JP5120251B2 - Thermoplastic polymer composition and molded article comprising the composition - Google Patents

Description

  The present invention relates to a thermoplastic polymer composition comprising a specific fluororesin and a specific cross-linked fluororubber. The present invention also relates to a molded article, a fuel tube and a fuel hose made of the thermoplastic polymer composition.

  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 the fuel is large, and this improvement is demanded. 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.

  Under the above circumstances, “Dyneon THV” has been developed as a resin that is flexible, has a fuel barrier property, and is melt-moldable and recyclable (for example, Modern Fluoropolymers: high performance polymers for diverse applications, John Wiley & Sons, Chichster, (1997) Chapter 13, JP 2000-274562 A and JP 2002-276862 A). However, as a characteristic of the resins described in these documents, there is a problem that if the fuel barrier property is increased, the hardness and elastic modulus are increased, and if the hardness and elastic modulus are decreased, the fuel barrier property is remarkably deteriorated. There is a point, and the compatibility between the flexibility and the fuel barrier property is insufficient.

  An object of the present invention is to provide a thermoplastic polymer composition which has excellent heat resistance, chemical resistance and oil resistance, is flexible, has a high fuel barrier property, and can be melt-molded. Moreover, the objective of this invention is providing the molded article, fuel tube, and fuel hose which consist of this thermoplastic polymer composition.

  That is, the present invention relates to a thermoplastic polymer composition comprising a fluororesin (A) containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit and a crosslinked fluororubber (B) which is at least partially crosslinked.

The cross-linked fluororubber (B) is preferably a product obtained by dynamically cross-linking the fluororubber composition (b) in the presence of the fluororesin (A) under the melting conditions of the fluororesin (A). The resin (A) is preferably a fluororesin that further contains a monomer (a) unit copolymerizable with chlorotrifluoroethylene and tetrafluoroethylene.

Monomer (a) is ethylene, vinylidene fluoride, perfluoro (alkyl vinyl ether) and general formula (1):
CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (1)
(In the formula, X ^{1 to} X ³ are the same or different and are each a hydrogen atom, a fluorine atom or —CF ₃ ; X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom; Is an integer)
It is preferable that it is one or more monomers chosen from the group which consists of vinyl monomers shown by these.

  The present invention also relates to a molded article, a fuel tube and a fuel hose formed from the thermoplastic polymer composition.

  The present invention comprises a fluororesin (A) containing a chlorotrifluoroethylene (hereinafter referred to as CTFE) unit and a tetrafluoroethylene (hereinafter referred to as TFE) unit and a crosslinked fluororubber (B) which is at least partially crosslinked. The present invention relates to a thermoplastic polymer composition.

  The fluororesin (A) is not particularly limited as long as it contains CTFE units and TFE units.

  It is preferable to contain 2-98 mol% of CTFE units in a fluororesin (A), and it is more preferable to contain 10-90 mol%. If it is less than 2 mol%, the chemical liquid permeability tends to deteriorate and the melt processing tends to be difficult. If it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

  It is preferable to contain 2-98 mol% of TFE units in a fluororesin (A), and it is more preferable to contain 10-90 mol%. If it is less than 2 mol%, the heat resistance and chemical resistance at the time of molding may be deteriorated. If it exceeds 98 mol%, the chemical liquid permeability tends to be deteriorated, and melt processing tends to be difficult.

  Further, from the viewpoint of stress crack resistance, chemical resistance, and heat resistance, a fluororesin that further contains a monomer (a) unit copolymerizable with CTFE and TFE is preferable.

The monomer (a) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, but ethylene, vinylidene fluoride (hereinafter referred to as VdF), perfluoro (alkyl vinyl ether) (hereinafter, PAVE), general formula (1):
CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (1)
(In the formula, X ^{1 to} X ³ are the same or different and are each a hydrogen atom, a fluorine atom or —CF ₃ ; X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom; Is an integer)
A vinyl monomer represented by the general formula (2):
_{CF 2 = CF-OCH 2 -R} f 1 (2)
(Wherein R _f ¹ is a C 1-5 perfluoroalkyl group)
Among them, one or more monomers selected from the group consisting of ethylene, VdF, PAVE and vinyl monomers represented by the general formula (1) can be used. It is preferable that it is PAVE, and it is more preferable that it is PAVE.

  Examples of PAVE in this case include perfluoro (methyl vinyl ether) (hereinafter referred to as PMVE), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), etc. Among these, PMVE, perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether) are preferable.

The vinyl monomer represented by the general formula (1) is not particularly limited, and examples thereof include hexafluoropropylene (hereinafter referred to as HFP), perfluoro (1,1,2-trihydro-1-hexene), and perfluoroethylene. Fluoro (1,1,5-trihydro-1-pentene), general formula (3):
CH ₂ = CX ³ R _f ² (3)
(Wherein X ³ is the same as above, and R _f ² is a C 1-10 perfluoroalkyl group)
Perfluoroalkylethylene represented by the formula:

  As the perfluoroalkylethylene represented by the general formula (3), perfluorobutylethylene is preferable.

As the alkyl perfluorovinyl ether represented by the general formula (2), those in which R _f ¹ 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. .

  Among these, as the fluororesin (A), the thermoplastic polymer composition obtained is excellent in fuel permeability and flexibility and easy to process, so that it contains CTFE units and TFE units. It is preferably a ternary fluororesin, or a ternary fluororesin containing CTFE units, TFE units and PAVE units, and a ternary fluororesin or CTFE unit containing CTFE units, TFE units and perfluoro (methyl vinyl ether) units, TFE. It is more preferably a ternary fluororesin containing units and perfluoro (propyl vinyl ether) units.

  In the case of a binary fluororesin, the composition ratio (molar ratio) is preferably CTFE / TFE = 2/98 to 98/2, more preferably 5/95 to 90/10. More preferably, it is / 90-80 / 20. If the CTFE unit is less than 2 mol%, the chemical permeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

  In the case of a ternary fluororesin, the monomer (a) unit is 0.1 to 10 mol%, and the CTFE unit and the TFE unit are 90 to 99.9 mol% in total. If the monomer (a) is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance are likely to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance and mechanical properties. It tends to be inferior in productivity. Further, the CTFE unit is preferably 10 to 90 mol% of the total of the CTFE unit and the TFE unit. If the CTFE unit in the total of the CTFE unit and the TFE unit is less than 10 mol%, the chemical solution low permeability may be insufficient, and if it exceeds 90 mol%, the polymerization rate is drastically decreased and the productivity is lowered. In addition to lowering, chemical resistance may be reduced or heat resistance may be insufficient. A more preferred lower limit is 15 mol%, a still more preferred lower limit is 20 mol%, a more preferred upper limit is 80 mol%, and a still more preferred upper limit is 70 mol%.

  Although it does not specifically limit as a manufacturing method of a fluororesin (A), The method as described in Unexamined-Japanese-Patent No. 2005-298702, international publication 2005/100420 pamphlet, etc. can be mention | raise | lifted.

  Moreover, the thermoplastic polymer composition of the present invention may contain a resin other than the fluororesin (A).

  Moreover, it is preferable that it is 130-330 degreeC, as for melting | fusing point of a fluororesin (A), it is more preferable that it is 140-320 degreeC, and it is further more preferable that it is 150-310 degreeC. When the melting point of the fluororesin (A) is less than 130 ° C., the heat resistance of the resulting thermoplastic polymer composition tends to decrease. When the melting point exceeds 330 ° C., fluorine exists in the presence of the fluororesin (A). When the fluororubber is dynamically cross-linked under the melting condition of the resin (A), it is necessary to set the melting temperature to be higher than the melting point of the fluororesin (A). There is.

  The crosslinked fluororubber (B) used in the present invention is not particularly limited as long as at least a part of at least one fluororubber composition (b) is crosslinked.

  Examples of the fluororubber include perfluorofluororubber (b1), non-perfluorofluororubber (b2), and fluorine-containing thermoplastic elastomer (b3).

  Examples of the perfluorofluororubber (b1) include a TFE / PAVE copolymer and a TFE / hexafluoropropylene (hereinafter referred to as HFP) / PAVE copolymer.

  Examples of the non-perfluorofluororubber (b2) include VdF polymers and TFE / propylene copolymers, and these may be used alone or in any combination as long as the effects of the present invention are not impaired. Can be used.

  Moreover, what was illustrated as said perfluoro fluororubber or non-perfluoro fluororubber is the structure of a main monomer, and what copolymerized the monomer for crosslinking, a modified monomer, etc. can be used suitably. As the crosslinking monomer or the modifying monomer, a known crosslinking monomer such as an iodine atom, bromine atom, or one containing a double bond, a transfer agent, a modified monomer such as a known ethylenically unsaturated compound, or the like can be used. .

  Specific examples of the VdF polymer include a VdF / HFP copolymer, a VdF / TFE / HFP copolymer, a VdF / TFE / propylene copolymer, and a VdF / ethylene / HFP copolymer. VdF / TFE / PAVE copolymer, VdF / PAVE copolymer, VdF / CTFE copolymer, and the like. More specifically, it is preferably a fluorine-containing copolymer composed of 25 to 85 mol% of VdF and 75 to 15 mol% of at least one other monomer copolymerizable with VdF, more preferably , A fluorine-containing copolymer comprising 50 to 80 mol% of VdF and 50 to 20 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, pentafluoropropylene, trifluorobutene, tetra Examples thereof include fluorine-containing monomers such as fluoroisobutene, PAVE and vinyl fluoride, and non-fluorine monomers such as ethylene, propylene and alkyl vinyl ether. These can be used alone or in any combination.

  Among the fluororubbers, from the viewpoint of heat resistance, compression set, workability, and cost, fluororubbers containing VdF units are preferable, and fluororubbers having VdF units and HFP units are more preferable.

  From the viewpoint of good compression set, it is preferably at least one rubber selected from the group consisting of VdF / HFP fluororubber, VdF / TFE / HFP fluororubber, and TFE / propylene fluororubber, From the viewpoint of low fuel permeability, VdF / TFE / HFP fluororubber is more preferable.

  The fluororubber used in the present invention can be produced by a usual emulsion polymerization method. What is necessary is just to determine suitably polymerization conditions, such as temperature at the time of superposition | polymerization, time, etc. with the kind of monomer, and the target elastomer.

  Although it does not specifically limit as a fluorine-containing thermoplastic elastomer (b3), From the point which is excellent in compatibility with a fluororesin, at least 1 sort (s) of elastomeric polymer segment (p-1) and at least 1 sort (s) are included. It is preferably composed of a non-elastomeric polymer segment (p-2), and at least one of the elastomeric polymer segment (p-1) and the non-elastomeric polymer segment (p-2) is a fluorine-containing polymer segment. .

The elastomeric polymer segment (p-1) imparts flexibility to the polymer, and the glass transition point is preferably 25 ° C or lower, more preferably 0 ° C or lower. Examples of the structural unit include TFE, CTFE, HFP, and general formula (4):
_{CF 2 = CFO (CF 2 CFX} 1 O) p - (CF 2 CF 2 CF 2 O) q -R f 4 (4)
(In the formula, X ¹ is a fluorine atom or —CF ₃ ; R _f ⁴ is a C 1-5 perfluoroalkyl group; p is an integer of 0-5; q is an integer of 0-5. )
Perhaloolefins such as perfluorovinyl ether represented by: Fluorine-containing monomers such as VdF, trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride; Non-fluorine monomers such as ethylene, propylene, and alkyl vinyl ethers; and any monomer that provides a crosslinking site.

As a monomer which gives a crosslinking site, for example, general formula (5):
CX ⁵ ₂ = CX ⁵ -R _f ⁵ CHR ¹ X ⁶ (5)
Wherein X ⁵ is the same or different and is a hydrogen atom, a fluorine atom or —CH ₃ ; R _f ⁵ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group; R ¹ is a hydrogen atom or —CH ₃ ; X ⁶ is an iodine atom or a bromine atom), an iodine or bromine-containing monomer represented by the general formula (6):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 7 (6)
(Wherein, m is an integer of 0 to 5; n is an integer of 1 to 3; X ⁷ is a cyano group, a carboxyl group, an alkoxycarbonyl group, or a bromine atom) These monomers can be used, and these can be used alone or in any combination.

Next, as structural units of the non-elastomeric polymer segment (p-2), TFE, CTFE, PAVE, HFP, general formula (7):
CF ₂ = CF (CF ₂ ) _r X ⁸ (7)
(Wherein r is an integer of 1 to 10; X ⁸ is a fluorine atom or a chlorine atom), perhaloolefins such as perfluoro-2-butene; VdF, vinyl fluoride, tri Fluoroethylene, general formula (8):
^{_{CH 2 = CX 9 - (CF}} 2) s -X 9 (8)
(Wherein X ⁹ is a hydrogen atom or a fluorine atom; s is an integer of 1 to 10), a partially fluorinated olefin such as CH ₂ ═C (CF ₃ ) ₂ ; ethylene, propylene, chloride Examples thereof include non-fluorine monomers such as vinyl, vinyl ether, carboxylic acid vinyl ester, and acrylic acid.

  Among these, the elastomeric polymer segment (p-1) is a TFE / VdF / HFP copolymer, and the non-elastomeric polymer segment (p-2) is a TFE / ethylene copolymer. A certain fluorine-containing thermoplastic elastomer is preferable, the elastomeric polymer segment (p-1) is TFE / VdF / HFP = 0 to 35/40 to 90/5 to 50 mol%, and the non-elastomeric polymer segment (p -2) is more preferably a fluorine-containing thermoplastic elastomer having TFE / ethylene = 20-80 / 80-20 mol%.

  The fluorine-containing thermoplastic elastomer is a fluorine-containing multi-segmented polymer in which an elastomeric polymer segment (p-1) and a non-elastomeric polymer segment (p-2) are bonded in the form of a block or graft in one molecule. Preferably, the fluorine-containing thermoplastic elastomer comprises one elastomeric polymer segment (p-1) and two non-elastomeric polymer segments (p-2), and at least one of them is a fluorine-containing polymer segment. It preferably consists of a certain triblock polymer.

  As a method for producing a fluorine-containing thermoplastic elastomer, an elastomeric polymer segment (p-1) and a non-elastomeric polymer segment (p-2) are connected in the form of a block or graft to form a fluorine-containing multi-segmented polymer. Various known methods can be employed. Among them, the method for producing a block type fluorine-containing multi-segmented polymer disclosed in Japanese Patent Publication No. 58-4728 and the like, and Japanese Patent Application Laid-Open No. 62-34324 have been disclosed. A production method of a graft type fluorine-containing multi-segmented polymer can be preferably employed.

  In particular, since the segmentation rate (blocking rate) is high and a homogeneous and regular segmented polymer can be obtained, Japanese Patent Publication No. 58-4728, collection of polymer articles (Vol. 49, No. 10, 1992). A block-type fluorine-containing multi-segmented polymer synthesized by the so-called iodine transfer polymerization method described above is preferred.

  As a preferable production method of the fluorine-containing thermoplastic elastomer, a known iodine transfer polymerization method can be given as a production method of the fluororubber. For example, the perhaloolefin and, if necessary, a monomer that provides a curing site are stirred under pressure in an aqueous medium in the presence of an iodine compound, preferably a diiodine compound, substantially in the absence of oxygen. However, there is a method in which emulsion polymerization is carried out in the presence of a radical initiator.

  The thermoplastic polymer composition of the present invention is obtained by dynamically crosslinking the fluororubber composition (b) in the presence of the fluororesin (A) and under the melting conditions of the fluororesin (A). It is preferable. Here, the dynamic crosslinking treatment means that the fluororubber is dynamically crosslinked simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an 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 crosslinking, the phase structure of the fluororesin (A) and the crosslinked fluororubber (B) and the dispersion of the crosslinked fluororubber (B) can be controlled.

  In order to crosslink at least one fluororubber composition (b) to the thermoplastic polymer composition of the present invention, it is preferable to further add a crosslinking agent (C).

  As a crosslinking agent (C), it can select suitably according to the kind and melt-kneading conditions of the fluororubber composition (b) to bridge | crosslink.

  The cross-linking system used in the present invention may be appropriately selected depending on the type of the cure site or the use of the molded product obtained when the fluororubber contains a cross-linkable group (cure site). As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

  Here, in the case of crosslinking by a polyol crosslinking system, it is preferable in that it has a carbon-oxygen bond at the crosslinking point, has a small compression set, good moldability, and excellent sealing properties. is there.

  When cross-linking by an organic peroxide cross-linking system, since it has a carbon-carbon bond at the cross-linking point, a polyol cross-linking system having a carbon-oxygen bond at the cross-linking point and a polyamine cross-linking system having a carbon-nitrogen double bond Compared to, it has a feature of excellent chemical resistance and steam resistance.

  In the case of cross-linking 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, the compression set tends to increase as compared with the case of crosslinking using a polyol crosslinking system or an organic peroxide crosslinking system.

  Therefore, in the present invention, it is preferable to use a polyol crosslinking type or organic peroxide crosslinking type crosslinking agent, and it is more preferable to use a polyol crosslinking type crosslinking agent from the viewpoint of excellent sealing properties as described above.

  As the crosslinking agent (C) in the present invention, polyamine-based, polyol-based, and organic peroxide-based crosslinking agents can be used.

  Examples of the polyamine crosslinking agent include polyamine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

  As the polyol crosslinking agent, a compound conventionally known as a crosslinking agent for fluororubber can be used. For example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

  The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) 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-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

  The organic peroxide cross-linking agent may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. Specifically, for example, 1,1-bis (T-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumylper Oxide, α, α-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Di (t-butylperoxy) -hexyne-3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyi Examples include sopropyl carbonate. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferable.

  Among these, a polyhydroxy compound is preferable from the viewpoint of small compression set such as a molded article to be obtained and excellent moldability, a polyhydroxy aromatic compound is more preferable because of excellent heat resistance, and bisphenol AF is preferable. Further preferred.

  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 intramolecular double bonds in the dehydrofluorination reaction of the fluororubber main chain.

  As the polyol crosslinking-type crosslinking accelerator (D), an onium compound is generally used. The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Of these, quaternary ammonium salts and quaternary phosphonium salts are preferred.

  The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5, 4,0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 , 4,0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5 4,0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5, 4,0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl-1, 8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropylene ) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl- Examples thereof include 2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  Further, as the crosslinking accelerator (D), a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can be used.

  Examples of the organic peroxide crosslinking accelerator (D) include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, Dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1 , 3,5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl phosphor Amide, N, N, N ′, N′-tetraali Phthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite Etc. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  As addition amount of a crosslinking agent (C) and a crosslinking accelerator (D), it is the quantity adjusted so that 90% completion time T90 of vulcanization | cure in the temperature at the time of carrying out a dynamic crosslinking process may be 2 to 6 minutes. The vulcanization 90% completion time T90 is more preferably adjusted to 3 to 5 minutes. When the optimum vulcanization time T90 is less than 2 minutes, the dispersion of the crosslinked rubber tends to be uneven and coarse, and when it exceeds 6 minutes, it takes a long time for the rubber to be crosslinked, and There is a tendency to not completely crosslink.

  Here, vulcanization 90% completion time T90 is the temperature at the time of dynamic vulcanization using JSR type curlastometer type II and V type at the time of primary press vulcanization of fluororubber composition (b). A vulcanization curve is obtained, and a time for reaching 90% of the maximum torque value is defined as a 90% vulcanization completion time (T90).

  As a specific method for determining the addition amount of the crosslinking agent (C) and the crosslinking accelerator (D), the 90% vulcanization 90% completion time T90 at 170 ° C. is 2 to 6 minutes, preferably 3 to 5 minutes. First, X parts by weight of the crosslinking agent (C) with respect to 100 parts by weight of the fluororubber and Y parts by weight of the crosslinking accelerator (D) are obtained.

Next, based on the amount of X and Y,
(I) Amount of crosslinking agent (C): X weight, Amount of crosslinking accelerator (D): 0.2Y to 0.5Y parts by weight, preferably 0.3Y to 0.4Y parts by weight, or (ii) Crosslinking The amount of the agent (C): 2X to 5X parts by weight, the amount of the crosslinking accelerator (D): 0.4Y to 2.5Y parts by weight of the preferred crosslinking agent (C) and crosslinking accelerator (D) in the present invention. Addition amount.

  When the crosslinking accelerator (D) is less than 0.2 Y parts by weight, the crosslinking of the fluororubber does not proceed sufficiently, and the heat resistance and oil resistance of the resulting thermoplastic polymer composition tend to decrease. When the amount exceeds 5 Y parts by weight, the mechanical strength of the resulting thermoplastic polymer composition tends to decrease.

  The melting condition means a temperature at which the fluororesin (A) and the fluororubber composition (b) are melted. The melting temperature varies depending on the glass transition temperature and / or melting point of the fluororesin (A) and the fluororubber composition (b), respectively, but is preferably 120 to 330 ° C, more preferably 130 to 320 ° C. preferable. If the temperature is lower than 120 ° C, the dispersion between the fluororesin (A) and the fluororubber tends to become coarse, and if it exceeds 330 ° C, the fluororubber tends to be thermally deteriorated.

  The obtained thermoplastic polymer composition has a structure in which the fluororesin (A) forms a continuous phase and the crosslinked rubber (B) forms a dispersed phase, or the fluororesin (A) and the crosslinked fluororubber (B) Although it can have a structure which forms a co-continuity, among them, it is preferable to have a structure in which the fluororesin (A) forms a continuous phase and the crosslinked rubber (B) forms a dispersed phase.

  Even when the fluororubber initially forms a matrix, as the crosslinking reaction proceeds, the fluororubber becomes a cross-linked fluororubber (B), so that the melt viscosity increases and the cross-linked fluororubber (B) becomes a dispersed phase. Or forms a co-continuous phase with the fluororesin (A).

  When such a structure is formed, the thermoplastic polymer composition of the present invention exhibits excellent heat resistance, chemical resistance, and oil resistance, and can achieve both low fuel permeability and flexibility, and is even better. It will have a good moldability. At that time, the average dispersed particle size of the crosslinked fluororubber (B) is preferably 0.01 to 30 μm. If the average dispersed particle size is less than 0.01 μm, the fluidity tends to decrease, and if it exceeds 30 μm, the strength of the resulting thermoplastic polymer composition tends to decrease.

  Further, the thermoplastic polymer composition of the present invention has a fluorine resin (A) as a preferred form thereof forming a continuous phase and a part of the structure in which the crosslinked fluororubber (B) forms a dispersed phase. A co-continuous structure of the resin (A) and the crosslinked fluororubber (B) may be included.

  The weight ratio of the fluororesin (A) and the cross-linked fluororubber (B) is 98/2 to 10/90, and preferably 95/5 to 20/80. If the fluororesin (A) is less than 10% by weight, the fluidity of the resulting thermoplastic polymer composition tends to deteriorate and the moldability tends to deteriorate. If it exceeds 98% by weight, the resulting thermoplasticity There is a tendency for the balance between flexibility and fuel permeability of the polymer composition to deteriorate.

The fuel permeation coefficient of the molded article made of the thermoplastic composition of the present invention is preferably 40 g · mm / m ² · day or less, more preferably 20 g · mm / m ² · day or less, and more preferably 10 g · more preferably at most mm / m ² · day, particularly preferably not more than ^{5g · mm / m 2 · day} . 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 / day · m ² , the fuel permeation resistance is low, and in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product, which is economically undesirable. . Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability. On the other hand, when the fuel permeation coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

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 method defined in JIS Z 0208, and is a method for measuring 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, CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel is placed in a SUS container (open area 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. Put 18 mL, and set the sheet-like test piece in the container open part and seal it to make a test body. The test body is placed in a thermostatic device (60 ° C.), the weight of the test body is measured, and when the weight reduction per unit time becomes constant, the fuel permeability coefficient is obtained by the following formula.

  The tensile modulus of the molded article made of the thermoplastic composition of the present invention is preferably 1000 MPa or less, more preferably 800 MPa or less, further preferably 700 MPa or less, and particularly preferably 600 MPa or less. preferable. Although it does not specifically limit as a lower limit of a tensile elasticity modulus, it is preferable that it is 5 Mpa or more, and it is more preferable that it is 10 Mpa or more. When the tensile elastic modulus exceeds 1000 MPa, there is a tendency that it is not suitable for a molded product requiring flexibility.

  In addition, the thermoplastic polymer composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester, polyurethane, inorganic filler such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black, and barium sulfate. The effects of the present invention include materials, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, mold release agents, foaming agents, perfumes, oils, softening agents, etc. It can be added in a range that does not affect the above.

  The thermoplastic polymer composition of the present invention can be molded using a general molding method or molding apparatus. As the 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 thermoplastic polymer composition of the present invention is intended for use. Depending on the shape, it is formed into a molded body having an arbitrary shape.

  Furthermore, the present invention relates to a molded article obtained by using the thermoplastic polymer composition of the present invention, and the molded article includes a molded article of a sheet or a film, It includes a laminated structure having a layer made of a thermoplastic polymer composition and a layer made of another material.

  In the laminated structure of at least one layer made of the thermoplastic polymer composition of the present invention and at least one layer made of another material, the other material depends on required properties, intended use, etc. And select the appropriate one. 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, vinyl chloride resin. (PVC), thermoplastic polymers such as vinylidene chloride resin (PVDC), ethylene-propylene-diene rubber (EPDM), crosslinked rubber such as butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, and thermoplastics such as polypropylene / EPDM composite Elastomer, metal, glass, wood, ceramic and the like can be mentioned.

  In the molded article having the laminated structure, an adhesive layer may be interposed between a layer made of the thermoplastic polymer composition of the present invention and a base material layer made of another material. By interposing the adhesive layer, the layer made of the thermoplastic polymer composition of the present invention and the base material layer made of another material can be firmly joined and integrated. Examples of the adhesive used in the adhesive layer include acid anhydride-modified products of diene polymers; acid anhydride-modified products of polyolefins; polymer polyols (for example, glycol compounds such as ethylene glycol and propylene glycol, and adipic acid) Polyester polyol obtained by polycondensation of a dibasic acid with a mixture of a partially saponified product of a copolymer of vinyl acetate and vinyl chloride and a polyisocyanate compound (for example, 2,4-tolylene diisocyanate) (For example, a reaction product of a molar ratio of 1: 2 between a glycol compound such as 1,6-hexamethylene glycol and a diisocyanate compound such as 2,4-tolylene diisocyanate; a triol compound such as trimethylolpropane and 2,4- Molar ratio 1 with diisocyanate compounds such as tolylene diisocyanate 3 of the reaction 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 also be used.

  The present invention includes a fuel hose or fuel container comprising a single layer of the thermoplastic polymer composition of the present invention. The use of the fuel hose is not particularly limited, and examples thereof include an automobile filler hose, an evaporation 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.

  The present invention also includes a multilayer fuel hose or multilayer fuel container comprising a layer comprising the thermoplastic polymer composition of the present invention. The multi-layer fuel hose or multi-layer fuel container includes a layer made of the thermoplastic polymer composition of the present invention and at least one layer made of another material, and these layers do not interpose an adhesive layer, or They are interposed and bonded to each other.

  And as a layer which consists of another material, the layer which consists of rubbers other than the thermoplastic polymer composition of this invention, and the layer which consists of thermoplastic resins are mention | raise | lifted.

  As the rubber, from the viewpoint of chemical resistance and flexibility, acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, EPDM and acrylic rubber Preferred is a rubber comprising at least one selected from the group consisting of acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluororubber, and epichlorohydrin rubber. More preferably, it is made of at least one kind of rubber.

  In addition, from the viewpoint of fuel barrier properties, the thermoplastic resin may be selected from the group consisting of fluororesins, polyamide resins, polyolefin resins, polyester resins, polyvinyl alcohol resins, polyvinyl chloride resins, and polyphenylene sulfide resins. A thermoplastic resin consisting of at least one selected from the group is preferable, and a thermoplastic resin consisting of at least one selected from the group consisting of a fluororesin, a polyamide-based resin, a polyvinyl alcohol-based resin, and a polyphenylene sulfide-based resin is more preferable.

  The fuel hose or fuel container composed of the thermoplastic polymer composition layer obtained according to the present invention and the layer composed of other rubber or other thermoplastic resin is not particularly limited. Fuel hose such as filler hose for automobile, evaporation hose, breather hose, etc .; fuel container for automobile, fuel container for motorcycle, fuel container for small generator, fuel container for lawn mower, etc.

  Among these, as a fuel hose comprising a layer made of the thermoplastic polymer composition of the present invention and a layer made of another rubber, acrylonitrile-butadiene rubber or its hydrogenated rubber, acrylonitrile-butadiene rubber and polyvinyl chloride are used. A fuel hose comprising three layers of an outer layer made of blend rubber or epichlorohydrin rubber, an intermediate layer made of the thermoplastic polymer composition of the present invention, and an inner layer made of fluororubber, or acrylonitrile-butadiene rubber or its hydrogenation A fuel hose comprising two layers of rubber, an outer layer made of a blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride or epichlorohydrin rubber, and an inner layer made of the thermoplastic polymer composition of the present invention is an excellent fuel. In terms of barrier properties, flexibility and chemical resistance Masui.

  Moreover, when producing the laminated structure which has the layer which consists of a fuel barrier material of this invention, and the layer which consists of another material, you may surface-treat to the fuel barrier material of this invention as needed. The type of 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 / naphthalene liquid treatment Etc. 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 performed, the surface of the fluororesin that has not been surface-treated can be treated, but the surface of the fuel barrier material that has been previously subjected to plasma discharge treatment, corona discharge treatment, metal sodium / naphthalene liquid treatment, etc. Further primer treatment is more effective.

  The thermoplastic polymer composition of the present invention and a molded article comprising the composition can be suitably used in the following fields.

  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, packing, sealing materials, tubes, rolls, coatings Linings, gaskets, diaphragms, hoses, etc. These include CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation equipment, exhaust equipment, chemical piping, gas Can be used for piping. Specifically, as a gate valve O-ring, seal material, quartz window O-ring, seal material, chamber O-ring, seal material, gate O-ring, seal material, bell jar O-ring, seal material As an O-ring for a coupling, as a sealing material, as an O-ring for a pump, as a sealing material, as a diaphragm, as an O-ring for a semiconductor gas control device, as a sealing material, as an O-ring for a resist developer, as a stripping solution, as a sealing material As a wafer cleaning solution hose and tube, as a wafer transfer roll, as a resist developer bath, a stripping solution bath lining, as a coating, as a wafer cleaning bath lining, as a coating or as a wet etching bath lining, as a coating Can do. In addition, sealing materials and sealants, optical fiber quartz coatings, electronic parts for insulation, vibration proofing, waterproofing and moisture proofing, circuit board potting, coating, adhesive sealing, gaskets for magnetic storage devices, epoxies, etc. Used as a sealing material modifier, sealant for clean rooms and clean facilities, etc.

  In the automotive field, gaskets, shaft seals, valve stem seals, sealing materials and hoses can be used for engines and peripheral devices, hoses and sealing materials can be used for AT devices, O (square) rings, tubes, packings. The valve core material, hose, sealing material and diaphragm can be used for fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, manifold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, injector packing, fuel Pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston seal, cylinder liner seal, valve stem seal, automatic transmission front pump seal, rear axle pinion seal, universal joint gasket, speed Meter pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas reburner seal, bearing Lumpur, EGR tubes, Tsuinkyabu tube, the sensor diaphragm of the carburetor, rubber vibration isolator (engine mount, exhaust part, etc.), afterburners hoses, can be used as an oxygen sensor bush.

  In the aircraft field, the rocket field, and the marine field, there are diaphragms, O (square) rings, valves, tubes, packings, hoses, sealing materials, and the like, which can be used for fuel systems. 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 seal, diesel engine intake / exhaust valve stem seal, butterfly valve seal, butterfly valve shaft seal, etc.

  In the field of chemical products such as plants, linings, valves, packing, rolls, hoses, diaphragms, O (square) rings, tubes, sealing materials, chemical-resistant coatings, etc., these are pharmaceuticals, agricultural chemicals, paints, resins, etc. It can be used in chemical manufacturing processes. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packing for sulfuric acid production equipment, pesticide sprayers, pesticide transfer pump seals, gas pipe seals, plating solutions Seals, packing for high-temperature vacuum dryers, roller seals for papermaking belts, fuel cell seals, wind tunnel joint seals, rolls for trichrene (for fiber dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH meter It can be used as packing for tube joints, chlorine gas transfer hoses, benzene, rainwater drain hoses for toluene storage tanks, seals for analytical instruments, physics and chemistry instruments, tubes, diaphragms, valve parts, and the like.

  In the pharmaceutical field such as pharmaceuticals, it can be used as a medicine stopper.

  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, there are rolls and the like, which can be used for a film developing machine, an X-ray film developing machine, a printing roll and a coating roll, respectively. Specifically, as a developing roll of a film developing machine / X-ray film developing machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating roll, a guide of a magnetic tape manufacturing coating line It can be used as a 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 , Rolls, printing press rolls, belts, and the like.

  Tubes can also be used in the field of analysis and physics and chemistry.

  In the field of food plant equipment, linings, valves, packings, rolls, hoses, diaphragms, O (square) rings, tubes, sealing materials, belts and the like can be mentioned and used in food production processes. Specifically, it can be used as a seal for a plate heat exchanger, a solenoid valve seal for a vending machine, or the like.

  In the field of nuclear plant equipment, packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes and the like can be mentioned.

  In the steel field such as iron plate processing equipment, rolls and the like can be mentioned, and they can be used for iron plate processing rolls and the like.

  In general industrial fields, 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, roll blades, belts Etc. Specifically, hydraulic, lubrication machinery seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seals (vacuum) valves, automatic packaging machine seals, air It is used for diaphragms (pollution measuring devices) for analysis of sulfurous acid gas and chlorine gas in the inside, rolls for printing presses, belts, pickling rolls for pickling.

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

  In the fuel cell field, specifically, it is used as a sealing material between electrodes and separators, a seal for hydrogen / oxygen / product water piping, and the like.

  Specifically, in the field of electronic components, it is used as a heat radiation material, an electromagnetic shielding material, a modified material of a printed wiring board prepreg resin such as epoxy, an anti-scattering material such as a light bulb, and a gasket of a hard disk drive of a computer.

  There are no particular limitations on what can be used for on-site molding, such as metal gasket coatings for automobile engines, engine oil pan gaskets, copier / printer rolls, architectural sealants, Gaskets for magnetic recording devices, sealants for filter units for clean rooms, coating agents for printed boards, fixing agents for electrical and electronic components, insulation and moisture-proof treatment of electrical equipment lead wire terminals, oven seals for electric furnaces, sheathed heaters Examples include end treatment, microwave window frame seals, adhesion of CRT wedges and necks, adhesion of automotive electrical components, joint seals for kitchens, bathrooms, washrooms, and the like.

  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, packing, roller, tube or hose.

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

<Vulcanization characteristics>
The vulcanization curves at 170 ° C, 220 ° C and 250 ° C were obtained using JSR type curlastometer type II, and the minimum viscosity (ML), vulcanization degree (MH), induction time (T10) and optimum were determined from the change in torque. Vulcanization time (T90) was determined. If no change in torque is observed even after 30 minutes in the heated state, the vulcanization reaction is considered not progressing.

<Kneading with Laboplast Mill>
Kneading of the fluororesin (A) and the fluororubber composition (b) is performed using a Laboplast Mill (manufactured by Toyo Seiki Seisakusho). The total amount of the fluororesin (A) and fluororubber composition (b) to be kneaded is adjusted so that the total volume thereof is 77% by volume of the total volume of the kneading part of the lab plast mill. The temperature of the lab plast mill is set to a temperature 30 to 70 ° C. higher than the melting point of the fluororesin (A) used in the composition. After the temperature of the lab plast mill is stabilized, the fluororesin is added and stirred at 10 rpm for 5 to 10 minutes to melt the fluororesin. The fluororubber composition is added to the molten fluororesin, and immediately after the addition, the number of stirring is increased to 100 rpm. From the time when the torque showed the maximum value (corresponding to T90 measured with Curlast type II), the mixture was stirred for 10 minutes to obtain a thermoplastic polymer composition.

<Hardness>
Using the pellets of the thermoplastic polymer composition produced in the examples and comparative examples, compression molding was performed under the conditions of 270 ° C. and 5 MPa using a hot press machine to produce a sheet-like test piece having a thickness of 2 mm. A hardness was measured according to JIS-K6301.

<Tensile breaking strength, tensile breaking elongation, tensile elastic modulus>
Using the pellets of the thermoplastic polymer composition produced in the examples and comparative examples, the pellets were compression-molded under a condition of 270 ° C. and 5 MPa using a hot press machine to prepare a sheet-like test piece having a thickness of 2 mm. A dumbbell-shaped test piece having a width of 3.18 mm is punched out using an ASTM V-type dumbbell. Using the obtained dumbbell-shaped test piece, using an autograph (AGS-J 5 kN, manufactured by Shimadzu Corporation), in accordance with ASTM D638, at 50 ° C. under a condition of tensile breaking elongation at 25 ° C. Measure the tensile strength at break and tensile modulus.

<Fuel permeability>
Using the pellets of the thermoplastic polymer composition produced in the examples and comparative examples, the pellets were compression-molded under a condition of 270 ° C. and 5 MPa using a hot press machine, and a sheet-like test piece having a thickness of 0.5 mm was obtained. Produced. 18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is put in a SUS container (open area 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the sheet A test specimen is prepared by setting a cylindrical test piece in the container opening and sealing it. 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.

<Fluidity>
Using the pellets of the thermoplastic polymer composition produced in the examples and comparative examples, using a melt flow rate measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a condition of a load of 297 ° C., 5 kg or 10 kg The melt flow rate (MFR) was measured.

<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 a sheet treated with the surface of the sheet test piece and a rubber composition are set in a stacking die, and a 3 MPa load is applied at 170 ° C. for 15 to 30 minutes by a heat press machine to vulcanize rubber. -A fuel barrier material laminate was molded. The vulcanized rubber-fuel barrier material laminate was cut into strips each having a width of 1.0 cm and a width of 10 cm to produce a test piece for adhesion test. This test piece was subjected to JIS-K-6256 (adhesion of vulcanized rubber). In accordance with the method described in “Test method”, a peel test was performed at 25 ° C. at a tensile speed of 50 mm / min.

<Atmospheric pressure plasma treatment>
The surface of the sheet of fuel barrier material is set to 3 mm between the electrodes of the high voltage electrode and the low voltage electrode by an atmospheric pressure plasma processing machine, a 2.2 kV voltage is applied using an AC power source with a frequency of 5 kHz, and Ar / He Plasma treatment was performed under the conditions of (vol) ratio = 50/50, hydrogen concentration 2 ((vol)%), and plasma energy density 2 (J / cm ² ).

<Corona discharge treatment>
The discharge electrode (30 cm width) of the corona treatment apparatus was covered with an acrylic resin container, and air was allowed to flow at 10 L / min under atmospheric pressure. The surface of the sheet of fuel barrier material was treated at a corona output of 250 W and a sheet moving speed of 1 mm / min using a Tantech HV05-2 power source.

<Metal sodium / naphthalene solution treatment>
The sheet of the fuel barrier material was immersed in a metal sodium / naphthalene solution (Tetra Etch, manufactured by Junko 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.

<Fluorine rubber>
Ternary rubber composed of VdF, TFE and HFP (VdF: TFE: HFP = 50: 20: 30 mol%, Mooney viscosity at 100 ° C. = 88)

<Crosslinking agent (C1)>
Polyol-based crosslinking agent: 2,2-bis (4-hydroxyphenyl) perfluoropropane (“Bisphenol AF” manufactured by Daikin Industries, Ltd.)

<Crosslinking agent (C2)>
Polyamine-based cross-linking agent: N, N′-dicinnamylidene-1,6-hexamethylenediamine (“V-3” manufactured by Daikin Industries, Ltd.)

<Crosslinking accelerator (D)>
Benzyltriphenylphosphonium chloride (BTPPC, manufactured by Hokuko Chemical Co., Ltd.)

<Thermoplastic resin (non-fluorine type)>
Kuraray Co., Ltd. ethylene vinyl alcohol resin “Eval F101” (melting point: 183 ° C.) As a result of evaluating the physical properties by the above methods, the tensile modulus was 2000 MPa or more, and the fuel permeability coefficient was 0.3 (g · mm) / ( m ² · day).

<Thermoplastic elastomer (fluorine type)>
“THV 200G” manufactured by Dyneon (Comparative Example 1), “THV 500G” manufactured by Dyneon (Comparative Example 2), or “THV 815G” manufactured by Dyneon (Comparative Example 3)

Production Example 1 (Production of thermoplastic resin (fluorine))
392 kg of demineralized pure water was charged into a jacketed stirring polymerization tank capable of containing 1316 L of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 307 kg of octafluorocyclobutane, 20.41 kg of CTFE, 35.3 kg of TFE, and 22.42 kg of perfluoro (propyl vinyl ether) (PPVE) were injected, the temperature was adjusted to 35 ° C., and stirring was started. Here, 4.49 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate (NPP) was added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition was polymerized while being additionally charged so that the pressure in the tank was maintained at 0.69 MPa, and then the residual gas in the tank was exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 183.7 kg of a granular powder CTFE copolymer. Next, melt kneading was performed at a cylinder temperature of 280 ° C. using a φ50 mm short-axis extruder to obtain pellets. Next, the obtained pellet-like CTFE copolymer was heated at 180 ° C. for 24 hours.

The composition of the thermoplastic resin (fluorine-based) was CTFE / TFE / PPVE = 44.5 / 53.4 / 2.1 (mol%), and the melting point was 221 ° C. Further, as a result of evaluating the physical properties by the above methods, the tensile elastic modulus was 520 MPa, and the fuel permeability coefficient was 0.3 (g · mm) / (m ² · day).

Production Example 2 (Preparation of fluororubber composition (b-2-1))
To 100.0 parts by weight of the fluororubber, 2.0 parts by weight (X) of a crosslinking agent (C1), 1.0 part by weight (Y) of a crosslinking accelerator (D), magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry ( Co.)) 3.0 parts by weight was added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b-2-1).

  Table 1 shows the composition of the fluororubber composition (b-2-1) and the vulcanization characteristics thereof. In the fluororubber composition (b-2-1), the vulcanization reaction did not proceed at 170 ° C., and the vulcanization time T90 at 250 ° C. was 4.0 minutes.

Production Example 3 (Preparation of fluororubber composition (b-2-2))
To 100.0 parts by weight of the fluororubber, 2.0 parts by weight (X) of a crosslinking agent (C1), 0.77 parts by weight (Y) of a crosslinking accelerator (D), magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry ( Co.)) 3.0 parts by weight and calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Co., Ltd.) 6.0 parts by weight were added and kneaded using an 8-inch open roll, and the fluororubber composition (b -2-2) was produced.

  Table 1 shows the composition of the fluororubber composition (b-2-2) and the vulcanization characteristics thereof. In the fluororubber composition (b-2-2), the vulcanization reaction did not proceed at 170 ° C., and the vulcanization time T90 at 220 ° C. was 4.2 minutes.

Example 1
90 parts by weight of the above-described thermoplastic resin (fluorine-based) and 10 parts by weight of the fluororubber composition (b-2-1) are melt-kneaded in a lab plast mill under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm, A plastic polymer composition was obtained. Table 2 shows the results of evaluation of hardness, tensile breaking strength, tensile breaking elongation, tensile elastic modulus, fuel permeability, and melt flow rate using the obtained thermoplastic polymer composition pellets by the methods described above. Show.

Example 2
70 parts by weight of the above-described thermoplastic resin (fluorine-based) and 30 parts by weight of the fluororubber composition (b-2-1) are melt-kneaded in a lab plast mill under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm. A plastic polymer composition was obtained. Table 2 shows the results of evaluation of hardness, tensile breaking strength, tensile breaking elongation, tensile elastic modulus, fuel permeability, and melt flow rate using the obtained thermoplastic polymer composition pellets by the methods described above. Show.

Example 3
50 parts by weight of the above-described thermoplastic resin (fluorine-based) and 50 parts by weight of the fluororubber composition (b-2-1) are melt-kneaded in a lab plast mill under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm. A plastic polymer composition was obtained. Table 2 shows the results of evaluation of hardness, tensile breaking strength, tensile breaking elongation, tensile elastic modulus, fuel permeability, and melt flow rate using the obtained thermoplastic polymer composition pellets by the methods described above. Show.

Example 4
30 parts by weight of the above-described thermoplastic resin (fluorine-based) and 70 parts by weight of the fluororubber composition (b-2-1) are melt-kneaded in a lab plast mill under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm, A plastic polymer composition was obtained. Table 2 shows the results of evaluation of hardness, tensile breaking strength, tensile breaking elongation, tensile elastic modulus, fuel permeability, and melt flow rate using the obtained thermoplastic polymer composition pellets by the methods described above. Show.

Comparative Examples 1-3
Using pellets of “THV 200G” (Comparative Example 1) manufactured by Dyneon, “THV 500G” (Comparative Example 2) manufactured by Dyneon, or “THV 815G” (Comparative Example 3) manufactured by Dyneon, the hardness and tensile strength at break were measured in the manner described above. Table 2 shows the results of measurements of tensile elongation at break, tensile modulus, fuel permeability and melt flow rate.

Comparative Example 4
70 parts by weight of the above-mentioned thermoplastic resin (non-fluorine-based) and 30 parts by weight of the fluororubber composition (b-2-1) are melt-kneaded in a lab plast mill under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm, A thermoplastic polymer composition was obtained. An attempt was made to produce a sheet by the above-described method using the obtained pellets of the thermoplastic polymer composition, but a sheet having good film quality could not be obtained. When the tensile test of this sheet was performed, the tensile strength at break was 3 MPa or less and the tensile elongation at break was 50% or less. Similarly, a fuel permeation test could not be performed due to film quality problems. The evaluation results are shown in Table 2.

Comparative Example 5
70 parts by weight of the above-mentioned thermoplastic resin (non-fluorine type) and 30 parts by weight of the fluororubber composition (b-2-2) are melt-kneaded in a lab plast mill under the conditions of a temperature of 220 ° C. and a screw rotation speed of 100 rpm, A thermoplastic polymer composition was obtained. An attempt was made to produce a sheet by the above-described method using the obtained pellets of the thermoplastic polymer composition, but a sheet having good film quality could not be obtained. When the tensile test of this sheet was performed, the tensile strength at break was 3 MPa or less and the tensile elongation at break was 50% or less. Similarly, a fuel permeation test could not be performed due to film quality problems. The evaluation results are shown in Table 2.

  The thermoplastic resin compositions obtained in Examples 1 to 4 are superior in fuel permeability as compared with the thermoplastic elastomer (fluorine type) used in Comparative Examples 1 to 3, and also have fuel permeability and flexibility. It was found that the balance of sex is excellent.

  In addition, the thermoplastic resin compositions obtained in Examples 1 to 4 were obtained by observing the morphology with a scanning electron microscope (manufactured by JEOL Ltd.). It was found that the rubber (B) has a structure that forms a dispersed phase. In Examples 1 to 4, the dispersed particle diameter of the crosslinked fluororubber (B) was 20 μm or less.

Production Example 4 (Preparation of fluororubber composition (b-2-3))
100.0 parts by weight of fluororubber, 2.0 parts by weight of crosslinking agent (C1), 0.5 part by weight of crosslinking accelerator (D), 3.0 parts by weight of magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry Co., Ltd.) , Calcium hydroxide (Caldic 2000, Omi Chemical Co., Ltd.) 6.0 parts by weight, carbon black (Thermax N-990, Cancarb Ltd.) 20.0 parts by weight was added and kneaded using an 8-inch open roll. Thus, a fluororubber composition (b-2-3) was produced.

Production Example 5 (Preparation of fluororubber composition (b-2-4))
Fluoro rubber 100.0 parts by weight, crosslinking agent (C2) 3.0 parts by weight, magnesium oxide (Kyowa Mag 30, Kyowa Chemical Industry Co., Ltd.) 15.0 parts by weight, carbon black (Thermax N-990, Cancarb Ltd.). ) 20.0 parts by weight were added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b-2-4).

Production Example 6 (Preparation of epichlorohydrin rubber composition)
4. Epichlorohydrin rubber (Epichromer CG, Daiso Co., Ltd.) 100.0 parts by weight, carbon black (N-550, Cancarb Ltd.) 80 parts by weight, Plasticizer (ADK sizer RS-107, Asahi Denka Kogyo Co., Ltd.) 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 hydrotalcite (DHT-4A, Kyowa Chemical) Industrial Co., Ltd.) 3.0 parts by weight, Magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight, DBU phenol resin salt (P-152) 1.5 parts by weight, 6-methylquinoxaline- 2,3-dithiocarbonate (Daisonette XL-21S, Daiso Corporation) 1.5 layers Part was added and kneaded using an 8-inch open roll to prepare epichlorohydrin rubber composition.

  Sheet of fuel barrier material obtained in Example 2, fluorine rubber composition (b-2-3) obtained by the production method shown in Production Example 4, and fluorine obtained by the production method shown in Production Example 5 The adhesion evaluation test with the rubber composition (b-2-4) and the epichlorohydrin rubber composition obtained by the production method shown in Production Example 6 was conducted by the above method. The peel strength is 9 N / cm when the fluororubber composition (b-2-3) is used, 22 N / cm when the fluororubber composition (b-2-4) is used, and the epichlorohydrin rubber composition. When the product was used, it was 8 N / cm, and the interface between the fuel barrier material and the vulcanized rubber sheet was peeled off regardless of the type of the rubber composition used.

  The sheet of the fuel barrier material obtained in Example 2 was subjected to atmospheric pressure plasma treatment and surface-treated, and the fluororubber composition (b-2-3) obtained by the production method shown in Production Example 4 ), An adhesive evaluation test with the fluororubber composition (b-2-4) obtained by the production method shown in Production Example 5 and the epichlorohydrin rubber composition obtained by the production method shown in Production Example 6. The above method was used. 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 N / cm or more.

The sheet of the fuel barrier material sheet obtained in Example 2 was subjected to corona discharge treatment and surface-treated, and the fluororubber composition (b-2-3) obtained by the production method shown in Production Example 4 The adhesive evaluation test with the fluororubber composition (b-2-4) obtained by the production method shown in Production Example 5 and the epichlorohydrin rubber composition obtained by the production method shown in Production Example 6 The method was performed. 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 N / cm or more.
The surface of the sheet of the fuel barrier material obtained in Example 2 was treated with a metallic sodium / naphthalene solution, and the fluororubber composition (b-2) obtained by the production method shown in Production Example 4 -3) Adhesive evaluation with the fluororubber composition (b-2-4) obtained by the production method shown in Production Example 5 and the epichlorohydrin rubber composition obtained by the production method shown in Production Example 6 The test was conducted by the method described above. 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 N / cm or more.

  The molded product obtained from the thermoplastic polymer composition of the present invention has excellent fuel permeability and flexibility and excellent molding processability by using a specific fluororesin.

Claims (7)

At least a part of the fluororesin (A) containing 90 to 99.9 mol% of chlorotrifluoroethylene units and tetrafluoroethylene units and 0.1 to 10 mol% of perfluoro (alkyl vinyl ether) is crosslinked. A thermoplastic polymer composition comprising the crosslinked fluororubber (B).   The crosslinked fluororubber (B) is obtained by dynamically crosslinking the fluororubber composition (b) in the presence of the fluororesin (A) under the melting conditions of the fluororesin (A). 2. The thermoplastic polymer composition according to 1.   The thermoplastic polymer according to claim 1 or 2, wherein the fluororesin (A) is a fluororesin further comprising a monomer (a) unit copolymerizable with chlorotrifluoroethylene and tetrafluoroethylene. Composition. Monomer (a) is ethylene, vinylidene fluoride, perfluoro (alkyl vinyl ether) and general formula (1):
CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (1)
(In the formula, X ^{1 to} X ³ are the same or different and are each a hydrogen atom, a fluorine atom or —CF ₃ ; X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom; Is an integer)
The thermoplastic polymer composition according to claim 3, wherein the thermoplastic polymer composition is one or more monomers selected from the group consisting of vinyl monomers.   A molded article formed from the thermoplastic polymer composition according to any one of claims 1 to 4.   A fuel tube formed from the thermoplastic polymer composition according to any one of claims 1 to 4.   A fuel hose formed from the thermoplastic polymer composition according to any one of claims 1 to 4.