WO2007116876A1

WO2007116876A1 - Thermoplastic polymer composition and molded body made of the composition

Info

Publication number: WO2007116876A1
Application number: PCT/JP2007/057439
Authority: WO
Inventors: Toshiki Ichisaka; Tomihiko Yanagiguchi; Takeshi Inaba; Haruhisa Masuda
Original assignee: Daikin Industries, Ltd.
Priority date: 2006-04-04
Filing date: 2007-04-03
Publication date: 2007-10-18
Also published as: JP5120251B2; JPWO2007116876A1

Abstract

Disclosed is a melt-moldable thermoplastic polymer composition which is excellent in heat resistance, chemical resistance and oil resistance, while having flexibility and high fuel barrier property. Also disclosed are a molded article, a fuel tube and a fuel hose respectively made of such a thermoplastic polymer composition. Specifically disclosed is a thermoplastic polymer composition containing a fluororesin (A) containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit, and a crosslinked fluororubber (B) obtained by crosslinking at least a part of at least one fluororubber. The crosslinked fluororubber (B) is specifically obtained by dynamically crosslinking a fluororubber composition (b) in the presence of the fluororesin (A) under melting conditions of the fluororesin (A).

Description

Specification

Thermoplastic polymer composition and molded article comprising the composition

Technical field

The present invention relates to a thermoplastic polymer composition comprising a specific fluorine resin and a specific crosslinked fluororubber. The present invention also relates to a molded article, a fuel tube and a fuel hose made of the thermoplastic polymer composition.

Background art

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

[0003] Under the circumstances described above, “Dyneon THV” has been developed as a resin that is flexible, has a fuel barrier property, and has melt moldability and recyclability (for example, Modern Fluoropolymers: high performance polymers). for diverse applications, John Wiley & Sons, Hichster, (1997) Chapter 13, JP 2000-274562 and JP 2002-276862). However, as the properties of the resin described in these documents, the hardness and elastic modulus increase as the fuel barrier property increases, and the fuel barrier property decreases as the hardness and elastic modulus decrease. However, both the flexibility and the fuel barrier property are inadequate.

Disclosure of the invention

[0004] The object of the present invention is to combine excellent heat resistance 'chemical resistance' and oil resistance, flexible, and fuel It is an object of the present invention to provide a thermoplastic polymer composition having high noria properties and capable of being melt-molded. Another object of the present invention is to provide a molded article, a fuel tube and a fuel hose made of the thermoplastic polymer composition.

[0005] That is, the present invention relates to a thermoplastic resin that also has a strength of a cross-linked fluororubber (B) that is at least partially cross-linked with a fluororesin (A) containing a black-mouthed trifluoroethylene unit and a tetrafluoroethylene unit. The present invention relates to a polymer composition.

[0006] The cross-linked fluororubber (B) is obtained by dynamically cross-linking the fluororubber composition (b) in the presence of the fluorocobalt (A) and under the melting conditions of the fluorocobalt (A). Preferably it is a copolymerizable monomer (a) It is preferably a fluorine resin containing units.

[0007] Monomer (a) Force Ethylene, Bi-Ridene Fluoride, Perfluoro (Alkyl Buerte) and General Formula (1):

cx'x ^ cx'CCF) X ⁴ (1)

2 n

(Wherein x ^ x ³ is the same or different and each represents a hydrogen atom, a fluorine atom or —CF, X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer from 1 to 10.

Three

Number)

It is preferable that one or more monomers selected by the group power of vinyl monomer power represented by

[0008] The present invention also relates to a molded article, a fuel tube, and a fuel hose formed from the thermoplastic polymer composition.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] The present invention is at least partially cross-linked with a fluororesin (A) containing a black trifluoroethylene (hereinafter referred to as CTFE) unit and a tetrafluoroethylene (hereinafter referred to as TFE) unit. The present invention relates to a thermoplastic polymer composition having a cross-linked fluororubber (B) force.

[0010] Fluororesin (A) is not particularly limited as long as it contains CTFE units and TFE units.

[0011] It is preferable to contain 2 to 98 mol% of CTFE units in the fluorine resin (A), more preferably 10 to 90 mol%. If it is less than 2 mol%, the chemical permeability deteriorates, Melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

[0012] It is preferable to contain 2 to 98 mol% of TFE units in the fluorine resin (A), more preferably 10 to 90 mol%. If it is less than 2 mol%, the heat resistance and chemical resistance at the time of molding may deteriorate, and if it exceeds 98 mol%, the chemical permeability tends to deteriorate and the melting power tends to be difficult. There is.

[0013] Further, from the viewpoint of stress crack resistance, chemical resistance and heat resistance, it is preferable that the fluorine resin further contains a monomer (a) unit copolymerizable with CTFE and TFE.

[0014] The monomer (a) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, but is not limited to ethylene, vinylidene fluoride (hereinafter referred to as VdF), perfluoro (alkyl). (Buel ether) (hereinafter referred to as PAVE), general formula (1):

cx'x ^ cx'CCF) X ⁴ (1)

2 n

Three

Number)

Vinyl monomer represented by general formula (2):

CF = CF— OCH— R ¹ (2)

2 2 f

(Wherein R ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms)

f

Among these, the ability to increase alkyl perfluorovinyl ether, etc. Among these, one or more unit forces selected from ethylene, VdF, PAVE, and a group force consisting of a bulle monomer represented by the general formula (1) PAVE is more preferable. It is more preferable that it is PAVE.

[0015] 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), and the like. Of these, PMVE, perfluoro (ethyl vinyl ether), and perfluoro (propyl butyl ether) are preferable.

[0016] The vinyl monomer represented by the general formula (1) is not particularly limited. Safluoropropylene (hereinafter referred to as HFP), perfluoro (1, 1, 2—trihydro 1 hexene), perfluoro (1, 1, 5 trihydr 1-pentene), general formula (3): CH = CX ³ R ² (3)

2 f

(Wherein X ³ is the same as above, and R ² is a perfluoroalkyl group having 1 to 10 carbon atoms) f

And perfluoroalkylethylene represented by the formula:

[0017] As the perfluoroalkylethylene represented by the general formula (3), perfluorobutylethylene is preferable.

[0018] As the alkyl perfluorobule ether represented by the general formula (2), R ¹ has a carbon number of f

CF = CF-OCH -CF CF is preferred because it is a perfluoroalkyl group of 1 to 3

2 2 2 Power is preferred.

Three

[0019] Among these, the fluororesin (A) is a CTFE unit because the thermoplastic polymer composition obtained has excellent flame resistance and flexibility and is easy to mold. CTFE units, TFE units, and perfluoro (methyl vinyl ether) units are preferred to be binary fluorine resins containing A and TFE units, or ternary fluorine resins containing CTFE units, TFE units and PAVE units. More preferred is a ternary fluorine resin containing or a ternary fluorine resin containing CTFE units, TFE units and perfluoro (propyl butyl ether) units! /.

[0020] In the case of binary fluorine resin, the composition ratio (molar ratio) is preferably CTFEZTFE = 2Z9 8 to 98Z2, more preferably 5Z95 to 90Z10, 10/90 to It is even more preferable that it is 80Ζ20! If the CTFE unit is less than 2 mol%, the chemical permeability tends to be poor and the melting power tends to be difficult. If it exceeds 98 mol%, the heat resistance and chemical resistance during molding are poor. There is a case.

[0021] In the case of ternary fluorine resin, the monomer (a) unit is 0.1 to 10 mol%, and the CTF E unit and 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. If it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, mechanical properties. It tends to be inferior in characteristics and productivity. Furthermore, the CTFE unit is preferably 10 to 90 mol% of the total of the CTFE unit and the TFE unit. CTF in the total of the above CTFE units and the above TFE units If the E unit is less than 10 mol%, the low chemical solution permeability may be insufficient, and if it exceeds 90 mol%, the polymerization rate will decrease rapidly, resulting in a decrease in productivity and a decrease in chemical resistance. Or the heat resistance may be insufficient. A more preferred lower limit is 15 mol%, further preferred correct lower limit is 20 mole ^_0/0, and more preferred upper limit is 80 mol ^_0/0, further preferred upper limit is 70 mol%.

[0022] The method for producing the fluorocobalt (A) is not particularly limited.

Examples include the methods described in 298702, WO 2005Z100420 pamphlet, and the like.

[0023] Further, the thermoplastic polymer composition of the present invention may contain a resin other than the fluorine resin (A).

[0024] Further, the melting point of the fluorocobalt (A) is preferably 130 to 330 ° C, more preferably 140 to 320 ° C, and more preferably 150 to 310 ° C. preferable. If the melting point of the fluororesin (A) is less than 130 ° C, the heat resistance of the resulting thermoplastic polymer composition tends to decrease, and if it exceeds 330 ° C, the fluororesin (A) When the fluororubber is dynamically cross-linked under the melting condition of the fluorocarbon resin (A), the melting temperature must be set above the melting point of the fluorocarbon resin (A). Fluoro rubber tends to be thermally deteriorated.

[0025] 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.

[0026] Examples of the fluororubber include perfluorofluororubber (bl), non-perfluorofluororubber (b2), and fluorine-containing thermoplastic elastomer (b3).

[0027] Examples of the perfluorofluororubber (bl) include TFEZPAVE copolymer, TFEZ hexafluoropropylene (hereinafter referred to as HFP!) ZPAVE copolymer, and the like.

[0028] Examples of the non-perfluorofluororubber (b2) include VdF-based polymers and TFEZ-propylene-based copolymers, which are used alone or in a range that does not impair the effects of the present invention. Any combination can be used.

[0029] Further, those exemplified as the perfluoro fluorine rubber and non-perfluoro fluorine rubber have a constitution of a main monomer, and those obtained by copolymerizing a crosslinking monomer, a modified monomer, etc. can be suitably used. Examples of crosslinking monomers and modifying monomers include iodine atoms, bromine Known crosslinking monomers such as those containing atoms and double bonds, transfer agents, modified monomers such as known ethylenically unsaturated compounds, and the like can be used.

[0030] Specific examples of the VdF polymer include a VdFZHFP copolymer, a VdFZTFE ZHFP copolymer, a VdFZTFEZ propylene copolymer, a VdFZ ethylene ZHFP copolymer, a VdFZTFEZPAVE copolymer, Examples thereof include VdFZPAVE copolymers and VdF ZCTFE copolymers. More specifically, the fluorine-containing copolymer is preferably composed of 25 to 85 mol% of VdF and 75 to 15 mol% of at least one other monomer copolymerizable with VdF. Preferred is a fluorine-containing copolymer having 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, penta Examples include fluorine-containing monomers such as fluoropropylene, trifluorobutene, tetrafluoroisobutene, PAVE, and fluorinated butyl, and non-fluorine monomers such as ethylene, propylene, and alkyl butyl ether. These can be used alone or in any combination.

[0032] Among the fluororubbers, it is preferred that the fluororubber contains VdF units from the viewpoint of heat resistance, compression set, workability, and cost. It is a fluororubber having VdF units and HFP units. It is more preferable.

[0033] From the viewpoint of good compression set, it is preferable that the fuel is at least one rubber selected from the group consisting of VdFZHFP-based fluororubber, VdFZTFEZ HFP-based fluororubber, and TFEZ propylene-based fluororubber. From the perspective of permeability, it is more preferable to use VdFZTFEZHFP-based fluoro rubber! /.

[0034] The fluororubber used in the present invention can be produced by a usual emulsion polymerization method.

Polymerization conditions such as temperature and time during polymerization may be appropriately determined depending on the type of monomer and the target elastomer.

[0035] The fluorine-containing thermoplastic elastomer (b3) is not particularly limited, but it has at least one elastomeric polymer segment because of its excellent compatibility with fluorine resin. (p—l) and at least one non-elastomeric polymer segment (p—2), an elastomeric polymer segment (p—1) and a non-elastomeric polymer segment (p—

Of 2), at least one is preferably a fluorine-containing polymer segment.

[0036] 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. For example, TFE, CTFE, HFP, and general formula (4):

CF = CFO (CF CFX'O)-(CF CF CF O) — R ⁴ (4)

2 2 p 2 2 2 q f

(In the formula, X ¹ is a fluorine atom or —CF; R ⁴ is a perfluoroalkyl having 1 to 5 carbon atoms.

3 f

A group; p is an integer of 0 to 5; q is an integer of 0 to 5)

Perhaloolefins such as perfluorobule ethers represented by: VdF, trifluoroethylene, triphenolopropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene And fluorine-containing monomers such as fluorinated butyl; non-fluorine monomers such as ethylene, propylene, and alkyl butyl ether; and any monomer that provides a crosslinking site.

[0037] Examples of the monomer that gives a crosslinking site include, for example, the general formula (5):

CX ⁵ = CX ⁵ -R ⁵ CHR ¹ X ⁶ (5)

2 f

(Wherein X ⁵ are the same force or different, hydrogen atom, fluorine atom or —CH; R ⁵ is fluoro

3 f Open-alkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group; R ¹ is a hydrogen atom or — CH; X ⁶ is an iodine atom

Three

Or iodine-containing monomer represented by the general formula (6): CF = CFO (CF CF (CF) 0) (CF) — X ⁷ (6)

2 2 3 m 2 n

(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) And the like, and these can be used alone or in any combination.

[0038] Next, as structural units of the non-elastomeric polymer segment (p-2), TFE, C TFE, PAVE, HFP ゝ General formula (7):

CF = CF (CF) X ⁸ (7) (Wherein, r is,. 1 to: L0 integer; X ⁸ is a fluorine atom or a chlorine atom in a) represented by reduction compounds with, par Haroo Lev-ins such as perfluoro-2-butene; VdF, Fukka Bulle , Trifluoroethylene, general formula (8):

CH = CX ⁹ — (CF) -X ⁹ (8)

2 2 s

(Wherein X ⁹ is a hydrogen atom or a fluorine atom; s is an integer of 1 to 10), partially fluorinated olefins such as CH 2 = C (CF 3); ethylene, propylene, butyl chloride, vinyl

2 3 2

-Non-fluorine monomers such as ruether, carboxylic acid bule ester, and acrylic acid.

[0039] Among these, the elastomeric polymer segment (p-1) is a copolymer of TFE / VdF / HFP, and the non-elastomeric polymer segment (p-2) is a copolymer of 1S TFE / ethylene. Polymeric segment (p— 1) 1S TFEZVdFZHFP = 0 to 35Z40 to 90Z5 to 50 mol%, and non-elastomeric polymer segment (p— 2) ) force TFEZ ethylene = 20 ~80Z80~20 mole ^_0/0 fluorinated thermoplastic elastomer one are more preferred.

[0040] The fluorine-containing thermoplastic elastomer is composed of an elastomeric polymer segment (ρ

A fluorine-containing multi-segmented polymer in which 1) and a non-elastomeric polymer segment (ρ-2) are bonded in the form of a block graft is preferred, and a fluorine-containing thermoplastic elastomer is a single elastomer. Preferably, the polymer segment (ρ-1) and two non-elastomeric polymer segments (ρ-2) force, and at least one of them is a triblock polymer force that is a fluorine-containing polymer segment.

[0041] As a method for producing a fluorine-containing thermoplastic elastomer, an elastomeric polymer segment (ρ

Among the strengths that can be used to connect various non-elastomeric polymer segments (ρ-2) in the form of block grafts, etc. to form fluorine-containing multi-segmented polymers, among others — The production method of block-type fluorine-containing multi-segment segment polymers described in Japanese Patent Publication No. 4728 and the production method of graft-type fluorine-containing multi-segmented polymers disclosed in Japanese Patent Application Laid-Open No. 62-34324. Preferably employed.

[0042] In particular, since a uniform and regular segmented polymer having a high segmentation rate (blocking rate) can be obtained, Japanese Patent Publication No. 58-4728, a collection of polymer papers (Vol. 49, No. Ten 1992)), a block type fluorine-containing multi-segmented polymer synthesized by a so-called iodine transfer polymerization method is preferred.

[0043] As a preferred method for producing a fluorine-containing thermoplastic elastomer, a known iodine transfer polymerization method can be given as a method for producing a fluororubber. For example, in a water medium, in the presence of an iodine compound, preferably in the presence of a diiodine compound, the perhaloolefin and, if necessary, a monomer that provides a curing site are stirred under pressure while being substantially oxygen-free. A method of carrying out emulsion polymerization in the presence of a radical initiator can be mentioned.

[0044] The thermoplastic polymer composition of the present invention dynamically changes the fluororubber composition (b) in the presence of the fluorine resin (A) under the melting condition of the fluorine resin (A). It is preferable to obtain it by crosslinking treatment. Here, the dynamic cross-linking treatment means that the fluororubber is dynamically cross-linked simultaneously with the melt kneading using a Banbury mixer, a pressure-kinder, 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 performing the crosslinking treatment, the phase structure of the fluorine resin (A) and the crosslinked fluororubber (B) and the dispersion of the crosslinked fluororubber (B) can be controlled.

[0045] In order to cross-link at least one fluororubber composition (b) to the thermoplastic polymer composition of the present invention, it is preferable to further add a cross-linking agent (C).

[0046] The crosslinking agent (C) can be appropriately selected depending on the type of the fluororubber composition (b) to be crosslinked and the melt-kneading conditions.

[0047] When the fluororubber contains a crosslinkable group (cure site), the cross-linking system used in the present invention may be appropriately selected depending on the type of cure site or the use of the obtained molded product. As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

[0048] Here, in the case of cross-linking by a polyol cross-linking system, it has a feature that it has a carbon-oxygen bond at the cross-linking point, has a small compression set, a good moldability, and an excellent sealing property. Is preferred.

[0049] In the case of crosslinking by an organic peroxide crosslinking system, since it has a carbon-carbon bond at the crosslinking point, a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine crosslinking system having a carbon-nitrogen double bond. Compared with, superior in chemical resistance and steam resistance There is a feature that.

[0050] Cross-linking by polyamine cross-linking 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 be larger than when crosslinking is performed using a polyol crosslinking system or an organic peroxide crosslinking system.

[0051] Therefore, in the present invention, it is preferable to use a polyol crosslinking type or organic peroxide crosslinking type crosslinking agent. As described above, a polyol crosslinking type crosslinking agent is used because of its excellent sealing properties. More preferred ,.

[0052] As the crosslinking agent (C) in the present invention, a polyamine-based, polyol-based or organic peroxide-based crosslinking agent can be used.

[0053] Examples of the polyamine cross-linking agent include hexamethylenediamine amine carbamate, N, N, unicinnamylidene 1,6 hexamethylenediamine, 4, 4'-bis (aminocyclohexenole) methane power rubamate And polyamine compounds. Of these, N, N'-dicinnamylidene 1, 6 hexamethylenediamine is preferred!

[0054] As the polyol cross-linking agent, a compound conventionally known as a fluororubber cross-linking agent can be used. For example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound having excellent heat resistance. A compound is preferably used.

[0055] The polyhydroxy aromatic compound is not particularly limited, and examples thereof include 2, 2 bis (4 hydroxyphenol) propane (hereinafter referred to as bisphenol A), 2, 2 bis (4 hydroxyphenol). ) Perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3 dihydroxybenzene, 1,7 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 4,4'-dihydroxydiphenyl 4, 4 'dihydroxystilbene, 2, 6 dihydroxyanthracene, hydroquinone, catechol, 2, 2-bis (4-hydroxyphenol) butane (hereinafter referred to as bisphenol B), 4, 4-bis (4— Hydroxyphenol) valeric acid, 2, 2 bis (4 hydroxyphenol) tetrafluorodiclonal propane, 4, 4, dihydroxydiphenol Ninoles norephone, 4, 4, -dihydroxydiphenyl ketone, tri (4-hydroxyphenol) methane, 3, 3 ', 5, 5, monotetrachlorobisphenol A, 3, 3', 5, 5, One tetrabromobisphenol A. These polyhydro The xyaromatic compound may be an alkali metal salt, an alkaline earth metal salt, or the like, but it is preferable that the above metal salt is not used when the copolymer is prayed using an acid.

[0056] The organic peroxide cross-linking agent may be an organic peroxide compound that can easily generate a peroxide radical in the presence of heat or a redox system. , 1 Bis (t butylperoxy)-3, 5, 5 Trimethylcyclohexane, 2, 5 Dimethyl hexane 2, 5 Dihydroperoxide, Di-t-butyl peroxide, t-Butylcumyl peroxide, Dicumyl peroxide, a , α Bis (t-butylperoxy) -p diisopropylbenzene, 2,5 dimethyl-2,5 di (t-butylperoxy) hexane, 2,5 dimethyl-2,5 di (t-butylperoxy) monohexyne-3, Ben Zoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, etc.Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferred.

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

[0058] In the polyol crosslinking system, a crosslinking accelerator (D) is usually used in combination with the polyol crosslinking agent. When the crosslinking accelerator (D) is used, the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

[0059] As the polyol crosslinking-type crosslinking accelerator (D), an organic compound is generally used. Ammonium compounds are not particularly limited. For example, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, monofunctional compounds Amine compounds are preferred, and among these, quaternary ammonium salts and quaternary phospho- um salts are preferred.

[0060] The quaternary ammonium salt is not particularly limited. For example, 8—methyl 1,8 diazabicyclo [5, 4, 0] —7 undese-um chloride, 8—methyl-1,8 diazabicyclo [ 5, 4, 0] — 7 Hundesseum Iodide, 8-Methyl-1, 8 Diazabicyclo [5, 4, 0] — 7 undese-um hydroxide, 8—methyl 1, 8 diazabicyclo [5,

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

5, 4, 0] —7 Undecem-bromide, 8 Propyl 1,8 Diazabicyclo [5, 4, 0] —7 Undecem-bromide, 8 Dodecyl 1,8 Diazabicyclo [5, 4, 0]-7 —Undece- Umchloride, 8 dodecyl 1,8 diazabicyclo [5, 4, 0] — 7 und dec-um hydroxide, 8 eicosyl— 1, 8 diazabicyclo [5, 4, 0]-7- undese-um chloride, 8—Tetracosyl 1,8 diazabicyclo [5, 4, 0] — 7 und dec-um chloride, 8 benzyl 1, 1, 8 diazabicyclo [5, 4, 0] — 7 und dec-um chloride (hereinafter referred to as DBU— B) , 8 Benzyl-1,8 diazabicyclo [5, 4, 0] 7 undecse-um hydroxide, 8 phenethyl 1, 8 diazabicyclo [5, 4, 0] — 7 undece-um chloride, 8— (3—hue- Rupropyl) — 1, 8 Gizabic mouth [5, 4, 0] — 7 Undeceth-um chloride Etc. Among these, DBU-B is preferable from the viewpoint of the crosslinkability and the physical properties of the cross-linked product.

[0061] The quaternary phospho-um salt is not particularly limited, and examples thereof include tetrabutyl phospho-um chloride, benzyl triphenyl phospho-um chloride (hereinafter referred to as BTPPC), benzyl trimethyl phospho-um chloride, benzyl. Examples thereof include tributylphosphomethylene chloride, tributylarylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, benzylphenol (dimethylamino) phosphonium chloride, and the like. Benzyltriphenyl-phosphomum chloride (BTPPC) is preferred.

[0062] Further, as a crosslinking accelerator (D), a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, chlorine disclosed in JP-A-11-147891 Free bridge accelerators can also be used.

[0063] Examples of the organic peroxide crosslinking accelerator (D) include triaryl cyanurate, triaryl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N, -m— Phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triaryl isocyanate (2, 3, 3 卜! ; Funore talent P 2 P P peninole) 1, 3, 5— Triazine—2, 4, 6-trione), Tris (diallylamin) —S-triazine, triaryl phosphite, N, N-diarylacrylamide, 1,6-dibi-dodecafluorooral hexane, hexaryl Phosphoramide, N, N, Ν ', Ν, monotetraallyl phthalamide, Ν, Ν, Ν', 一, 1 tetraallyl malonamide, tribule isocyanurate, 2,4,6-tribule Examples include methyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite. Among these, triallyl isocyanurate HTAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

[0064] The addition amount of the crosslinking agent (C) and the crosslinking accelerator (D) was adjusted so that the 90% completion time Τ90 at the temperature when dynamically crosslinking was 90 to 2 to 6 minutes. The preferred amount is vulcanized 90% completion time Τ90 is more preferably the amount adjusted to be 3-5 minutes. The optimal vulcanization time Τ90 is less than 2 minutes, the dispersion of the crosslinked rubber tends to be uneven and coarse, and if it exceeds 6 minutes, it takes a long time for the rubber to crosslink. And there is a tendency not to completely crosslink.

[0065] Here, vulcanization 90% completion time Τ90 means dynamic vulcanization using JSR type chilastometer type II and type V at the time of primary press vulcanization of fluororubber composition (b). The vulcanization curve at the hour temperature is obtained, and the time to reach 90% of the maximum torque value is defined as the vulcanization 90% completion time (T90).

[0066] As a specific method for determining the addition amount of the crosslinking agent (C) and the crosslinking accelerator (D), vulcanization 90% completion time T90 at 170 ° C is 2 to 6 minutes, preferably 3 to 5 First, obtain X parts by weight of crosslinking agent (C) and 100 parts by weight of fluoro rubber, and Y parts by weight of crosslinking accelerator (D).

[0067] 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 0.5% by weight, preferably 0.3% to 0.4% by weight, or

(ii) Amount of crosslinking agent (C): 2 to 5 parts by weight, Amount of crosslinking accelerator (D): 0.4 to 2.5 parts by weight Forces Preferred in the present invention, crosslinking agent (C) and crosslinking accelerator (D) is added.

[0068] If the crosslinking accelerator (D) is less than 0.2 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. Yes, 2. If the amount exceeds 5Y parts by weight, the mechanical strength of the resulting thermoplastic polymer composition tends to decrease.

[0069] The melting condition means a temperature at which the fluorocarbon resin (foam) and the fluororubber composition (b) are melted. The melting temperature varies depending on the glass transition temperature and the Z or melting point of the fluororesin (A) and the fluororubber composition (b), respectively, but is preferably 120 to 330 ° C, and is preferably 130 to 320 ° C. More preferably. If the temperature is lower than 120 ° C, the dispersion between the fluororesin (A) and the fluororubber tends to be coarsened, and if it exceeds 330 ° C, the fluorine rubber tends to be thermally deteriorated.

[0070] The obtained thermoplastic polymer composition has a structure in which the fluorine resin (A) forms a continuous phase and the crosslinked rubber (B) forms a dispersed phase, or the fluorine resin (A) and the crosslinked structure. The fluororubber (B) can have a structure that forms a co-continuity, and among them, the fluororesin (A) has a structure that forms a continuous phase and the crosslinked rubber (B) has a structure that forms a dispersed phase. I prefer it.

[0071] Even when the fluororubber initially forms a matrix, as the cross-linking reaction proceeds, the fluororubber becomes the 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 fluorocarbon resin (A).

[0072] When such a structure is formed, the thermoplastic polymer composition of the present invention exhibits excellent heat resistance, chemical resistance, and oil resistance, and is compatible with low fuel permeability and flexibility. In addition, it has better moldability. At that time, the average dispersed particle size of the crosslinked fluororubber (B) is preferably 0.01 to 30 / ζ πι. If the average dispersed particle size is less than 0.01 μm, the fluidity tends to decrease, and if it exceeds 30 / zm, the strength of the resulting thermoplastic polymer composition tends to decrease.

[0073] Further, in the thermoplastic polymer composition of the present invention, the preferred fluororesin (A) forms a continuous phase, and the crosslinked fluororubber (B) forms a dispersed phase. It is also possible to include a co-continuous structure of fluorine resin (A) and cross-linked fluororubber (B) as part of the structure.

[0074] The weight ratio of the fluorinated resin (A) to the crosslinked fluororubber (B) is 98Z2 to: LOZ90, and preferably 95/5 to 20Z80. If the amount of fluorine resin (Α) is less than 10% by weight, the fluidity of the resulting thermoplastic polymer composition tends to deteriorate and the molding processability tends to deteriorate. Flexibility and fuel permeability baluns of plastic polymer compositions. Tend to get worse.

[0075] 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, and preferably 20 g'mm / m ² 'day or less. More preferred is 10 g-mm / m ² · day or less, and particularly preferred is 5 g · / · day or less. 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'mmZdaym ² , the fuel permeation resistance is low, so that it is necessary to increase the thickness of the molded product in order to suppress the fuel permeation amount, which is not economically preferable. Note that the lower the fuel permeability coefficient, the better the fuel permeation preventing ability. On the contrary, if the fuel permeability coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

[0076] The fuel permeability coefficient was measured by a method in accordance with the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method stipulated 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, put 18 mL of simulated fuel CE10 (toluene Z isooctane Z ethanol = 45 Z45 Z10 vol%) into a SUS container (open area 1.26 X 10 " ³ m ² ) with a volume of 20 mL. Then, set the sheet-like test piece in the open part of the container and seal it to make a test piece.Place the test piece in a constant temperature device (60 ° C), measure the weight of the test piece, and measure the weight per unit time. When the weight loss becomes constant, the fuel permeability coefficient is obtained by the following formula.

[0077] [Equation 1] Fuel Permeability (g · mm / m ² 'day) =

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

[Open area 1, 2 6 X 1, 0 ³ (m ² )] X [Measurement interval (d. Ay)]

[0078] The tensile modulus of the molded article having the thermoplastic composition strength of the present invention is preferably lOOOMPa or less, more preferably 800 MPa or less, and even more preferably 700 MPa or less. It is particularly preferably 600 MPa or less. The lower limit value of the tensile modulus is not particularly limited, but it is preferably 5 MPa or more. More preferably. Tensile modulus over lOOOMPa tends to be unsuitable for molded products that require flexibility.

[0079] Further, the thermoplastic polymer composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester, polyurethane, calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate. Such as inorganic fillers, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, release agents, foaming agents, fragrances, oils, softeners, etc. Addition can be carried out within a range that does not affect the effects of the present invention.

[0080] 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 compact of any shape.

[0081] 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, Further, it includes a laminated structure having a layer made of the thermoplastic polymer composition of the present invention and a layer made of another material.

[0082] In the laminated structure of at least one layer as the thermoplastic polymer composition force of the present invention and at least one layer as the other material force, the other material is expected to have the required properties. What is necessary is just to select an appropriate thing according to a use. Examples of the other material include polyolefin (eg, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene propylene copolymer, polypropylene, etc.), nylon, polyester, salt Thermoplastic polymers such as bur resin (PVC) and salt vinylidene resin (PVDC), cross-linked rubber such as ethylene propylene gen rubber (EPDM), butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, polypropylene / EPDM composite Examples thereof include thermoplastic elastomers such as bodies, metals, glass, wood, and ceramics.

[0083] The molded article having the laminated structure is composed of the thermoplastic polymer composition of the present invention. An adhesive layer may be interposed between the layer and the base material layer made of other materials! 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. The adhesive used in the adhesive layer includes an acid anhydride modified product of a gen-based polymer; an acid anhydride modified product of polyolefin; a polymer polyol (for example, a glycol or a mixture of glycols such as ethylene glycol and propylene glycol). Polyols obtained by polycondensation of dibasic acids such as adipic acid; partially saponified products of copolymers of butyl acetate and butyl chloride and polyisocyanate compounds (eg, 2, 4- A mixture of a glycol compound such as 1,6-hexamethylene glycol and a diisocyanate compound such as 2,4-tolylene diisocyanate in a molar ratio of 1 to 2. Reaction product: molar ratio of triol compound such as trimethylolpropane to diisocyanate compound such as 2,4-tolylene diisocyanate 1 to 3 And the like can be used. For forming the laminated structure, a known method such as co-extrusion, co-injection, or extrusion coating can be used.

[0084] The present invention includes a fuel hose or a 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 a filler hose for automobiles, an evaporation hose, and a breather hose. Further, the use of the fuel container is not particularly limited, and examples thereof include a fuel container for an automobile, a fuel container for a motorcycle, a fuel container for a small generator, and a fuel container for a lawn mower.

[0085] Further, the present invention includes a multilayer fuel hose or a multilayer fuel container including a layer comprising the thermoplastic polymer composition of the present invention. The multi-layer fuel hose or multi-layer fuel container comprises 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. In other words, they are bonded to each other with or between them.

[0086] Examples of other material strength layers include layers made of rubber other than the thermoplastic polymer composition of the present invention and layers made of thermoplastic resin.

[0087] From the viewpoint of chemical resistance and flexibility, the rubber includes acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epoxy. Selected from the group consisting of chlorohydrin rubber, EPDM and acrylic rubber A rubber having at least one kind of strength is selected from the group consisting of acrylonitrile monobutadiene rubber or its hydrogenated rubber, a blend rubber of acrylonitrile monobutadiene rubber and polysilene rubber, fluororubber, and epichlorohydrin rubber. It is more preferable to have at least one kind of rubber!

[0088] Further, as the thermoplastic resin, from the viewpoint of fuel barrier properties, fluorine resin, polyamide-based resin, polyolefin-based resin, polyester-based resin, polybulu alcohol-based resin, polysalt-based resin Fluorine resin, polyamide resin, polybutyl alcohol resin, polyphenylene sulfide resin, which preferably has at least one thermoplastic resin selected from the group consisting of bur resin and polyphenylene sulfide resin More preferred is a thermoplastic rosin having at least one strength selected from the group consisting of fats.

[0089] The fuel hose or the fuel container including the layer composed of the thermoplastic polymer composition obtained by the present invention as described above and the layer composed of other rubber or other thermoplastic resin is particularly limited. For example, fuel hoses such as filler hose, evaporative hose, breather and hose for automobiles; fuel containers for automobiles, fuel containers for motorcycles, fuel containers for small generators, fuel containers for lawn mowers, etc. A fuel container.

[0090] Among them, as a fuel hose comprising a layer made of the thermoplastic polymer composition of the present invention and a layer made of other rubber, acrylonitrile monobutadiene rubber or its hydrogenated rubber, acrylonitrile butadiene rubber and polychlorinated A fuel hose composed of a three-layer force consisting of an outer layer that also has a rubber blend with bule or an epichlorohydrin rubber, an intermediate layer that also has the thermoplastic polymer composition of the present invention, and an inner layer that also has a fluororubber power, or acrylonitrile butadiene rubber A hydrogenated rubber, a blend rubber of acrylonitrile butadiene rubber and polysulphated bur is composed of two layers: an outer layer also having an epichlorohydrin rubber strength, and an inner layer composed of the thermoplastic polymer composition of the present invention. Fuel hose shows excellent fuel barrier properties, flexibility and chemical resistance It is preferable in point! / ヽ.

[0091] When a laminated structure having a layer made of the fuel barrier material of the present invention and a layer made of another material is produced, the surface of the fuel barrier material of the present invention is surfaced as necessary. Processing may be performed. The surface treatment is not particularly limited as long as it is a treatment method that enables adhesion. For example, discharge treatment such as plasma discharge treatment or corona discharge treatment can be used. And metal sodium z naphthalene solution treatment of wet and wet methods. A primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When the primer treatment is applied, the surface treatment can be performed to treat the surface of the fluorine resin, but the fuel barrier properties are pre-treated with plasma discharge treatment, corona discharge treatment, metal sodium Z naphthalene solution treatment, etc. It is more effective to further prime the surface of the material.

[0092] The thermoplastic polymer composition of the present invention and the molded article made of the composition can be suitably used in the following fields.

[0093] In semiconductor-related fields such as semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma addressed liquid crystal panels, field emission display panels, solar cell substrates, etc., o (square) rings, packings, sealing materials, tubes Rolls, coatings, linings, gaskets, diaphragms, hoses, etc., which are CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation equipment, exhaust equipment It can be used for chemical piping and gas piping. Specifically, as a gate valve O-ring and seal material, as a quartz window O-ring and seal material, as a chamber O-ring and seal material, as a gate O-ring and as a seal material, a bell jar O-ring and seal Coupling O-rings, seal materials, pump O-rings, sealing materials, diaphragms, semiconductor gas control device O-rings, sealing materials, resist developer, stripping solution O-rings As a sealing material, as a wafer cleaning solution hose, as a tube, as a wafer transfer roll, as a resist developer bath, as a coating for a stripping solution bath, as a coating, as a coating, as a wafer cleaning solution bath lining, as a coating or as a wet etching bath It can be used as a lining or coating. In addition, sealing materials' sealing agent, optical fiber quartz coating material, electronic parts for insulation, vibration proofing, waterproofing, moisture proofing, circuit board potting, coating, adhesive seals, gaskets for magnetic storage devices, It is used as a modifier for sealing materials such as epoxy, sealant for clean rooms and clean rooms.

[0094] In the automotive field, gaskets, shaft seals, valve stem seals, seals and hoses can be used for engines and peripheral devices. It can be used for AT devices, and 0 (square) rings, tubes, knocks, valve cores, hoses, seals and diaphragms 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, hold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, Ettater packing, fuel pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston packing, cylinder liner seal, knob stem seal, automatic transmission front pump seal, rear axle On-seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas re-burning unit scenery, bearing Shinore, EGR tubes, twin key bush tube for sensors Daiafuramu carburetor, rubber vibration isolator (engine mount, exhaust part, etc.), afterburners hoses, can be used as an oxygen sensor bush.

[0095] In the aircraft field, the rocket field, and the marine field, there are diaphragms, O (square) rings, valves, tubes, knockers, 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, gaskets for hydraulic equipment, firewall seals, etc. Used for propeller shaft stern seals for screws, intake / exhaust valve stem seals for diesel engines, valve seals for butterfly valves, shaft seals for butterfly valves, etc.

[0096] In the field of chemicals such as plants, linings, valves, knocks, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, chemical-resistant coatings, etc. are available. It can be used in the production process of chemicals such as agricultural chemicals, paints, and fats. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packings for sulfuric acid production equipment, pesticide sprayers, seals for pesticide transfer pumps, gas pipe seals, plating solutions Seals, high-temperature vacuum dryer packing, paper belt roller seals, fuel cell seals, wind tunnel joint seals, trichlene-resistant rolls (for textile dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH Packing of meter tube joint It can be used as a chlorine gas transfer hose, benzene, toluene rainwater drain hose, analytical instrument, scientific instrument seal, tube, diaphragm, valve part, etc.

[0097] In the pharmaceutical field such as pharmaceuticals, it can be used as a medicine stopper or the like.

[0098] In the photographic field such as a developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, rolls and the like can be mentioned. be able to. Specifically, as a developing roll of a film developing machine / coiled film image forming machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating tool, and a magnetic tape manufacturing coating It can be used as a line guide roll, various coating rolls, and the like. Furthermore, dry copying machine seals, printing equipment printing rolls, scrapers, tubes, valve parts, coating, coating equipment coating rolls, scrapers, tubes, valve parts, printer ink tubes, rolls, belts, dry copying machine belts It can be used as a roll, a roll for a printing press, a belt, or the like.

[0099] The tube can also be used in the field of analysis and science.

[0100] In the food plant equipment field, linings, valves, knockers, rolls, hoses, diaphragms, ο (square) rings, tubes, sealing materials, belts, and the like can be mentioned and used for food production processes. Specifically, it can be used as a plate-type heat exchanger seal, a solenoid valve seal of a vending machine, or the like.

[0101] In the nuclear plant equipment field, packing, ο ring, hose, sealing material, diaphragm

, Nozzles, rolls, tubes, etc.

[0102] In the steel field such as iron plate processing equipment, rolls and the like can be mentioned, which can be used for iron plate processing rolls and the like.

[0103] In the general industrial field, packing, scissors ring, hose, sealing material, diaphragm, valve, roll, tube, lining, mandrel, electric wire, flexible joint, belt, rubber plate, weather strip, roll of PPC copier, Examples include roll blades and belts. Specifically, oil pressure, lubrication machine seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seal (vacuum) valves, automatic packaging machine seals For analysis of sulfur dioxide and chlorine gas in the air Used for pump diaphragms (pollution measuring instruments), printing press rolls, belts, pickling squeeze rolls, etc.

[0104] In the electric field, specifically, it is used as an insulating oil cap for Shinkansen, a ventilator seal for a liquid ring transformer, a jacket for an oil well cable and the like.

[0105] In the fuel cell field, specifically, a sealant between electrodes and separators is used as a seal for hydrogen 'oxygen' product water piping.

[0106] In the electronic component field, specifically, it is used as a heat-dissipating material raw material, an electromagnetic shielding material raw material, a printed wiring board pre-preda resin modified material such as epoxy, an anti-scattering material such as a light bulb, and a hard disk drive gasket of a computer Used.

[0107] There are no particular limitations on what can be used for on-site molding, such as metal gasket coating agents for automobile engines, gaskets for engine oil pans, rolls for copiers and printers, Architectural sealant, gasket for magnetic recording device, sealant for clean room filter unit, coating agent for printed circuit board, electrical 'electronic component fixing agent, insulation moisture-proof treatment of electrical equipment lead wire terminal, electric furnace, etc. Examples include oven seals, end treatment of sheathed heaters, microwave oven window frame seals, adhesion of CRT wedges and necks, adhesion of automotive electrical components, joint seals for kitchens, bathrooms, and washrooms.

[0108] The molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable as a fuel peripheral part. In addition, the molded article of the present invention is particularly useful as a sealing material, knock, roller, tube or hose.

Example

[0109] Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

[0110] <Vulcanization characteristics>

Using the JSR type kilastometer type II, obtain vulcanization curves at 170 ° C, 220 ° C and 250 ° C. From the change in torque, minimum viscosity (ML), vulcanization degree (MH), induction time (T10 ) And optimum vulcanization time (T90). If no change in torque is observed even after 30 minutes in the heated state, the vulcanization reaction proceeds and is considered to be! / ヽ. [0111] Kneading with Laboplast Mill>

The kneading of the fluororesin (A) and the fluororubber composition (b) is performed using a lab plast mill (manufactured by Toyo Seiki Seisakusho). The total amount of the fluorinated resin (A) and the fluororubber composition (b) to be kneaded is adjusted so that the total volume thereof is 77% by volume of the total volume of the kneaded 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 fluorine resin (A) used in the composition. After the temperature of the lab plast mill is stabilized, add fluorine resin and stir at lOrpm for 5-10 minutes to melt the fluorine resin. The fluororubber composition is added to the molten fluorocarbon resin, and immediately after the addition, the number of stirring is increased to lOOrpm. From the point of time when the torque showed the maximum value (corresponding to T90 measured with CYLAST II type), the mixture was stirred for 10 minutes to obtain a thermoplastic polymer composition.

[0112] <Hardness>

Using the thermoplastic polymer composition pellets produced in the examples and comparative examples, compression molding was performed under the conditions of 270 ° C and 5 MPa from a hot press machine to produce a sheet-like specimen having a thickness of 2 mm. These were used to measure the A hardness according to JIS-K6301.

[0113] <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 by a hot press machine at 270 ° C and 5 MPa, and a sheet-like test piece having a thickness of 2 mm was obtained. Prepare and punch out a 3.18mm wide dumbbell specimen using ASTM V-type dumbbells. Using the obtained dumbbell-shaped test piece, using an autograph (AGS—J 5kN, manufactured by Shimadzu Corporation), in accordance with ASTM D638, under the condition of 50 mmZ, the tensile elongation at break at 25 ° C Measure the tensile strength at break and tensile modulus.

[0114] 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 having a thickness of 0.5 mm was formed. A test piece was prepared. Put 18 mL of simulated fuel CE10 (toluene Z isooctane Z ethanol = 45 Z45 Z10 vol%) in a SUS container (open area 1.26 X 10 3 m ² ) with a volume of 20 mL, and store the sheet-shaped test piece in the container Set it in the open part and seal it to make the specimen. Put the test body in a thermostat (60 ° C), measure the weight of the test body, When the weight loss per unit time became constant, the fuel permeability coefficient was calculated by the following formula.

[0115] [Equation 2] Fuel Permeability Coefficient << g · mm / m ² -day) =

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

Open area 1, 2 6 X 1, 0 ³ (m ² )] X [Measurement interval (d. Ay)]

[0116] <Liquidity>

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

[0117] <Adhesion evaluation test>

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

[0118] <Atmospheric pressure plasma treatment>

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

[0119] <Corona discharge treatment>

The discharge electrode (30 cm width) of the corona treatment device was covered with a container made of acrylic resin, and air was allowed to flow for 10 LZ at atmospheric pressure. The surface of the fuel barrier material sheet was treated at a corona output of 250 W using a HV05-2 type power source manufactured by Tantech Co., Ltd. at a sheet moving speed of ImmZ. [0120] Metal Sodium Z Naphthalene Solution Treatment>

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

[0121] <Fluoro rubber>

VdF, 3-way based rubber consisting of TFE and HFP (VdF: TFE: HFP = 50: 20: 30 Monore ^_0/0, beam one at 100 ° C - one viscosity = 88)

[0122] Crosslinking agent (Cl)>

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

[0123] Crosslinking agent (C2)>

Polyamine cross-linking agent: N, N, —dicinnamylidene-1, 6-hexamethylenediamine (“V-3” manufactured by Daikin Industries, Ltd.)

[0124] <Crosslinking accelerator (D)>

Benzyltriphenylphospho-um chloride (BTPPC, Hokuko Chemical Co., Ltd.) [0125] Thermoplastic resin (non-fluorinated)>

Kuraray Co., Ltd. ethylene bull alcohol resin “Eval F101” (melting point: 183 ° C) As a result of evaluating the physical properties by the above method, the tensile elastic modulus was 2000 MPa or more and the fuel permeability coefficient was 0.3 (g · mm; / (m 'day)

[0126] <Thermoplastic elastomer (fluorine-based)>

Dyneon "THV 200G" (Comparative Example 1), Dyneon "THV 500G" (Comparative Example 2) or Dyneon "THV 815G" (Comparative Example 3)

[0127] Production Example 1 (Production of thermoplastic resin (fluorine))

392kg of demineralized pure water was charged in a jacketed stirring polymerization tank capable of containing 1316L of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, press Kutafunole P Shik P Butane 307kg, CTFE20.41kg, TFE35. Started. Di-n-propyl peroxy dicarbonate as a polymerization initiator Polymerization was initiated by adding 4.49 kg of a 50 mass% methanol solution of NPP. 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 polymer thus produced was taken out, washed with demineralized pure water, and dried to obtain 183.7 kg of a CTFE copolymer in the form of granular powder. Next, the mixture was melt-kneaded 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.

[0128] The composition of the thermoplastic resin (fluorine-based) was CTFEZTFEZPPVE = 44.5 / 53. 4 / 2.1 (mol%), and the melting point was 221 ° C. As a result of evaluating the physical properties by the above method, the tensile modulus was 520 MPa, and the fuel permeability coefficient was 0.3 (g · mm) Z (m ² · day).

[0129] Production Example 2 (Preparation of fluororubber composition (b— 2— 1))

In 100.0 parts by weight of the above-mentioned fluororubber, 2.0 parts by weight of crosslinking agent (Cl) (X), 1.0 part by weight of crosslinking accelerator (D) (Y), magnesium oxide (150 mg of Kiyogi Mug, Kyowa Chemical Industry Co., Ltd.) 3.0 A weight part was added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b-2-1).

[0130] 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.

[0131] Production Example 3 (Preparation of fluororubber composition (b-2-2))

In the above fluororubber, 100.0 parts by weight, a crosslinking agent (Cl) 2.0 parts by weight (X), a crosslinking accelerator (D) 0.77 parts by weight (Y), magnesium oxide (Kyoto Mug 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by weight and calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Industry Co., Ltd.) 6. Add the weight part and use an 8-inch open roll. The mixture was kneaded to produce a fluororubber composition (b-2-2).

[0132] 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. [0133] [Table 1] Table 1

[0134] Example 1

Melting and kneading 90 parts by weight of the above-described thermoplastic resin (fluorine-based) and 10 parts by weight of fluororubber composition (b-2-1) at a temperature of 250 ° C and screw rotation speed lOOrpm in a lab plast mill As a result, a thermoplastic 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.

[0135] Example 2

Melting and kneading 70 parts by weight of the above-mentioned thermoplastic resin (fluorine-based) and 30 parts by weight of fluororubber composition (b-2-1) at a temperature of 250 ° C and screw rotation speed lOOrpm in a lab plast mill As a result, a thermoplastic 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.

[0136] Example 3

Melting 50 parts by weight of the above-mentioned thermoplastic resin (fluorine-based) and 50 parts by weight of fluororubber composition (b-2-1) in a lab plast mill under the conditions of a temperature of 250 ° C and a screw speed of lOOrpm. The mixture was kneaded to obtain a thermoplastic polymer composition. 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.

[0137] Example 4

Melting and kneading 30 parts by weight of the above-mentioned thermoplastic resin (fluorine-based) and 70 parts by weight of fluororubber composition (b-2-1) at a temperature of 250 ° C and a screw rotation speed of lOOrpm in a lab plast mill As a result, a thermoplastic 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.

[0138] Comparative Examples 1 to 3

Using pellets of Dyneon's "THV 200G" (Comparative Example 1), Dyneon's "THV 500G" (Comparative Example 2) or Dyneon's "THV 815G" (Comparative Example 3), hardness and tensile strength at break as described above Table 2 shows the results of measurements of tensile elongation at break, tensile modulus, fuel permeability and melt flow rate.

[0139] Comparative Example 4

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

[0140] Comparative Example 5

70 parts by weight of the above-mentioned thermoplastic resin (non-fluorine) and 30 parts by weight of fluororubber composition (b-2-2) were melted in a lab plast mill under the conditions of a temperature of 220 ° C and a screw speed of lOOrpm. The mixture was kneaded to obtain a thermoplastic polymer composition. An attempt was made to produce a sheet by the above-described method using the pellets of the obtained 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 The tensile elongation at break was 3% or less and 50% or less. Similarly, fuel permeation tests could not be performed due to membrane quality problems. The evaluation results are shown in Table 2.

[Table 2]

CM

The thermoplastic resin composition obtained in Examples 1 to 4 has excellent fuel permeability and fuel permeability compared to the thermoplastic elastomer (fluorine-based) used in Comparative Examples 1 to 3. sex The balance between flexibility and flexibility was strong.

[0143] In addition, the thermoplastic resin composition obtained in Examples 1 to 4 has a continuous thermoplastic resin (A) by morphological observation with a scanning electron microscope (manufactured by Nippon Electronics Co., Ltd.). It was found that the cross-linked fluororubber (B) has a structure that forms a dispersed phase. The dispersed particle size of the crosslinked fluororubber (B) was 20 / zm or less in all of Examples 1 to 4.

[0144] Production Example 4 (Preparation of fluororubber composition (b-2-3))

10.0 parts by weight of fluororubber, 2.0 parts by weight of cross-linking agent (Cl), 0.5 parts by weight of cross-linking accelerator (D), magnesium oxide (Kiyo Izuma Mag 150, Kyowa Chemical Industry Co., Ltd.) 3 0 parts by weight, calcium hydroxide (Caldic 2000, Omi Chemical Co., Ltd.) 6.0 parts by weight, carbon black (Thermax N-990, Cancarb Ltd.) 20. 0 parts by weight An 8-inch open roll was used and kneaded to prepare a fluororubber composition (b-2-3).

[0145] Production Example 5 (Preparation of fluororubber composition (b-2-4))

10.0 parts by weight of fluororubber, 3.0 parts by weight of crosslinking agent (C2), magnesium oxide (Kyoto 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).

[0146] Production Example 6 (Preparation of epichlorohydrin rubber composition)

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

[0147] The sheet of the fuel barrier material obtained in Example 2, the fluororubber composition (b-2-3) obtained by the production method shown in Production Example 4, and the production method shown in Production Example 5 were obtained. Hook The adhesion evaluation test with the raw rubber composition (b 2-4) and the epipic hydrin rubber composition obtained by the production method shown in Production Example 6 was performed by the above method. The peel strength is 9 NZcm when the fluororubber composition (b-2-3) is used, 22 NZcm when the fluororubber composition (b-2-4) is used, and the epichlorohydrin rubber composition is used. 8 NZ cm, and the interface between the fuel barrier material and the vulcanized rubber sheet was peeled off regardless of the type of rubber composition used.

[0148] The surface of the fuel barrier material sheet obtained in Example 2 was subjected to atmospheric pressure plasma treatment and surface treatment, and the fluororubber composition obtained by the production method shown in Production Example 4 (b — 2-3) Adhesion with fluororubber composition (b 2-4) obtained by the production method shown in Production Example 5 and epichlorohydrin rubber composition obtained by the production method shown in Production Example 6 The property evaluation test was conducted by the above method. Regardless of the type of rubber composition used, the material of the vulcanized rubber sheet was destroyed and the peel strength was 30 NZcm or more.

[0149] The surface 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) obtained by the production method shown in Production Example 4. 3) Adhesive evaluation test with fluororubber composition (b 2-4) obtained by the production method shown in Production Example 5 and epichlorohydrin rubber composition obtained by the production method shown in Production Example 6 Was carried out by the method described above. Regardless of the type of rubber composition used, it was found that the vulcanized rubber sheet was destroyed and its peel strength was 30 NZcm or higher. The surface of the sheet of the fuel barrier material obtained in Example 2 was treated with a metallic sodium Z naphthalene solution, and the fluororubber composition obtained by the production method shown in Production Example 4 (b 2— 3) Adhesiveness to 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 evaluation test was conducted by the above method. Regardless of the type of rubber composition used, it was found that the vulcanized rubber sheet part failed and the peel strength was 30 NZcm or more.

Industrial applicability

[0150] The strength of the thermoplastic polymer composition of the present invention is obtained by using a specific fluorine resin. As a result, it has excellent fuel permeability and flexibility, and has excellent moldability.

Claims

The scope of the claims

[1] Fluororesin containing black-mouthed trifluoroethylene units and tetrafluoroethylene units

A thermoplastic polymer composition comprising (A) and at least a part of the crosslinked fluororubber (B).

[2] The cross-linked fluororubber (B) is obtained by dynamically cross-linking the fluororubber composition (b) under the melting condition of the fluorocobalt (A) in the presence of the fluorocobalt (A). The thermoplastic polymer composition according to claim 1, wherein: The thermoplastic polymer composition according to claim 1 or 2, wherein the thermoplastic polymer composition is a fluorine resin containing a copolymerizable monomer (a) unit.

[4] Monomer (a) force Ethylene, bi-lidene fluoride, perfluoro (alkyl buer ter) and general formula (1):

CX'X ^ CX 'CCF) X ⁴ (1)

2 n

Three

Number)

4. 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.

[5] A molded article formed of the thermoplastic polymer composition according to any one of claims 1 to 4.

[6] A fuel tube formed of the thermoplastic polymer composition according to any one of claims 1 to 4.

[7] A fuel hose formed of the thermoplastic polymer composition according to any one of claims 1 to 4.