JP5273048B2 - Thermoplastic resin composition containing fluorine-containing resin and crosslinked fluororubber - Google Patents

Description

  The present invention relates to a thermoplastic resin composition comprising a fluorine-containing resin having a modified end and a crosslinked fluororubber that is at least partially crosslinked.

  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.

  Furthermore, since the material excellent in the fuel barrier property is used by being laminated with an elastomer layer such as acrylonitrile-butadiene rubber or epichlorohydrophosphorus rubber, for example, adhesion to such other materials is also required. The

  Under the circumstances, “Dyneon THV” has been developed as a resin that is flexible, has a fuel barrier property, and has a melt moldability and a recyclability (for example, Modern Fluoropolymers: high performance polymers for Jonson 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. However, there is insufficient compatibility between flexibility and fuel barrier properties, and there is room for improvement in adhesion to other materials.

  In addition, fluororubber has excellent heat resistance, chemical resistance, compression set, and other properties, so it is used in many applications in the automotive, semiconductor, and industrial fields. Is excellent in properties such as slidability, heat resistance, chemical resistance, weather resistance, and electrical properties, and is used in a wide range of fields such as automobiles, industrial machines, OA equipment, and electrical and electronic equipment. For the purpose of further improving the heat resistance of fluororubber, or for the purpose of imparting flexibility to the fluororesin, polymer alloys of fluororubber and fluororesin have been studied (for example, JP-A-61-57641). The polymer alloy is attracting attention in a fuel peripheral part such as a fuel tube material, which requires both fuel permeation resistance and flexibility.

  However, in such a polymer alloy of fluororubber and fluorine-containing resin, it is necessary to increase the fluorine-containing resin component in order to improve fuel permeation resistance. However, if the fluorine-containing resin component is increased, flexibility is increased. There is a problem of being damaged. On the other hand, in order to improve flexibility, it is necessary to increase the amount of the fluorine rubber component, but it becomes more difficult to uniformly disperse the rubber in the resin that becomes the continuous phase (sea component). As a result, there is a problem that the rubber of the dispersed phase (island component) forms a co-continuous phase and sufficient resin physical properties cannot be obtained. Furthermore, there is room for improvement in the adhesion between the polymer alloy and other materials such as elastomer.

  Further, a thermoplastic elastomer composition comprising a fluororesin comprising a tetrafluoroethylene / hexafluoropropylene copolymer (FEP) having excellent fuel permeation resistance and a fluororubber is known (for example, JP-A-10-101880). Gazette, Japanese Patent Laid-Open No. 10-219062). However, since the thermoplastic elastomer composition of the patent document contains more rubber components than the resin component, the resulting alloy has a low fuel barrier property and is not suitable for applications requiring high fuel barrier properties. There is also room for improvement in the adhesion between the elastomer composition and other materials.

  Further, JP-A-5-140401 discloses a fluorine-containing thermoplastic elastomer composition in which a cross-linked fluorine-containing elastomer is dispersed using a thermoplastic fluorocarbon resin that can be melt-molded as a continuous layer. However, since this composition has more rubber components than resin components, the resulting alloy has a low fuel barrier property and is not suitable for applications requiring high fuel barrier properties. Further, in order to improve the shortage of vulcanization, it has been proposed to use those having cross-linked sites such as epoxy groups, carboxylic acid groups, and sulfone groups as fluorine-containing elastomers dispersed in the composition. There has been no study on adhesiveness.

  An object of this invention is to provide the thermoplastic resin composition which is compatible with fuel-barrier property and a softness | flexibility, and is excellent in adhesiveness with another material.

The present invention is a thermoplastic resin composition comprising a fluororesin (A) and a crosslinked fluororubber (B),
The fluororesin (A) is a copolymer having a carbonyl group, an olefin group or an amino group at the main chain end or side chain end of the polymer, and the crosslinked fluororubber (B) is fluorine in the presence of the fluororesin (A). The present invention relates to a thermoplastic resin composition obtained by dynamically crosslinking a fluororubber (b) together with a crosslinking agent (c) under the melting condition of the resin (A).

  It is preferable that at least one polyfunctional compound (d) is contained in at least one of the fluororesin (A) and the cross-linked fluororubber (B).

  The fluororesin (A) is preferably a copolymer composed of tetrafluoroethylene and hexafluoropropylene, a copolymer composed of ethylene and tetrafluoroethylene, or a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene. .

  The crosslinked fluororubber (B) is preferably a crosslinked fluororubber crosslinked by at least one crosslinking reaction among polyol crosslinking, polyamine crosslinking, and peroxide crosslinking.

  It is preferable that at least one of the crosslinking agent (c) or the polyfunctional compound (d) is an amine compound.

  The fluororubber (b) is preferably vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene-based fluororubber.

  The polyfunctional compound (d) is preferably an amine compound.

The molded product formed from the thermoplastic resin composition preferably has a fuel permeability coefficient of 40 (g · mm) / (m ² · day) or less and a tensile modulus of 600 MPa or less.

  The present invention also provides a thermoplastic resin comprising a step of dynamically crosslinking the fluororubber (b) together with the crosslinking agent (c) under the melting condition of the fluororesin (A) in the presence of (A). It also relates to a method for producing the composition.

  The present invention also relates to a molded article formed from the thermoplastic resin composition.

  The present invention also relates to a fuel tube formed from the thermoplastic resin composition.

  Furthermore, the present invention also relates to a laminate comprising a thermoplastic resin layer formed from the thermoplastic resin composition and an elastomer layer formed from an elastomer composition.

  The elastomer composition in the elastomer layer is acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber or It is preferably made of acrylic rubber.

  It is preferable that the elastomer composition in the elastomer layer contains at least one compound selected from the group consisting of onium salts, amine compounds, and epoxy resins.

  The thermoplastic resin composition of the present invention comprises a fluororesin (A) having a functional group and a crosslinked fluororubber (B) that is at least partially crosslinked.

  The fluororesin (A) has a carbonyl group, an olefin group, or an amino group at the main chain end or side chain end of the polymer in order to improve the adhesion to other materials.

（式中、Ｒ²は炭素原子数１〜２０のアルキル基またはエーテル結合性酸素原子を含む炭素原子数２〜２０のアルキル基である）
で示される基、式：

（式中、Ｒ¹⁶は、炭素原子数１〜２０のアルキル基またはエーテル結合性酸素原子を含む炭素原子数２〜２０のアルキル基である）
で示される基、ハロホルミル基（−Ｃ（＝Ｏ）Ｘ¹、Ｘ¹はハロゲン原子）、ホルミル基（−Ｃ（＝Ｏ）Ｈ）、式（２）：

（式中、Ｒ³は、炭素原子数１〜２０の２価の有機基であり、Ｒ⁴は、炭素原子数１〜２０の１価の有機基である）
で示される基、カルボキシル基（−Ｃ（＝Ｏ）ＯＨ）、アルコキシカルボニル基（−Ｃ（＝Ｏ）ＯＲ⁵（式中、Ｒ⁵は、炭素原子数１〜２０の１価の有機基である））、アミド基（−Ｃ（＝Ｏ）ＮＲ⁶Ｒ⁷（式中、Ｒ⁶およびＲ⁷は、同じであっても異なっていてもよく、水素原子または炭素原子数１〜２０の１価の有機基である））、

イソシアネート基（−Ｎ＝Ｃ＝Ｏ）等があげられる。前記式（１）におけるＲ²の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などがあげられる。前記式（２）におけるＲ³の具体例としては、メチレン基、−ＣＦ₂−基、−Ｃ₆Ｈ₄−基などがあげられ、Ｒ⁴の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などがあげられる。Ｒ⁵の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などがあげられる。Ｒ⁶およびＲ⁷の具体例としては、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、フェニル基などがあげられる。A carbonyl group refers to a functional group having —C (═O) —. Specifically, for example, Formula (1):

(Wherein R ² is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom)
A group represented by the formula:

(In the formula, R ¹⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an etheric oxygen atom)
A haloformyl group (—C (═O) X ¹ , X ¹ is a halogen atom), a formyl group (—C (═O) H), formula (2):

(Wherein R ³ is a divalent organic group having 1 to 20 carbon atoms, and R ⁴ is a monovalent organic group having 1 to 20 carbon atoms)
, A carboxyl group (—C (═O) OH), an alkoxycarbonyl group (—C (═O) OR ⁵ , wherein R ⁵ is a monovalent organic group having 1 to 20 carbon atoms. ), An amide group (—C (═O) NR ⁶ R ⁷ , wherein R ⁶ and R ⁷ may be the same or different and are each a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Valent organic group)),

An isocyanate group (-N = C = O) etc. are mention | raise | lifted. Specific examples of R ² in the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ³ in the formula (2) include a methylene group, —CF ₂ — group, —C ₆ H ₄ — group, and specific examples of R ⁴ include a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, butyl group and the like. Specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

（式中、Ｒ²は炭素原子数１〜２０のアルキル基またはエーテル結合性酸素原子を含む炭素原子数２〜２０のアルキル基である）
で示される基、カルボキシル基、ハロホルミル基、アルコキシカルボニル基が好ましく、具体的には、−ＣＯＯＨ、−ＯＣ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＣＨ₃、−ＣＯＦ、−ＯＣ（＝Ｏ）ＯＣＨ（ＣＨ₃）₂がより好ましい。Among these carbonyl groups, from the viewpoint of ease of introduction into the fluororesin and reactivity with other materials, the formula:

(Wherein R ² is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom)
Group, a carboxyl group, a haloformyl group, and an alkoxycarbonyl group are preferable. Specifically, —COOH, —OC (═O) OCH ₂ CH ₂ CH ₃ , —COF, —OC (═O) OCH (CH ₃ ) ₂ is more preferable.

An olefin group is a functional group having a carbon-carbon double bond. Specifically, for example, Formula (3):
-CR ⁸ = CR ⁹ R ¹⁰ (3)
R ⁸ , R ⁹ and R ¹⁰ may be the same or different and are a hydrogen atom, a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms. Specific examples of formula _{(3), -CF = CF 2} , -CH = CF 2, -CF = CHF, -CF = CH 2, such as -CH = CH ₂ and the like.

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. Specifically, for example, Formula (4):
-NR ¹¹ R ¹² (4)
R ¹¹ and R ¹² may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Specific examples of the formula (4) include —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , —NH (C ₆ H ₅ ).

The number of terminal groups of the fluororesin (A) can be measured by the methods described in JP-B-37-3127 and WO99 / 45044. For example, when an infrared absorption spectrum analysis of a fluororesin (A) film sheet is performed using an infrared spectrophotometer and the number of functional groups is measured from an absorption band of a frequency specific to the functional group, for example, -COF terminal Is the absorption band of 1884 cm ^-1 , -COOH ends are absorption bands of 1813 cm ^-1 and 1775 cm ^-1 , -COOCH ₃ ends are absorption bands of 1795 cm ^-1 , -CONH ₂ ends are absorption bands of 3438 cm ^-1 , -CH ₂ OH terminus absorption band of 3648cm ^-1, -CF = CF ₂ ends can be calculated from the absorption band of 1790 cm ^-1.

  The method for introducing the functional group into the fluororesin (A) is not particularly limited. For example, a method of copolymerizing a monomer having the functional group at the time of polymerizing the fluororesin, the functional group or the functional group is converted to the functional group. A method of performing polymerization using a polymerization initiator having a functional group, a method of introducing the functional group into a fluororesin by a polymer reaction, a method of thermally decomposing a polymer main chain in the presence of oxygen, a twin screw extruder, etc. A method of converting the end of the fluororesin using a device capable of applying a strong shearing force can be given.

  The number of the functional groups of the fluororesin (A) is preferably 20 to 5000 per 1 million carbon atoms constituting the fluororesin, more preferably 30 to 4000, and 40 to 3000. More preferably it is. If the number is less than 20, the adhesive strength between the fluororesin layer and the elastomer layer tends to decrease, and if the number exceeds 5000, foaming tends to occur in the molded product.

  In addition, the fluororesin (A) having the functional group used in the present invention is only composed of molecules having the functional group at one end, both ends, or side chain ends of the main chain of one polymer. Alternatively, it may be a mixture of a molecule having the functional group at one end, both ends or side chain ends of the main chain of the polymer and a molecule not containing the functional group.

Although the monomer composition of a fluororesin (A) is not specifically limited, It is preferable that it is a fluororesin containing at least 1 type of fluorine-containing ethylenic polymer. The fluorinated ethylenic polymer preferably has a structural unit derived from at least one fluorinated ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene (hereinafter also referred to as TFE), formula (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
One or more perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: chlorotrifluoroethylene (hereinafter also referred to as CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (hereinafter, VdF), vinyl fluoride, formula (6):
CH ₂ = CX ² (CF ₂ ) _n X ³ (6)
(Wherein X ² represents a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10)
And the like.

  Further, the fluorine-containing ethylenic polymer may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Non-fluorinated ethylenic monomers other than fluoroolefins can be mentioned. Examples of the non-fluorine ethylenic monomer include ethylene, propylene, and alkyl vinyl ethers. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

Among these, from the point that the fluororesin composition obtained has excellent heat resistance, chemical resistance, and oil resistance and facilitates molding processability, the fluorine-containing ethylenic polymer is
(1) An ethylene-TFE copolymer composed of TFE and ethylene (hereinafter also referred to as ETFE).
(2) TFE and equation (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
For example, TFE-perfluoro (alkyl vinyl ether) copolymer (PFA) or TFE-hexafluoropropylene (hereinafter also referred to as HFP) is composed of one or more perfluoroethylenically unsaturated compounds represented by Polymer (FEP)
(3) TFE, ethylene and formula (5):
CF ₂ = CF-R _f ¹ (5)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² , and R _f ² is a C 1-5 perfluoroalkyl group)
An ethylene-TFE-HFP copolymer comprising a perfluoroethylenically unsaturated compound represented by the formula: ethylene-TFE-perfluoroethylenically unsaturated compound copolymer (4) polyvinylidene fluoride (PVDF)
(5) CTFE, TFE and equation (5):
CF ₂ = CF-R _f ¹ (5)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² , and R _f ² is a C 1-5 perfluoroalkyl group)
It is preferable that it is either the CTFE-TFE-perfluoroethylenically unsaturated compound copolymer which consists of a perfluoroethylenically unsaturated compound represented by these. From the viewpoint of fuel barrier properties and flexibility, the fluorine-containing ethylenic polymer represented by (1), (2), or (5) is particularly preferable.

  Next, preferred fluorine-containing ethylenic polymers (1), (2) and (5) will be described.

(1) ETFE
In the case of ETFE, in addition to the above-described effects, mechanical properties and fuel barrier properties are preferable. The content molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 38:62 to 85:15, and particularly preferably 37:63 to 80:20. Moreover, the 3rd component may be contained and the kind will not be limited as long as it can copolymerize with TFE and ethylene as a 3rd component. As the third component, the following formulas are generally used: CH ₂ = CX ³ R _f ³ , CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ , CH ₂ = C (R _f ³ ) ₂
(Wherein X ³ represents a hydrogen atom or a fluorine atom, and R _f ³ represents a fluoroalkyl group which may contain an etheric oxygen atom)
Among these, a fluorine-containing vinyl monomer represented by CH ₂ = CX ³ R _f ³ is more preferred, and a monomer having 1 to 8 carbon atoms in R _f ³ is particularly preferred.

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

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

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

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

  Moreover, it is preferable that it is 150-340 degreeC, as for melting | fusing point of a fluororesin (A), it is more preferable that it is 150-330 degreeC, and it is further more preferable that it is 170-320 degreeC. When the melting point of the fluorine-containing ethylenic polymer is less than 150 ° C, the heat resistance of the resulting thermoplastic resin composition tends to decrease, and when it exceeds 340 ° C, the melting condition of the fluororesin (A) is reduced. There is a tendency that the adhesiveness between the thermoplastic resin composition that can be thermally deteriorated by the functional group and other materials cannot be sufficiently developed.

  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.

  The fluororesin (A) includes other polymers such as polyethylene, polypropylene, polyamide, polyester, polyurethane, inorganic fillers such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate, and pigments. Flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc. It can be added as long as it does not reach.

  Examples of the fluororubber (b) in the crosslinked fluororubber (B) used in the present invention include non-perfluorofluororubber (b-1) and perfluorofluororubber (b-2). In addition, perfluoro fluororubber means the thing which 90 mol% or more consists of a perfluoro monomer among the structural units.

  Non-perfluoro fluororubber (b-1) includes VdF fluororubber, TFE / propylene fluororubber, TFE / propylene / VdF fluororubber, ethylene / HFP fluororubber, ethylene / HFP / VdF fluororubber, Examples include ethylene / HFP / TFE fluororubber, fluorosilicone fluororubber, or fluorophosphazene fluororubber, and these may be used alone or in any combination as long as the effects of the present invention are not impaired. However, it is preferable to use VdF fluororubber or TFE / propylene fluororubber.

As VdF type fluororubber, what is represented by following formula (7) is preferred.
^{- (M 1) - (M} 2) - (N 1) - (7)
(In the formula, the structural unit M ¹ is a structural unit derived from VdF (m ¹ ), the structural unit M ² is a structural unit derived from a fluorine-containing ethylenic monomer (m ² ), and the structural unit N ¹ is a single unit. (It is a repeating unit derived from monomer (n ¹ ) copolymerizable with monomer (m ¹ ) and monomer (m ² ))

Among the VdF type fluorine-containing rubbers represented by the formula (7), the structural unit M ¹ 30 to 85 mol%, preferably not containing a structural unit M ² fifty-five to fifteen mole%, more preferably 30 to the structural units M ¹ 80 mol%, the structural unit M ² 70 to 20 mol%. The structural unit N ¹ is preferably 0 to 10 mol% with respect to the total amount of the structural unit M ¹ and the structural unit M ² .

Examples of the fluorine-containing ethylenic monomer (m ² ) include TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and perfluoro (alkyl vinyl ether). (Hereinafter also referred to as “PAVE”) and fluorine-containing monomers such as vinyl fluoride. Among these, TFE, HFP, and PAVE are preferable.

The monomer (n ¹ ) may be any monomer as long as it is copolymerizable with the monomer (m ¹ ) and the monomer (m ² ). For example, ethylene, propylene, alkyl vinyl ether, etc. can give.

Further, as the monomer (n ¹ ), a monomer that gives a crosslinking site may be used. As a monomer that gives such a crosslinking site, for example, formula (8):
CY ¹ ₂ = CY ¹ −R _f ⁴ CHR ¹ X ⁴ (8)
Wherein Y ¹ is a hydrogen atom, a fluorine atom or CH ₃ , Rf ⁴ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and R ¹ is a hydrogen atom or CH ₃ and X ⁴ are iodine or bromine-containing monomers represented by formula (9):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 2 (9)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ² is a cyano group, a carboxyl group, an alkoxycarbonyl group, or a bromine atom). These can be used alone or in any combination.

  The iodine atom, bromine atom, cyano group, carboxyl group, and alkoxycarbonyl group can function as a crosslinking point.

  Specific examples of such VdF fluororubbers include VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VdF / PAVE rubber, VdF / Preferred examples include TFE / PAVE rubber, VdF / HFP / PAVE rubber, VdF / HFP / TFE / PAVE rubber, and the like.

As the TFE / propylene fluororubber, those represented by the formula (10) are preferable.
^{- (M 3) - (M} 4) - (N 2) - (10)
(In the formula, the structural unit M ³ is a structural unit derived from TFE (m ³ ), the structural unit M ⁴ is a structural unit derived from propylene (m ⁴ ), and the structural unit N ² is a monomer (m ³ ). And a repeating unit derived from the monomer (n ² ) copolymerizable with the monomer (m ⁴ )

Among the TFE / propylene type fluorine-containing rubbers represented by the formula (10), the structural unit M ³ 30 to 80 mol%, preferably not containing a structural unit M ⁴ 70 to 20 mol%, more preferably a structural unit M ³ 40 to 70 mol%, in which the structural unit M ⁴ 60 to 30 mol%. The structural unit N ² is preferably 0 to 40 mol% with respect to the total amount of the structural unit M ³ and the structural unit M ⁴ .

The monomer (n ² ) may be any monomer that can be copolymerized with the monomer (m ³ ) and the monomer (m ⁴ ). Is preferred.

  Examples of the monomer that gives such a crosslinking site include perfluoro (6,6-dihydro-6-iodo-3 as described in JP-B-5-63482 and JP-A-7-316234. Iodine-containing monomers such as -oxa-1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene), bromine-containing monomers described in JP-A-4-505341, Examples thereof include a cyano group-containing monomer, a carboxyl group-containing monomer, and an alkoxycarbonyl group-containing monomer as described in Kaihei 4-505345 and JP-A-5-500070.

As perfluoro fluororubber (b-2), what is represented by following formula (11) is preferable.
^{- (M 5) - (M} 6) - (N 3) - (11)
(In the formula, the structural unit M ⁵ is a structural unit derived from TFE (m ⁵ ), the structural unit M ⁶ is a structural unit derived from PAVE (m ⁶ ), and the structural unit N ³ is a monomer (m ⁵ ). And a repeating unit derived from the monomer (n ³ ) copolymerizable with the monomer (m ⁶ )

Among the perfluoro fluorine-containing rubbers represented by the formula (11) (b-2) , the structural unit M ⁵ 50 to 90 mol%, preferably not containing a structural unit M ⁶ 10 to 50 mol%, more preferably a structural unit M ⁵ 50-80 mol%, which comprises a structural unit M ⁶ 20 to 50 mol%, more preferably a structural unit M ⁵ 55 to 70 mol%, in which the structural unit M ⁶ 30-45 mole% . The structural unit N ³ is preferably 0 to 5 mol%, more preferably 0 to 2 mol%, based on the total amount of the structural unit M ⁵ and the structural unit M ⁶ . When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.

Examples of PAVE (m ⁶ ) include perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), and these can be used alone or in any combination.

The monomer (n ³ ) may be any monomer as long as it is copolymerizable with the monomer (m ⁵ ) and the monomer (m ⁶ ). preferable.

As a monomer that gives such a crosslinking site, for example, VdF, Formula (8):
CY ¹ ₂ = CY ¹ −R _f ⁴ CHR ¹ X ⁴ (8)
Wherein Y ¹ is a hydrogen atom, a fluorine atom or CH ₃ , R _f ⁴ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and R ¹ is a hydrogen atom Or CH ₃ and X ⁴ are iodine or bromine-containing monomers represented by formula (9):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 5 (9)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is a cyano group, a carboxyl group, an alkoxycarbonyl group, or a bromine atom). These can be used alone or in any combination.

  The iodine atom, bromine atom, cyano group, carboxyl group, and alkoxycarbonyl group can function as a crosslinking point.

  Specific examples of such perfluoro fluororubber (b-2) include International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Examples thereof include fluororubber described.

  The fluororubber (b) preferably has a number average molecular weight of 1000 to 1200000, and more preferably 5000 to 900000. If the molecular weight is less than 1000, the mechanical properties of the thermoplastic resin composition obtained by crosslinking not proceeding efficiently tend to be inferior, and if the molecular weight is 1200,000 or more, the cost is inferior due to the problem of fluororubber productivity.

  The non-perfluoro fluorine rubber (b-1) and the perfluoro fluorine rubber (b-2) described above can be produced by a conventional method.

  The fluororubber (b) in the present invention may further contain a crosslinking agent (c). Moreover, a crosslinking accelerator, a crosslinking assistant, and a co-crosslinking agent can be used together with the crosslinking agent (c). A crosslinking agent, a crosslinking assistant, a co-crosslinking agent, and a crosslinking accelerator are used for crosslinking the fluororubber (b). Here, cross-linking is to cross-link the same or different polymer chains of fluororubber with a cross-linking agent. By cross-linking in this way, the cross-linked fluororubber (B) has improved tensile strength, It has good elasticity.

  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 thermoplastic resin composition when the fluororubber contains a cross-linkable group (cure site). Examples of the crosslinking system include a polyamine crosslinking system, a polyol crosslinking system, a peroxide crosslinking system, an imidazole crosslinking system, a triazine crosslinking system, an oxazole crosslinking system, and a thiazole crosslinking system. Among these, the heat resistance and economy of the crosslinked structure are included. From the viewpoint of properties, a polyamine crosslinking system, a polyol crosslinking system, and a peroxide crosslinking system are preferable.

  As the crosslinking agent (c), any of a polyol crosslinking agent, a peroxide crosslinking agent, a polyamine crosslinking agent, an imidazole crosslinking crosslinking agent, a triazine crosslinking agent, an oxazole crosslinking agent, and a thiazole crosslinking agent. Can also be adopted. These crosslinking agents may be used alone or in combination.

  The polyamine crosslinking agent is not particularly limited. For example, hexamethylenediamine carbamate, N, N′-dicinenamylidene-1,6-hexamethylenediamine (hereinafter also referred to as V3), 4,4′-bis (aminocyclohexyl) methane. Aliphatic polyamine compound derivatives such as carbamate, 4,4′-diaminodiphenyl ether (hereinafter also referred to as DPE), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter also referred to as BAPP), p-phenylenediamine, m-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N′-dimethyl-1,4-phenylenediamine, 4,4′-methylenedianiline, dianilinoethane, 4, 4'-methylene-bis (3-nitroaniline), 4,4'-methylene Bis (2-chloroaniline), diaminopyridine, an aromatic polyamine compound such as melamine may be used. Among these, V3, DPE, and BAPP are preferable from the viewpoint of good adhesive force between the obtained thermoplastic resin composition and other materials.

  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, and examples thereof include 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) Trafluorodichloropropane, 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 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, dicumyl peroxide, 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, from the viewpoint that the moldability of the obtained thermoplastic resin composition is excellent, polyol crosslinking is preferable, and since heat resistance is excellent, a polyhydroxy aromatic compound is more preferable, and bisphenol AF is more preferable. Polyamine cross-linking is preferable in terms of adhesiveness with the other material of the obtained thermoplastic resin composition. In order to achieve both of these advantages, it is more preferable to use polyol crosslinking and polyamine crosslinking in combination.

  In the polyol crosslinking system, a crosslinking accelerator is usually used in combination with the polyol crosslinking agent. When a crosslinking accelerator 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. Further, since polyamine crosslinking also undergoes a hydrofluoric acid dehydration reaction of the fluororubber main chain in the same manner as polyol crosslinking, the crosslinking reaction can be promoted even in a polyamine crosslinking system by using these crosslinking accelerators.

  As the crosslinking accelerator for the polyol crosslinking system, generally an onium salt is used. The onium salt is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. Among these, quaternary ammonium salts are exemplified. A quaternary phosphonium salt is preferred.

（式中、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は、同じであっても異なっていてもよく、水素原子、または炭素数１〜３０の１価の有機基であり、Ｘ^1-は１価の陰イオンである）
で示される化合物、
式（１３）：

（式中、ｎは、０〜５０の整数である）
で示される化合物、および
式（１４）：

などがあげられる。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, , 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 also 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, formula (12):

(In the formula, R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ¹⁻ is a monovalent group. Anion)
A compound represented by
Formula (13):

(In the formula, n is an integer of 0 to 50)
And a compound of formula (14):

Etc.

のように、窒素原子を含んでいてもよい。In formula (12), R ¹³ , R ¹⁴ , and R ¹⁵ are the same or different and each is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, but monovalent having 1 to 30 carbon atoms. The organic group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aryl group such as a phenyl group, and a benzyl group. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁶ ₃ , —C ₂ X ⁶ ₅ , —CH ₂ X ⁶ , —CH ₂ CX ⁶ ₃ , —CH ₂ C ₂ X ⁶ _5, etc., a halogen atom-containing alkyl group having 1 to 30 carbon atoms (X ⁶ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; A benzyl group; a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with a fluorine atom such as —C ₆ F ₅ or —CH ₂ C ₆ F ₅ ; —C ₆ H _5-n (CF ₃ ) _n , -CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5) or the like, and a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with -CF _3. . Also,

As such, it may contain a nitrogen atom.

Among these, DBU-B or R ¹³ , R ¹⁴ , and R ¹⁵ are each an alkyl group having 1 to 20 carbon atoms from the viewpoint of good adhesive strength between the obtained thermoplastic resin composition and other materials. Benzyl group, X ¹⁻ is a monovalent anion, halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), OH ⁻ , RO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , SO _{4 ^{2-, SO 3 2-, SO 2}} -, RSO 3 2-, CO 3 2-, NO 3 - (R is a monovalent organic group) are preferred, such as formula represented by (12) or formula (13) In the formula (12), X ¹⁻ is more preferably Cl ⁻ . In the formula (13), n is more preferably an integer of 0 to 10, and further preferably an integer of 1 to 5, from the viewpoint of dispersibility during kneading with fluororubber.

で示される化合物であることが好ましい。Among these, especially

It is preferable that it is a compound shown by these.

  The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter also referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2. -Methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride and the like can be mentioned, and among these, BTPPC is preferred from the viewpoint of good adhesion between the obtained thermoplastic resin composition and other materials.

  Further, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a compound disclosed in JP-A-11-147891 can also be used.

The organic peroxide crosslinking accelerator or co-crosslinking agent may be any compound having a reactive activity with respect to peroxy radicals and polymer radicals, for example, CH ₂ ═CH—, CH ₂ ═CHCH ₂ —, CF ₂ = A polyfunctional compound having a functional group such as CF-. For example, triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, tri Allyl 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, hexaallylphosphoramide, N, N, N ′, N′-tetraallyl Phthalamide, N, N, N ′, N′-tetraallyl Ron'amido, trivinyl isocyanurate, 2,4,6-vinyl methyl trisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite. Among these, TAIC is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  As a compounding quantity of a crosslinking accelerator, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of fluororubber (b), More preferably, it is 0.05-8 mass parts. If the crosslinking accelerator is less than 0.01 parts by mass, the fluororubber cannot be sufficiently crosslinked, and the mechanical properties of the thermoplastic resin composition tend to decrease. If the crosslinking accelerator exceeds 10.0 parts by mass, the fluororubber is dispersed in the fluororubber. However, the moldability of the thermoplastic resin composition tends to deteriorate.

  In addition, usual additives blended in the fluororubber as necessary, for example, fillers, processing aids, plasticizers, colorants, stabilizers, adhesion aids, acid acceptors, mold release agents, imparting electrical conductivity Various additives such as additives, thermal conductivity-imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc. can be blended. One or more agents may be blended.

  In the thermoplastic resin composition of the present invention, at least a part of the fluororubber is crosslinked in the fluororesin (A) by dynamically crosslinking the fluororubber (b) in the molten fluororesin (A). The crosslinked fluororubber (B) can be obtained, and the crosslinked fluororubber (B) can be uniformly dispersed in the fluororesin (A).

  Here, the dynamic cross-linking treatment means that the fluororubber composition is dynamically cross-linked simultaneously with the melt kneading under the melting condition of the fluororesin (A) using a Banbury mixer, a pressure kneader, an extruder or the like. That means. Among these, it is preferable to use an extruder such as a twin screw extruder because a high shear force can be applied.

  Moreover, a molten state means the state under the temperature which a fluororesin (A) melts. The melting temperature varies depending on the glass transition temperature and / or melting point of the fluororesin (A), but is preferably 150 to 340 ° C, more preferably 150 to 330 ° C, and 170 to 320 ° C. Is more preferable. When the melting point of the fluorine-containing ethylenic polymer is less than 150 ° C, the heat resistance of the resulting thermoplastic resin composition tends to decrease, and when it exceeds 340 ° C, the melting condition of the fluororesin (A) is reduced. There is a tendency that the adhesiveness between the thermoplastic resin composition that can be thermally deteriorated by the functional group and other materials cannot be sufficiently developed.

  The thermoplastic resin composition of the present invention preferably comprises 95 to 20% by mass of the fluororesin (A) and 5 to 80% by mass of the crosslinked fluororubber (B), and 92 to 30% by mass of the fluororesin (A) and crosslinked. More preferably, the fluororubber (B) consists of 8 to 70 mass%, more preferably 90 to 60 mass% of the fluororesin (A) and 10 to 40 mass% of the crosslinked fluororubber (B). The thermoplastic resin composition obtained when the fluororesin (A) is less than 20% by mass tends to deteriorate the fluidity of the resulting thermoplastic resin composition and lower the molding processability, and exceeds 95% by mass. There is a tendency for the balance between the flexibility and the fuel barrier property to deteriorate.

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

  Even when the fluororubber composition initially forms a matrix, as the cross-linking reaction proceeds, the fluororubber composition becomes a cross-linked fluororubber (B), whereby the melt viscosity increases, and the cross-linked fluororubber (B ) May be a dispersed phase, or may form a co-continuous phase with the fluororesin (A).

  When such a structure is formed, the thermoplastic resin composition of the present invention exhibits excellent heat resistance, chemical resistance and oil resistance, and also has good adhesion to the elastomer layer. At that time, the average dispersed particle size of the crosslinked fluororubber is preferably 0.01 to 30 μm. When the average dispersed particle size is less than 0.01 μm, the fluidity is lowered and the moldability is deteriorated. Moreover, when it exceeds 30 micrometers, there exists a tendency for the intensity | strength of the thermoplastic resin composition obtained to fall.

  In addition, the thermoplastic resin composition of the present invention includes a fluororesin in a part of the structure in which the fluororesin (A) as a preferred form forms a continuous phase and the cross-linked fluororubber (B) forms a dispersed phase. A co-continuous structure of (A) and crosslinked fluororubber (B) may be included.

  In order to improve the adhesion between the thermoplastic resin composition and the other material, the fluororesin (A) or the crosslinked fluororubber (B) can contain at least one polyfunctional compound (d). The polyfunctional compound (c) is a compound having two or more functional groups having the same or different structures in one molecule.

  The functional group possessed by the polyfunctional compound (d) is generally known to have reactivity, such as a carbonyl group, a carboxyl group, a haloformyl group, an amide group, an olefin group, an amino group, an isocyanate group, a hydroxy group, and an epoxy group. Any functional group can be used. Compounds having these functional groups are expected not only to have high affinity with other materials, but also to react with the functional groups or fluororubber of the fluororesin (A) to further improve the adhesion.

  Specific examples of the polyfunctional compound (d) include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, 4,4′- Diaminodiphenyl ether (hereinafter also referred to as DPE), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), p-phenylenediamine, m-phenylenediamine, 2,5-dimethyl-1,4 -Phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine, 4,4'-methylenedianiline, dianilinoethane, 4,4'-methylene-bis (3-nitroaniline), 4,4'-methylene -Bis (2-chloroaniline), diaminopyridine, melamine, 4-aminophenol, etc. Amine compounds, triallyl cyanurate, triallyl isocyanurate (TAIC), trimethallyl isocyanurate, TAIC prepolymer, triacryl formal, triallyl trimellitate, N, N'-n-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, hexaallylphosphoramide, N, N, N , N′-tetraallyltetraphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2- Olefin compounds such as methylene) cyanurate and triallyl phosphite, epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, 2,2-bis (4-hydroxyphenyl) propane (hereinafter, 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-dihydroxynaphth Len, 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, hydroxy compounds such as 3,3', 5,5'-tetrabromobisphenol A, and the like. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine, DPE, BAPP, and bisphenol AF are preferable from the viewpoint of good adhesive strength between the thermoplastic resin composition and other materials.

  These polyfunctional compounds (d) may be used alone or in any combination with polyfunctional compounds (d) having other structures. In particular, when the polyfunctional compound (d) is added to the fluororubber, the polyfunctional compound (d) may or may not affect the cross-linking of the fluororubber. Further, the polyfunctional compound (d) may be the same substance as the crosslinking agent (c) or may be a different substance. It is preferable that at least one of the polyfunctional compound (d) or the crosslinking agent (c) is an amine compound from the viewpoint of good adhesive strength between the thermoplastic resin composition and the other material. In particular, the polyfunctional compound (d) is preferably an amine compound.

  0.1-10.0 mass parts is preferable with respect to 100 mass parts of obtained thermoplastic resin compositions, and, as for the compounding quantity of a polyfunctional compound (d), 0.2-8.0 mass parts is more preferable. 0.3 to 7.0 parts by mass is more preferable. If the blending amount of the polyfunctional compound (d) is less than 0.1 parts by mass, the adhesiveness between the thermoplastic resin composition and the other material tends to be insufficient, and heat exceeding 10.0 parts by mass. There exists a tendency for the dispersibility to a plastic resin composition to deteriorate and for the mechanical property of a thermoplastic resin composition to fall.

  As a method for adding the polyfunctional compound (d) to the fluororesin (A), when the fluororesin is melt-kneaded above the melting point of the fluororesin (A) using a Banbury mixer, a pressure kneader, an extruder, or the like And a method of co-coagulating by adding the polyfunctional compound (d) to the emulsion of the fluororesin (A). Examples of the method of adding the polyfunctional compound (d) to the fluororubber include a method of adding using a Banbury mixer, a pressure kneader, an extruder, and the like. Further, when the fluororubber (b) is dynamically cross-linked with the cross-linking agent (c) under the melting condition of the fluororesin (A) in the presence of the fluororesin (A), the polyfunctional compound (d) The method of adding can also be mentioned.

The fuel permeation coefficient of the molded article formed from the thermoplastic resin composition of the present invention is preferably 40 (g · mm) / (m ² · day) or less, and preferably 30 (g · mm) / (m ² · Day) or less, more preferably 20 (g · mm) / (m ² · day) or less, and further preferably 5 (g · mm) / (m ² · day) or less. Particularly preferred. The lower limit value of the fuel permeation coefficient is not particularly limited and is preferably as low as possible. However, the lower limit is preferably 0.01 (g · mm) / (m ² · day) or more. If the fuel permeation coefficient exceeds 40 (g · mm) / (m ² · day), the fuel barrier property is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product. Is not preferable. 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 is 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 specimen is placed in a thermostatic apparatus (60 ° C.), the mass of the test specimen is measured, and when the mass reduction per unit time becomes constant, the fuel permeability is obtained by the following formula.

  The tensile modulus of the molded article formed from the fuel barrier material of the present invention is preferably 600 MPa or less, more preferably 550 MPa or less, and further preferably 500 MPa or less. 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 600 MPa, there is a tendency that it is not suitable for applications requiring flexibility.

  The thermoplastic resin composition of the present invention can be molded using a general molding method or molding apparatus. As a molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding, etc. can be adopted, and the fuel barrier material of the present invention is used according to the purpose of use. And molded into a molded body having an arbitrary shape.

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

  In the laminated structure of at least one layer made of the thermoplastic resin composition of the present invention and at least one layer made of another material, the other material depends on required properties, intended use, etc. Choose the right 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 resin 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 resin 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, a partially saponified product of a copolymer of vinyl acetate and vinyl chloride, and a polyisocyanate compound (for example, a glycol compound such as 1,6-hexamethylene glycol) A reaction product of a molar ratio of 1 to 2 with a diisocyanate compound such as 2,4-tolylene diisocyanate; a molar ratio of a triol compound such as trimethylolpropane and a diisocyanate compound such as 2,4-tolylene diisocyanate of 1: 3 A mixture with a reaction product 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 tube, a fuel hose or a fuel container composed of a single layer of the thermoplastic resin 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.

  Further, the present invention includes a multilayer fuel tube, a multilayer fuel hose or a multilayer fuel container including a layer made of the thermoplastic resin composition of the present invention. The multilayer fuel tube, multilayer fuel hose or multilayer fuel container comprises a layer made of the thermoplastic resin 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.

  And as a layer which consists of other materials, the layer (elastomer layer) which consists of elastomer compositions other than the thermoplastic resin composition of this invention, and the layer which consists of thermoplastic resins are mention | raise | lifted.

  As the elastomer composition, 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, ethylene- Propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, silicone rubber, butyl rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, α, β-unsaturated nitrile-conjugated diene copolymer rubber or hydride thereof. Among these, acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrophosphorus rubber from the viewpoint of heat resistance, oil resistance, weather resistance, and extrusion moldability. Is preferred.

  Moreover, at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin is blended in the elastomer composition from the viewpoint of improving the adhesive strength between the thermoplastic resin composition and the elastomer composition. It is preferable. These onium salts, amine compounds, and epoxy resins may be used alone or in any combination.

  The onium salt is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. Among these, quaternary ammonium salts are exemplified. A quaternary phosphonium salt is preferred.

（式中、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は、同じであっても異なっていてもよく、水素原子、または炭素数１〜３０の１価の有機基であり、Ｘ^1-は１価の陰イオンである）
で示される化合物、
式（１３）：

（式中、ｎは、０〜５０の整数である）
で示される化合物、および
式（１４）：

などがあげられる。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, , 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 (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-phenylpropyl) -1 , 8-diazabicyclo [5,4,0] -7-undecenium chloride, formula (12):

(In the formula, R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ¹⁻ is a monovalent group. Anion)
A compound represented by
Formula (13):

(In the formula, n is an integer of 0 to 50)
And a compound of formula (14):

Etc.

のように、窒素原子を含んでいてもよい。In formula (12), R ¹³ , R ¹⁴ , and R ¹⁵ are the same or different and each is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, but monovalent having 1 to 30 carbon atoms. The organic group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aryl group such as a phenyl group, and a benzyl group. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁶ ₃ , —C ₂ X ⁶ ₅ , —CH ₂ X ⁶ , —CH ₂ CX ⁶ ₃ , —CH ₂ C ₂ X ⁶ _5, etc., a halogen atom-containing alkyl group having 1 to 30 carbon atoms (X ⁶ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; A benzyl group; a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with a fluorine atom such as —C ₆ F ₅ or —CH ₂ C ₆ F ₅ ; —C ₆ H _5-n (CF ₃ ) _n , -CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5) or the like, and a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with -CF _3. . Also,

As such, it may contain a nitrogen atom.

Among these, DBU-B, or R ¹³ , R ¹⁴ , and R ¹⁵ are alkyl groups having 1 to 20 carbon atoms or the above-mentioned DBU-B from the viewpoint of good adhesive strength between the obtained thermoplastic resin composition and other materials. Benzyl group, X ¹⁻ is a monovalent anion, halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), OH ⁻ , RO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , SO ₄ ^{2 _{-, SO 3 2-, SO 2}} -, RSO 3 2-, CO 3 2-, NO 3 - (R is a monovalent organic group) are preferred, such as formula represented by (12), or formula (13) In the formula (12), X ¹⁻ is more preferably Cl ⁻ . In the formula (13), n is more preferably an integer of 0 to 10, and further preferably an integer of 1 to 5, from the viewpoint of dispersibility during kneading with fluororubber.

で示される化合物であることが好ましい。Among these, especially

It is preferable that it is a compound shown by these.

  The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium. Examples thereof include chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, BTPPC is preferred from the viewpoint of good adhesive strength between the thermoplastic resin composition and the elastomer composition.

  Further, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a compound disclosed in JP-A-11-147891 can also be used.

  The blending amount of the onium salt is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 with respect to 100 parts by mass of the elastomer composition. Part by mass is more preferable. If the blending amount of the onium salt is less than 0.1 parts by mass, the adhesion between the thermoplastic resin composition and the elastomer composition tends to be insufficient, and if it exceeds 10.0 parts by mass, the elastomer composition There is a tendency for the dispersibility to a thing to deteriorate and the mechanical property of this elastomer composition to fall.

  It does not specifically limit as an amine compound, For example, aliphatic, such as a hexamethylenediamine carbamate, N, N'- dicinnamylidene-1,6-hexamethylenediamine (V3), 4,4'-bis (aminocyclohexyl) methanecarbamate Polyamine compound derivatives, 4,4′-diaminodiphenyl ether (DPE), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter also referred to as BAPP), p-phenylenediamine, m-phenylenediamine 2,5-dimethyl-1,4-phenylenediamine, N, N′-dimethyl-1,4-phenylenediamine, 4,4′-methylenedianiline, dianilinoethane, 4,4′-methylene-bis (3- Nitroaniline), 4,4′-methylene-bis (2-chloroaniline), di Minopirijin, it can be used aromatic polyamine compounds such as melamine. Among these, V3, DPE, and BAPP are preferable from the viewpoint of good adhesive strength between the thermoplastic resin composition and the elastomer composition.

  The compounding amount of the amine compound is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 with respect to 100 parts by mass of the elastomer composition. Part by mass is more preferable. If the compounding amount of the amine compound is less than 0.1 parts by mass, the adhesiveness between the thermoplastic resin composition and the elastomer composition tends to be insufficient, and if the compounding amount exceeds 10.0 parts by mass, the elastomer composition There is a tendency for the dispersibility to a thing to deteriorate and the mechanical property of this elastomer composition to fall.

で表わされる化合物等があげられる。ここで、式（１５）において、ｎは０．１〜３が好ましく、０．１〜０．５がより好ましく、０．１〜０．３がさらに好ましい。ｎが０．１未満であると、他材との接着力が低下する傾向がある。一方、ｎが３をこえると、粘度が高くなり、エラストマー中での均一な分散が困難になる傾向がある。Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Of these, the bisphenol A type epoxy resin has the formula (15):

And the like. Here, in Formula (15), n is preferably 0.1 to 3, more preferably 0.1 to 0.5, and still more preferably 0.1 to 0.3. If n is less than 0.1, the adhesive strength with other materials tends to decrease. On the other hand, when n exceeds 3, the viscosity increases, and uniform dispersion in the elastomer tends to be difficult.

  0.1-20.0 mass parts is preferable with respect to 100 mass parts of this elastomer composition, as for the compounding quantity of an epoxy resin, 0.3-15 mass parts is more preferable, and 0.5-10 mass parts is further. preferable. When the blending amount of the epoxy resin is less than 0.1 parts by mass, the adhesiveness between the thermoplastic resin composition and the elastomer composition tends not to be sufficiently developed, while the blending amount of the epoxy resin is 20 parts by mass. Above this, the flexibility of the elastomer composition tends to decrease.

  In addition, the elastomer composition in the present invention may be either an uncrosslinked elastomer or a crosslinked one.

  As the crosslinking agent, any crosslinking agent used for ordinary elastomers can be used. For example, sulfur crosslinking agent, peroxide crosslinking agent, polythiol crosslinking agent, quinoid crosslinking agent, resin crosslinking agent, metal oxide, diamine crosslinking agent, polythiols, 2-mercaptoimidazoline, polyol crosslinking agent, There are crosslinking agents such as polyamine crosslinking agents, and among them, peroxide crosslinking agents, polyol crosslinking agents, polyamine crosslinking agents and the like are preferable from the viewpoint of adhesive properties and mechanical properties of the obtained crosslinked elastomer.

  As a compounding quantity of the crosslinking agent mix | blended in this elastomer composition, 0.2-10 mass parts is preferable with respect to 100 mass parts of elastomers, and 0.5-8 mass parts is more preferable. If the cross-linking agent is less than 0.2 parts by mass, the cross-linking density tends to be low and compression set tends to be large, and if it exceeds 10 parts by mass, the cross-linking density tends to be too high and tends to break during compression. There is.

  In addition, the elastomer composition may be added to the elastomer as required by conventional additives such as fillers, processing aids, plasticizers, colorants, stabilizers, crosslinking aids, adhesion aids, acid acceptors. Various additives such as a release agent, a conductivity imparting agent, a thermal conductivity imparting agent, a surface non-adhesive agent, a flexibility imparting agent, a heat resistance improving agent, a flame retardant, etc. You may mix | blend 1 or more types of a different usual crosslinking agent and crosslinking accelerator.

  The elastomer composition in the present invention generally uses other compounding agents such as an elastomer, an onium salt, an amine compound and / or an epoxy resin, a crosslinking agent, a crosslinking aid, a co-crosslinking agent, a crosslinking accelerator, and a filler. It can be obtained by kneading using a rubber kneading apparatus. As the rubber kneading apparatus, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.

  In particular, when a polyol-based cross-linking agent is used as the cross-linking agent, the melting point of the cross-linking agent / cross-linking accelerator is often relatively high. A method of kneading while mixing at a high temperature of 120 to 200 ° C. and then kneading other compounding agents such as a filler at a relatively low temperature below this is preferable. There is also a method of uniformly dispersing using a solid solution in which a crosslinking agent and a crosslinking accelerator are once melted to lower the melting point.

  As the thermoplastic resin composition in the layer made of the other material, from the viewpoint of fuel barrier properties, fluororesin, polyamide resin, polyolefin resin, polyester resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyphenylene A thermoplastic resin consisting of at least one selected from the group consisting of sulfide resins is preferred, and a thermoplastic resin consisting of at least one selected from the group consisting of fluororesins, polyamide resins, polyvinyl alcohol resins, and polyphenylene sulfide resins. More preferred.

  The fuel tube, the fuel hose or the fuel container composed of the layer composed of the thermoplastic resin composition obtained by the present invention as described above and the layer composed of other elastomer or other thermoplastic resin is not particularly limited, For example, fuel hoses such as filler hose, evaporation hose, and breather hose for automobiles; fuel containers such as automobile fuel containers, motorcycle fuel containers, small generator fuel containers, lawn mower fuel containers, etc. It is done.

  Among these, as a fuel tube and a fuel hose composed of the thermoplastic resin composition of the present invention and other elastomer layers, acrylonitrile-butadiene rubber or its hydrogenated rubber, acrylonitrile-butadiene rubber and polyvinyl chloride are used. Fuel hose comprising three layers of an outer layer made of blend rubber or epichlorohydrin rubber, an intermediate layer made of the thermoplastic resin composition of the present invention, and an inner layer made of fluoro rubber, or acrylonitrile-butadiene rubber or hydrogenated rubber thereof A fuel hose comprising 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 resin composition of the present invention has excellent fuel barrier properties・ Points showing flexibility and chemical resistance Preferred.

  In the method for laminating a laminate of the present invention, a thermoplastic resin composition and another material are coextruded in two layers by an extruder, or an outer layer is extruded onto an inner layer by two extruders. And a laminate composed of the outer layer and the outer layer can be extruded and integrated to produce. When the other material is an elastomer composition, it can be produced by extrusion and then bonded by crosslinking. The crosslinking conditions may be appropriately determined depending on the type of the crosslinking agent to be used. Usually, firing is performed at a temperature of 150 to 300 ° C. for 1 minute to 24 hours. In addition, as a crosslinking method, a crosslinking reaction is performed under any conditions, not only in a method commonly used such as steam crosslinking, but also under normal pressure, increased pressure, reduced pressure, and in air. be able to.

  Moreover, when producing the laminated structure which has the layer which consists of a thermoplastic resin composition of this invention, and the layer which consists of another material, you may surface-treat the thermoplastic resin composition 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 thermoplastic resin composition that has been previously subjected to plasma discharge treatment, corona discharge treatment, metal sodium / naphthalene liquid treatment, etc. It is more effective to further treat the primer.

  The thermoplastic resin composition of the present invention and a molded product comprising the composition can be suitably used in the fields shown below.

  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 recombustion device seal, bearing case Le, 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 steal seals, fuel supply hoses, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc., and in the marine field, screw propellers. Used for shaft stern seals, diesel engine intake / exhaust valve stem seals, butterfly valve seals, butterfly valve shaft seals, etc.

  In the field of chemical plants, there are linings, valves, packings, rolls, hoses, diaphragms, O (square) rings, tubes, sealing materials, chemical-resistant coatings, etc. These are chemicals such as pharmaceuticals, agricultural chemicals, paints, resins, etc. It can be used in the manufacturing process. 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 coatings for metal gaskets for automobile engines, gaskets for engine oil pans, rolls for copiers and printers, sealants for construction, 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 an industrial hose, industrial tube, fuel hose, or fuel tube.

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

<Preparation of sheet-shaped test piece (thermoplastic resin composition, fluororesin)>
A thermoplastic resin composition or a fluororesin is set in a mold, held at 290 ° C. for 15 to 30 minutes by a heat press machine, and after the thermoplastic resin composition is melted, a load of 3 MPa is applied for 1 minute. Compression molding is performed to produce a sheet-like test piece having a predetermined thickness.

<Preparation of sheet-like test piece (rubber composition for adhesion test)>
Various compounding agents such as a crosslinking agent and a filler were added to various raw rubbers with an 8-inch open roll to produce a full compound. A sheet-shaped test piece having a predetermined thickness was produced from the full compound using an open roll.

<Production of laminate>
By the above method, a fluororesin sheet having a thickness of 0.5 mm and a rubber composition sheet having a thickness of 1.5 mm were prepared. These sheet test pieces were stacked and set in a mold heated to 170 ° C., and a load of 3 MPa was applied at 170 ° C. for 20 minutes with a heat press machine to prepare a fluororesin layer-elastomer layer laminate.

<Adhesion evaluation test>
The obtained 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, and an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) was used for this test piece. Then, in accordance with the method described in JIS K 6256 (crosslinking rubber adhesion test method), a peel test was performed at 25 ° C. and a tensile speed of 50 mm / min. Moreover, the peeling mode was observed and evaluated according to the following criteria.

(Adhesion evaluation)
A: The fluororesin layer / elastomer layer interface did not peel, and the elastomer layer was destroyed.
○: Peeled at the fluororesin layer / elastomer layer interface, but was sufficiently adhered and difficult to peel.
Δ: Peeled relatively easily at the fluororesin layer / elastomer layer interface.
X: The fluororesin layer and the elastomer layer did not exhibit adhesiveness.

<Functional group analysis by infrared absorption spectrum>
A sheet having a thickness of 0.15 to 0.30 mm was prepared by the above-described method, and an infrared absorption spectrum was analyzed using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by PerkinElmer). The obtained infrared absorption spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of a predetermined peak was measured. The film thickness was measured using a micrometer.

<Measurement of copolymer composition>
The copolymer composition of the fluororesin and fluororubber was determined by ¹⁹ F-NMR, ¹ H-NMR and fluorine elemental analysis.

<Measurement of tensile strength at break, tensile elongation at break and tensile modulus>
A sheet-like test piece having a thickness of 2 mm is prepared by the above method, and a dumbbell-like test piece having a width of 3.18 mm and a distance between marked lines of 1.0 mm is punched out using an ASTM V type dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. and a tensile speed of 50 mm / min according to ASTM D638 using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation). It was.

<Fuel permeability>
A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. 18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is placed in a SUS container (open area 1.26 × 10 ⁻³ m ² ) 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 apparatus (60 ° C.), the mass 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.

<Measurement of melting point>
Using a Seiko differential scanning calorimeter [DSC], the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

<Measurement of melt flow rate (MFR)>
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), at each measurement temperature, the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a 5 kg load was measured. .

<Production example>
In the examples and comparative examples, the following materials were used.

(Fluorine resin (raw material of thermoplastic resin composition))
Fluororesin (a-1): FEP having a —COOH group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 372 ° C. is 18 g / 10 min. The number of —COOH groups is 480 (per 1 million carbon atoms). Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-2): FEP having —OC (═O) OCH ₂ CH ₂ CH ₃ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.8 / 7.6 / 0.6 (molar ratio). 261 ° C. The MFR at 372 ° C. is 20 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 410 (per 1 million carbon atoms). Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-3): FEP having a -COF group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 372 ° C. is 22 g / 10 min. The number of —COF groups is 450 (per 1 million carbon atoms). The tensile modulus is 590 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-4): FEP having —CF═CF ₂ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 372 ° C. is 22 g / 10 min. -CF = CF ₂ groups is 380 pieces (per million carbon atoms). Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-5): FEP having —NH ₂ group. After melting 80 g of FEP (a-2) in a lab plast mill with an internal volume of 80 ml heated to 280 ° C. (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 1 g of polyfunctional compound V3 (manufactured by Daikin Industries, Ltd.) Was added and melt-kneaded to obtain the fluororesin. 261 ° C. The MFR at 372 ° C. is 32 g / 10 min. From the infrared absorption spectrum, an absorption band of 1744 cm ⁻¹ that was not observed in FEP (a-2) was observed. The tensile modulus is 570 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluororesin (a-6): FEP having —NH ₂ group. After melting 80 g of FEP (a-3) in an 80 ml lab plast mill heated to 280 ° C. (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a polyfunctional compound DPE (manufactured by Wakayama Seika Co., Ltd.) 1 g was added and melt-kneaded to obtain the fluororesin. Melting point 260 ° C. The MFR at 372 ° C. is 28 g / 10 min. From the infrared absorption spectrum, since an absorption band of 1744 cm ⁻¹ that was not observed in FEP (a-3) was observed, it was confirmed that at least a part of FEP and the polyfunctional compound was bonded by an amide bond. It is suggested. The tensile modulus is 590 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluororesin (a-7): FEP having —NH ₂ group. After melting 80 g of FEP (a-3) in an 80 ml lab plast mill heated to 280 ° C. (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a polyfunctional compound DPE (manufactured by Wakayama Seika Co., Ltd.) 3 g was added and melt-kneaded to obtain the fluororesin. Melting point 260 ° C. The MFR at 372 ° C. is 31 g / 10 min. From the infrared absorption spectrum, since an absorption band of 1744 cm ⁻¹ that was not observed in FEP (a-3) was observed, it was confirmed that at least a part of FEP and the polyfunctional compound was bonded by an amide bond. It is suggested. The tensile modulus is 580 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluororesin (a-8): FEP having —NH ₂ group. After melting 80 g of FEP (a-4) in a lab plast mill with an internal volume of 80 ml heated to 280 ° C. (manufactured by Toyo Seiki Seisakusho), polyfunctional compound BAPP (manufactured by Wakayama Seika Co., Ltd.) 1 g was added and melt-kneaded to obtain the fluororesin. Melting point 260 ° C. The MFR at 372 ° C. is 27 g / 10 min. From the infrared absorption spectrum, an absorption band of 1744 cm ⁻¹ that was not observed in FEP (a-4) was observed, and therefore it was confirmed that at least a part of FEP and the polyfunctional compound was bonded by an amide bond. It is suggested. The tensile modulus is 590 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluororesin (a-9): ETFE having —OC (═O) OCH ₂ CH ₂ CH ₃ group. The monomer composition is TFE / ethylene / 2,3,4,4,5,5-heptafluoro-1-pentene = 63.4 / 34.2 / 2.4 (molar ratio). 225 ° C. The MFR at 297 ° C. is 30 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 510 (per 1 million carbon atoms). The tensile modulus is 490 MPa. The fuel permeability coefficient is 4.0 (g · mm) / (m ² · day).

Fluororesin (a-10): CTFE-TFE copolymer having —OC (═O) OCH (CH ₃ ) ₂ groups. The monomer composition is CTFE / TFE / perfluoro (propyl vinyl ether) = 44.5 / 53.4 / 2.1 (molar ratio). Melting point 221 ° C. The MFR at 297 ° C. is 35 g / 10 min. -OC (= O) OCH (CH 3) 2 radix 600 (carbon atoms per million). Tensile modulus is 520 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-11): FEP having —CF ₃ group and —CF ₂ H group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 372 ° C. is 18 g / 10 min. -COOH _{group, -OC (= O) OCH 2} CH 2 CH 3 group, -OC (= O) OCH ( CH 3) 2 group, -COF groups, -CF = CF ₂ group, are both -NH ₂ group Less than 20 (per million carbon atoms). Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-12): After melting 80 g of the fluororesin (a-1) with an 80 ml internal volume Laboplast mill (Toyo Seiki Seisakusho Co., Ltd.) heated to 280 ° C., oxidized with an inorganic filler 1.6 g of zinc type 1 (manufactured by Sakai Chemical Industry Co., Ltd.) was added and melt-kneaded to obtain the fluororesin. Melting point 260 ° C. The MFR at 372 ° C. is 27 g / 10 min. Tensile modulus is 600 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluororesin (a-13): After melting 80 g of fluororesin (a-2) in a lab plastmill with an internal volume of 80 ml heated to 280 ° C. (manufactured by Toyo Seiki Seisakusho Co., Ltd.), oxidized with an inorganic filler 1.6 g of zinc type 1 (manufactured by Sakai Chemical Industry Co., Ltd.) was added and melt-kneaded to obtain the fluororesin. Melting point 260 ° C. The MFR at 372 ° C. is 26 g / 10 min. The tensile modulus is 590 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

(Fluoro rubber composition (raw material of thermoplastic resin composition))
Production Example 1 (Preparation of fluororubber composition (b-1))
As shown in Table 1, the fluororubber 1 (VdF / TFE / HFP = 50/20/30 mol%, fluorine concentration = 71 mass%) is added to 100.0 mass parts with a crosslinking agent bisphenol AF (manufactured by Daikin Industries, Ltd.) Add 2.0 parts by weight, 1.0 part by weight of crosslinking accelerator BTPPC (made by Hokuko Chemical Co., Ltd.), 3.0 parts by weight of magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry Co., Ltd.), and open 8 inches. The fluororubber composition (b-1) was produced by kneading using a roll.

Production Example 2 (Preparation of fluororubber composition (b-2))
As shown in Table 1, the fluororubber 2 (VdF / TFE / HFP = 30/40/30 mol%, fluorine concentration = 73 mass%) was added to 100.0 parts by mass of the crosslinking agent bisphenol AF (manufactured by Daikin Industries, Ltd.) 2.0 parts by mass, 1.0 part by mass of crosslinking accelerator BTPPC (Hokuko Chemical Co., Ltd.), 6.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) are added, and 8 inches are added. The fluororubber composition (b-2) was produced by kneading using an open roll.

Production Example 3 (Preparation of fluororubber composition (b-3))
As shown in Table 1, fluororubber 2 (VdF / TFE / HFP = 30/40/30 mol%, fluorine concentration = 73 mass%) was added to 100.0 parts by mass of a crosslinking agent V3 (manufactured by Daikin Industries, Ltd.) 3 0.0 part by mass and 3.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) were added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b-3). .

Production Example 4 (Preparation of fluororubber composition (b-4))
As shown in Table 1, fluororubber 1 (VdF / TFE / HFP = 50/20/30 mol%, fluorine concentration = 71% by mass) is added to 100.0 parts by mass with a crosslinking agent DPE (manufactured by Wakayama Seika Co., Ltd.) 3.0 parts by mass and 3.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) are added and kneaded using an 8-inch open roll to produce a fluororubber composition (b-4). did.

Production Example 5 (Preparation of fluororubber composition (b-5))
As shown in Table 1, fluororubber 1 (VdF / TFE / HFP = 50/20/30 mol%, fluorine concentration = 71% by mass) is added to 100.0 parts by mass with a crosslinking agent BAPP (manufactured by Wakayama Seika Co., Ltd.). 3.0 parts by mass and 3.0 parts by mass of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) are added and kneaded using an 8-inch open roll to produce a fluororubber composition (b-5). did.

Production Example 6 (Preparation of fluororubber composition (b-6))
As shown in Table 1, fluororubber 1 (VdF / TFE / HFP = 50/20/30 mol%, fluorine concentration = 71% by mass) is added to 100.0 parts by mass with a crosslinking agent DPE (manufactured by Wakayama Seika Co., Ltd.) 3.0 parts by mass, 2.0 parts by mass of a crosslinking agent bisphenol AF (produced by Daikin Industries, Ltd.), 1.0 part by mass of a crosslinking accelerator BTPPC (produced by Hokuko Chemical Industries, Ltd.), magnesium oxide (Kyowa Mag 150, Kyowa) Chemical Industry Co., Ltd.) 3.0 parts by mass was added and kneaded using an 8-inch open roll to prepare a fluororubber composition (b-6).

(Adhesion test partner)
Production Example 7 (Preparation of bonding partner material (z-1))
Ternary fluororubber raw rubber (G-558BP, manufactured by Daikin Industries, Ltd., VdF / TFE / HFP = 58/20/22 mol%) to 100 parts by mass of bisphenol AF (manufactured by Daikin Industries) 2.2 parts by mass , DBU-B (manufactured by Wako Pure Chemical Industries, Ltd.) 0.56 parts by mass, carbon black (seest S, manufactured by Tokai Carbon Co., Ltd.), 13 parts by mass, magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass and 6.0 parts by mass of calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Co., Ltd.) were added and kneaded using an 8-inch open roll.

Production Example 8 (Preparation of bonding partner material (z-2))
NBR full compound. 100 parts by mass of acrylonitrile-butadiene rubber (N530, manufactured by JSR Corporation), 43 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 7 parts by mass of zinc oxide (manufactured by Hystec Co., Ltd.), wet silica (Nipsil VN3, Nippon Silica Kogyo Co., Ltd.) 21 parts by mass, stearic acid (Lunac, Kao Co., Ltd.) 1.4 parts by mass, anti-aging agent (A.O.224, manufactured by KING INDUSTRIES) 3 parts by mass, plasticizer ( Thiokol TP95, manufactured by Morton International 21 parts by mass, wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.) 3 parts by mass is added to an 8-inch open roll. Were kneaded using.

Production Example 9 (Preparation of bonding partner material (z-3))
100 parts by mass of acrylonitrile-butadiene rubber (N530, manufactured by JSR Corporation), 43 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 7 parts by mass of zinc oxide (manufactured by Hystec Co., Ltd.), wet silica (Nipsil VN3, 21 parts by mass of Nippon Silica Kogyo Co., Ltd., 1.4 parts by mass of stearic acid (Lunac, manufactured by Kao Corporation), 3 parts by mass of anti-aging agent (A.O.224, KING INDUSTRIES), plasticizer (Thiokol) 21 parts by mass of TP95, manufactured by Morton International, wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), 3 parts by mass of peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.), V3 (Daikin Industries, Ltd.) 6 parts by mass and Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.) And kneaded using an 8-inch open roll. The structural formula of Epicoat 828 is shown below (Formula (15)).

（式中、ｎは０．１である）

(Where n is 0.1)

Production Example 10 (Preparation of bonding partner material (z-4))
100 parts by mass of epichlorohydrin rubber (Epichromer CG, manufactured by Daiso Corporation), 80 parts by mass of carbon black (N-550, manufactured by Cancarb Ltd.), Plasticizer (ADK Cizer RS-107, manufactured by Asahi Denka Kogyo Co., Ltd.) 5 0.0 part by mass, Lubricant (Splender R-300) 2.0 parts by mass, anti-aging agent (NOCRACK NBC, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 2.0 parts by mass, synthetic hydrotalcite (DHT-4A, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, DBU phenol resin salt (P-152) 1.5 parts by mass, 6 -Methylquinoxaline-2,3-dithiocarbonate (Daisonette XL-21S, manufactured by Daiso Corporation) It was kneaded using an addition for 8-inch open rolls 1.5 parts by weight.

Examples 1-38
The compound of the said fluororesin (a-1 to a-10, a-12 and a-13) and a fluororubber composition (b-1 to b-6) is used so that it may become the compounding quantity shown in Tables 2-6. The mixture was added and kneaded using a lab plast mill (manufactured by Toyo Seiki Seisakusho). The total amount of the fluororesin and fluororubber 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, and the temperature of the lab plast mill is adjusted to include the temperature used in the composition. The temperature was set to 300 ° C., which is 40 ° C. higher than the melting point of the fluororesin of about 260 ° C. After the temperature of the Laboplast Mill was stabilized, the fluororesin and fluororubber composition shown in Tables 2 to 5 were added, and immediately after the addition, the number of stirring was increased to 100 rpm. From the time when the torque showed the maximum value, the mixture was stirred for 10 minutes to obtain a thermoplastic resin composition. Various measurements were carried out by the above-described methods using the obtained pellets.

Comparative Examples 1-2
A compound of the fluororesin (a-11) and fluororubber composition (b-1 or b-2) was added so as to have a mass ratio of 70/30, and Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.). ). The total amount of the fluororesin and fluororubber 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, and the temperature of the lab plast mill is adjusted to include the temperature used in the composition. The temperature was set to 300 ° C., which is 40 ° C. higher than the melting point of the fluororesin of about 260 ° C. After the temperature of the lab plast mill was stabilized, the fluororesin and fluororubber composition shown in Table 7 were added, and immediately after the addition, the number of stirring was increased to 100 rpm. From the time when the torque showed the maximum value, the mixture was stirred for 10 minutes to obtain a thermoplastic resin composition. Various measurements were carried out by the above-described methods using the obtained pellets.

Comparative Example 3
Various measurements were performed by the above-mentioned method using pellets of “THV 200G” (VdF / TFE / HFP = 57/33/10 mol%, melting point 118 ° C.) manufactured by Dyneon. Since this material has a melting point of about 120 ° C., no adhesion test was conducted.

Comparative Example 4
Various measurements were performed by the method described above using pellets of “THV 500G” (VdF / TFE / HFP = 38/52/10 mol%, melting point 168 ° C.) manufactured by Dyneon.

Comparative Example 5
Various measurements were performed by the above-mentioned method using pellets of “THV 815G” (VdF / TFE / HFP = 20/74/6 mol%, melting point 222 ° C.) manufactured by Dyneon.

  The fuel barrier materials obtained in Examples 1 to 38 were obtained by observing the morphology with a scanning electron microscope (manufactured by JEOL Ltd.), the fluororesin (A) forming a continuous phase, and the crosslinked fluororubber (B). Was found to have a structure forming a dispersed phase. The dispersion particle diameters of the crosslinked fluororubber (B) were all 20 μm or less in Examples 1 to 38.

  In addition, as shown in Tables 2 to 7, the thermoplastic resin composition in which the fluororesin (A) is a copolymer having a carbonyl group, an olefin group, or an amino group at the main chain end or side chain end of the polymer is good. Therefore, it has been found that it is useful as a fuel peripheral material because it exhibits both good fuel barrier properties and flexibility and exhibits good adhesion to other materials.

  According to the present invention, since it is a thermoplastic resin containing a cross-linked fluororubber and a fluororesin, it has excellent fuel barrier properties and flexibility. Moreover, since it has a functional group at the terminal of the fluororesin, the obtained thermoplastic resin can improve adhesiveness with other materials.

Claims (14)

A thermoplastic resin composition comprising a fluororesin (A) and a crosslinked fluororubber (B),
The fluororesin (A) is a copolymer having a carbonyl group, an olefin group or an amino group at the main chain end or side chain end of the polymer,
The crosslinked fluororubber (B) is obtained by dynamically crosslinking the fluororubber (b) together with the crosslinking agent (c) under the melting condition of the fluororesin (A) in the presence of the fluororesin (A). is there,
Thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, which contains at least one polyfunctional compound (d) in at least one of the fluororesin (A) and the cross-linked fluororubber (B).   The fluororesin (A) is a copolymer composed of tetrafluoroethylene and hexafluoropropylene, a copolymer composed of ethylene and tetrafluoroethylene, or a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene. The thermoplastic resin composition according to any one of Items 1 to 2.   The heat according to any one of claims 1 to 3, wherein the crosslinked fluororubber (B) is a crosslinked fluororubber crosslinked by at least one crosslinking reaction among polyol crosslinking, polyamine crosslinking, and peroxide crosslinking. Plastic resin composition.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein at least one of the crosslinking agent (c) and the polyfunctional compound (d) is an amine compound.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the fluororubber (b) is vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene fluororubber.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the polyfunctional compound (d) is an amine compound. The fuel permeation coefficient of a molded article formed from the thermoplastic resin composition is 40 (g · mm) / (m ² · day) or less and the tensile modulus is 600 MPa or less. 8. The thermoplastic resin composition according to any one of items 7.   The method according to claim 1, comprising a step of dynamically crosslinking the fluororubber (b) together with the crosslinking agent (c) under the melting condition of the fluororesin (A) in the presence of the fluororesin (A). The manufacturing method of the thermoplastic resin composition in any one of Claim 8.   A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 8.   A fuel tube formed from the thermoplastic resin composition according to any one of claims 1 to 8.   A laminate comprising a thermoplastic resin layer formed from the thermoplastic resin composition according to any one of claims 1 to 8 and an elastomer layer formed from the elastomer composition.   The elastomer composition in the elastomer layer is acrylonitrile-butadiene rubber or hydrogenated rubber thereof, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluororubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber or The laminate according to claim 12, comprising an acrylic rubber.   The laminate according to claim 12 or 13, wherein the elastomer composition in the elastomer layer contains at least one compound selected from the group consisting of onium salts, amine compounds, and epoxy resins.