JP5115382B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition containing a synthetic resin, crosslinked fluorine-containing elastomer particles and an inorganic filler. Such a resin composition is particularly excellent in substance permeation blocking properties, and by selecting a synthetic resin or an inorganic filler, a molded article having excellent mechanical properties, heat resistance, flame retardancy, conductivity, etc. can be provided. .

  In order to impart various physical or chemical properties to the synthetic resin, not only the improvement of the synthetic resin but also various fillers are widely used.

  As such a filler, a nano-order filler called a nanofiller has recently attracted attention.

  In particular, for the purpose of imparting a function of blocking the permeation of a gas such as air or oxygen, or a liquid such as water or fuel, it has been proposed to blend a nanofiller with a synthetic resin (Patent Document 1).

  In Patent Document 1, a surface-modified nanofiller obtained by modifying the surface of an inorganic filler such as a nanocarbon filler, a metal heteroatom compound filler, or a metal nanofiller with a fluorine compound is blended with a fluororesin or fluororubber as a matrix, A composition having excellent material permeation blocking properties is obtained.

WO2006 / 137475 pamphlet

  The present invention is a resin composition that is particularly excellent in substance permeation blocking properties, and that can give a molded product excellent in mechanical properties, heat resistance, flame retardancy, conductivity, etc. by selecting a synthetic resin or an inorganic filler. The purpose is to provide goods.

  That is, the present invention relates to a resin composition containing (A) a synthetic resin, (B) a crosslinked fluorine-containing elastomer particle, and (C) an inorganic filler.

  The average primary particle diameter of the crosslinked fluorine-containing elastomer particles (B) is preferably 10 to 500 nm.

  The crosslinked fluorine-containing elastomer particles (B) include an aqueous dispersion containing peroxide-crosslinkable fluorine-containing elastomer particles (b1), a peroxide (b2), and a polyfunctional unsaturated compound (b3). Crosslinked fluorine-containing elastomer fine particles obtained by subjecting the fluorine-containing elastomer particles (b1) to peroxide crosslinking by heating are preferred.

Further, the fluorine-containing elastomer constituting the fluorine-containing elastomer particles (b1) is tetrafluoroethylene, vinylidene fluoride, and formula (1):
CF ₂ = CF-R _f ¹ (1)
Wherein R _f ¹ is selected from the group consisting of perfluoroethylenically unsaturated compounds represented by —CF ₃ or —OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group). It is preferable to include a structural unit derived from at least one monomer.

  The inorganic filler (C) is preferably an inorganic nanofiller, such as a nanocarbon filler, a metal heteroatom compound filler, and / or a metal nanofiller.

  Moreover, it is preferable that the surface of the said inorganic filler (C) is processed with the fluorine compound.

  The synthetic resin (A) is preferably a thermoplastic resin, more preferably a fluororesin.

As the fluororesin, preferably
(1) a fluororesin containing a tetrafluoroethylene unit and an ethylene unit,
(2) Tetrafluoroethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
(3) Tetrafluoroethylene unit, ethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
And (4) at least one fluororesin selected from the group consisting of fluororesins containing vinylidene fluoride units.

  Furthermore, it is preferable that the fluororesin contains at least the fluororesin (2).

  It is preferable that 5 to 1000 parts by mass of the crosslinked fluorine-containing elastomer particles (B) is contained with respect to 100 parts by mass of the synthetic resin, and 0% of the inorganic filler (C) with respect to 100 parts by mass of the synthetic resin. It is preferable that 0.01-100 mass parts is contained.

  The present invention also relates to a resin molded product obtained by molding these resin compositions.

  According to the resin composition of the present invention, it is particularly excellent in material permeation blocking properties, and by selecting a synthetic resin or an inorganic filler, a molded product excellent in mechanical properties, heat resistance, flame retardancy, conductivity, etc. Can be given.

  The resin composition of the present invention contains (A) a synthetic resin, (B) a crosslinked fluorine-containing elastomer particle, and (C) an inorganic filler.

  The synthetic resin (A) may be, for example, a curable resin, but is preferably a thermoplastic resin from the viewpoint of utilizing the characteristics of the crosslinked fluorine-containing elastomer fine particles (B) as an elastomer.

  Thermoplastic resins include fluorine resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, acrylonitrile-butadiene-styrene resin, acrylic resin, polyamide, polyacetal, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, Examples thereof include polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyimide, and polyamideimide. Of these, a fluororesin is preferred from the viewpoint of good mechanical strength and fuel barrier properties.

As the fluororesin, preferably,
(1) a fluororesin containing a tetrafluoroethylene unit and an ethylene unit,
(2) Tetrafluoroethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
(3) Tetrafluoroethylene unit, ethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
And (4) at least one fluororesin selected from the group consisting of fluororesins containing vinylidene fluoride units.

  Especially, it is preferable that the fluororesin (2) is included at least from the viewpoint of good mechanical strength and fuel barrier properties.

  Specific examples of the fluororesin include perfluoro copolymers such as tetrafluoroethylene (TFE) -perfluoro (alkyl vinyl ether) copolymer (PFA) and TFE-hexafluoropropylene (HFP) copolymer (FEP); Examples thereof include TFE-ethylene copolymer (ETFE) and TFE-HFP-ethylene copolymer (EFEP).

  The average primary particle diameter of the crosslinked fluorine-containing elastomer particles (B), which is another component of the resin composition of the present invention, is preferably 10 to 500 nm. When the average primary particle diameter is in this range, the dispersibility with the resin, the mechanical strength, and the fuel barrier property are improved. More preferably, it is 0.4 μm or less, particularly 0.3 μm or less, and 0.05 μm or more, particularly 0.1 μm or more is preferable.

The crosslinked fluorine-containing elastomer particles (B) are obtained by crosslinking the fluorine-containing elastomer particles (b1). Examples of the fluorine-containing elastomer constituting the fluorine-containing elastomer particles (b1) include tetrafluoroethylene and vinylidene. Fluoride and formula (1):
CF ₂ = CF-R _f ¹ (1)
Wherein R _f ¹ is selected from the group consisting of perfluoroethylenically unsaturated compounds represented by —CF ₃ or —OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group). It is preferable to include a structural unit derived from at least one monomer.

  The fluorine content of the cross-linked fluorine-containing elastomer particles (B) varies depending on the type and amount of the cross-linking agent to be used, but it is 65% by mass or more, and 70% by mass or more improves the composite dispersibility with the fluororesin. From the point of view, it is preferable.

  The degree of cross-linking of the cross-linked fluorine-containing elastomer particles (B) may be adjusted depending on the purpose of use. For example, when used for automobile materials, the degree that the portion not dissolved in acetone (insoluble matter) is 80% by mass or more is From the viewpoint of mechanical strength. More preferably, the insoluble content in acetone is 90% by mass or more. The upper limit is 100% by mass.

  Further, the method for producing the crosslinked fluorine-containing elastomer particles (B) is not particularly limited, but the fluorine-containing elastomer particles (b1), peroxide (b2) and polyfunctional unsaturated compound (b3) capable of peroxide crosslinking are used. A method of subjecting the fluorine-containing elastomer particles (b1) to peroxide crosslinking by heating an aqueous dispersion containing

  By adopting this production method, the crosslinked fluorine-containing elastomer particles (B) can be finely dispersed in the synthetic resin (A), and flexibility can be imparted without impairing the physical properties of the resin (A).

  That is, by not performing the crosslinking during the polymerization, it is advantageous in that the crosslinkable monomer does not inhibit the polymerization, and high molecular weight and high strength crosslinked fluorine-containing elastomer fine particles can be produced. Since it is not after separation (coagulation), it is advantageous in that crosslinked fluorine-containing elastomer fine particles retaining the form of primary particles can be obtained.

  Further, when the obtained crosslinked fluorine-containing elastomer fine particles are blended with a resin, moldability is improved, mechanical properties such as strength and elongation are improved, and fuel impermeability can be remarkably improved.

  Such a method for producing the crosslinked fluorine-containing elastomer particles is a novel method, in which the peroxide-crosslinkable fluorine-containing elastomer particles (b1) are in the state of an aqueous dispersion (dispersion) and are mixed with a peroxide (b2). It is characterized by peroxide crosslinking by heating in the presence of a saturated compound (b3).

As the fluorine-containing elastomer constituting the peroxide-crosslinkable fluorine-containing elastomer particles (b1) used in the present invention, a peroxide-crosslinkable fluorine rubber is suitable, and among them, tetrafluoroethylene, vinylidene fluoride and the formula ( 1):
CF ₂ = CF-R _f ¹ (1)
Wherein R _f ¹ is selected from the group consisting of perfluoroethylenically unsaturated compounds represented by —CF ₃ or —OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group). The inclusion of a structural unit derived from at least one monomer is preferred from the viewpoint of obtaining particles having properties as a rubber elastic body.

  The peroxide-crosslinkable fluororubber is also preferably peroxide-crosslinkable non-perfluorofluororubber and peroxide-crosslinkable perfluorofluororubber.

  Non-perfluorofluororubbers include vinylidene fluoride (VdF) fluororubber, tetrafluoroethylene (TFE) / propylene fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluororubber, ethylene / Hexafluoroethylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine rubber, fluoro Examples thereof include silicone-based fluororubber, fluorophosphazene-based fluororubber, and the like, which can be used alone or in any combination as long as the effects of the present invention are not impaired. Among these, vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber are more preferable.

  The vinylidene fluoride-based fluororubber is a fluorine-containing copolymer comprising 45 to 85 mol% of vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. Say. Preferably, it refers to a fluorine-containing copolymer comprising 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

  Examples of at least one other monomer copolymerizable with vinylidene fluoride include tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoropropylene (HFP), and trifluoropropylene. , Fluorine-containing monomers such as tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro (alkyl vinyl ether) (PAVE), and vinyl fluoride; non-fluorine monomers such as ethylene, propylene, and alkyl vinyl ether The body is mentioned. These can be used alone or in any combination. Of these, tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether) are preferable.

  Specific rubbers include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, VdF-CTFE-TFE rubber, and the like.

  Tetrafluoroethylene / propylene-based fluororubber is composed of 45 to 70 mol% tetrafluoroethylene and 55 to 30 mol% propylene, and further has a crosslinking site capable of peroxide crosslinking with respect to the total amount of tetrafluoroethylene and propylene. A fluorine-containing copolymer containing 5 mol% or less of the monomer to be given.

Examples of the monomer that provides a crosslinking site capable of peroxide crosslinking include, for example, the general formula (2):
CX ¹ ₂ = CX ¹ -R _f ¹ CHR ¹ X ² (2)
Wherein X ¹ is H, F or CH ₃ ; R _f ¹ is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group; R ¹ is H or CH ₃ X ² is an iodine atom or bromine atom), or an iodine or bromine-containing monomer represented by the general formula (3):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 3 (3)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ³ is a bromine atom). In addition, perfluoro (6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro (5) as described in JP-B-5-63482 and JP-A-7-316234 are disclosed. Examples include iodine-containing monomers such as (iodo-3-oxa-1-pentene), and these can be used alone or in any combination.

  These non-perfluorofluororubbers can be produced by a conventional method.

  Examples of the perfluorofluororubber include those made of a monomer that provides a cross-linking site capable of cross-linking tetrafluoroethylene / perfluoro (alkyl vinyl ether) / peroxide. The composition of tetrafluoroethylene / perfluoro (alkyl vinyl ether) is preferably 50 to 90/10 to 50 mol%, more preferably 50 to 80/20 to 50 mol%, still more preferably 55. -70 / 30-45 mol%. Further, the monomer that gives a peroxide-crosslinkable crosslinking site is preferably 5 mol% or less, preferably 2 mol% or less, based on the total amount of tetrafluoroethylene and perfluoro (alkyl vinyl ether). Is more preferable. When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.

  Examples of the perfluoro (alkyl vinyl ether) in this case include perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), and these can be used alone or in any combination.

  Examples of the monomer that gives a peroxide-crosslinkable crosslinking site include an iodine or bromine-containing monomer represented by the general formula (2) and a monomer represented by the general formula (3). In addition, perfluoro (6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro as described in JP-B-5-63482 and JP-A-7-316234 are used. Examples include iodine-containing monomers such as 5-iodo-3-oxa-1-pentene, and these can be used alone or in any combination.

  These perfluoro fluororubbers can be produced by a conventional method.

  Specific examples of such perfluoro fluorine rubber include fluorine described in International Publication No. 97/24381 pamphlet, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. For example, rubber.

As a preferable method for producing the fluorine-containing elastomer, a known iodine transfer polymerization method can be given as a method for producing the fluororubber. For example, a crosslinking site capable of peroxide crosslinking, if necessary, in the presence of an iodine compound, preferably a diiodine compound, in the presence of an iodine compound, preferably a monomer constituting the fluorine-containing elastomer, in an aqueous medium. There is a method in which emulsion polymerization is carried out in the presence of a radical initiator while stirring the monomer that gives the pressure. As a typical example of the diiodine compound to be used, for example,
R ² I _x Br _y (8)
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms which may contain an oxygen atom). The iodine atom or bromine atom thus introduced functions as a crosslinking point capable of peroxide crosslinking.

Examples of the compound represented by the formula (8) include 1,3-diiodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5- Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane , diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF _{2 Br, BrCF 2 CFBrOCF 3,} 1- bromo-2-Yodopafuru Loethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2- Bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted, (2-iodoethyl) and (2-bromoethyl) -substituted, etc. These may be used alone or in combination with each other.

  Among these, it is preferable to use 1,4-diiodoperfluorobutane, diiodomethane, etc. from the viewpoints of polymerization reactivity, crosslinking reactivity, availability, and the like.

  The addition amount of the diiodine compound is preferably 0.0001 to 5 mass% with respect to the total weight of the fluorine-containing elastomer.

  The fluorine content of the fluorine-containing elastomer constituting the fluorine-containing elastomer particles (b1) may be appropriately selected depending on the purpose of use and the like, but it is 65% by mass or more, more preferably 70% by mass or more. It is preferable from the viewpoint of improvement of dispersibility. From the viewpoint of peroxide crosslinking, an elastomer having an iodine group at the polymer terminal is preferred.

  The average particle size of the fluorine-containing elastomer particles (b1) is preferably 0.01 to 0.5 μm from the viewpoint of improving the composite dispersibility with a synthetic resin, particularly a fluororesin, and improving physical properties. More preferably, it is 0.3 μm or less, particularly 0.2 μm or less, and 0.05 μm or more, particularly 0.1 μm or more is preferable.

  In order to initiate peroxide crosslinking, peroxide (b2) is used as a crosslinking agent. As peroxide (b2) to be used, persulfate or organic peroxide may be used, or these may be used in combination. Also good.

  Examples of the persulfate include ammonium persulfate (APS), sodium persulfate (SPS), and potassium persulfate (KPS). Of these, APS is preferred because of its good half-life temperature and crosslinking efficiency. It can also be used in combination with a reducing agent such as sulfites.

  Examples of the organic peroxide include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, and 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, 2,5-dimethyl-2,5-di (benzoyl) Peroxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-e Examples thereof include tilhexanoate, t-hexylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, and the like. Among them, preferred is a dialkyl type. Furthermore, t-butylperoxy-2-ethylhexanoate is particularly preferred. In general, the type and amount of the organic peroxide are selected in consideration of the amount of active —O—O—, decomposition temperature and the like. Of these, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5 have good half-life temperature and crosslinking efficiency. -Di (2-ethylhexanoylperoxy) hexane is preferred.

  Of these peroxides (b2), persulfates are preferred from the viewpoint of good crosslinking efficiency, and APS and KPS are particularly preferred because of their good crosslinking efficiency.

  The compounding amount of the peroxide (b2) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer particles (b1) in the aqueous dispersion from the viewpoint of good crosslinking efficiency. A more preferable blending amount is 10 parts by mass or less, particularly 5 parts by mass or less, and 0.1 part by mass or more, particularly 1.0 parts by mass based on 100 parts by mass of the fluorine-containing elastomer particles (b1) in the aqueous dispersion. More than part by mass.

The polyfunctional unsaturated compound (b3) is not particularly limited as long as it is a polyfunctional unsaturated compound that can act as a crosslinking aid in peroxide crosslinking in an aqueous dispersion. For _{example, CH 2 = CH-, CH 2} = CHCH 2 -, CF 2 = CF -, - polyfunctional compound having a functional group such as CH = CH- and the like.

  Preferably, at least one compound selected from the group consisting of an oxime nitroso compound, a di (meth) acrylate compound, a triester compound, a triallyl isocyanurate compound, and a polybutadiene compound from the viewpoint of good crosslinking efficiency. Can be illustrated.

  Examples of the oxime nitroso compound include dinitrosobenzene.

  Examples of the di (meth) acrylate compound include NK ester 9G (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Examples of the triester compound include High Cloth M (manufactured by Seiko Chemical Co., Ltd.), NK ester TMTP (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

  Examples of triallyl isocyanurate compounds include triallyl isocyanurate (TAIC) and trimethallyl isocyanurate (TMAIC).

  Examples of polybutadiene compounds include NISSO-PB (manufactured by Nippon Soda Co., Ltd.).

  Of these, triallyl isocyanurate (TAIC) can be preferably used from the viewpoint of good crosslinking efficiency.

  The blending amount of the polyfunctional unsaturated compound (b3) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer particles (b1) in the aqueous dispersion, from the viewpoint of good crosslinking efficiency. Further preferable blending amount is 10 parts by mass or less, particularly 5 parts by mass or less, and 0.5 parts by mass or more, especially 1.0 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer particles (b1) in the aqueous dispersion. More than part by mass.

  In the production method of the present invention, an aqueous dispersion containing a peroxide-crosslinkable fluorine-containing elastomer particle (b1), a peroxide (b2), and a polyfunctional unsaturated compound (b3) is prepared.

  The aqueous dispersion was prepared by (I) adding the fluorine-containing elastomer particles (b1) to an aqueous medium, adding the peroxide (b2) and the polyfunctional unsaturated compound (b3) and stirring and dispersing; II) Peroxide (b2) and polyfunctional unsaturated compound (b3) are added to an aqueous dispersion (polymerized aqueous dispersion) containing fluorine-containing elastomer particles (b1), which is a polymerization product mixture by iodine transfer polymerization. It can be carried out by a method of adding and dispersing the mixture and adjusting the concentration appropriately.

  Preparation method (I) may use a surfactant to stabilize the dispersion. However, the amount is preferably 5 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the fluorine-containing elastomer particles (b1) from the viewpoint of stability during crosslinking.

Examples of the surfactant that can be used include C ₇ F ₁₅ COONH ₄ and C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) CFCF ₃ COONH ₄ .

  The preparation method (II) is advantageous because the production system of the fluorine-containing elastomer particles (b1) can be inherited as it is. Even when a surfactant is present in the polymerization field, it can be used as it is in the production method of the present invention.

  The concentration of the fluorine-containing elastomer particles (b1) in the aqueous dispersion is preferably 5 to 50% by mass from the viewpoint of good polymerization efficiency and crosslinking efficiency. More preferably, it is 10% by mass or more, particularly 20% by mass or more, and 40% by mass or less, particularly preferably 30% by mass or less.

  The crosslinking reaction starts by cleaving the peroxide (b2) in the aqueous dispersion and generating peroxy radicals.

  When the peroxide (b2) is a thermal decomposition type compound, since it is a reaction in an aqueous dispersion, the heating temperature is 50 ° C. or higher and 100 ° C. or lower, preferably crosslinking efficiency, at normal pressure (1 atm). From this point, it is 60 ° C. or higher and 90 ° C. or lower.

  The reaction time is usually 2 to 10 hours, and further 3 to 6 hours.

  In addition, the crosslinking reaction may be initiated by irradiating active energy rays such as ultraviolet rays and radiation at room temperature. In this case, a crosslinking aid, a sensitizer, and the like may coexist.

  In this production method, the peroxide crosslinking reaction and the active energy ray crosslinking reaction may be used in combination. In addition, the form which makes active energy ray crosslinking reaction essential, ie, the active energy ray is irradiated at normal temperature to the aqueous dispersion containing the fluorine-containing elastomer particles (b1) capable of peroxide crosslinking and the polyfunctional unsaturated compound (b3) Thus, a method for producing crosslinked fluorine-containing elastomer fine particles in which the fluorine-containing elastomer particles (b1) are crosslinked by active energy rays is also a preferred embodiment of the present invention.

  After completion of the crosslinking reaction, the resulting crosslinked fluorine-containing elastomer fine particles can be separated and recovered by a method such as a freeze coagulation method, a salting out method, or an acid coagulation method. Of these, the freeze coagulation method is preferred because the particle shape after coagulation is good.

  The blending amount of the synthetic resin (A), particularly the fluororesin and the cross-linked fluorine-containing elastomer particles (B), may be appropriately selected depending on the type, use, purpose of use, etc. of each component, and usually 100 parts by mass of the synthetic resin (A) The cross-linked fluorine-containing elastomer particles (B) are preferably 5 to 1000 parts by mass, more preferably 5 to 400 parts by mass, and particularly preferably 5 to 200 parts by mass.

  As the inorganic filler (C), which is another component of the resin composition of the present invention, carbon black, glass fiber, carbon fiber, silica, talc, calcium carbonate and the like that are usually used as a reinforcing agent can be used. In order to exhibit more, a filler having a large anisotropy and a small particle size is preferable. Among them, at least one part (for example, length, width, height, thickness, diameter, etc.) has a nano-level (0.1 nm to 1000 nm) structure (particle shape, sheet shape, layer shape, needle shape, rod shape, fiber shape) Inorganic fillers having a cylindrical shape, so-called inorganic nanofillers are preferable.

  Specific examples include inorganic fillers such as nanocarbon materials, metal heteroatom compounds, and metal nanoparticles described in International Publication No. 2006/137475, and surface-modified inorganic fillers obtained by surface modification thereof. .

  The nanocarbon material is a compound composed of carbon atoms having a nano-level structure, and examples include fullerene, carbon nanoball (carbon black), carbon nanofiber, and carbon nanotube. Among these, carbon nanofibers and carbon nanotubes are preferable from the viewpoint of good dispersibility with the resin composition and mechanical strength, and carbon nanotubes are particularly preferable. As the nanocarbon material, for example, an average diameter of 0.1 to 50 nm and an average length of 30 to 2000 nm, particularly an average diameter of 1 to 20 nm and an average length of 50 to 200 nm are preferable.

  Metal heteroatom compounds consist of metals (for example, alkali metals, alkaline earth metals, transition metals, as well as typical metal elements such as aluminum, silicon, gallium, indium, tin, bismuth, lead) and heteroatoms (boron, nitrogen, phosphorus , Arsenic, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine, iodine, etc.), and metal oxides (clay minerals, double hydroxides, pebroskite, other metal oxides) Metal phosphates, metal chalcogenides, etc.). Of these, metal oxides are preferred from the viewpoint of good dispersibility with the resin composition and good mechanical strength. When the metal heteroatom compound is granular, the average particle size is preferably 0.5 to 50 nm, more preferably 1 to 30 nm. In addition, if the average particle size is less than 0.5 nm, the fluidity of the molten resin tends to decrease and the moldability tends to deteriorate, and if it exceeds 50 nm, it becomes difficult to finely disperse and the mechanical strength tends to decrease. .

  The metal heteroatom compound can be blended in the form of a layer, a sheet, a needle, a rod, a fiber, a cylinder, etc., but a layer is preferable from the viewpoint of good fuel barrier properties.

  Among the metal oxides, the clay mineral (also referred to as clay) is not particularly limited. For example, montmorillonite, bentonite, kaolinite, imogonite, mica (including fluorinated mica), hectorite, or the like Two or more types can be exemplified. Of these, montmorillonite and mica are preferred from the viewpoint of good dispersibility with the resin composition and fuel barrier properties. These clay minerals are preferably layered or sheet-like. When the clay mineral is layered or sheet-like, the aspect ratio (flatness) is preferably 5 or more, more preferably 10 or more. If the aspect ratio is less than 5, sufficient fuel barrier properties tend not to be obtained. Here, the aspect ratio refers to the ratio of the major axis to the thickness of the clay mineral.

The double hydroxide has the formula:
[M ^II _1-x M ^III _x (OH) ₂ ] ^{x +} [A ⁿ⁻ _{x / y} · H ₂ O] ^x−
(Wherein, M ^II is a divalent metal, M ^III is a trivalent metal, A ^n-anion containing an anion of aromatic amino carboxylic acids, n represents the valence of the anion, x is 0 to 0.4 (Where y is a real number greater than 0) and is a layered compound in which positively charged divalent and trivalent relative hydroxide sheets are stacked in layers. These double hydroxides can be blended in the form of particles, layers, sheets, needles, rods, and fibers, and layered ones are particularly preferable. When the double hydroxide is layered, the aspect ratio (flatness) is preferably 5 or more, more preferably 10 or more. If the aspect ratio is less than 5, sufficient fuel barrier properties tend not to be obtained. Here, the aspect ratio refers to the ratio of the major axis to the thickness of the double hydroxide.

Pebroskite is a kind of tetragonal crystal structure, and a typical example is a transition metal oxide composed of a ternary system of RMO ₃ such as BaTiO ₃ . Specific examples include those described in Catalysts, 47, 290-294 (2005). These pebrotites can be blended in the form of particles, layers, sheets, needles, rods, and fibers, and layered ones are particularly preferred.

  Examples of other metal oxides include silica, alumina, iron oxide, zinc oxide, zirconia, titania and the like, as well as those described in Catalyst, Vol. 47, pages 279-294 (2005). These metal oxides can be blended in the form of layers, sheets, needles, rods, fibers, cylinders, and the like.

Among the metal heteroatom compounds, the metal phosphate includes the formula: M (HPO ₄ ) ₂ (M is Ti, Zr, Ce, or Sn), or the formula: Zr (ROPO ₃ ) ₂ (R is H, Rh or methyl). These metal phosphates can be blended in the form of particles, layers, sheets, needles, rods, and fibers, and layered ones are particularly preferred.

Among the metal heteroatom compounds, the metal chalcogen (sulfur, selenium, tellurium) compound has the formula MX ₂ (M is Ti, Zr, Hf, V, Nb, Ta, Mo or W; X is sulfur or Se). Or the formula: MPX ₃ (M is Mg, V, Mn, Fe, Co, Ni, Zn, Cd or In; X is sulfur or Se).

  The metal nanoparticles in the inorganic filler are preferably metal particles having a particle diameter of 1 to 100 nm. Examples of the metal include Ag, Au, Cu, Pt, Pd, W, Ni, Ta, In, Sn, Cr, Fe, Co, and Si. These single or two or more types of alloys can be used.

  In this invention, you may use the said inorganic filler as it is, and may mix | blend as the surface treatment inorganic filler which performed various surface treatments on the surface of these inorganic fillers.

  Although the method of surface treatment is not specifically limited, For example, the surface modification (fluorination) treatment etc. which were described in the international publication 2006/137475 pamphlet etc. are suitable.

  The surface fluorination modification treatment can be carried out by allowing a fluorine atom-containing organic cation, a fluorine atom-containing organic anion, or an organic fluorinating agent to act on the inorganic filler. Regarding these fluorine atom-containing organic cations, fluorine atom-containing organic anions, and organic fluorinating agents, ions and compounds described in WO 2006/137475 can be used in the present invention.

  Of these, fluorine atom-containing phosphonium ions, fluorine atom-containing imidazolium ions, fluorine atom-containing ammonium ions and the like are preferable.

  The ratio of the crosslinked fluorine-containing elastomer particles (B) and the inorganic filler (C) is not particularly limited. For example, (B) / (C) (mass ratio) is 0.1 / 99.9 to 99.9. It may be appropriately selected depending on the purpose within the range of /0.1.

  The composition of the synthetic resin (A), in particular, the fluororesin, the cross-linked fluorine-containing elastomer particles (B) and the inorganic filler (C) exhibits excellent performance as a fuel hose, a dynamic sealing material, and a soft resin.

  When preparing a composition for a fuel hose, it is preferable to use FEP, PFA, or ETFE as the fluororesin. Part, further 20 to 70 parts by mass, and 0.1 to 30 parts by mass, and further 1 to 10 parts by mass of the inorganic filler (C) are preferable from the viewpoint of good fuel barrier properties.

  When preparing a composition for a dynamic sealing material, it is preferable to use FEP, PFA, or ETFE as the fluororesin. In this case, the cross-linked fluorine-containing elastomer particles (B) are added to 5 to 100 parts by mass of the fluororesin. 200 parts by mass, further 30 to 80 parts by mass, and 0.1 to 30 parts by mass, and further 1 to 10 parts by mass of the inorganic filler (C) are preferably blended from the viewpoint of good rubber elasticity.

  When preparing a composition for a soft resin, it is preferable to use FEP, PFA, or ETFE as the fluororesin. In this case, 5 to 200 mass of the cross-linked fluoroelastomer particles (B) with respect to 100 mass parts of the fluororesin. Parts, further 20 to 90 parts by mass, and 0.1 to 30 parts by mass, and further 1 to 10 parts by mass of the inorganic filler (C) are preferable from the viewpoint of good rubber elasticity.

  The composition of the synthetic resin (A), the crosslinked fluorine-containing elastomer particles (B) and the inorganic filler (C) is prepared by a dry blend method using a mixer such as a Banbury mixer or a rotary stirrer (even if mixing at a temperature lower than the melting point is used) The above-mentioned mixing may be performed), or an aqueous dispersion of crosslinked fluorine-containing elastomer particles (B) (aqueous dispersion after crosslinking) and an aqueous dispersion of synthetic resin (A) fine particles may be mixed, After making a uniform mixture by co-coagulation, the inorganic filler (C) may be mixed.

  In the present invention, particularly in a field where high purity and non-staining properties are not required, usual additives blended into the resin composition as necessary, for example, other than the crosslinked fluorine-containing elastomer particles (B) and the inorganic filler (C) Fillers, processing aids, plasticizers, colorants and the like can be blended, and one or more conventional crosslinking agents and crosslinking aids different from those described above may be blended.

  EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited only to these examples.

The measurement method used in the present invention is the following method.
(1) Fluorine content Calculated from data measured by NMR analysis (JNM-EX270 manufactured by JEOL Co., Ltd.).
(2) Average particle diameter It calculates from the data obtained by transmission electron microscope (TEM) observation.
(3) Preparation of sheet-like test piece The compositions produced in Examples 1 to 4 and Comparative Example 1 were set in a mold and held at 290 ° C. for 15 to 30 minutes with a heat press machine. After making it into a molten state, a 3 MPa load is applied for 1 minute and compression molding is performed to produce a sheet-like test piece having a predetermined thickness specified in each test.
(4) Measurement of tensile breaking strength, tensile breaking elongation and tensile elastic modulus A 2 mm-thick sheet-like test piece was prepared by the method of (3) above, and a dumbbell having a distance between marked lines of 3.18 mm using an ASTM V-type dumbbell. Punch a specimen. Using the obtained dumbbell-shaped test piece, using an autograph (AGS-J 5 kN, manufactured by Shimadzu Corporation), in accordance with ASTM D638, under a condition of 50 mm / min, a tensile elongation at break at 25 ° C. Measure the tensile strength at break and tensile modulus.
(5) Fuel permeability A sheet-like test piece having a thickness of 0.5 mm is produced by the method (3). 18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is put in a SUS container (open area 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the sheet A test specimen is prepared by setting a cylindrical test piece in the container opening and sealing it. The test body is placed in a thermostatic device (60 ° C.), the weight of the test body is measured, and when the weight reduction per unit time becomes constant, the fuel permeability coefficient is obtained by the following formula.

Production Example 1 (Production of fluorine-containing elastomer particles)
In a 3000 mL internal volume pressure-resistant reaction tank, put 1500 mL of pure water and 7.5 g of ammonium perfluorooctanoate, and after filling and replacing the internal space with a TFE / VdF / HFP (11/19/70 molar ratio) mixed gas, 1.47 MPa · G (15 kg / cm ² G) was pressurized and I (CF ₂ CF ₂ ) ₂ I 0.3 mL (25 ° C.) was injected, and the mixture was stirred at 80 ° C. and 10 mL of APS 0.2% aqueous solution was injected. Since a pressure drop occurs after an induction time of about 0.5 hours, the TFE / VdF / HFP (20/50/30 molar ratio) mixed gas is reduced to 1.27 MPa · G (13 kg / cm ² G). Repressurize to 47 MPa · G (15 kg / cm ² G). Thereafter, polymerization was continued in the pressure range of 1.27 to 1.47 MPa · G (13 to 15 kg / cm ² G) by this method. After 20 hours, the temperature was rapidly lowered and the pressure was released to stop the polymerization.

  The fluorine-containing elastomer particles in the produced aqueous dispersion had a concentration of 25% by mass, an average particle size of 0.2 μm, and a fluorine content of 71% by mass.

Production Example 2 (Production of crosslinked fluorine-containing elastomer particles A)
Inside the polymerization vessel containing the aqueous dispersion (fluorinated elastomer particle concentration: 25% by mass) after polymerization of the fluorine-containing elastomer particles (average particle size 0.2 μm; fluorine content 71% by mass) obtained in Production Example 1 After replacing with nitrogen gas, the mixture was heated to 80 ° C.

  To this aqueous dispersion (25 parts by mass of fluorine-containing elastomer particles), 3 parts by mass of triallyl isocyanurate (TAIC) was added and stirred for 45 minutes. Subsequently, 1.14 parts by mass of ammonium persulfate (APS) was added to initiate the crosslinking reaction. The reaction was allowed to proceed with stirring for 5 hours and then cooled to room temperature to stop the reaction, whereby an aqueous dispersion of crosslinked fluorine-containing elastomer particles was obtained. A part of the mixture was frozen and coagulated at −20 ° C. for 24 hours, and then filtered and dried to recover the crosslinked fluorine-containing elastomer particles as a powder.

  The average particle diameter of the obtained crosslinked fluorine-containing elastomer particles A was 0.2 μm.

Example 1
30 parts by mass of the powder of crosslinked fluorine-containing elastomer particles A obtained in Production Example 2, 70 parts by mass of pellets of tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and Example 2 of International Publication No. 2006/137475 3 parts by mass of C ₄ F ₉ CH ₂ CH ₂ P (Bu) ₃ -montmorillonite powder (thickness: 1 nm, diameter: 500 nm) prepared in the same manner as in the above A composition was prepared by kneading with a plast mill 655).

Examples 2-4
A composition was obtained in the same manner as in Example 1 except that the synthetic resin (A), the crosslinked fluorine-containing elastomer particles (B) and the inorganic filler (C) shown in Table 1 were used.

In addition, the inorganic filler mix | blended in Examples 2-4 is the following, It produced according to description of the international publication 2006/137475 pamphlet.
Example _{2: C 6 F 13 CH 2} CH 2 P (Bu) 3 - montmorillonite (thickness: 1 nm, diameter: 500 nm)
Example _{3: C 4 F 9 CH 2} CH 2 P (Bu) 3 - Mica (thickness: 1 nm, diameter: 5000 nm)
Example _{4: C 6 F 13 CH 2} CH 2 P (Bu) 3 - Mica (thickness: 1 nm, diameter: 5000 nm)

Comparative Example 1
A comparative composition was obtained in the same manner as in Example 1 except that the inorganic filler was not blended.

Test example 1
The mechanical properties of the compositions obtained in Examples 1 to 4 and Comparative Example 1 were examined. The results are shown in Table 1.

Test example 2
The compositions obtained in Examples 1 to 4 and Comparative Example 1 were examined for fuel (gasoline) permeability. The results are shown in Table 1.

Claims (6)

(A) a synthetic resin, saw-containing (B) a fluorine-containing elastomer particles are crosslinked and (C) an inorganic filler,
5 to 1000 parts by mass of the crosslinked fluorine-containing elastomer particles (B) and 0.01 to 100 parts by mass of the inorganic filler (C) with respect to 100 parts by mass of the synthetic resin (A),
The synthetic resin (A) is a fluororesin,
The average primary particle diameter of the crosslinked fluorine-containing elastomer particles (B) is 10 to 500 nm,
The inorganic filler (C) is a metal heteroatom compound having at least one portion of 0.1 nm to 1000 nm, is a layer having an aspect ratio of 5 or more, and has a surface treated with a fluorine compound. <br/> Resin composition. The crosslinked fluorine-containing elastomer particles (B) heat an aqueous dispersion containing peroxide-crosslinkable fluorine-containing elastomer particles (b1), a peroxide (b2), and a polyfunctional unsaturated compound (b3). The resin composition according to claim 1 , wherein the resin composition is a crosslinked fluorine-containing elastomer fine particle obtained by subjecting the fluorine-containing elastomer particles (b1) to peroxide crosslinking. The fluorine-containing elastomer constituting the fluorine-containing elastomer particles (b1) is tetrafluoroethylene, vinylidene fluoride and formula (1):
CF ₂ = CF-R _f ¹ (1)
Wherein R _f ¹ is selected from the group consisting of perfluoroethylenically unsaturated compounds represented by —CF ₃ or —OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group). The resin composition according to claim 2 , comprising a structural unit derived from at least one monomer. The fluororesin is
(1) a fluororesin containing a tetrafluoroethylene unit and an ethylene unit,
(2) Tetrafluoroethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
(3) Tetrafluoroethylene unit, ethylene unit and formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ or —OR _f ² (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)), a fluororesin containing a perfluoroethylenically unsaturated compound unit,
And (4) vinylidene fluoride resin composition according to any one of claims 1 to 3 is at least one fluorine resin selected from the group consisting of fluorine resin containing chloride units. The resin composition according to claim 4 , wherein the fluororesin comprises at least the fluororesin (2). The resin molded product obtained by shape | molding the resin composition in any one of Claims 1-5 .