WO2007111334A1 - Fluoroelastomer composition, fluororesin composition, and molding thereof - Google Patents

Abstract

A fluoroelastomer composition that simultaneously has satisfactory fuel barrier performance and mechanical properties; and a fluororesin composition that has excellent resistance to fuel permeation. Further, it is intended to provide a molded article, hose and tube produced from the composition. There is provided a fluoroelastomer composition comprising a fluoroelastomer and sericite. Further, there is provided a fluororesin composition comprising fluororesin (A) and crosslinked fluororubber (B) obtained by crosslinking of the fluoroelastomer composition. Still further, there are provided a molded article, hose and tube comprised of the composition.

Description

 Specification

 Fluorine-containing elastomer composition, fluororesin composition, and molded article formed from the composition

 Technical field

 [0001] The present invention relates to a fluorine-containing elastomer composition containing a fluorine-containing elastomer and sericite, a fluorine resin composition containing a crosslinked fluororubber obtained by crosslinking the composition, and a composition formed from the composition. Related to molded products, hoses and tubes.

 Background art

ヽて広く使用されて!、る。 [0002] Fluorine-containing elastomers have excellent chemical resistance, solvent resistance, and heat resistance, and therefore are used as sealing materials in harsh environments, such as automobile industry, semiconductor industry, and chemical industry.

Widely used!

 [0003] For example, in the automobile industry, it is used as a sealant in engines and peripheral equipment, AT equipment, fuel systems and peripheral equipment, etc., but due to recent environmental regulations, SHED (Sealed Housing for Evaporative Determination regulations have been strengthened, and the development of fuel-based rubber materials with particularly excellent fuel barrier properties is desired. In addition to fuel barrier properties, fuel rubber materials are also required to have various properties such as processability, oil resistance, and cold resistance.

 [0004] As such a fuel rubber material, a fluorine-containing rubber having excellent characteristics such as heat resistance and oil resistance has attracted attention. However, in fluorine-containing rubber, when the fluorine content is increased due to the fuel barrier property, the processability tends to be lowered, and it has been considered difficult to achieve both of these characteristics. As a means for improving the fuel barrier property, it is known to add fillers (fillers) such as carbon, my strength, and glass beads to fluororubber (see, for example, JP-A-2004-131543). . However, when a large amount of filler is added to improve the fuel barrier property, there is a problem that the mechanical strength is lowered, and it is difficult to balance the fuel barrier property and the mechanical strength.

[0005] Accordingly, there is currently no filler-containing fluorine-containing elastomer composition having both sufficient fuel barrier properties and mechanical properties. [0006] In addition to the elastomeric material, thermoplastic resins such as polyphenylene sulfide-based resins, ethylene-bulb alcohol-based resins, and liquid-crystalline polyester-based resins are known as materials having excellent fuel barrier properties. Further, as a material having excellent fuel barrier properties, a polymer alloy of fluorine rubber and fluorine resin is known (for example, see JP-A-61-57641). However, in order to reduce weight, reduce costs, improve handleability, etc., a thin film of the barrier layer is required, and further improvement in the noirality is required for the thin film. As a means for solving this problem, a method of reducing the amount of fluororubber in the polymer alloy has been studied. However, this method has a problem that flexibility is impaired. In addition, molded products made of fuel barrier materials are required to have a certain degree of flexibility because they are required to be assembled and have a greater degree of design freedom. For controlling the balance between fuel barrier properties and flexibility. There is a limit and it is difficult to obtain high tolerance.

[0007] Accordingly, there is currently no fluorine resin composition that has both sufficient fuel barrier properties and flexibility!

 Disclosure of the invention

 [0008] An object of the present invention is to provide a fluorine-containing elastomer composition having both sufficient fuel barrier properties and mechanical properties, and a fluorine resin composition having excellent fuel permeability resistance. Another object of the present invention is to provide a molded article, a hose, and a tube in which the composition force is also formed.

 That is, the present invention relates to a fluorine-containing elastomer composition containing fluorine-containing elastomer and sericite.

 [0010] The amount of added sericite is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer.

 [0011] The present invention also relates to a molded article, a hose, and a tube formed from the fluorine-containing elastomer composition.

 [0012] Furthermore, the present invention relates to a fluorine resin composition comprising a fluorine resin (A) and a crosslinked fluorine rubber (B) obtained by crosslinking the fluorine-containing elastomer yarn and composition.

[0013] It is preferable that the cross-linked fluororubber (B) is obtained by dynamically cross-linking the fluorine-containing elastomer composition under the melting condition of the fluororesin (A). [0014] Further, the present invention relates to a molded article, a hose, and a tube in which the fluororesin composition strength is also formed.

 BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a fluorine-containing elastomer composition containing fluorine-containing elastomer and sericite.

 [0016] The sericite used in the present invention is a flake-like filler, and by adding sericite, the fuel barrier property of a molded product having a fluorine-containing elastomer composition or a fluorinated resin composition is remarkably improved. And high mechanical strength can be obtained. The sericite may be natural sericite or synthetic sericite.

[0017] Sericite can be obtained by a grinding method such as wet grinding or dry grinding. The wet pulverization has a clear surface, and the dry pulverization has the characteristics of simple manufacturing process and low cost.

 [0018] The aspect ratio (flatness) of sericite is preferably 10 or more, more preferably 20 or more, still more preferably 50 or more, and particularly preferably 100 or more. If the aspect ratio is less than 10, sufficient fuel barrier properties tend not to be obtained. Here, the aspect ratio is the ratio of the major axis to the thickness of the sericite crystal. The average particle size is preferably 20 μm or less, more preferably 5 μm or less. Above 20 μm, differential scattering is difficult and mechanical strength tends to decrease.

 [0019] The amount of sericite added is preferably 2 to 40 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer so that the sericite power is 50 to 50 parts by weight. It is more preferable to add so that it is 3 to 40 parts by weight. It is more preferable to add so that it is 5 to 30 parts by weight. It is particularly preferable to add 10 to 25 parts by weight. More preferably, it is added so as to be part. If the sericite content is less than 2 parts by weight, sufficient fuel barrier properties tend not to be obtained. If the sericite content exceeds 50 parts by weight, it becomes difficult to finely disperse the sericite and the mechanical strength tends to decrease significantly.

In the present invention, the fluorine-containing elastomer is not particularly limited, and examples thereof include fluororubber ( _a ), thermoplastic fluororubber (b), and rubber compositions having these fluororubber strengths. More preferably, the fluororubber (a) is used. [0021] Examples of the fluororubber (a) include non-perfluorofluororubber ( _a -1) and perfluorofluororubber ( _a- 2). Note that the Pafuruorofutsu containing rubbers, Chi caries its constituent units, refers to the 90 mole _^0/0 or consisting par full O b monomer.

 [0022] Non-perfluorofluorinated rubber (a-1) includes bi-lidene fluoride (hereinafter referred to as VdF) based fluoro rubber, tetrafluoroethylene (hereinafter referred to as TFE) Z propylene based fluoro rubber. , TFEZ propylene ZVdF fluorine rubber, ethylene Z hexafluoropropylene (hereinafter referred to as HFP) fluorine rubber, ethylene ZHFPZVdF fluorine rubber, ethylene ZHF P / TFE fluorine rubber, fluorosilicone fluorine Rubber, fluorophosphazene-based fluororubber, etc. These can be used alone or in any combination as long as the effects of the present invention are not impaired. VdF-based fluororubber, TFEZ It is preferable to use ropylene-based fluororubber.

 [0023] As the VdF-based fluororubber, those represented by the following general formula (1) are preferable.

(M ¹ )-(M ² )-(N ¹ )-(1)

(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 fluorinated ethylenic monomer (m ² ), and the structural unit N ¹ is It is a repeating unit derived from a monomer (n ¹ ) that is copolymerizable with a monomer (m ¹ ) and a monomer (m ² )

[0024] Formula Among VdF type fluorine-containing rubbers represented by (1), the structural unit M ¹ 25 to 85 mole _^0/0, preferably those containing structural units M ² 75 to 15 mol%, the structural unit M ¹ 30-80 mole _^0/0, the more preferred instrument structural unit M ¹ is intended to include structural units M ² 70 to 20 mol% 70 to 80 mol%, those comprising structural units M ² 30 to 20 mol% Further preferred. The structural unit N ¹ is preferably 0 to 10 mol% based on the total amount of the structural unit M ¹ and the structural unit M ² U.

[0025] Examples of the fluorine-containing ethylenic monomer (m ² ) include TFE, black trifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, HFP, trifluoropropylene, and tetrafluoro. Fluorine-containing monomers such as propylene, pentafluoropropylene, trifluorobutene, tetrafluoroloy sobutene, perfluoro (alkyl butyl ether) (hereinafter referred to as PAVE), vinyl fluoride, and the like. Of these, TFE, HFP, and PAVE are preferred.

[0026] The monomer (n ¹ ) may be any one that is copolymerizable with the monomer (m ¹ ) and the monomer (m ² ). Any of these may be used, and examples thereof include ethylene, propylene, alkyl butyl ether, and a monomer that gives a crosslinking site. Among these, a monomer that gives a crosslinking site is preferable.

 [0027] As a monomer that gives such a crosslinking site, for example, VdF, general formula (2):

CY ¹ = CY ¹ -R ¹ CHR ¹ X ¹ (2)

 2 f

(Where Y ¹ is a hydrogen atom, fluorine atom or CH 2, R ¹ is a fluoroalkylene group,

 3 f

A fluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, R ¹ is a hydrogen atom or CH, and X ¹ is an iodine atom or a bromine atom).

 Three

 Iodine or bromine containing monomers, general formula (3):

CF = CFO (CF CF (CF) 0) (CF) —X ² (3)

 2 2 3 m 2 n

(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X ² is a cyano group, a carboxyl group, an alkoxycarbonyl group, a bromine atom)

 These can be used alone or in any combination.

 [0028] The iodine atom, bromine atom, cyan group, carboxyl group, and alkoxycarbonyl group can function as a crosslinking point.

 [0029] Specific examples of such VdF fluororubbers include VdFZHFP rubber, VdFZHFP ZTFE rubber, VdFZCTFE rubber, VdFZCTFEZTFE rubber, VdFZPAVE rubber, VdFZTFEZPAVE rubber, VdFZHFPZPAVE rubber, VdFZHFPZPAVE rubber, VdFZTFEZ propylene rubber, VdFZ ethylene ZHFP rubber and the like are preferable.

[0030] As the TFEZ propylene fluorine rubber, preferably those represented by the following general formula (4) /ヽone (M ³⁾ one (M ⁴⁾ -! (N ²⁾ one (4)

(Wherein 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 a monomer (n ² ) copolymerizable with the monomer (m ⁴ )

Among the TFEZ propylene-based fluororubbers represented by the general formula (4), the structural unit M ³ is 40 70 mol%, the structural unit M ⁴ of 60 to 30 mol%, including ones more preferably preferably tool the structural unit M ³ 50-60 mole _^0/0, the structural unit M ⁴ fifty to forty mole _^0/0 containing It is a waste. 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 .

[0032] As the monomer (n ² ), V may be used as long as it is copolymerizable with the monomer (m ³ ) and the monomer (m ⁴ ). Preferred to be a monomer that gives.

 [0033] Examples of the monomer that gives such a cross-linking site include perfluoro (6, 6 dihydro-1, 6-3, oxa) as described in JP-B-5-63482 and JP-A-7-316234, for example. 1) iodine-containing monomers such as 1-hexene) and perfluoro (5-3 oxa 1 pentene), benzene-containing monomers described in JP-A-4-505341, JP-A-4-505345, Examples thereof include a cyano group-containing monomer, a carboxyl group-containing monomer, and an alkoxycarboxyl group-containing monomer as described in JP-A-5-500070.

[0034] As the perfluoro fluororubber (a-2), those represented by the following general formula (5) are preferable: 1 (M ⁵ ) 1 (M ⁶ )-(N ³ ) 1 (5)

(In the formula, structural unit M ⁵ is a structural unit derived from TFE (m ⁵ ), structural unit M ⁶ is a structural unit derived from PAVE (m ⁶ ), and structural unit N ³ is a monomer (m ⁵ ). And a repeating unit derived from a monomer (n ³ ) copolymerizable with the monomer (m ⁶ ))

[0035] Among the perfluoro fluorine-containing rubbers represented by the general formula (5) (a- 2), the structural unit M ⁵ 50 to 90 mol%, preferably those comprising structural units M ⁶ 10 to 50 mol% instrument more preferably the structural unit M ⁵ and 50 to 80 mole _^0/0, which the structural unit M ⁶ comprising 20 to 50 mole _^0/0, further preferred properly structural unit M ⁵ and 55 to 70 mole _^0/0, the structural unit M ⁶ are those containing 30 to 45 mole _^0/0. 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 close to those of rosin.

[0036] Examples of PAVE (m ⁶ ) include perfluoro (methyl vinyl ether), perfluoro (propyl butyl ether), and the like. Can be used in combination.

[0037] Further, as the monomer (n), the monomer (m ⁵ ) and any of the above monomers that can be copolymerized with the monomer (m ⁶ ) may be used. Among these, a monomer that gives a crosslinking site is preferable.

[0038] Examples of monomers that give such a crosslinking site include VdF, the general formula (2), (3

), And the like. These can be used alone or in any combination.

[0039] The iodine atom, bromine atom, cyano group, carboxyl group, alkoxycarbonyl group

, Can function as a crosslinking point.

[0040] Specific examples of strong perfluorinated rubber (a-2) include WO 97Z24381 pamphlet, JP-B 61-57324, JP-B 4-81608, JP-B 5-

Examples thereof include fluororubber described in Japanese Patent No. 13961.

[0041] The fluororubber ( _a ) preferably has a number average molecular weight of 1,000 to 500,000! /.

[0042] Examples of the non-perfluorofluororubber (a-1) and perfluorofluororubber (a-2) are the constitution of the main monomer. Those obtained by copolymerizing a polymerizable monomer or the like can also be suitably used.

[0043] Among the fluorine-containing elastomers, a fluororubber containing a VdF unit is preferred from the viewpoint of heat resistance, compression set, workability, and cost. A fluororubber having a VdF unit and an HFP unit. More preferred,

 [0044] From the viewpoint of good compression set, VdFZTFEZHFP is preferably at least one rubber selected from the group consisting of VdFZHFP-based fluororubber, VdFZTFEZ HFP-based fluororubber, and TFEZ propylene-based fluororubber. More preferred is fluororubber.

 [0045] The non-perfluorofluororubber (a-1) and perfluorofluororubber (a

-2) is a power that can be produced by a conventional method. As a preferred production method, a known iodine transfer polymerization method can be given as a production method of fluororubber. Polymerization conditions such as temperature and time during polymerization may be appropriately determined depending on the type of monomer and the desired elastomer. [0046] In the present invention, a composition comprising the fluororubber (a) and the thermoplastic fluororubber (b) as described above can also be used.

[0047] The fluorine-containing elastomer scratch, in the fluorine-containing elastomer first composition of the present invention, it is more preferably from 20 to 98 weight _^0/0 is a preferred tool 30-95 wt%.

 [0048] Further, the fluorine-containing elastomer composition of the present invention preferably contains a crosslinking agent, but the type of the crosslinking agent is not particularly limited, depending on the type of fluorine-containing elastomer and the melt-kneading conditions. And can be selected as appropriate.

 [0049] When the fluorine-containing elastomer contains a crosslinkable group (cure site), the crosslinking system used in the present invention is appropriately selected depending on the type of the cure site or the use of the obtained molded product. That's fine. As the crosslinking system, any of 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 can be employed. Among these, a polyol crosslinking system in which a polyamine crosslinking system, a polyol crosslinking system, and a peroxide crosslinking system are preferable, and a polyol in which a peroxide crosslinking system is more preferable, since both fuel barrier properties and processability are possible. Particularly preferred is a cross-linking system or a combined cross-linking system of a polyol cross-linking system and a peroxide cross-linking system.

 [0050] Here, the cross-linking by the polyol cross-linking system is preferable in that it has a carbon-oxygen bond at the cross-linking point, and has a feature that the compression set is small and the moldability is excellent.

 [0051] In the case of crosslinking with a peroxide crosslinking system, V has a carbon-carbon bond at the crosslinking point, so a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine crosslinking system having a carbon-nitrogen double bond. Compared with, it is characterized by excellent chemical resistance and steam resistance.

 [0052] When crosslinked by polyamine crosslinking, it has a carbon-nitrogen double bond at the crosslinking point and is characterized by excellent dynamic mechanical properties. However, compression set tends to increase as compared with the case of crosslinking using a polyol crosslinking system or a peroxide crosslinking system.

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

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

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

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

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

 [0058] The addition amount of the crosslinking agent is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer, and more preferably 0.1 to 10 parts by weight. 0.3 to 7.0 parts by weight is even more preferred. 1 to 5 parts by weight is particularly preferred. If the cross-linking agent is less than 0.05 parts by weight, the degree of cross-linking is insufficient, and the performance of the molded product tends to be impaired, such as heat resistance and oil resistance. If it exceeds 10 parts by weight, the cross-linking density is high. In addition to being liable to be too long, the crosslinking time tends to be long. In addition, it is not economically preferable, and the molding processability of the resulting fluorinated resin composition tends to decrease.

 [0059] In the polyol crosslinking system, a crosslinking assistant is usually used in combination with the polyol crosslinking agent. When a crosslinking aid 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.

 [0060] As a crosslinking aid for the polyol crosslinking system, generally an organic compound is used. The onium compound is not particularly limited, and examples thereof include an ammonium compound such as a quaternary ammonium salt, a phosphonium compound such as a quaternary phosphonium salt, an oxonium compound, a sulfone compound, Examples include cyclic amines and monofunctional amine compounds, among which quaternary ammonium salts and quaternary phosphonium salts are preferred.

[0061] Specifically, for example, tetraptylammonum bromide, tetraptylammonum chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, tetraptylammonium hydrogensulfate, tetraptyl Quaternary ammonium salts such as ammonium hydroxide; 8—methyl-1,8 diazabicyclo [5, 4, 0] —7 undecse-um chloride, 8—methyl-1,8 diazabicyclo [5, 4, 0] — 7 Undesse-muai odide, 8-methyl-1,8 diazabicyclo [5, 4, 0] —7 Undesse-umhide mouth, 8—methyl-1,8 diazabicyclo [5, 4, 0] —7 Undeceumumsulfate, 8 ethyl 1, 8 Gizabicyclo [5, 4, 0] —7 Undese-Umbromi 8 Propyl-1,8 diazabicyclo [5, 4, 0] —7 Undecethum bromide, 8—Dodecyl 1,8 diazabicyclo [5, 4, 0] —7 Undece-um chloride, 8 Dodecil 1,8 diazabicyclo [ 5, 4, 0] — 7 Hundesce-um Hydroxide, 8 Ekosil 1, 8 Diazabicyclo [5, 4, 0] —7 Undecese-um Chloride, 8-Tetracosiru 1, 8 Gizabicyclo [5, 4, 0 ] —7 Undece-um chloride, 8 benzyl 1 1,8 diazabicyclo [5, 4, 0] —7 Undece-um chloride (hereinafter referred to as DBU—B), 8 Benzyl 1,8 diazabicyclo [5, 4, 0] — 7 Hundesce-um Hydroxide, 8 Phenethyl 1, 8 Diazabicyclo [5, 4, 0] — 7 Wundeth-um Chloride, 8 — (3-Fupropyl) 1 1, 8 Diazabicyclo [5, 4, 0] — 7 Wundesseumuk Lid, 1, 8 Gizabicyclo [5. 4. 0] —Cyclic amines such as undecene 7; monofunctional amines such as benzylmethylamine and benzylethanolamine; tetrabutylphosphomum chloride, benzyltriphenylphosphomum chloride (hereinafter referred to as BTPPC), And quaternary phosphonium salts such as benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tribubutylphosphoryl chloride, tributyl-2-methoxypropylphosphonium chloride, and benzylphenol (dimethylamino) phosphonium chloride. It is done.

 Among these, DBU-B and BTPPC are preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

[0063] Further, as a crosslinking aid, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, a chlorine-free crosslinking aid disclosed in JP-A-11-147891 Use agent.

[0064] Examples of crosslinking assistants for organic peroxides include triaryl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N, 1 m-phenol-bismaleimide, Dipropargyl terephthalate, diallyl phthalate, tetralyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1, 3, 5 HJ (2, 3, 3 卜!; Funole P 2 P P Peninole) 1, 3, 5 HJ Azin 1, 2, 4, 6 Trion), Tris (Dialylamine) S Triazine, Trisyl phosphite, N, N-Diallylacrylamide, 1, 6 Divilde decafluor mouth Hexane, hexarylphosphoramide, N, N, Ν ', Ν, monotetraarylphthalamide, Ν, Ν, Ν', Ν, Examples include triaryl malonamide, tribyl isocyanurate, 2,4,6-tribylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite. Among these, triallyl isocyanurate HTAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

 [0065] The addition amount of the crosslinking aid is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer, and more preferably 0.1 to 10 parts by weight. More preferably, it is 0.3 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight. If the crosslinking aid is less than 0.1 parts by weight, the crosslinking time becomes unusable for practical use, and the heat resistance and oil resistance of the resulting molded product tend to be lowered. Furthermore, in addition to the crosslinking time becoming too fast, the compression set of the molded product also decreases, and the moldability of the resulting fluororesin composition tends to decrease.

 [0066] The fluorine-containing elastomer composition of the present invention may be prepared by adding usual additives, for example, a filler, a processing aid, a plasticizer, a colorant, and the like, as needed, to a composition that can be used as a fluorine-containing elastomer. Antioxidants, anti-aging agents, ozone degrading agents, UV absorbers, etc. can be blended, and each of these can be blended with one or more conventional crosslinking agents and crosslinking aids different from the above. The ingredients can be prepared by mixing using conventional elastomer processing machines such as open rolls, Banbury mixers, aders and the like. This method using a hermetic mixer can also be prepared by the co-coagulation method with the emulsion mixing force.

 [0067] Further, the obtained fluorine-containing elastomer composition is crosslinked and molded according to a conventional method. In other words, it is molded by compression molding, injection molding, extrusion molding, calender molding, or melt molding in a solvent and then by die molding or coating.

 [0068] The crosslinking conditions vary depending on the molding method and the shape of the molded product, but are generally in the range of several seconds to 180 minutes at 100 to 200 ° C. Further, secondary crosslinking may be performed in order to stabilize the physical properties of the crosslinked product. The secondary cross-linking condition is 150 to 300 ° C for 30 minutes to 30 hours.

[0069] The fuel permeability coefficient of the molded article formed from the fluorine-containing elastomer composition of the present invention is preferably 35 g · mm / m ² · day or less, and preferably 30 g · / · day or less. Yo More preferably, it is 25 g'mm / m ² 'day or less. The lower limit value of the fuel permeation coefficient is not particularly limited, and the lower value is preferable. If the fuel permeation coefficient exceeds 35 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, which is not economically preferable. The lower the fuel permeation coefficient, the better the fuel permeation prevention capability. Conversely, the fuel permeation coefficient is large, V, and the fuel permeates easily! /.

[0070] The fuel permeability coefficient was measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method stipulated in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, put 18 mL of simulated fuel CE10 (toluene Z isooctane Z ethanol = 45 Z45 ZlO volume%) into a SUS container (open area 1.26 X 10 " ³ m ² ) with a volume of 20 mL. Then, set the sheet-like test piece in the open part of the container and seal it to make a test piece.Place the test piece in a thermostatic device (40 ° C), measure the weight of the test piece, and measure the weight per unit time. When the weight loss becomes constant, the fuel permeability is obtained by the following formula.

 [0071] [Equation 1]

Fuel permeability coefficient (g-mmZm ² -day) =

 [Reduced weight (g)] _X __ [sheet thickness (mm)]

[Open area 1. (m ² )] X 〖measurement interval (day)]

[0072] The tensile strength at break of the molded article formed from the fluorine-containing elastomer composition of the present invention is preferably 6 MPa or more, more preferably 8 MPa, and particularly preferably lOMPa. . The upper limit of the tensile strength at break is not particularly limited. If the tensile strength at break is less than 6 MPa, it tends to be unsuitable for molded products that require mechanical strength.

 [0073] The present invention also relates to a fluorine resin composition comprising a fluorine resin (A) and a crosslinked fluororubber (B) obtained by crosslinking the fluorine-containing elastomer composition.

[0074] Fluororesin (A) is not particularly limited, but at least one fluorine-containing resin Preferred is a fluorine resin containing the ethylenic polymer (a). The fluorinated ethylenic polymer (a) preferably has a structural unit derived from at least one fluorinated ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include TFE and general formula (6): CF = CF-R ² (6)

 2 f

(Wherein R ² is —CF or OR ³ , and R ³ is a perfluoroalkyl having ^{3 to} 5 carbon atoms, f 3 ff

 Group)

 Perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: CT FE, trifluoroethylene, hexafluoroisobutene, VdF, fluorinated butyl, general formula (7):

CH = CX ³ (CF) X ⁴ (7)

 2 2 n

(Wherein X ³ is a hydrogen atom or a fluorine atom, X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10)

 Fluoro refin etc. can be given.

 [0075] The fluorine-containing ethylenic polymer (a) may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Non-fluorinated ethylenic monomers other than the above-mentioned fluororefin and perfluororefin can be mentioned. Examples of the non-fluorinated ethylenic monomer include ethylene, propylene, and alkyl butyl ethers. Here, the alkyl bulle ether is an alkyl bur ether having an alkyl group having 1 to 5 carbon atoms.

 [0076] Among these, the fluorine-containing ethylenic polymer (a) has the heat resistance, chemical resistance, oil resistance, and ease of molding processability of the obtained fluorocoagulant composition.

 (a—l) An ethylene TFE copolymer (ETFE) composed of TFE and ethylene,

 (a 2) TFE PAVE copolymer (PFA) or TFE-HFP copolymer (FEP) consisting of TFE and perfluoroethylenically unsaturated compound represented by the general formula (1),

 (a-3) Ethylene TFE—HFP copolymer (Et—TFE—HFP copolymer) composed of TFE, ethylene and a perfluoroethylenically unsaturated compound represented by the general formula (1), ethylene TFE-PAVE copolymer,

(a— 4) Polyvinylidene fluoride (PVDF) It is preferable that it is a fluorine-containing ethylenic polymer represented by (a-1) or (a-2).

 [0077] Next, preferred fluorine-containing ethylenic polymers (a-l) and (a-2) will be described.

 [0078] (a- l) ETFE

In the case of ETFE, in addition to the above-described effects, mechanical properties and fuel barrier properties are preferable. The molar ratio of TFE units to ethylene units is preferably 20:80 to 90:10 62:38 to 90:10 is preferred, 63:37 to 80:20 is particularly preferred, ₀ or The third component may be! /, And the type of the third component is not limited as long as it is copolymerizable with TFE and ethylene. As the third component, usually the following formula

CH = CX ⁵ R ⁴ , CF = CFR ⁴ , CF = CFOR ⁴ , CH = C (R ⁴ )

 2 f 2 f 2 f 2 f 2

(Where X ⁵ is a hydrogen atom or fluorine atom, R ⁴ does not contain an etheric oxygen atom, f

 You can! / Represents a fluoroalkyl group)

Among these, the fluorine-containing polymer represented by CH = CX ⁵ R ⁴ is used.

 2 f

-Monomers are more preferred R ⁴ monomers having 1 to 8 carbon atoms are particularly preferred.

 f

[0079] Specific examples of the fluorine-containing butyl monomer represented by the above formula include 1,1-dihydroperfluoropropene 1, 1,1-dihydroperfluorobutene 1, 1, 1, 5 trihydronofluoropentene 1, 1, 1 , 7 Trihydroperfluoroheptene 1, 1, 1, 2 Trihydroperfluorohexene 1, 1, 1, 2—Trihydroperfluorootaten 1, 2, 2, 3, 3, 4, 4 , 5, 5-octafluoropentyl vinyl ether, perfluoro (methyl vinylenoleatenore), perfnoreo mouth (propinorebi-noreatenore), hexafnoreo mouth propene, perfluorobutene ₃ , ₃₎ 3 trifluoro 2 (trifluo Romethyl) propene 1, 2, 3, 3, 4, 4, 5, 5 Heptafluo 1-pentene (CH = CFCF CF CF

 2 2 2 2

H).

[0080] The content of the third component is 0. 1 to the fluorine-containing ethylenic polymer (a): LO mol% are preferred, 0.1 to 5 mole _^0/0, more preferably tool 0. 2 to 4 mol _^0/0 are particularly preferred.

 [0081] (a— 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. T It is an FE units 90 to 99 mole _^0/0 and formula (1) per full O represented by b ethylenically unsaturated compound unit 10 mol% Ca also the fluorine-containing ethylenic polymer (a) Is more preferable. In addition, the fluorine-containing ethylenic polymer (a) composed of TFE and the perfluoroethylenically unsaturated compound represented by the general formula (1) is a third component which may contain a third component. The type is not limited as long as it is copolymerizable with TFE and the perfluoroethylenically unsaturated compound represented by the general formula (1).

[0082] The melting point of the fluorine-containing ethylenic polymer (a) is preferably 150 to 310 ° C, more preferably 150 to 290 ° C, and 170 to 250 ° C. Is more preferable. If the melting point of the fluorinated ethylenic polymer ( _a ) is less than 150 ° C, the heat resistance of the resulting fluorocobalt composition tends to decrease, and if it exceeds 310 ° C, the fluorinated resin (A) When the fluorine-containing elastomer composition is dynamically cross-linked in the molten state of fluorine resin (A) in the presence of cerite and sericite, the melting temperature is set to be higher than the melting point of the fluorine-containing ethylenic polymer (a). Although necessary, the fluorine-containing elastomer composition tends to be thermally deteriorated.

 [0083] The weight ratio of fluorinated resin (A) Z-crosslinked fluororubber (B) is preferably 98Z2 to 40Z60, more preferably 95/5 to 50/50 weight%, more preferably force S, 83/17 More preferably, it is ˜50 / 50 parts by weight. When the weight ratio of fluorinated resin (Α) exceeds 98Ζ2, sufficient flexibility tends not to be imparted, and when it is less than 40Ζ60, the cross-linked fluororubber (Β) does not disperse uniformly and becomes partially co-continuous. There is a tendency for the mechanical strength to decrease significantly and the fluidity to decrease significantly.

 [0084] The fluorinated resin composition of the present invention can be obtained by uniformly dispersing the crosslinked fluorinated rubber (含 む) containing sericite in the fluorinated resin (Α). In a molten state, it is preferable to dynamically crosslink the fluorine-containing elastomer composition so that at least a part of the composition is crosslinked.

 Here, the dynamic crosslinking treatment means that the fluorine-containing elastomer composition is dynamically cross-linked simultaneously with melt kneading using a Banbury mixer, a pressure mixer, an extruder, or the like. Say. Among these, it is preferable to use an extruder such as a twin screw extruder because a high shear force can be applied.

[0086] Further, the molten state means a state at a temperature at which the fluorine resin (soot) melts. Melting The temperature to be changed varies depending on the glass transition temperature and Z or melting point of the fluororesin (A), but is preferably 120 to 330 ° C, more preferably 130 to 320 ° C. If the temperature is less than 120 ° C, the dispersion between the fluorocobalt (A) and the fluorine-containing elastomer composition tends to become coarse, and if it exceeds 330 ° C, the fluorine-containing elastomer composition Tend to heat deteriorate.

 [0087] The obtained fluorinated resin composition has a structure in which the fluorinated resin (A) forms a continuous phase and the crosslinked fluorinated rubber (B) forms a dispersed phase, or the fluorinated resin composition (A) is crosslinked with the fluorinated resin (A). The fluororubber (B) can have a structure that forms a co-continuity, and among them, the fluororesin (A) forms a continuous phase and the cross-linked fluororubber (B) forms a dispersed phase. Preferred to have.

 [0088] Even when the fluorine-containing elastomer composition forms an initial dispersion matrix! /, The fluorine-containing elastomer composition becomes a crosslinked fluororubber (B) as the crosslinking reaction proceeds. The melt viscosity is increased, and the crosslinked fluororubber (B) becomes a dispersed phase or forms a co-continuous phase with the fluorocarbon resin (A).

 [0089] When such a structure is formed, the fluororesin composition of the present invention exhibits excellent heat resistance, chemical resistance and oil resistance, as well as high fuel barrier properties and good moldability. It becomes. At that time, the average dispersed particle size of the crosslinked fluororubber (B) is preferably 0.01-30 μm. If the average dispersed particle size is less than 0.01 m, the fluidity tends to decrease, and if it exceeds 30 / z m, the strength of the resulting fluorocobalt composition tends to decrease.

[0090] In addition, the preferred fluorinated resin composition of the present invention is that the preferred fluorinated resin (A) forms a continuous phase, and the crosslinked fluororubber (B) forms a dispersed phase. It is also possible to include a co-continuous structure of fluorine resin (A) and crosslinked fluororubber (B) as part of the structure.

[0091] Fuel permeability coefficient of a molded article using a fluorine榭脂composition of the present invention, it is more favorable 20g'mmZm ² 'd is preferably ay is less instrument 10g'mmZm ^2' is day or less More preferably, it is 5 g-mmZm ² 'day or less. The lower limit value of the fuel permeation coefficient is not particularly limited, and it is preferably as low as possible. If the fuel permeation coefficient exceeds ²⁰ g-mm / day • m ² , 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, which is not economically preferable. The lower the fuel permeability coefficient, The ability to prevent fuel permeation is improved. Conversely, when the fuel permeation coefficient is large, the fuel permeates. The fuel permeation coefficient can be measured using the same method as described above.

 [0092] The tensile modulus of elasticity is 400 MPa or less, more preferably 350 MPa or less, and even more preferably 300 MPa or less. The lower limit value of the tensile elastic modulus is not particularly limited and is preferably as low as possible. If the tensile modulus of elasticity exceeds OOMPa, the flexibility of the molded product is impaired, and the assemblability is liable to deteriorate and the degree of freedom in design tends to be extremely limited.

 [0093] The tensile strength at break of a molded article using the fluororesin composition of the present invention is preferably lOMPa or more, more preferably 15 MPa or more, and particularly preferably 20 MPa or more. preferable. The upper limit of the tensile strength at break is not particularly limited. If the tensile breaking strength is less than 15 MPa, it tends to be unsuitable for molded products that require mechanical strength.

 [0094] The fluorine resin composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents. An agent, an ultraviolet absorber, an antioxidant, a release agent, a foaming agent, a fragrance, an oil, a softening agent, and the like can be added as long as the effects of the present invention are not affected.

 [0095] The fluorinated resin composition of the present invention can be molded using a general molding method or molding apparatus. As the molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding and the like can be adopted, and the fluororesin composition of the present invention is intended for use. Depending on the shape, it is formed into a molded body of any shape.

 [0096] Further, the present invention relates to a force relating to a molded article obtained by using the fluorine-containing elastomer composition or the fluorine resin composition of the present invention. The molded article includes a sheet or a film. The molded body includes a laminate structure including a layer formed from the fluorine-containing elastomer composition or fluorine resin composition of the present invention and a layer formed from other materials.

[0097] The strength of the fluorine-containing elastomer composition or fluorine resin composition of the present invention In a laminated structure of at least one layer and at least one layer formed from another material

The other materials may be selected appropriately according to the required characteristics and intended use. Examples of such 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, salt Thermoplastic polymers such as vinyl resin (PVC) and salt vinylidene resin (PVDC), crosslinked rubber such as ethylene-propylene-gene rubber, butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, metal, glass, Wood, ceramic, etc. can be raised.

 [0098] In the molded article having the laminated structure, a layer formed from the fluorine-containing elastomer composition or the fluorine resin composition of the present invention and a base material layer formed from another material are used. An adhesive layer may be interposed. By interposing the adhesive layer, the layer formed from the fluororesin composition of the present invention and the base material layer formed from another material can be firmly joined and integrated. Examples of the adhesive used in the adhesive layer include acid anhydride modified products of gen-based polymers; acid anhydride modified products of polyolefins; polymer polyols (eg, glycol compounds such as ethylene glycol and propylene glycol, and adipic acid) Polyester polyols obtained by polycondensation of dibasic acids of the above; partial conjugated products of copolymers of vinyl acetate and vinyl chloride, etc.) and polyisocyanate compounds (eg, 2, 4 tolylene diisocyanate, etc.) (For example, a reaction product of a diol compound such as 1,6 hexamethylene glycol and a diisocyanate compound such as 2,4 tolylene diisocyanate in a molar ratio of 1: 2; trio such as trimethylolpropane) 1 to 3 molar ratio of 1 to 3 compound and diisocyanate compound such as 2,4 tolylene diisocyanate Response product, etc.); or the like can be used. In order to form a laminated structure, a known method such as co-extrusion, co-injection, or extrusion coating can be used.

[0099] Further, when producing a laminated structure having a layer in which the fluororesin composition strength of the present invention is formed and a layer having other material strength, it is formed from the fluororesin composition of the present invention as necessary. Surface treatment may be performed on the layer. The surface treatment is not particularly limited as long as it is a treatment method that enables adhesion, for example, plasma discharge treatment, corona discharge treatment or other discharge treatment, wet metal sodium Z naphthalene treatment. Etc. It is done. A primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When primer treatment is performed, the surface of the layer formed from the non-surface-treated fluororesin composition can be primed. Plasma discharge treatment, corona discharge treatment, metal sodium z naphthalene solution treatment, etc. are applied beforehand. It is more effective if the surface of the layer formed from the fluorinated resin composition is further primed

[0100] The fluorine-containing elastomer composition, fluorine resin composition, and molded product using the composition of the present invention include, for example, a semiconductor manufacturing apparatus, a liquid crystal panel manufacturing apparatus, a plasma panel manufacturing apparatus, and a plasma addressed liquid crystal panel. Semiconductor related fields such as field emission display panels and solar cell substrates; Automotive field; Aircraft field; Rocket field; Ship field; Chemical field such as plant; Pharmaceutical field such as pharmaceutical; Photo field such as developing machine; Printing machine In the fields such as printing field such as painting equipment; coating field such as coating equipment; analysis · physics and chemistry machine field; food plant equipment field; nuclear power plant equipment field; steel field such as iron plate processing equipment; general industrial field; electrical field; Although it can be used preferably, among these, it can be used more preferably in the automobile field.

 [0101] In the automotive field, gaskets, shaft seals, valve stem seals, seals and hoses can be used for engines and peripherals.

It can be used for AT devices, and 0 (square) rings, tubes, packings, valve cores, hoses, seals and diaphragms can be used for fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, hold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, Etater packing, fuel pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston packing, cylinder liner seal, knob stem seal, automatic transmission front pump seal, rear axle On-seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas re-burning unit scenery, bearing Shinore, EGR tube, twin key bush tube, carburetor It can be used as a sensor diaphragm, anti-vibration rubber (engine mount, exhaust part, etc.), recombustion device hose, oxygen sensor bushing, etc.

 [0102] The molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable for industrial hoses, industrial tubes, fuel hoses, and fuel tubes.

 Example

 [0103] Next, the present invention will be described by way of examples, but the present invention is not limited only to the powerful examples.

[0104] In the examples and comparative examples, the following materials were used.

[0105] <Fluorine-containing elastomer 1>

VdF, 3-way based rubber consisting of TFE and HFP (VdF: TFE: HFP = 58: 20: 22 Monore _^0/0, 100 ° beam one at C - one viscosity = 45)

[0106] <Fluorine-containing elastomer 1>

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

[0107] Fluororesin (A)>

 TFE-ethylene copolymer (EP-610, manufactured by Daikin Industries, Ltd., melting point 218 to 228 ° C, 2 97 ° C · MFR at 5000g load = 25 to 35gZl0min)

[0108] <Serisite>

 Sericite (Sericite) (manufactured by Yodogawa Industries Co., Ltd., Yodogawa My Force Z20, shape: phosphorus flake, aspect ratio: 110, average particle size: 2 / ζ πι)

[0109] <Mica>

 Made by Co-op Chemical Co., Ltd., Micromy strength ΜΚ—100, Shape: flake, Aspect ratio: 30, Average particle size: 4 m

[0110] <Carbon filler>

 Tokai Carbon Co., Ltd., sheath 1 S, shape: granular, average particle size: 0.07 m

[0111] <Crosslinking agent>

Polyol-based cross-linking agent: 2, 2-bis (4-hydroxyphenol) perfluoropropane (Daikin Industries, Ltd., trade name Bisphenol AF) [0112] <Crosslinking aid 1>

 DBU— B (Wako Pure Chemical Industries, Ltd.)

[0113] <Crosslinking aid 2>

 Benzyltriphenylphospho-um chloride (BTPPC) (made by Hokuko Chemical Co., Ltd., trade name)

)

 [0114] Example 1

 1 100 parts by weight of the above-mentioned fluorine-containing elastomer, 2 parts by weight of a crosslinking agent, 1 part by weight of a crosslinking aid, and an acid acceptor (produced by Kyowa Chemical Industry Co., Ltd., acid magnesium “MA150”) 3 6 parts by weight of calcium hydroxide “Caldic 2000” (Ohmi Chemical Industry Co., Ltd.) is mixed, and 10 parts by weight of the above sericite is mixed and kneaded with a roll by a conventional method. Thus, a crosslinkable fluorine-containing elastomer composition was prepared.

 [0115] This fluorine-containing elastomer composition was subjected to crosslinking by first pressing at 170 ° C for 15 minutes, followed by crosslinking in an oven at 230 ° C for 24 hours by oven crosslinking. A shape was obtained. The tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test of the molded product were measured by the following methods. The results are shown in Table 1.

 [0116] Example 2

 A molded article formed from a fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the amount of sericite added was changed to the amount shown in Table 1. The tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.

[0117] Examples 3 and 4

 A molded article formed from a fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the amount of sericite added was changed to the amount shown in Table 1. The tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.

[0118] Comparative Example 1

A molded article formed from the fluorine-containing elastomer composition was obtained in the same manner as in Example 1, except that sericite was not added. Tensile strength at break (Tb) and tensile fracture The elongation (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.

[0119] Comparative Examples 2 and 3

 Except that the sericite was changed to the above-mentioned My strength and the addition amount was changed to the amount shown in Table 1, a molded article having a fluorine-containing elastomer composition strength was obtained in the same manner as in Example 1. The bow I tensile strength (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.

[0120] Comparative Examples 4 and 5

 A molded article formed from the fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the sericite was changed to the carbon filler and the addition amount was changed to the amount shown in Table 1. The tensile breaking strength (Tb), tensile breaking elongation (Eb), hardness (Shore A), and fuel permeation test of the molded product were measured by the following methods. The results are shown in Table 1.

 [0121] (Standard crosslinking conditions)

 Kneading method: Roll kneading

 Primary press crosslinking: 15 minutes at 170 ° C

 Secondary oven crosslinking: 24 hours at 230 ° C

 [0122] <Tensile breaking strength (Tb) and tensile breaking elongation (Eb)>

 The compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 are subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to obtain a sheet having a thickness of 2 mm, and the measurement is performed according to JIS-K6251.

 [0123] <Hardness (Shore A)>

 The compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 are subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to obtain a sheet having a thickness of 2 mm, and the measurement is performed according to JIS-K6253.

 [0124] <Fuel barrier properties>

The compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 were subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to produce sheet test pieces having a thickness of 0.5 mm. Put 18mL of a simulated fuel CE10 (Torue emissions Z isooctane Z ethanol = 45Z45Z10 capacity _^0/0) made of SUS container (opening area 1. 26 X 10 "V) with 20mL of volume, the sheet-shaped test piece Is set in a container open part and sealed to obtain a test body. The specimen was placed in the apparatus (40 ° C), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was obtained by the following formula.

[0125] [Equation 2]

Fuel permeability coefficient (g * mmZm ² 'day) =

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

[Open area 1.26 X 10

[0126] [Table 1]

The fluorine-containing elastomer compositions obtained by 2 and 3 are the same as those in Examples 1 and 2. Although it has the same hardness as the fluorine-containing elastomer composition, it has poor fuel permeability. In order to give the comparative fluorine-containing elastomer composition the same fuel permeability as the fluorine-containing elastomer composition of the example, it is necessary to add a large amount of My power. Due to the high hardness, it is not suitable as an elastomer composition.

 [0128] Therefore, the fluorine-containing elastomer compositions obtained in the examples have a low fuel permeability coefficient, excellent balance between fuel barrier properties and flexibility, and sufficient mechanical strength (breaking strength). I understood.

 [0129] Examples 5 to 9

 With respect to 100 parts by weight of the fluorine-containing elastomer described above, 20 parts by weight of sericite, 2 parts by weight of a crosslinking agent, 1 part by weight of a crosslinking aid 21, and an acid acceptor (produced by Kyowa Chemical Industry Co., Ltd. 3 parts by weight of Gnesium “MA150”) were kneaded with two rolls to produce a fluorine rubber (b-1) compound.

 [0130] Subsequently, a compound of fluororubber (b-1) was blended and mixed in the ratio shown in Table 3 with the above-described fluorocoating resin (A), and melt-kneaded by the following kneading method. Each rosin composition was produced. Table 3 shows the results of measurements of tensile strength at break, tensile elongation at break, tensile elastic modulus, MFR, and fuel barrier properties using the obtained fluorocoagulant composition by the following methods.

 [0131] Comparative Example 6

 Table 3 shows the results of measurement of tensile strength at break, tensile elongation at break, tensile elastic modulus, MFR, and fuel barrier properties by the following methods using the above-described fluorocoagulant (A) alone.

[0132] Comparative Examples 7-8

 Fluorine-containing resin composition was prepared in the same manner as in Example 5 except that 1 part by weight of sericite was mixed with 100 parts by weight of fluorine-containing elastomer to prepare a compound of fluororubber (b-2). Each was manufactured. Table 3 shows the results of measuring the tensile strength at break, tensile elongation at break, tensile modulus, MFR, and fuel barrier properties by the following methods using the obtained fluorocoagulant composition.

[0133] Comparative Example 9 Fluorine-containing elastomer 1 2 100 parts by weight kneaded 55 parts by weight of sericite to prepare a fluorine rubber (b-3) compound. The thing was manufactured. Table 3 shows the results of measurement of tensile strength at break, tensile elongation at break, tensile elastic modulus, MFR, and fuel barrier properties by the following methods using the obtained fluorocoagulant composition.

 [0134] <Production of sheet-like test piece>

 From the melting point (220 ° C) of the fluorine resin (A) used in the composition, the fluorine resin composition produced in Examples 5 to 9 and Comparative Examples 6 to 9 was set in a mold, and then heated with a heat press. Hold at 60 ° C high and temperature (280 ° C) for 15-30 minutes, make the dynamic vulcanized composition into a molten state, then apply a 3MPa load for 1 minute, compress it, and then press the sheet A test specimen is prepared.

 [0135] <Measurement of tensile strength at break and tensile elongation at break>

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

 [0136] <Fuel barrier properties>

A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. Put 18mL the SU S-made container (opening area 1.26X10 "V) is simulated fuel to CE10 (toluene Z Isoota Tan Z ethanol = 45Z45Z10 capacity _^0/0) with 20mL volume, volumes of the sheet-like test piece The specimen is placed in the open part of the vessel and sealed to make a specimen.The specimen is placed in a thermostatic device (60 ° C), and the weight of the specimen is measured. By the way, the fuel permeability coefficient was calculated by the following formula.

 [0137] [Equation 3]

Fuel permeability coefficient (g 'mmZm ² ' day) =

 [Reduced weight (g)] J, [Sheet thickness (mm)]

[Opening area ^{1. 26 X 1 0- 3 (m} 2) ] X [Measurement interval (day)]

[0138] <Liquidity> Using the fluororesin compositions produced in Examples 5 to 9 and Comparative Examples 6 to 9, the melt flow was measured under a condition of 297 ° C and 5000 g load using a melt flow measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Mouth rate (MFR) was measured.

 [0139] <Kneading method>

 The fluorine-containing elastomer 2 and sericite were kneaded by a roll by a conventional method to prepare crosslinkable fluorine-containing elastomer compositions (b-1 to b-3) shown in Table 2.

 [0140] The kneading of the fluororesin (A) and the crosslinkable fluorine-containing elastomer composition (b-l to b-3) was performed using a laboplast mill (manufactured by Toyo Seiki Seisakusho). The total amount of the fluorinated resin (A) and the crosslinkable fluorine-containing elastomer composition to be kneaded was adjusted so that the total volume was 77% by volume of the total volume of the kneaded part of the lab plast mill. The temperature of the lab plast mill was set to 40 ° C higher than the melting point (220 ° C) of the fluororesin (A) used in the composition, and the temperature (260 ° C). After the temperature of the lab plast mill has stabilized, add the fluorocarbon resin (A), stir at 10 rpm for 5-10 minutes to melt the fluorocarbon resin (A), and melt the fluorocarbon resin (A) Then, the crosslinkable fluorine-containing elastomer composition was added, and immediately after the addition, the number of stirring was increased to lOOrpm. From the time when the torque showed the maximum value, the mixture was stirred until 10 minutes later to obtain a fluorinated resin (A) Z-crosslinked fluororubber (B) Z sericite dynamic vulcanized composition.

 [0141] [Table 2]

[0142] [Table 3] s * s * si5§5iit £ J ^ it: l0143> ill9lOni // ~~

Table 3

It was found that it has an excellent balance between fuel barrier properties and flexibility and sufficient mechanical strength (breaking strength).

Industrial applicability

 In the present invention, by dispersing sericite in a fluorine-containing elastomer, a molded article having excellent heat resistance, chemical resistance, and oil resistance, and having excellent fuel barrier properties and high mechanical properties can be obtained. A fluorine-containing elastomer composition which can be provided is provided. The present invention also provides a molded article having excellent fuel barrier properties, heat resistance, chemical resistance, oil resistance and flexibility by including a crosslinked fluororubber obtained by crosslinking the fluorine-containing elastomer composition. A fluororesin composition that can be obtained and can be melt-molded can be provided.

Claims

The scope of the claims  [1] A fluorine-containing elastomer composition containing a fluorine-containing elastomer and sericite.  [2] The fluorine-containing elastomer composition according to claim 1, wherein the amount of sericite added is 2 to 50 parts by weight per 100 parts by weight of the fluorine-containing elastomer. [3] A molded article formed by the composition of the fluorine-containing elastomer according to claim 1 or 2.  [4] A hose formed by the composition of the fluorine-containing elastomer according to claim 1 or 2.  [5] A tube formed by the composition of the fluorine-containing elastomer according to claim 1 or 2.  [6] A fluorine resin composition comprising a fluorine resin (A) and a crosslinked fluorine rubber (B) obtained by crosslinking the fluorine-containing elastomer composition according to claim 1 or 2.  [7] The fluorine according to claim 6, wherein the cross-linked fluororubber (B) is obtained by dynamically cross-linking the fluorine-containing elastomer composition under the melting condition of the fluororesin (A). A rosin composition.  [8] A molded article formed by the composition of the fluororesin composition according to claim 6 or 7. [9] A hose formed with the composition of the fluororesin composition according to claim 6 or 7. [10] A tube formed with the composition of the fluororesin composition according to claim 6 or 7.