcohol having 1 to 4 carbon atoms, a hydrocarbon having 1 to 4 carbon atoms, and a fluorination having 1 to 4 carbon atoms in that the dispersibility and uniformity are good in the reaction system. It is preferably at least one selected from the group consisting of hydrocarbons and persulfates. The chain transfer agent may be at least one selected from the group consisting of methane, ethane, n-butane, isobutane, methanol, n-propyl alcohol, HFC-134a, HFC-32, DSP, APS, and KPS. More preferred is at least one selected from the group consisting of n-propyl alcohol, methanol and isobutane.

The composition of the present invention may contain one of these fluororesins, or may contain two or more.

In the present invention, when the fluororesin has a specific reactive functional group at the end, adhesion to other layers is improved when a multilayer molded article is formed. Therefore, it is possible to provide a molded article (for example, a fuel tank) having excellent impact resistance and strength.

When the fluororesin is a perhalopolymer, chemical resistance and fuel barrier properties are more excellent. A perhalopolymer is a polymer in which halogen atoms are bonded to all the carbon atoms constituting the main chain of the polymer.
The fluororesin preferably has a fuel permeability coefficient of 2.0 g · mm / m ² / day or less.
When the fuel permeability coefficient is 2.0 g · mm / m ² / day or less, excellent low fuel permeability is exhibited. The fuel permeability coefficient is more preferably 1.5 g · mm / m ² / day or less, still more preferably 0.8 g · mm / m ² / day or less, and 0.55 g · mm / day. m ² / day or less is even more preferable, and 0.5 g · mm / m ² / day or less is particularly preferable.

The uncrosslinked fluororubber is a fluororubber that is not partially crosslinked and has no history of crosslinking. Usually, the uncrosslinked fluororubber obtained by polymerization is kneaded with a crosslinking agent, a crosslinking aid, a crosslinking accelerator, etc., and then crosslinked to be used as a crosslinked fluororubber. However, the composition of the present invention is characterized in that it contains an uncrosslinked fluororubber.

The uncrosslinked fluororubber is an amorphous fluoropolymer. “Amorphous” means a melting peak (ΔH) that appears in differential scanning calorimetry [DSC] (temperature rise temperature 10 ° C./min) or differential thermal analysis [DTA] (temperature rise rate 10 ° C./min) of a fluoropolymer. ) Is 4.5 J / g or less. The uncrosslinked fluororubber exhibits elastomeric properties when crosslinked. By elastomeric properties is meant a property that allows the polymer to be stretched and retain its original length when the force required to stretch the polymer is no longer applied.

The uncrosslinked fluororubber is preferably at least one selected from the group consisting of partially fluorinated rubber and perfluororubber, and more preferably partially fluorinated rubber.

Partially fluorinated rubbers include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber. , Ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine rubber Etc. Of these, at least one selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber is preferable, and vinylidene fluoride-based fluororubber is more preferable.

The vinylidene fluoride-based fluororubber is preferably a copolymer composed of 45 to 85 mol% of vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. . More preferably, the copolymer is composed of 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, Trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, general formula (6): CH ₂ = CFRf ⁶¹ (wherein Rf ⁶¹ is a straight chain having 1 to 12 carbon atoms) Or a branched fluoroalkyl group), a general formula (7): CH ₂ ═CH— (CF ₂ ) _n —X ² (wherein X ² is H or F, and n is 3 to Is an integer of 10.) and gives a crosslinking site. Monomers monomers, ethylene, propylene, and a non-fluorinated monomer such as an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE.

Examples of the fluoroalkyl vinyl ether include:
Formula (5): CF ₂ = CF-ORf ⁵
(Wherein Rf ⁵ represents a perfluoro organic group),
Formula (9): CF ₂ ═CF—OCH ₂ —Rf ⁹¹
(Wherein Rf ⁹¹ is a perfluoroalkyl group having 1 to 5 carbon atoms),
Formula (10): CF ₂ = CFOCF ₂ ORf ¹⁰¹
(Wherein Rf ¹⁰¹ is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. A linear or branched perfluorooxyalkyl group of
Formula _{_{(11): CF 2 = CFO}} (CF 2 CF (Y) O) m (CF 2) n F
(Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, n is an integer of 1 to 4), and
Formula (18): CF ₂ ═CF—O— (CF ₂ CFY ¹ —O) _n — (CFY ² ) _m —A ²
(In the formula, Y ¹ represents a fluorine atom, a chlorine atom or a perfluoroalkyl group. N represents an integer of 0 to 3. The n Y ^{1 s} may be the same or different. Y ² represents a fluorine atom or a chlorine atom, m represents an integer of 1 to 5. m Y ² may be the same or different, and A ² represents- Represents SO ₂ X. X represents a halogen atom, and is preferably at least one selected from the group consisting of fluoromonomers.

As the fluoromonomer represented by the general formula (5), among others,
Formula (8): CF ₂ = CF-ORf ⁸¹
(Wherein Rf ⁸¹ represents a perfluoroalkyl group having 1 to 10 carbon atoms). Rf ⁸¹ is more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

More preferably, the fluoroalkyl vinyl ether is at least one selected from the group consisting of fluoromonomers represented by the general formulas (8), (10) and (11).

Specific examples of vinylidene fluoride-based fluororubber are represented by VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VDF / general formula (6). Fluoromonomer rubber, VDF / fluoromonomer / TFE rubber represented by general formula (6), VDF / perfluoro (methyl vinyl ether) [PMVE] rubber, VDF / PMVE / TFE rubber, VDF / PMVE / Examples include TFE / HFP rubber. VDF / CH ₂ = CFCF ₃ rubber is preferable as the fluoromonomer rubber represented by VDF / general formula (6), and as the fluoromonomer / TFE rubber represented by VDF / general formula (6), VDF / TFE / CH ₂ = CFCF ₃ rubber is preferred.

The VDF / CH ₂ = CFCF ₃ rubber is preferably a copolymer comprising VDF 40 to 99.5 mol% and CH ₂ = CFCF ₃ 0.5 to 60 mol%, and VDF 50 to 85 mol%. And more preferably a copolymer consisting of 15 to 50 mol% of CH ₂ = CFCF ₃ , and a copolymer consisting of 50 to 85 mol% of VDF and 20 to 50 mol% of CH ₂ = CFCF _3. More preferably.

The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .

The fluoro rubber may be perfluoro rubber. Examples of the perfluoro rubber include perfluoro rubbers containing TFE, such as TFE / general formula (8), (10) or (11) fluoromonomer copolymer and TFE / general formula (8), (10 ) Or (11) is preferably at least one selected from the group consisting of a fluoromonomer / monomer copolymer that provides a crosslinking site.
In the case of a TFE / PMVE copolymer, the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
In the case of a monomer copolymer that provides a TFE / PMVE / cross-linking site, it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), and more preferably 55 to 77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
In the case of a fluoromonomer copolymer represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms, preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
In the case of TFE / monomer copolymer giving a fluoromonomer / crosslinking site represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms, preferably 50 to 89.9 / 10 To 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and still more preferably 65 to 84. 8/15 to 34.8 / 0.2 to 3.
When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.

Examples of the perfluoro rubber include TFE / fluoromonomer represented by the general formula (11) / fluoromonomer copolymer that gives a crosslinking site, TFE / perfluorovinyl ether copolymer represented by the general formula (11), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (8) and a fluoromonomer represented by TFE / the general formula (8) / a monomer copolymer giving a crosslinking site It is preferable that

Examples of the perfluoro rubber include perfluoro rubber described in International Publication No. 97/24381 pamphlet, Japanese Examined Patent Publication No. 61-57324, Japanese Examined Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. be able to.

The uncrosslinked fluororubber has a glass transition temperature of preferably −70 ° C. or higher, more preferably −60 ° C. or higher, and preferably −50 ° C. or higher in view of excellent compression set at high temperatures. Further preferred. Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −3 ° C. or lower.

The glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo, DSC822e) to obtain a DSC curve by raising the temperature of 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the midpoint of the two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.

The uncrosslinked fluororubber has a Mooney viscosity ML (1 + 20) at 170 ° C. of preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, in terms of good heat resistance. . Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

The uncrosslinked fluororubber has a Mooney viscosity ML (1 + 20) at 140 ° C. of preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, from the viewpoint of good heat resistance. . Moreover, it is preferable that it is 180 or less at a point with favorable workability, It is more preferable that it is 150 or less, It is still more preferable that it is 110 or less.

The uncrosslinked fluororubber has a Mooney viscosity ML (1 + 10) at 100 ° C. of preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more from the viewpoint of good heat resistance. . Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less.

The Mooney viscosity can be measured according to JIS K6300 at 170 ° C. or 140 ° C. and 100 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.

It is preferable that the composition of the present invention does not contain a crosslinking agent, a crosslinking aid and a crosslinking accelerator. It is also preferred that the composition of the present invention does not contain an acid acceptor. By not containing these components, the composition of the present invention can obtain a molded product without crosslinking the uncrosslinked fluororubber even when molded under the usual molding conditions required for fluororesin and fluororubber. It is possible to achieve the desired effects of the present invention by including the uncrosslinked fluororubber in the molded article.

The composition of the present invention may also contain a conductive material. By including the conductive material, conductivity can be imparted to the obtained molded product.

The conductive material is not particularly limited, and examples thereof include conductive simple powders such as metals and carbon or conductive simple fibers; powders of conductive compounds such as zinc oxide; surface conductive powders.

The conductive single powder or conductive single fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon fiber, and Japanese Patent Laid-Open No. 3-174018. Examples thereof include carbon fibrils.

The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide.

The method for the surface conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating.

Among the conductive materials, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation. As the conductive material, conductive carbon black, graphite, surface graphitized carbon black, carbon black grafted with an organic polymer, or the like can be used.

The composition of the present invention preferably contains 0.01 to 25% by mass of the conductive material, more preferably 1 to 20% by mass, and further preferably 5 to 16% by mass with respect to the composition. preferable.

The MFR of the composition of the present invention is preferably 0.5 to 50 g / 10 minutes, more preferably 1 to 35 g / 10 minutes. If the MFR is too small, the fluidity is small and the moldability may be reduced.

The composition of the present invention preferably has a volume resistivity of 1 × 10 ⁰ to 1 × 10 ⁹ Ω · cm. A more preferred lower limit is 1 × 10 ² Ω · cm, and a more preferred upper limit is 1 × 10 ⁸ Ω · cm.

The fuel permeability coefficient of the composition of the present invention is preferably 10 g · mm / m ² / day or less. The fuel permeability coefficient is more preferably 8 g · mm / m ² / day or less, further preferably 6 g · mm / m ² / day or less, and 5 g · mm / m ² / day or less. Is more preferably 3 g · mm / m ² / day or less, and most preferably 2 g · mm / m ² / day or less.
The above fuel permeability coefficient was obtained by preparing a 0.15 mm sheet-shaped test piece from the composition of the present invention and using a simulated fuel in a SUS container (open area 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. 18 mL of a certain CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is put, and the above-mentioned sheet-like test piece is set in an open part of the container and sealed, and is calculated from a weight change measured at 60 ° C. is there.

The composition of the present invention preferably does not break when subjected to an Izod impact test at −40 ° C. The Izod impact test is performed by measuring notched Izod impact strength according to ASTM D256 using a U-F impact tester manufactured by Ueshima Seisakusho. When the Izod impact test does not break, it means that the resin piece does not break into two or more pieces.

The composition of the present invention comprises a filler, a plasticizer, a processing aid, a release agent, a pigment, a flame retardant, a lubricant, a light stabilizer, a weathering stabilizer, an antistatic agent, an ultraviolet absorber, an antioxidant, and a foaming agent. , Fragrances, oils, softening agents, and the like may be included as long as the effects of the present invention are not affected.

In order to further reduce fuel permeability, smectite lamellar viscous minerals such as montmorillonite, beidellite, saponite, nontronite, hectorite, soconite, and stevensite, and microlamellar minerals with high aspect ratio such as mica are used. It may be added.

The composition of the present invention can be produced by kneading the fluororesin and the uncrosslinked fluororubber above the melting point of the fluororesin under the condition that the uncrosslinked fluororubber is not crosslinked. Examples of the conditions in which the uncrosslinked fluororubber is not crosslinked include conditions in which the crosslinking agent, the crosslinking aid, and the crosslinking accelerator are not present.

The composition of the present invention can be molded into a desired shape by a method such as a heat compression molding method, a transfer molding method, an extrusion molding method, an injection molding method, or a calender molding method to obtain a molded product. In the above method, a crosslinking step is not necessary. For molding, commonly used fluoropolymer molding machines, such as injection molding machines, blow molding machines, extrusion molding machines, and various coating devices, can be used to produce molded products of various shapes such as sheets and tubes. Is possible. Moreover, it can be set as multilayer molded articles, such as a multilayer tube, a multilayer hose, a multilayer tank, by molding methods, such as multilayer extrusion molding, multilayer blow molding, and multilayer injection molding.

The present invention is also a molded article comprising a layer formed from the composition described above. The molded article may be a single-layer molded article having only a layer formed from the above composition, or a layer formed from the above composition and other layers such as a rubber layer and a resin layer. It may be a multilayer molded product comprising

Examples of the rubber layer include a layer (fluorinated rubber layer) obtained by crosslinking the uncrosslinked fluororubber, a layer (nonfluorinated rubber layer) obtained by crosslinking uncrosslinked non-fluorinated rubber, and the like.

Examples of the non-fluorine rubber include acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), and isoprene rubber. (IR) diene rubber, ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, chlorinated polyethylene (CPE), polyblend of acrylonitrile-butadiene rubber and vinyl chloride ( PVC-NBR) and ethylene propylene diene rubber (EPDM).
As the termonomer of the ethylene-propylene-teromer copolymer rubber, a monomer constituting a diene rubber such as natural rubber, butadiene rubber (BR), isoprene rubber, butyl rubber, chloroprene rubber is preferable.

Examples of the resin layer include the fluororesin, polyamide resin, polyolefin resin, vinyl chloride resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyacetal resin, polycarbonate resin, acrylic resin. Strength such as resin, styrene resin, acrylonitrile / butadiene / styrene resin (ABS), cellulose resin, polyetheretherketone resin (PEEK), polysulfone resin, polyethersulfone resin (PES), polyetherimide resin Resins made of ethylene / vinyl alcohol copolymer, polyphenylene sulfide resin, polybutylene naphthalate resin, polybutylene terephthalate resin, polyphthalate De (PPA), such as fuel or gas permeability is low resin include a resin layer containing (hereinafter, also referred to the low permeability resin). Of these, a polyamide-based resin layer is preferable from the viewpoint of good moldability and adhesiveness. When subjected to vulcanization as a molded article, it is desirable that the melting point of the resin is higher than the temperature of the heat treatment.

The molded article may include a plurality of layers formed from the above-described composition, or may include a plurality of other layers. The molded article preferably includes a polyamide resin layer or a rubber layer.

When the molded article is used for an application that comes into contact with fuel such as a fuel piping tube, it is preferable that the layer formed from the above-described composition is provided so as to come into contact with the fuel. For example, when the shape of the molded product of the present invention is a tube shape, it is preferable that the layer formed from the above composition forms the innermost layer. By adopting such a configuration, it is possible to effectively suppress the permeation of fuel from the molded product and the charging of static electricity generated by the friction between the molded product and the fuel.

The molded article may also include a metal layer, an adhesive layer, or a surface treatment for each layer. What is necessary is just to select suitably the thickness, shape, etc. of each layer according to a use purpose, a use form, etc.

When the molded article is a multilayer molded article, the molded article may have a two-layer structure of a layer formed from the composition of the present invention and a rubber layer, or a layer formed from the composition of the present invention and a resin layer. It may be a two-layer structure. The molded article may have a three-layer structure in which a layer formed from the composition of the present invention, a resin layer and / or a rubber layer are laminated. For example, a layer formed from the composition of the present invention-rubber layer-rubber layer, a layer formed from the composition of the present invention-resin layer-rubber layer or resin layer, resin layer-formed from the composition of the present invention. A three-layer structure such as a layer-resin layer may be used.
Further, it may be a multilayer structure of three or more layers in which polymer layers other than the layer, rubber layer, and resin layer formed from the composition of the present invention are bonded.

The polymer layer includes a layer formed from the composition of the present invention—a polyamide resin layer, a layer formed from the composition of the present invention—a fluororesin layer—a polyamide resin layer, and the composition of the present invention. Layer—polyamide resin layer—ethylene / vinyl alcohol copolymer layer—polyamide resin layer—polyamide resin layer, polyamide resin layer—layer formed from the composition of the present invention—polyamide resin layer, polyamide system Resin layer-layer formed from the composition of the present invention-polyamide-based resin layer, layer formed from the composition of the present invention-epichlorohydrin rubber layer, layer formed from the composition of the present invention-chlorinated polyethylene layer, Layer formed from the composition of the present invention-acrylonitrile-blend layer of butadiene rubber and acrylic rubber, layer formed from the composition of the present invention-acrylonite Blend layer of ru-butadiene rubber and ethylene propylene rubber, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber and acrylonitrile-blend layer of butadiene rubber and polyvinyl chloride, layer formed from the composition of the present invention -Acrylonitrile-butadiene rubber layer-chloroprene rubber layer, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-epichlorohydrin rubber layer, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-isoprene Rubber layer, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-acrylonitrile-blend layer of butadiene rubber and polyvinyl chloride, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-chlorine Polyethylene Layer, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-acrylonitrile-blend layer of butadiene rubber and ethylene propylene rubber, layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-acrylonitrile -Blend layer of butadiene rubber and acrylic rubber, acrylonitrile-butadiene rubber layer-Layer formed from the composition of the present invention-Epichlorohydrin rubber layer, acrylonitrile-Blend layer of butadiene rubber and polyvinyl chloride-From the composition of the present invention Layer formed-epichlorohydrin rubber layer, acrylonitrile-butadiene rubber layer-layer formed from the composition of the present invention-acrylonitrile-blended layer of butadiene rubber and polyvinyl chloride, acrylonitrile-butadiene rubber layer-composition of the present invention A layer formed from a product-a chlorinated polyethylene layer, an acrylonitrile-butadiene rubber layer-a layer formed from the composition of the present invention-an acrylonitrile-a blend layer of butadiene rubber and an acrylic rubber, an acrylonitrile-butadiene rubber layer- Layer formed from the composition-acrylonitrile-butadiene rubber layer-acrylonitrile-butadiene rubber and polyvinyl chloride blend layer, acrylonitrile-butadiene rubber layer-layer formed from the composition of the present invention-acrylonitrile-butadiene rubber layer-chlorine Polyethylene layer, acrylonitrile-butadiene rubber layer-layer formed from the composition of the invention-epichlorohydrin rubber layer-acrylonitrile-blend layer of butadiene rubber and polyvinyl chloride, acrylonitrile-butadiene rubber layer-invention set Layer formed from a product-epichlorohydrin rubber layer-chlorinated polyethylene layer, fluorine rubber layer-epichlorohydrin rubber layer-layer formed from the composition of the present invention-epichlorohydrin rubber layer, fluorine rubber layer-acrylonitrile-butadiene rubber layer-this Layers formed from the composition of the invention-acrylonitrile-butadiene rubber layer, fluororubber layer-layers formed from the composition of the invention-epichlorohydrin rubber layer, fluororubber layer-layers formed from the composition of the invention- Examples include acrylonitrile-butadiene rubber layer-chlorinated polyethylene layer.

Next, the layer structure of the molded product of the present invention will be described in more detail.
(1) Layer formed from the composition of the present invention-rubber layer two-layer structure (2) Layer formed from the composition of the present invention-two-layer structure of resin layer

(3) Three-layer structure of layer-rubber layer-rubber layer formed from the composition of the present invention Three-layer structure of layer-fluorine rubber layer-non-fluorine rubber layer formed from the composition of the present invention, and the present invention A three-layer structure of a layer formed from the composition of the invention—a non-fluororubber layer—a fluororubber layer.
(4) Three-layer structure of layer-resin layer-rubber layer or resin layer formed from the composition of the present invention Three-layer structure of layer-fluorine resin layer-rubber layer formed from the composition of the present invention, the present invention A three-layer structure of a layer formed from a composition of the present invention—a fluororesin layer—a non-fluororesin layer, a three-layer structure of a layer formed from the composition of the present invention—a non-fluororesin layer—a fluororesin layer, A layer formed from a product—a non-fluororesin layer—a rubber layer, a three-layer structure, a layer formed from the composition of the present invention—a non-fluororesin layer—a three-layer structure of a fluororesin layer, formed from the composition of the present invention There is a three-layer structure of layer to be formed-non-fluorine resin layer-non-fluorine resin layer.

(5) Resin layer-layer formed from the composition of the present invention-three-layer fluororesin layer of resin layer-layer formed from the composition of the present invention-three-layer structure of fluororesin layer, fluororesin layer- A layer formed from the composition of the present invention—a non-fluorine resin layer can be mentioned. The inner and outer resin layers may be of the same type or different types.

(6) Three-layer structure of resin layer-layer formed from the composition of the present invention-polymer layer

(7) Four-layer structure or more In addition to the three-layer structure of (3) to (6), an optional fluororubber layer, non-fluororubber layer, fluororesin layer or non-fluororesin layer is laminated depending on the purpose. Also good. Further, a layer such as a metal foil may be provided, or an adhesive layer may be interposed.

Furthermore, it can be laminated with a polymer layer to form a lining body.

In addition, what is necessary is just to select the thickness of each layer, a shape, etc. suitably according to a use purpose, a use form, etc.
In addition, for the purpose of improving pressure resistance, a reinforcing layer such as a reinforcing yarn may be provided as appropriate.

The molded product of the present invention is excellent in low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, weather resistance, ozone resistance, and under severe conditions Can be used for various purposes.

In addition to excellent fuel barrier properties, the molded products have excellent heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and can withstand use under severe conditions. It can be used for various purposes.

For example, automotive engine engines, main motion systems, valve systems, lubrication / cooling systems, fuel systems, intake / exhaust systems, drive system transmission systems, chassis steering systems, brake systems, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact and contact type packings (self-sealing) such as basic electrical parts, control system electrical parts, and equipped electrical parts (Packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.), etc., and suitable characteristics as bellows, diaphragm, hose, tube, electric wire, etc.

Specifically, it can be used for the applications listed below.

Engine body cylinder head gasket, cylinder head cover gasket, oil pan packing, gaskets such as general gaskets, seals such as O-rings, packing, timing belt cover gaskets, hoses such as control hoses, anti-vibration rubber for engine mounts, hydrogen Sealing material for high pressure valves in storage systems.

Shaft seals such as crankshaft seals and camshaft seals for main motion systems.

Valve stem seals for engine valves, etc.

Engine oil cooler hose, oil return hose, seal gasket, etc. for lubrication / cooling engine oil cooler, water hose around radiator, vacuum pump oil hose for vacuum pump, etc.

Fuel system, fuel pump oil seal, diaphragm, valve, etc. Filler (neck) hose, fuel supply hose, fuel return hose, fuel hose such as vapor (evaporation) hose, fuel tank in-tank hose, filler seal, tank For carburetors such as packing, in-tank fuel pump mount, fuel pipe tube body and connector O-ring, fuel injector injector cushion ring, injector seal ring, injector O-ring, pressure regulator diaphragm, check valve, etc. Needle valve petals, acceleration pump pistons, flange gaskets, control hoses, etc., composite air control (CAC) valve seats, diaphragms, etc.

Inlet / exhaust manifold manifold manifold packing, exhaust manifold packing, EGR diaphragm, control hose, emission control hose, BPT diaphragm, AB valve afterburn prevention valve seat, etc. Throttle body packing, turbocharger turbo oil hose (supply), turbo oil hose (return), turbo air hose, intercooler hose, turbine shaft seal etc.

Transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, etc. AT transmission oil hoses, ATF hoses, O-rings, packings, etc.

Steering power steering oil hose, etc.

Brake oil seal, O-ring, packing, brake oil hose, etc. Master back atmospheric valve, vacuum valve, diaphragm, etc. Master cylinder piston cup (rubber cup), caliper seal, boots, etc.

Tubes for harness exterior parts such as electric wire (harness) insulators and sheaths for basic electrical components.

Coating materials for various sensor wires for control system electrical components.

Car air conditioner O-ring, packing, cooler hose, exterior wiper blade, etc.

In addition to automobiles, for example, oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemicals, etc. Similar packings in plants, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings, similar packings in food plant equipment and food equipment (including household products), O- Rings, hoses, seals, belts, diaphragms, valves, rolls, tubes, similar packings in nuclear power plant equipment, O-rings, hoses, seals, diaphragms, valves, tubes, similar packings in general industrial parts, O-ring, hose, sealing material, diaphragm Is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine. For example, the backup rubber material of the PTFE diaphragm has a problem that it is worn out or torn during use because of its poor sliding property. However, this problem can be improved by using the molded product of the present invention. Can be used for

In addition, in food rubber seal material applications, there is a problem that flavoring properties or rubber fragments are mixed into food in conventional rubber seal materials, but this problem can be improved by using the molded product of the present invention, and preferably Can be used. Rubber seal materials for pipes that use solvents for pharmaceutical and chemical applications have a problem that the rubber materials swell in the solvent. By using the molded article of the present invention, the rubber material can be improved. In the general industrial field, for the purpose of improving the strength, slipperiness, chemical resistance and permeability of rubber materials, it can be suitably used for rubber rolls, O-rings, packings, sealing materials and the like. In particular, it can be preferably used for packing of lithium ion batteries because both chemical resistance and sealing can be maintained at the same time. In addition, it can be suitably used in applications where slidability with low friction is required.

In addition, medical applications include medicine plugs, bottle cap seals, can seals, medicinal tapes, medicinal pads, syringe syringe packings, transdermal drug substrates, suckers for baby bottles, medical bags, catheters, infusions, etc. Set, mixed injection tube, cap liner, vacuum blood collection tube cap, syringe gasket, infusion tube, medical device gasket cap, syringe tip, grommet, blood collection cap, cap seal, backing, O-ring, sheath introducer, Dilator, guiding sheath, blood circuit, cardiopulmonary circuit, rotablator tube, indwelling needle, infusion set, infusion tube, closed infusion system, infusion bag, blood bag, blood component separation bag, blood component separation Tube for tube, artificial blood vessel, arterial cannula Stent, Endoscope treatment tube, Endoscope scope tube, Endoscope top over tube, Throat passage guide tube, Coronary artery bypass tube, Ileus tube, Percutaneous transhepatic biliary drainage tube, Electric Examples include a female outer tube, an ultrasonic female outer tube, a peeling forceps outer tube, and a cell culture bag.

In addition, examples of offshore molded products to which the molded product of the present invention can be applied include subsea oil field tubes or hoses (including injection tubes and crude oil transfer tubes).

Among these, the molded article of the present invention is preferably used for a fuel piping tube or a hose in terms of heat resistance and fuel barrier properties.

The fuel piping tube or hose made of the molded article of the present invention can be produced by an ordinary method and is not particularly limited. The fuel pipe tube includes a corrugated tube.

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

Example 1
A twin-screw extruder (apparatus name: PCM46 / 2) was prepared so that the fluororesin (1) and fluororubber (VdF / HFP (molar ratio) = 78/22) described in Table 2 were in the amounts described in Table 3. -35, caliber 46 mm, L / D35, manufactured by Ikekai Co., Ltd.), and carbon black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) in the amount shown in Table 3 is fed into the extruder through an intermediate feed. Pellets were produced by melt-kneading under conditions of a temperature of 280 ° C. and a screw rotation speed of 90 rpm.

Examples 2 to 3 and Comparative Examples 1 to 4
In the same manner as in Example 1, pellets having the composition shown in Table 3 were produced.

Example 4
The pellets of Example 1, NBR, were continuously extruded using an extruder. The pellet of Example 1 was used as the inner layer material, and NBR was used as the outer layer material. The obtained molded product was steam vulcanized using a vulcanizing can to obtain a fuel hose having the above two-layer structure.
The molding conditions and steam vulcanization conditions during extrusion molding are as follows.
1) Outer layer (NBR) extruder setting screw temperature control: 60 ° C
Cylinder 1: 70 ° C
Cylinder 2: 70 ° C
Head: 80 ° C
Molded product thickness: 3mm

2) Inner layer (pellet of Example 1) extruder setting cylinder 1: 260 ° C
Cylinder 2: 265 ° C
Cylinder 3: 270 ° C
Shell clamp: 270 ° C
Neck: 270 ° C
Die: 270 ° C
Head: 270 ° C
Molded product thickness: 0.3 mm

3) Steam vulcanization conditions for molded products 160 ° C x 45 minutes

Each numerical value of an Example and a comparative example was measured with the following method.

Melt flow rate (MFR)
Using a melt indexer (manufactured by Toyo Seiki Seisakusyo), 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 5 kg load at 297 ° C. is measured.

Tensile rupture strength, tensile rupture elongation, tensile modulus of elasticity The pellets obtained in the examples and comparative examples were set in a mold and held at 270 to 300 ° C. for 15 to 30 minutes with a heat press machine to melt the pellets. Then, a 3 MPa load was applied for 1 minute and compression molded to produce a sheet-like test piece having a thickness of 2 mm. The sheet-like test piece was punched out to obtain a dumbbell-like test piece having a distance between marked lines of 3.18 mm using an ASTM D638 Type V dumbbell. Using the obtained dumbbell-shaped test piece, using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation), the tensile elongation at break and tension at 25 ° C. under conditions of 50 mm / min according to ASTM D638. The breaking strength and tensile modulus were measured.

The pellets obtained in the volume resistivity examples and comparative examples were set in a mold, held at 270 to 300 ° C. for 15 to 30 minutes by a heat press machine, and the pellets were melted, and then a load of 3 MPa was applied. Compression molding was applied for a minute to produce a 0.5 mm sheet-shaped test piece. About the obtained sheet-like test piece, it measured by DC300V in 90 degreeC and dry air atmosphere with the digital super insulation meter / microammeter.

Fuel Permeability Coefficients The pellets obtained in Examples and Comparative Examples were set in a mold, held at 270 to 300 ° C. for 15 to 30 minutes by a heat press machine, the pellets were melted, and then a load of 3 MPa was applied. Compression molding was applied for 1 minute to produce a 0.15 mm sheet-shaped test piece. 18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ), and the sheet-shaped test piece is placed in the container. A test specimen was prepared by sealing it in an open part. 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.

The pellets obtained in the Izod impact test examples and comparative examples were set in a mold, held at 270 to 300 ° C. for 15 to 30 minutes by a heat press machine, the pellets were melted, and then a load of 3 MPa was applied. Compression molding was applied for a minute to produce a 0.5 mm sheet-shaped test piece. Using a U-F impact tester manufactured by Ueshima Seisakusho, the Izod impact strength with a notch at −40 ° C. is measured according to ASTM D256. When the Izod impact test does not break, it means that the test piece does not break into two or more pieces.

Claims

A composition comprising a fluororesin containing a chlorotrifluoroethylene unit and an uncrosslinked fluororubber.
The composition according to claim 1, which does not contain a crosslinking agent, a crosslinking assistant and a crosslinking accelerator.
Furthermore, the composition of Claim 1 or 2 containing an electroconductive material.
The composition according to claim 1, 2 or 3, wherein the fluororesin is at least one selected from the group consisting of polychlorotrifluoroethylene and chlorotrifluoroethylene copolymer.
The composition according to claim 1, 2, 3 or 4, wherein the fluororesin further comprises a tetrafluoroethylene unit.
A molded article comprising a layer formed from the composition according to claim 1, 2, 3, 4 or 5.
Furthermore, the molded article of Claim 6 provided with a polyamide-type resin layer or a rubber layer.
The molded article according to claim 6 or 7, which is a fuel piping tube or a hose.