WO2007135875A1 - Silicone-containing thermoplastic fluororesin composition, article molded therefrom, and process for preparing silicone-containing thermoplastic fluororesin composition - Google Patents

Silicone-containing thermoplastic fluororesin composition, article molded therefrom, and process for preparing silicone-containing thermoplastic fluororesin composition Download PDF

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Publication number
WO2007135875A1
WO2007135875A1 PCT/JP2007/059794 JP2007059794W WO2007135875A1 WO 2007135875 A1 WO2007135875 A1 WO 2007135875A1 JP 2007059794 W JP2007059794 W JP 2007059794W WO 2007135875 A1 WO2007135875 A1 WO 2007135875A1
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Prior art keywords
silicone
group
thermoplastic fluororesin
containing thermoplastic
composition
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PCT/JP2007/059794
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French (fr)
Inventor
Katsuhide Ohtani
Tsuyoshi Ono
Haruhisa Masuda
Ron Klein
Masakazu Irie
Kazuo Kobayashi
Igor Chorvath
Tanya Collins
Lauren Tonge
Original Assignee
Daikin Industries, Ltd.
Dainkin America, Inc.
Dow Corning Toray Co., Ltd.
Dow Corning Corporation
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Application filed by Daikin Industries, Ltd., Dainkin America, Inc., Dow Corning Toray Co., Ltd., Dow Corning Corporation filed Critical Daikin Industries, Ltd.
Publication of WO2007135875A1 publication Critical patent/WO2007135875A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed, a molded article comprising the same, and a process for preparing the silicone-containing thermoplastic fluororesin composition.
  • NEOFLONTM FEP As a jacket material for LCC, for example, NEOFLONTM FEP is known. However, although a jacket using the NEOFLONTM FEP is excellent in heat resistance, there has been a problem that printing is difficult on the surface of a cable.
  • the present invention relates to a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed, a molded article comprising the composition, and a process for preparing the silicone-containing thermoplastic fluororesin composition.
  • the present invention relates to a silicone-containing thermoplastic fluororesin composition comprising a fluororesin (A) and a silicone rubber (B), wherein the fluororesin (A) comprises a fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the silicone rubber (B) is crosslinked at least in a part thereof.
  • a melting point of the fluorine-containing ethylenic polymer (a) is 120 to 310 0 C.
  • silicone rubber (B) is dynamically crosslinked in the presence of the fluororesin (A).
  • the fluororesin (A) is a copolymer of tetrafluoroethylene with a perfluoro ethylenically unsaturated compound represented by the following general formula (1):
  • Rf 1 represents -CF3 and/or -ORf 2
  • Rf 2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
  • the fluororesin (A) is a copolymer comprising 20 to 80 % by mole of a tetrafluoroethylene unit and 80 to 20 % by mole of an ethylene unit, or a copolymer comprising 19 to 90 % by mole of a tetrafluoroethylene unit, 9 to 80 % by mole of an ethylene unit and 1 to 72 % by mole of a perfluoro ethylenically unsaturated compound unit represented by the following general formula (1):
  • CF 2 CF-Rf 1 (1) wherein Rf 1 represents -CF3 and/ or -ORf 2 , and Rf 2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
  • the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by a condensation reaction, a hydro silylation reaction, or a radical reaction with an organic peroxide.
  • the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by a hydro silylation reaction. It is preferable that the silicone rubber (B) is a crosslinked product of the crosslinkable silicone rubber composition comprising an organopolysiloxane (b- 1 ) .
  • the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group
  • the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom
  • the crosslinking catalyst (b-3) is a hydro silylation reaction catalyst.
  • the silicone-containing thermoplastic fluororesin composition comprises an inorganic filler (D).
  • the inorganic filler (D) is at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide, and hydrotalcite.
  • the present invention relates to a molded article and an electric wire jacket, which are formed from the silicone-containing thermoplastic fluororesin composition. Further, the present invention relates to a cable, particularly a LAN cable, having the electric wire jacket.
  • the crosslinkable silicone rubber composition further comprises the crosslinking agent (b-2) and the crosslinking catalyst (b-3).
  • the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group
  • the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom
  • the crosslinking catalyst (b-3) is a hydrosilylation reaction catalyst.
  • the preparation process comprises:
  • a dynamic crosslinking method of simultaneously carrying out the mixing and the crosslinking is used. It is preferable that a twin screw extruder is used.
  • the melting point of the fluororesin (A) is less than 120 0 C, heat resistance of the obtained silicone-containing thermoplastic fluororesin composition tends to be lowered, and when it exceeds 310 0 C, it is required to set the melting temperature at the melting point or more of the fluororesin (A) when dynamic crosslinking is carried out in the presence of the fluororesin (A), thereby the silicone rubber (B) tends to be thermally degraded at that time.
  • R 3 is a divalent organic group having 1 to 20 carbon atoms
  • R 1 is an alkyl group having 1 to 5 carbon atoms is preferable from the viewpoint that compatibility with a silicone rubber is enhanced, and a carboxyl group and the group represented by the general formula (2) are more preferable.
  • a process for introducing a carbonyl group-containing end group into the fluororesin (A) is not specifically limited, and examples are a process of copolymerizing a monomer having the carbonyl group-containing end group at polymerization of the fluororesin (A), a process of carrying out polymerization by using a polymerization initiator having a carbonyl group or a functional group which can be converted to a carbonyl group, and a process of thermally decomposing polymer main chains under the coexistence of oxygen.
  • the number of carbonyl group-containing end groups of the fluororesin can be measured by the methods described in JP-B-37-3127 and WO 99/45044 pamphlet.
  • the number of carbonyl group-containing end groups in the fluororesin (A) is preferably 100 to 1,000, more preferably 200 to 800, further preferably 300 to 700 per 1,000,000 carbon atoms. When it is less than 100, compatibility with the silicone rubber (B) tends to be lowered, and when it exceeds 1,000, foams tend to be generated in a molded article.
  • Examples of the ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) are perfluoroolefins such as tetrafluoroethylene (hereinafter referred to as
  • Rf 1 represents -CF3 and/ or -ORf 2 and Rf 2 represents a perfluoroalkyl group having 1 to 5 carbon atoms; fluoroolefins such as chlorotrifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (hereinafter referred to as VdF), vinyl fluoride, and one represented by the general formula (3):
  • CTFE chlorotrifluoroethylene
  • VdF vinylidene fluoride
  • X 2 represents a hydrogen atom or a fluorine atom
  • X 3 represents a hydrogen atom, a fluorine atom or a chlorine atom
  • n represents an integer of 1 to 10.
  • examples of the ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) are non-fluorine-containing ethylenically unsaturated compounds other than the above-mentioned fluoroolefins and perfluoroolefins.
  • examples of the non-fluorine-containing ethylenically unsaturated compound are ethylene, propylene, and alkyl vinyl ethers.
  • the alkyl vinyl ether is an alkyl vinyl ether having an alkyl group with 1 to 5 carbon atoms.
  • the fluorine-containing ethylenic polymer (a) comprising TFE and ethylene is preferable from the viewpoint that the heat resistance and oil resistance of the obtained silicone-containing thermoplastic fluororesin composition are excellent and molding process is easy, and the fluorine-containing ethylenic polymer (a) comprising 20 to 80 % by mole of a TFE unit and 80 to 20 % by mole of an ethylene unit is more preferable.
  • An amount of the third component is preferably 0.1 to 3 % by mole based on the fluorine-containing ethylenic polymer (a) .
  • the fluorine-containing ethylenic polymer (a) comprising TFE and the perfluoro ethylenically unsaturated compound represented by the general formula (1) is preferable from the viewpoint that the obtained silicone-containing thermoplastic fluororesin composition is excellent in heat resistance, oil resistance, electrical property, and flame retardance, and molding process becomes easy.
  • TFE/hexafluoropropylene hereinafter referred to as HFP
  • TFE/ CF 2 CF-ORf 2
  • the fluorine-containing ethylenic polymer (a) comprising TFE and the perfluoro ethylenically unsaturated compound represented by the general formula (1) may also contain other third components.
  • a melting point is preferably 120 to 270 0 C from the viewpoint that molding process of the obtained silicone-containing thermoplastic fluororesin composition is easy.
  • the melting point can be set by a copolymerization ratio of TFE to the perfluoro ethylenically unsaturated compound represented by the above-mentioned general formula (1).
  • the fluorine-containing ethylenic polymer (a) comprising TFE, ethylene and the perfluoro ethylenically unsaturated compound represented by the general formula (1) is preferable from the viewpoint that the obtained silicone-containing thermoplastic fluororesin composition has an excellent heat resistance and oil resistance, and molding process is easy
  • the fluorine-containing ethylenic polymer (a) comprising 19 to 90 % by mole of a TFE unit, 9 to 80 % by mole of an ethylene unit and 1 to 72 % by mole of a perfluoro ethylenically unsaturated compound unit represented by the general formula (1) is more preferable
  • the fluorine-containing ethylenic polymer (a) comprising 20 to 70 % by mole of a TFE unit, 20 to 60 % by mole of an ethylene unit and 1 to 60 % by mole of the perfluoro ethylenically unsaturated compound unit represented by the general formula (1) is further preferable.
  • An amount of the additional component is preferably 0.1 to
  • the silicone rubber (B) used in the present invention is not specifically limited, and is crosslinked at least in a part thereof, and is preferably a rubber dynamically crosslinked in the presence of the fiuororesin (A) from the viewpoint that dispersibility in the fluororesin is excellent, and productivity is improved.
  • the dynamic crosslinking treatment means that the crosslinkable silicone rubber composition is melt-kneaded and at the same time dynamically crosslinked using a Banbury mixer, a compression kneader, an extruder or the like.
  • extruders such as a twin screw extruder are preferably used from the viewpoint that high shearing force can be added.
  • a composition in which the silicone rubber (B) is uniformly dispersed in the fluororesin (A) can be obtained by carrying out the dynamic crosslinking treatment under the melting condition of the fluororesin (A) .
  • under the melting condition means "at a temperature at which the fluororesin (A) is melted”.
  • the melting temperature varies depending on a glass transition temperature and /or a melting point of the fluororesin (A), and is preferably 120 to 330°C, more preferably 130 to 320 0 C.
  • the temperature is less than 120 0 C, the dispersion between the fluororesin (A) and the silicone rubber (B) tends to be rough, and when it exceeds 330 0 C, the silicone rubber (B) tends to be thermally deteriorated.
  • the silicone rubber (B) is preferably a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a condensation reaction, a hydrosilylation reaction or a radical reaction with an organic peroxide.
  • a crosslinked product which is obtained by crosslinking by the hydrosilylation reaction is preferable from the viewpoint that any by-product is not generated in the crosslinking reaction.
  • crosslinkable silicone rubber composition a crosslinkable silicone rubber composition comprising the organopolysiloxane (b-1) is preferable, and a crosslinkable silicone rubber composition further comprising the crosslinking catalyst (b-3) and the crosslinking agent (b-2) if necessary is more preferable.
  • the crosslinkable silicone rubber composition preferably comprises the organopolysiloxane (b-1) containing at least two crosslinkable reaction groups in one molecule thereof, the crosslinking agent (b-2) and the crosslinking catalyst (b-3).
  • the crosslinkable silicone rubber composition preferably comprises the organopolysiloxane (b-1) and the crosslinking catalyst (b-3).
  • organopolysiloxane (b-1) examples include diorganopolysiloxanes containing at least two crosslinkable reaction groups in one molecule thereof such as diorganopolysiloxane containing an alkenyl group, diorganopolysiloxane containing an alkoxy group, and diorganopolysiloxane containing a hydroxyl group.
  • crosslinkable reaction group examples include alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, and a hexenyl group; alkoxy groups having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; and a hydroxyl group.
  • alkenyl groups having 2 to 10 carbon atoms are preferable from the viewpoint that crosslinking can be carried out by the hydrosilylation reaction without generating by-products and a pseudo-crosslinking reaction hardly occurs during preservation and a vinyl group is preferable from the viewpoint of economical efficiency in particular.
  • These crosslinkable reaction groups may exist at the molecular end of the organopolysiloxane (b-1), may exist at the side chain of a molecule, and may exist at both of them.
  • Examples of a group bonded with a silicon atom other than the crosslinkable reaction group are alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isobutyl group, a hexyl group, and an octyl group; an aryl group such as a phenyl group; an aralkyl group such as a tolyl group; and a halogenated alkyl group such as a 3,3,3-trifluoropropyl, and an alkyl group having 1 to 8 carbon atoms is preferable.
  • At least 50 % of groups bonded with a silicon atom are methyl groups and it is more preferable that the whole is substantially methyl groups.
  • 1 to 50 % of groups bonded with a silicon atom may be fluorinated alkyl groups such as 3,3,3-trifluoropropyl.
  • a molecular structure of the organopolysiloxane (b-1) is preferably a linear chain structure or a linear chain structure partly having a branch from the viewpoint that the flexibility of the silicone-containing thermoplastic fluororesin composition of the present invention is excellent.
  • a weight average molecular weight of the organopolysiloxane (b-1) is not specifically limited, and is preferably 1,000 to 9,000,000, more preferably 100,000 to 9,000,000, and particularly preferably 450,000 to 4,500,000.
  • the weight average molecular weight of organopolysiloxane (b-1) is within the range, it is preferable from the viewpoint that workability in handling is improved, mixing with the fluororesin (A) is also easy, and flexibility of the obtained silicone-containing thermoplastic fluororesin composition is excellent.
  • the weight average molecular weight of the organopolysiloxane (b-1) can be measured as a value calculated in polystyrene conversion by gel permeation chromatography (GPC).
  • the organopolysiloxane (b-1) is preferably a diorganopolysiloxane containing at least two alkoxy groups in one molecule thereof as the crosslinkable reaction group, or a diorganopolysiloxane containing at least two hydroxyl groups in one molecule thereof as the crosslinkable reaction group.
  • the alkoxy group an alkoxy group having at most 3 carbon atoms is preferable.
  • an example of the crosslinking agent (b-2) is a silicon compound having, in one molecule thereof, at least 3 groups which are hydrolyzable with the crosslinkable reaction groups such as an alkoxy group and a hydroxyl group in the organopolysiloxane (b-1) to carry out a condensation reaction. It is preferably a silicon compound containing an alkoxy group, and examples thereof are alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane and methyltriethoxysilane, or methyltrihydrosilane.
  • the compounding amount of the above-mentioned crosslinking agent (b-2) is preferably 2 to 15 parts by weight based on 100 parts by weight of organopolysiloxane (b-1).
  • a compounding amount of the above-mentioned catalyst (b-3) for a condensation reaction is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 5 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
  • an example of the crosslinking agent (b-2) is an organopolysiloxane containing silicon atom-bonded hydrogen atoms which has at least 2 hydrogen atoms bonded with a silicon atom in one molecule thereof.
  • organopolysiloxane containing silicon atom-bonded hydrogen atoms which has at least 2 of hydrogen atoms bonded with a silicon atom in one molecule thereof are a dimethylpolysiloxane end-capped with hydrogen atoms, a dimethylsiloxane-methylhydrogensiloxane copolymer end-capped with trimethylsilyl groups, cyclic methylhydrogenpolysiloxane, organopolysiloxane comprising a siloxane unit represented by the formula (CHs)HSiO 1 ⁇ and a siloxane unit represented by the formula SiO4 / 2, and a mixture of at least 2 of these.
  • a dimethylpolysiloxane end-capped with hydrogen atoms a dimethylsiloxane-methylhydrogensiloxane copolymer end-capped with trimethylsilyl groups
  • cyclic methylhydrogenpolysiloxane organopolysiloxane comprising
  • examples of the crosslinking catalyst (b-3) are platinum catalysts such as chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, platinum black, and platinum supported on silica; rhodium catalysts such as rhodium chloride and rhodium chloride complex; and palladium catalysts such as palladium chloride and palladium supported on carbon.
  • platinum-based catalysts are preferable from the viewpoint of high reactivity thereof.
  • a curing retardant (b-4) is preferably further contained from the viewpoint that storage stability and handling workability of the crosslinkable silicone rubber are improved, and dispersibility to the fluororesin (A) is improved.
  • curing retardant (b-4) examples include acetylene compounds such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-l-hexyn-3-ol and 2-phenyl-3-butyn-2-ol: enyne compounds such as 3-methyl-3-penten-l-yne and 3,5-dimethyl-3-hexen-l-yne; organosiloxane compounds having at least 5 % by weight of vinyl groups in one molecule thereof such as
  • the organopolysiloxane (b-1) is preferably diorganopolysiloxane containing at least 2 alkenyl groups in one molecule thereof as a crosslinkable reaction group.
  • examples of the crosslinking catalyst (b-3) are organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, orthomethylbenzoyl peroxide, para-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1 , 1 -bis(t-butylperoxy) -3,3, 5-trimethylcyclohexane , 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,2-bis(t-butylperoxy) ⁇ p-diisopropylbenzene, t-buiyl peracetate and t-butylcumyl peroxide.
  • organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, orthomethylbenzoyl peroxide, para-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1
  • a compounding amount of the crosslinking catalyst (b-3) can be a catalyst amount, and is preferably 0.1 to 5 parts by weight based on 100 parts by weight of organopolysiloxane (b-1).
  • the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a radical reaction with an organic peroxide, it is not essential to compound the crosslinking agent (b-2) but the above-mentioned crosslinking agent (b-2) may be compounded if necessary.
  • Reinforcing fillers such as precipitated silica, fumed silica, fumed silica surface-treated for making the surface hydrophobic, and carbon black; non-reinforcing fillers such as quartz powder, diatom earth, calcium carbonate such as precipitated calcium carbonate and ground calcium carbonate may be compounded if necessary in the crosslinkable silicone rubber composition used in the present invention.
  • reinforcing silica fillers such as fumed silica and fumed silica surface-treated for making the surface hydrophobic and/ or non reinforcing fillers such as quartz powder and diatom earth are preferably contained from the viewpoint that workability in handling and flame retardance of the silicone rubber (B), and dispersibility to the fluororesin (A) may be improved in some cases.
  • the reinforcing fillers and non-reinforcing fillers are previously compounded in the organopolysiloxane (b- 1 ) .
  • An addition amount of the reinforcing silica fillers is preferably 1 to 100 parts by weight, more preferably 10 to 60 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
  • an addition amount of the non-reinforcing fillers is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
  • the surface of the reinforcing silica filler is made hydrophobic by simultaneously compounding with a hydroxyl group-containing low molecular weight diorganopolysiloxane, hexaorganodisilazane, and the like.
  • the fine particles of crosslinked silicone rubber particles obtained by finely graining the crosslinked silicone rubber can be also used.
  • the particle shape of the crosslinked silicone rubber particles are spherical shape and irregular shape, and spherical particles are preferable.
  • a diameter of the particles is not specifically limited, and an average particle diameter is preferably 0.1 to 200 ⁇ m, particularly preferably 0.1 to 100 ⁇ m from the viewpoint that poor appearance is not caused by large particles.
  • crosslinked silicone rubber particles which contain a fluorine-containing organic group are preferable in order to improve affinity for the fluororesin (A).
  • the preparation processes 2 to 5 are preferable, and the preparation process 5 is particularly preferable from the viewpoint that the diameter and the shape of the obtained crosslinked silicone rubber particles are easily controlled.
  • Preparation process 2 A process of crosslinking the crosslinkable silicone rubber composition to be a powder.
  • Preparation process 3 A process of crosslinking the crosslinkable silicone rubber composition in dispersed state in water.
  • Preparation process 4) A process of crosslinking the crosslinkable silicone rubber composition containing a surfactant to be a powder.
  • Preparation process 5 A process of crosslinking the crosslinkable silicone rubber composition in an aqueous solution of a surfactant in a dispersed state, and then removing water.
  • the crosslinkable silicone rubber composition obtained by these preparation processes is a crosslinked product obtained by crosslinking by a hydro silylation reaction, a condensation reaction and a radical reaction with an organic peroxide, and is preferably a crosslinked product obtained by crosslinking by the a hydrosilylation reaction or a condensation reaction.
  • the crosslinked silicone rubber particles those which are commercially available as "TREPIL E POWDER” from Dow Corning Toray Co., Ltd. can be used.
  • a mixing proportion of the fluororesin (A) and the silicone rubber (B) in the silicone-containing thermoplastic fluororesin composition of the present invention is preferably 99/ 1 to 30/70 in a weight ratio, more preferably 95/5 to 70/30.
  • the silicone-containing thermoplastic fluororesin composition of the present invention is preferable from the viewpoint that the fluororesin (A) forms a continuous phase and the silicone rubber (B) forms a dispersion phase, thereby enabling moldability to be enhanced.
  • the silicone-containing thermoplastic fluororesin composition of the present invention may contain a co-continuous phase structure between the fluororesin (A) and the silicone rubber (B) in a part of a structure in which the fluororesin (A) forms a continuous phase and the silicone rubber (B) forms a dispersion phase as a preferred embodiment.
  • An average particle diameter of the crosslinked particles of the silicone rubber (B) is not specifically limited, and is preferably 0.01 to 30 ⁇ m, more preferably 0.1 to 20 ⁇ m, further preferably 0.3 to 10 ⁇ m.
  • the average particle diameter is less than 0.01 ⁇ m, preparation of crosslinked particles tends to be difficult, and when it exceeds 30 ⁇ m, dispersibility of the silicone rubber becomes poor, and moldability tends to be lowered.
  • the silicone-containing thermoplastic fluororesin composition of the present invention preferably contains the flame retardant (C) from the viewpoint of flame retardance.
  • the flame retardant (C) is not specifically limited, and those generally used may be optionally used.
  • examples are titanium oxide, cerium oxide, metal hydroxides such as magnesium hydroxide and aluminum hydroxide; a phosphoric acid flame retardant; and halogen flame retardants such as a bromine flame retardant and a chlorine flame retardant.
  • titanium oxide and cerium oxide are preferable from the viewpoint that heat resistance of the silicone rubber can be improved.
  • flame retardant aids such as antimony trioxide and zinc borate, and fuming inhibitors such as molybdenum oxide may be used in combination. These flame retardants may be used alone or a plural number of these may be used in combination. Further, it is preferable from the viewpoint of handling workability that they are used as a mixture of flame retardants dispersed in the organopolysiloxane (b-1).
  • a compounding amount of the flame retardant (C) is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight based on 100 parts by weight of the total of the fluororesin (A) and the silicone rubber (B).
  • the silicone-containing thermoplastic fluororesin composition of the present invention preferably further contains the inorganic filler (D) from the viewpoint that char is formed at combustion and the flame retardance can be further improved.
  • the inorganic filler (D) is not specifically limited, and examples are reinforcing inorganic fillers such as talc, clay and barium sulfate.
  • the inorganic filler (D) is preferably at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide, and hydrotalcite from the viewpoint that rigid char can be formed.
  • Wollastonite is known as calcium metasilicate, and a high aspect ratio thereof is preferable. Typically, the aspect ratio is at least 2 : 1, preferably at least 3 : 1.
  • an average particle diameter of wollastonite is preferably 2 to 30 ⁇ m, more preferably 5 to 15 ⁇ m.
  • Preferable wollastonite is supplied by NYCO (registered trademark) Minerals Inc., Willsboro NY or JFE Mineral Co., Ltd.
  • a compounding amount of the inorganic filler (D) is preferably 1 to 70 parts by weight, more preferably 3 to 15 parts by weight based on 100 parts by weight of the total of the fluororesin (A), the silicone rubber (B) and the flame retardant (C).
  • flame-retardant effect by addition of the inorganic filler (D) is not specifically observed, and when it exceeds 70 parts by weight, moldability and flexibility of the obtained molded article tend to be inferior.
  • the silicone-containing thermoplastic fluororesin composition of the present invention is characterized by having high flame retardance, but when it contains the flame retardant (C) or the inorganic filler (D), the flame retardance is further heightened. When both of them are contained together, the flame retardance can be further improved.
  • a peak of heat release rate (HRR) and a peak of released smoke rate (RSR) which are measured by a cone calorimeter can be used.
  • the peak value of HRR of the silicone-containing thermoplastic fluororesin composition of the present invention can be at most 70 kW/m 2 , and the peak value of the RSR can be at most 6 /sec.
  • the preparation process of the silicone-containing thermoplastic fluororesin composition of the present invention comprises (1) a step of mixing the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the crosslinkable silicone rubber composition containing organopolysiloxane (b-1), and (2) a step of crosslinking the crosslinkable silicone rubber composition in a mixture of the fluorine-containing ethylenic polymer (a) and the crosslinkable silicone rubber composition.
  • the process for preparing the silicone-containing thermoplastic fluororesin composition comprising (1) a step of preparing a mixture comprising the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, the organopolysiloxane (b-1) and the crosslinking catalyst (b-3) without containing the crosslinking agent (b-2), thereafter, (2) a step of adding the crosslinking agent (b-2), and (3) a step of crosslinking the organopolysiloxane (b-1) in the mixture is preferable from the viewpoint that an average particle diameter of the crosslinked particles of the silicone rubber (B) can be lowered.
  • silicone-containing thermoplastic fluororesin composition of the present invention other polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane, a pigment, a lubricant, a photostabilizer, a weather resistant stabilizer, an antistatic agent, an ultraviolet absorbent, an antioxidant, a mold releasing agent, a foaming agent, a perfume, an oil, a softening agent and the like can be added, within a range not affecting the effect of the present invention.
  • polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane, a pigment, a lubricant, a photostabilizer, a weather resistant stabilizer, an antistatic agent, an ultraviolet absorbent, an antioxidant, a mold releasing agent, a foaming agent, a perfume, an oil, a softening agent and the like can be added, within a range not affecting the effect of the present invention.
  • the silicone-containing thermoplastic fluororesin composition of the present invention can be molded using general molding processes and molding equipments.
  • the molding process optional processes such as injection molding, extrusion molding, compression molding, blow molding, calender molding, and vacuum molding can be adopted, and the silicone-containing thermoplastic fluororesin composition of the present invention is molded into molded articles with an optional shape in accordance with its intended purpose.
  • the present invention includes molded articles such as a sheet or a film, and an electric wire jacket which are formed from the silicone-containing thermoplastic fluororesin composition of the present invention, and includes a laminated structure having a layer comprising the silicone-containing thermoplastic fluororesin composition of the present invention, and a layer comprising other materials.
  • the above-mentioned electric wire jacket is generally used in a wire or a cable for electronic equipments such as a computer for imparting flame retardance and preventing mechanical damage, and it has a tube shape storing a copper wire and its covering material.
  • Its molding process is not particularly limited and, for example, known processes such as a process of carrying out extrusion molding by a cross head and a single screw extruder are exemplified.
  • the electric wire jacket comprises the above-mentioned composition, it is excellent in moldability and flexibility, exhibits excellent heat resistance in particular, and can be also used suitably as a jacket for LCC (Limited Combustible Cable) which is required to have higher flame retardance than a conventional one.
  • a thickness of the electric wire jacket of the present invention can be appropriately set in accordance with its use, and it has usually a thickness range from 0.2 to 1.0 mm. Since the electric wire jacket of the present invention has a thickness of the above-mentioned range, it is excellent in flexibility in particular.
  • the electric wire jacket of the present invention is obtained by molding the silicone-containing thermoplastic fluororesin composition of the present invention, and is excellent in properties such as flame retardance and flexibility.
  • the electric wire jacket of the present invention can be used, for example, for electric wires for wiring electronic equipments, a 600 V insulating electric wire for electric equipments, and communication cables such as a LAN cable.
  • the above-mentioned LAN cable is a cable used for the Local Area Network.
  • a cable used for the LAN characterized by being equipped with the electric wire jacket of the present invention is also one of the present invention.
  • An example of the cable used for the LAN is a plenum cable, and the above-mentioned LCC is suitable.
  • a thickness of the cable jacket used for the LAN of the present invention can be optionally set, and the cable is usually molded to have a thinness of 0.2 to 1.0 mm. Since the cable used for the LAN of the present invention is equipped with the electric wire jacket of the present invention, it is excellent in flame retardance and flexibility.
  • the silicone-containing thermoplastic fluororesin composition of the present invention, and a molded article, a sheet, and a film comprising the composition can be used for automobile parts, mechanical parts, electrical and electronic parts, OA parts, daily- necessaries, building materials, sundries and the like, and the laminated structure can be used as food containers, fuel containers, a tube, a hose and the like.
  • sheet-shaped test pieces having a thickness of 2 mm were prepared by compression-molding the pellets by a thermal pressing machine at 280 0 C for the fluororesins (a-1 and a-2), and at 200 0 C for the fluororesin (a-3) under the condition of 3.5 MPa, and sheet-shaped test pieces having a thickness of 2 mm, a length of 50 mm and a width of 50 mm were cut out from the sheets.
  • fluorine-containing ethylenic polymer (a-1), fluorine-containing ethylenic polymer (a-2), fluorine-containing ethylenic polymer (a-3), organopolysiloxane (b-1), crosslinking agent (b-2), crosslinking catalyst (b-3), flame retardant (C), inorganic filler (D-I), inorganic filler (D-2), and crosslinked silicone rubber particles (E) were used.
  • AEROSIL 200 trade name
  • ⁇ Crosslinking agent (b-2)> A mixture comprising 100 parts by weight of a dimethylsiloxane-methylhydrogensiloxane copolymer (an amount of silicon atom-bonded hydrogen atom 0.83 % by weight) end-capped with trimethylsilyl groups and having a viscosity of 12 mPa-s and 20 parts by weight of fumed silica (REOLOSIL DM-30: trade name, available from Tokuyama Corporation), which is surface-treated with dimethyldichloro silane .
  • ⁇ Flame retardant (C) >
  • Crosslinked fluoro silicone rubber particles with an average particle diameter of 0.5 ⁇ m which are prepared by the following process:
  • the composition was emulsified in an aqueous solution comprising 8 parts by weight of polyoxyethylene lauryl ether and 40 parts by weight of pure water, and further uniformly emulsified by a colloid mill, thereafter, 140 parts by weight of pure water was added for dilution, to prepare an emulsion of the liquid fluorosilicone rubber composition.
  • a catalyst for a condensation reaction prepared by dispersing 1 part by weight of tin octylate in an aqueous solution comprising 1 part by weight of polyoxyethylene lauryl ether and 10 parts by weight of pure water was mixed in the emulsion, and the solution was allowed to stand at room temperature for one day, to obtain the homogeneous aqueous suspension of crosslinked fluorosilicone rubber particles and then water was removed by a hot-air drier at 300 0 C to obtain the crosslinked fluorosilicone rubber particles.
  • a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.3 part of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5), 0.01 part of the crosslinking catalyst (b-3), 4.8 parts of the curing retardant (b-4), and 7.6 parts of the flame retardant (C) with a rubber roll).
  • a premixed silicone rubber a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.3 part of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA)
  • the screw rotational number was immediately increased to 80 rpm, and the mixture was kneaded for 10 minutes.
  • the melted mixture was taken out from the laboplastmill and naturally cooled to a room temperature.
  • the solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets.
  • the tensile strength of the pellets was 16.4 MPa, and the tensile elongation at break was 212 %.
  • Pellets were obtained in the same manner as in Example 1 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-1).
  • the tensile strength of the pellets was 8.0 MPa, and the tensile elongation at break was as low as 57 %.
  • Pellets were obtained in the same manner as in Example 1 except that the fluorine-containing ethylenic polymer (a-3) was used in place of the fluorine-containing ethylenic polymer (a-1), and a kneading temperature was 200 0 C.
  • the tensile strength of the pellets was 11.0
  • the temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 200 0 C, and 65 g of the fluorine-containing ethylenic polymer (a-3) was charged at a screw rotational number of 10 rpm. After confirming that the resin was completely melted after 5 minutes, thereto were charged 16.25 g of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.01 part of the crosslinking catalyst (b-3), and 7.6 parts of the flame retardant (C) with a rubber roll).
  • a premixed silicone rubber a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.01 part of the crosslinking catalyst (b-3), and 7.6 parts of the flame retard
  • the screw rotational number was immediately raised to 80 rpm, and the mixture was kneaded for 5 minutes. Then, 0.049 g of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5) was added, and the mixture was further kneaded for 5 minutes. The melted mixture was taken out from the laboplastmill, and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 12.7 MPa, and the tensile elongation at break was 250 %.
  • the crosslinking agent (b-2) the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 :
  • Pellets were obtained in the same manner as in Example 3 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-3), and a kneading temperature was 280 0 C.
  • the tensile strength of the pellets was 8.2 MPa, and the tensile elongation at break was as low as 70 %.
  • the temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 280 0 C, and 65 g of the fluorine-containing ethylenic polymer (a-1) was charged at a screw rotational number of 10 rpm.
  • the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5) was added, and the mixture was further kneaded for 5 minutes. The melted mixture was taken out from the laboplastmill and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 13.9 MPa and the tensile elongation at break was 250 %. Further, the peak value of HRR in the cone calorimeter combustion test was 36.3 kW/m 2 , and the peak value of RSR was 3.7/ sec.
  • the tensile strength of the pellets was 11.5 MPa, and the tensile elongation at break was 135 %.
  • the tensile strength of the pellets was 10.1 MPa, and the tensile elongation at break was 102 %.
  • Pellets were obtained in the same manner as in Example 4 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-1).
  • the tensile strength of the pellets was 8.4 MPa, and the tensile elongation at break was as low as 27 %.
  • Pellets were obtained in the same manner as in Example 4 except that the fluorine-containing ethylenic polymer (a-3) was used in place of the fluorine-containing ethylenic polymer (a-1) and a kneading temperature was 200 0 C.
  • the tensile strength of the pellets was 17.8
  • Pellets were obtained in the same manner as in Example 4 except that the inorganic filler (D-2) was used in place of the inorganic filler (D-I).
  • the tensile strength of the pellets was 12.0 MPa, and the tensile elongation at break was 261 %. Further, the peak value of
  • HRR in the cone calorimeter combustion test was 28.1 kW/m 2 , and the peak value of RSR was 1.2 /sec.
  • Pellets were obtained in the same manner as in Example 7 except that the inorganic filler (D-2) was used in place of the inorganic filler (D-I).
  • the tensile strength of the pellets was 17.4 MPa, and the tensile elongation at break was 321 %.
  • the peak value of HRR in the cone calorimeter combustion test was 55.9 kW/m 2 , and the peak value of RSR was 3.9 /sec.
  • the tensile strength of the pellets was 14.9 MPa, and the tensile elongation at break was 296 %.
  • the peak value of HRR in the cone calorimeter combustion test was 39.1 kW/m 2 , and the peak value of RSR was 2.9 /sec.
  • Cat.6 4-pair UTP cable was produced by using the pellets of the silicone-containing thermoplastic fluororesin composition as a material for a jacket.
  • NEOFLON FEP NP-101 available from Daikin Industries, Ltd. was used as an insulating covering material and a cross web for a primary copper wire.

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Abstract

The present invention provides a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed, a molded article comprising the composition, and a process for preparing the silicone-containing thermoplastic fluororesin composition. Specifically, the present invention relates to a silicone-containing thermoplastic fluororesin composition comprising a fluororesin (A) and a silicone rubber (B), wherein the fluororesin (A) comprises a fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the silicone rubber (B) is crosslinked at least in a part thereof.

Description

DESCRIPTION
SILICONE-CONTAINING THERMOPLASTIC FLUORORESIN
COMPOSITION, ARTICLE MOLDED THEREFROM, AND PROCESS FOR PREPARING SILICONE-CONTAINING
THERMOPLASTIC FLUORORESIN COMPOSITION
TECHNICAL FIELD The present invention relates to a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed, a molded article comprising the same, and a process for preparing the silicone-containing thermoplastic fluororesin composition.
BACKGROUND ART
Since flame propagation by fire caused by an electric wire, which run on a ceiling and the plenum part under floor, a cable coating material and the like recently has been a problem, particularly, excellent heat resistance is required for an electric wire jacket in addition to moldability and flexibility. As a material of the electric wire jacket, a fluororesin excellent in properties such as sliding property, heat resistance, chemical resistance, weather resistance, and electrical properties is used. Further, since a jacket for LCC (Limited Combustible Cable) requires higher flame retardance than a plenum cable, development of a material having moldability, flexibility and mechanical properties and further having excellent heat resistance is desired.
As a jacket material for LCC, for example, NEOFLON™ FEP is known. However, although a jacket using the NEOFLON™ FEP is excellent in heat resistance, there has been a problem that printing is difficult on the surface of a cable.
Further, a material in which zinc oxide is added to a fluororesin is disclosed (for example, see the specification of US Patent
Application Publication No. 2005/0187328). However, there is a problem that a jacket using the material is inadequate in flexibility. Further, a composite material obtained by treating a fluororesin and a silicone rubber by dynamic crosslinking is known (for example, see WO 2005/059009 pamphlet). However, since the composite material is low in compatibility of the fluororesin with the silicone rubber, there is a problem that adequate mechanical properties cannot be obtained.
Consequently, in the present situation, a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed has not existed yet.
DISCLOSURE OF INVENTION
The present invention relates to a silicone-containing thermoplastic fluororesin composition having excellent flame retardance, flexibility and mechanical properties and enabling an obtained crosslinked product to be printed, a molded article comprising the composition, and a process for preparing the silicone-containing thermoplastic fluororesin composition. Namely, the present invention relates to a silicone-containing thermoplastic fluororesin composition comprising a fluororesin (A) and a silicone rubber (B), wherein the fluororesin (A) comprises a fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the silicone rubber (B) is crosslinked at least in a part thereof.
It is preferable that a melting point of the fluorine-containing ethylenic polymer (a) is 120 to 3100C.
It is preferable that the silicone rubber (B) is dynamically crosslinked in the presence of the fluororesin (A).
It is preferable that the fluororesin (A) is a copolymer of tetrafluoroethylene with a perfluoro ethylenically unsaturated compound represented by the following general formula (1):
CF2=CF-Rf1 (1)
wherein, Rf1 represents -CF3 and/or -ORf2, and Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
It is preferable that the fluororesin (A) is a copolymer comprising 20 to 80 % by mole of a tetrafluoroethylene unit and 80 to 20 % by mole of an ethylene unit, or a copolymer comprising 19 to 90 % by mole of a tetrafluoroethylene unit, 9 to 80 % by mole of an ethylene unit and 1 to 72 % by mole of a perfluoro ethylenically unsaturated compound unit represented by the following general formula (1):
CF2=CF-Rf1 (1) wherein Rf1 represents -CF3 and/ or -ORf2, and Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
It is preferable that the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by a condensation reaction, a hydro silylation reaction, or a radical reaction with an organic peroxide.
It is preferable that the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by a hydro silylation reaction. It is preferable that the silicone rubber (B) is a crosslinked product of the crosslinkable silicone rubber composition comprising an organopolysiloxane (b- 1 ) .
It is preferable that the crosslinkable silicone rubber composition further comprises a crosslinking agent (b-2) and a crosslinking catalyst (b-3).
It is preferable that the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group, the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom, and the crosslinking catalyst (b-3) is a hydro silylation reaction catalyst.
It is preferable that the carbonyl group-containing end group in the fluororesin (A) is at least one group selected from the group consisting of a carboxyl group, a fluoride carbonyl group and a group represented by the general formula (2):
-O-C(=O)-OR! (2) wherein R1 is an alkyl group having 1 to 5 carbon atoms.
It is preferable that the number of carbonyl group-containing end groups in the fluororesin (A) is 100 to 1,000 based on 1,000,000 carbon atoms. It is preferable that the silicone-containing thermoplastic fluororesin composition comprises a flame retardant (C) .
It is preferable that the silicone-containing thermoplastic fluororesin composition comprises an inorganic filler (D).
It is preferable that the inorganic filler (D) is at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide, and hydrotalcite.
Further, the present invention relates to a molded article and an electric wire jacket, which are formed from the silicone-containing thermoplastic fluororesin composition. Further, the present invention relates to a cable, particularly a LAN cable, having the electric wire jacket.
The present invention further relates to a process for preparing the silicone-containing thermoplastic fluororesin composition comprising: (1) a step of mixing the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group and the crosslinkable silicone rubber composition comprising the organopolysiloxane (b-1), and (2) a step of crosslinking the crosslinkable silicone rubber composition in a mixture of the fluorine-containing ethylenic polymer (a) and the crosslinkable silicone rubber composition.
It is preferable that the crosslinkable silicone rubber composition further comprises the crosslinking agent (b-2) and the crosslinking catalyst (b-3).
It is preferable that the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group, the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom and the crosslinking catalyst (b-3) is a hydrosilylation reaction catalyst.
It is preferable that the preparation process comprises:
(1) a step of preparing a mixture comprising the fluorine-containing ethylenical polymer (a) having a carbonyl group-containing end group, the organopolysiloxane (b-1), and the crosslinking catalyst (b-3), without containing the crosslinking agent (b-2), thereafter,
(2) a step of adding the crosslinking agent (b-2), and
(3) a step of crosslinking the organopolysiloxane (b-1) in the mixture.
It is preferable that a dynamic crosslinking method of simultaneously carrying out the mixing and the crosslinking is used. It is preferable that a twin screw extruder is used.
BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to the silicone-containing thermoplastic fluororesin composition comprising the fluororesin (A) and the silicone rubber (B), wherein the fluororesin (A) comprises the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the silicone rubber (B) is crosslinked at least in a part thereof. A melting point of the fluororesin (A) used in the present invention is preferably 120 to 3100C, more preferably 150 to 270°C, further preferably 170 to 2500C. When the melting point of the fluororesin (A) is less than 1200C, heat resistance of the obtained silicone-containing thermoplastic fluororesin composition tends to be lowered, and when it exceeds 3100C, it is required to set the melting temperature at the melting point or more of the fluororesin (A) when dynamic crosslinking is carried out in the presence of the fluororesin (A), thereby the silicone rubber (B) tends to be thermally degraded at that time.
The fluororesin (A) may be a polymer comprising the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and is not specifically limited.
Herein, the carbonyl group-containing end group indicates a functional group having -C(=O)-. Specific examples are a group represented by the general formula (3):
-O-C(=O)-OR2 (3)
wherein R2 is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms which contains an ether bonding oxygen atom, a haloformyl group (-C(=O)X1, X1 is a halogen atom), a formyl group (-C(=O)H), a group represented by the general formula (4):
-R3-C(=O)-R4 (4)
wherein R3 is a divalent organic group having 1 to 20 carbon atoms, and R4 is a monovalent organic group having 1 to 20 carbon atoms, a carboxyl group (-C(=O)OH), an alkoxycarbonyl group (-C(=O)OR3), -C(=O)-O-C(=O)-,
and an isocyanate group (-N=C=O).
Among these, at least one group selected from the group consisting of a carboxyl group, a fluoride carbonyl group and a group represented by the general formula (2):
-O-C(=O)-ORi (2)
wherein R1 is an alkyl group having 1 to 5 carbon atoms is preferable from the viewpoint that compatibility with a silicone rubber is enhanced, and a carboxyl group and the group represented by the general formula (2) are more preferable.
A process for introducing a carbonyl group-containing end group into the fluororesin (A) is not specifically limited, and examples are a process of copolymerizing a monomer having the carbonyl group-containing end group at polymerization of the fluororesin (A), a process of carrying out polymerization by using a polymerization initiator having a carbonyl group or a functional group which can be converted to a carbonyl group, and a process of thermally decomposing polymer main chains under the coexistence of oxygen.
The number of carbonyl group-containing end groups of the fluororesin can be measured by the methods described in JP-B-37-3127 and WO 99/45044 pamphlet. The number of carbonyl group-containing end groups in the fluororesin (A) is preferably 100 to 1,000, more preferably 200 to 800, further preferably 300 to 700 per 1,000,000 carbon atoms. When it is less than 100, compatibility with the silicone rubber (B) tends to be lowered, and when it exceeds 1,000, foams tend to be generated in a molded article.
Examples of the ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) are perfluoroolefins such as tetrafluoroethylene (hereinafter referred to as
TFE) and a perfluoro ethylenically unsaturated compound represented by the general formula (1):
CF2=CF-Rf1 (1)
wherein Rf1 represents -CF3 and/ or -ORf2 and Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms; fluoroolefins such as chlorotrifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, hexafluoroisobutene, vinylidene fluoride (hereinafter referred to as VdF), vinyl fluoride, and one represented by the general formula (3):
CH2=CX2(CF2)nX3 (3)
wherein X2 represents a hydrogen atom or a fluorine atom, X3 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10.
Further, examples of the ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) are non-fluorine-containing ethylenically unsaturated compounds other than the above-mentioned fluoroolefins and perfluoroolefins. Examples of the non-fluorine-containing ethylenically unsaturated compound are ethylene, propylene, and alkyl vinyl ethers. Herein, the alkyl vinyl ether is an alkyl vinyl ether having an alkyl group with 1 to 5 carbon atoms. Among these, the fluorine-containing ethylenic polymer (a) comprising TFE and ethylene is preferable from the viewpoint that the heat resistance and oil resistance of the obtained silicone-containing thermoplastic fluororesin composition are excellent and molding process is easy, and the fluorine-containing ethylenic polymer (a) comprising 20 to 80 % by mole of a TFE unit and 80 to 20 % by mole of an ethylene unit is more preferable. Further, the fluorine-containing ethylenic polymer (a) comprising TFE and ethylene may contain the third component, and an example of the third component is 2,3,3,4,4,5,5-heptafluoro-l-pentene (CH2=CFCF2CF2CF2H). An amount of the third component is preferably 0.1 to 3 % by mole based on the fluorine-containing ethylenic polymer (a) .
The fluorine-containing ethylenic polymer (a) comprising TFE and the perfluoro ethylenically unsaturated compound represented by the general formula (1) is preferable from the viewpoint that the obtained silicone-containing thermoplastic fluororesin composition is excellent in heat resistance, oil resistance, electrical property, and flame retardance, and molding process becomes easy.
Specifically, the combinations such as
TFE/hexafluoropropylene (hereinafter referred to as HFP), TFE/ CF2=CF-ORf2, and TFE/ HFP/ CF2=CF-ORf2 can be exemplified. Examples of CF2=CF-ORf2 are perfluoro (alkyl vinyl ether) such as perfluoro(methyl vinyl ether), perfluoro (ethyl vinyl ether) and perfluoro(propyl vinyl ether).
Among these, TFE/ HFP/ CF2=CF-ORf2 is preferable from the viewpoint that stress crack resistance is excellent and economical efficiency is also advantageous, the fluorine-containing ethylenic polymer (a) comprising 77 to 95 % by mole of a TFE unit, 5 to 20 % by mole of a HFP unit, and 0.1 to 3 % by mole of CF2=CF-ORf3 unit is more preferable, and the fluorine-containing ethylenic polymer (a) comprising 90 to 93 % by mole of a TFE unit, 7 to 10 % by mole of a HFP unit and 0.3 to 1 % by mole of CF2=CF-ORf3 unit is further preferable.
Further, the fluorine-containing ethylenic polymer (a) comprising TFE and the perfluoro ethylenically unsaturated compound represented by the general formula (1) may also contain other third components. Particularly in the case of such a copolymer of TFE with the perfluoro ethylenically unsaturated compound represented by the general formula (1), a melting point is preferably 120 to 2700C from the viewpoint that molding process of the obtained silicone-containing thermoplastic fluororesin composition is easy. The melting point can be set by a copolymerization ratio of TFE to the perfluoro ethylenically unsaturated compound represented by the above-mentioned general formula (1).
Further, the fluorine-containing ethylenic polymer (a) comprising TFE, ethylene and the perfluoro ethylenically unsaturated compound represented by the general formula (1) is preferable from the viewpoint that the obtained silicone-containing thermoplastic fluororesin composition has an excellent heat resistance and oil resistance, and molding process is easy, the fluorine-containing ethylenic polymer (a) comprising 19 to 90 % by mole of a TFE unit, 9 to 80 % by mole of an ethylene unit and 1 to 72 % by mole of a perfluoro ethylenically unsaturated compound unit represented by the general formula (1) is more preferable, and the fluorine-containing ethylenic polymer (a) comprising 20 to 70 % by mole of a TFE unit, 20 to 60 % by mole of an ethylene unit and 1 to 60 % by mole of the perfluoro ethylenically unsaturated compound unit represented by the general formula (1) is further preferable. Further, the fluorine-containing ethylenic polymer (a) comprising TFE, ethylene and the perfluoro ethylenically unsaturated compound represented by the general formula (1) may contain an additional component, and an example of the additional component is 2,3,3,4,4,5,5-heptafluoro-l-ρentene (CH2=CFCF2CF2CF2H). An amount of the additional component is preferably 0.1 to
3 % by mole based on the fluorine-containing ethylenic polymer (a).
The silicone rubber (B) used in the present invention is not specifically limited, and is crosslinked at least in a part thereof, and is preferably a rubber dynamically crosslinked in the presence of the fiuororesin (A) from the viewpoint that dispersibility in the fluororesin is excellent, and productivity is improved.
Herein, the dynamic crosslinking treatment means that the crosslinkable silicone rubber composition is melt-kneaded and at the same time dynamically crosslinked using a Banbury mixer, a compression kneader, an extruder or the like. Among these, extruders such as a twin screw extruder are preferably used from the viewpoint that high shearing force can be added. A composition in which the silicone rubber (B) is uniformly dispersed in the fluororesin (A) can be obtained by carrying out the dynamic crosslinking treatment under the melting condition of the fluororesin (A) .
Further, "under the melting condition" means "at a temperature at which the fluororesin (A) is melted". The melting temperature varies depending on a glass transition temperature and /or a melting point of the fluororesin (A), and is preferably 120 to 330°C, more preferably 130 to 3200C. When the temperature is less than 1200C, the dispersion between the fluororesin (A) and the silicone rubber (B) tends to be rough, and when it exceeds 3300C, the silicone rubber (B) tends to be thermally deteriorated.
The silicone rubber (B) is preferably a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a condensation reaction, a hydrosilylation reaction or a radical reaction with an organic peroxide. A crosslinked product which is obtained by crosslinking by the hydrosilylation reaction is preferable from the viewpoint that any by-product is not generated in the crosslinking reaction.
As the crosslinkable silicone rubber composition, a crosslinkable silicone rubber composition comprising the organopolysiloxane (b-1) is preferable, and a crosslinkable silicone rubber composition further comprising the crosslinking catalyst (b-3) and the crosslinking agent (b-2) if necessary is more preferable.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the condensation reaction or hydrosilylation reaction, the crosslinkable silicone rubber composition preferably comprises the organopolysiloxane (b-1) containing at least two crosslinkable reaction groups in one molecule thereof, the crosslinking agent (b-2) and the crosslinking catalyst (b-3).
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a radical reaction with an organic peroxide, the crosslinkable silicone rubber composition preferably comprises the organopolysiloxane (b-1) and the crosslinking catalyst (b-3).
Examples of the organopolysiloxane (b-1) are diorganopolysiloxanes containing at least two crosslinkable reaction groups in one molecule thereof such as diorganopolysiloxane containing an alkenyl group, diorganopolysiloxane containing an alkoxy group, and diorganopolysiloxane containing a hydroxyl group.
Examples of the crosslinkable reaction group are alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, and a hexenyl group; alkoxy groups having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; and a hydroxyl group. Among these, alkenyl groups having 2 to 10 carbon atoms are preferable from the viewpoint that crosslinking can be carried out by the hydrosilylation reaction without generating by-products and a pseudo-crosslinking reaction hardly occurs during preservation and a vinyl group is preferable from the viewpoint of economical efficiency in particular. These crosslinkable reaction groups may exist at the molecular end of the organopolysiloxane (b-1), may exist at the side chain of a molecule, and may exist at both of them.
Examples of a group bonded with a silicon atom other than the crosslinkable reaction group are alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isobutyl group, a hexyl group, and an octyl group; an aryl group such as a phenyl group; an aralkyl group such as a tolyl group; and a halogenated alkyl group such as a 3,3,3-trifluoropropyl, and an alkyl group having 1 to 8 carbon atoms is preferable.
Among these, it is preferable from the viewpoint of being excellent in flexibility and cold resistance, and advantageous for economical efficiency that at least 50 % of groups bonded with a silicon atom are methyl groups and it is more preferable that the whole is substantially methyl groups. In order to improve affinity with the fluororesin (A), 1 to 50 % of groups bonded with a silicon atom may be fluorinated alkyl groups such as 3,3,3-trifluoropropyl.
A molecular structure of the organopolysiloxane (b-1) is preferably a linear chain structure or a linear chain structure partly having a branch from the viewpoint that the flexibility of the silicone-containing thermoplastic fluororesin composition of the present invention is excellent.
Further, a weight average molecular weight of the organopolysiloxane (b-1) is not specifically limited, and is preferably 1,000 to 9,000,000, more preferably 100,000 to 9,000,000, and particularly preferably 450,000 to 4,500,000. When the weight average molecular weight of organopolysiloxane (b-1) is within the range, it is preferable from the viewpoint that workability in handling is improved, mixing with the fluororesin (A) is also easy, and flexibility of the obtained silicone-containing thermoplastic fluororesin composition is excellent. The weight average molecular weight of the organopolysiloxane (b-1) can be measured as a value calculated in polystyrene conversion by gel permeation chromatography (GPC).
Specific examples of preferable organopolysiloxane (b-1) are diorganopolysiloxanes such as a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with hydroxyl groups, a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with trimethylsilyl groups, a dimethylpolysiloxane end-capped with dimethylvinylsilyl groups, a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with dimethylvinylsilyl groups, a trifluoropropylmethylsiloxane-methylvinylsiloxane copolymer end-capped with hydroxy groups, a trifluoropropylmethylsiloxane-methylvinylsiloxane-dimethylsiloxane copolymer end-capped with hydroxy groups, a trifluoropropylmethylpolysiloxane end-capped with dimethylvinylsilyl groups, a trifiuoropropylmethylsiloxane-dimethylsiloxane copolymer end-capped with dimethylvinylsilyl groups, a trifluoropropylmethylsiloxane-methylvinylsiloxane copolymer end-capped with dimethylvinylsilyl groups, and a trifluoropropylmethylsiloxane-methylvinylsiloxane-dimethylsiloxane copolymer end-capped with dimethylvinylsilyl groups.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the condensation reaction, the organopolysiloxane (b-1) is preferably a diorganopolysiloxane containing at least two alkoxy groups in one molecule thereof as the crosslinkable reaction group, or a diorganopolysiloxane containing at least two hydroxyl groups in one molecule thereof as the crosslinkable reaction group. As the alkoxy group, an alkoxy group having at most 3 carbon atoms is preferable.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the condensation reaction, an example of the crosslinking agent (b-2) is a silicon compound having, in one molecule thereof, at least 3 groups which are hydrolyzable with the crosslinkable reaction groups such as an alkoxy group and a hydroxyl group in the organopolysiloxane (b-1) to carry out a condensation reaction. It is preferably a silicon compound containing an alkoxy group, and examples thereof are alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane and methyltriethoxysilane, or methyltrihydrosilane. The compounding amount of the above-mentioned crosslinking agent (b-2) is preferably 2 to 15 parts by weight based on 100 parts by weight of organopolysiloxane (b-1).
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the condensation reaction, the crosslinking catalyst (b-3) is a catalyst for promoting the crosslinking reaction by the condensation reaction of the crosslinkable silicone rubber composition, and examples thereof are tin catalysts such as di-n-butyltin diacetate, di-n-butyltin di-2-ethylhexoate, n-butyltin tri-2-ethylhexoate, di-n-butyltin dilaurate, di-n-butyltin dioctoate, tin octylate, tin octenoate, tin laurate, tin naphthenate, and tin oleate; organic titanate compounds such as tetra-n-butyl titanate, tetra-isopropyl titanate, tetra-2-ethylhexyl titanate and ethylene glycol titanate; titanium catalysts such as diisopropoxybis(acetylacetone)titanium, diisopropoxybis(ethyl acetoacetate)titanium, diisoproρoxybis(methyl acetoacetate)titanium, dimethoxybis(methyl acetoacetate)titanium, dibuthoxybis(ethyl acetoacetate)titanium and titanium naphthenate; organic acid salt catalysts of a metal such as ferric stanooctenate, lead octenoate, lead laurate, zinc octenoate, cobalt naphthenate, iron naphthenate, zinc naphthenate, zinc stearate, and iron octenoate; and amine catalysts such as n-hexylamine and guanidine; or a mixture of 2 or more of these catalysts for a condensation reaction. A compounding amount of the above-mentioned catalyst (b-3) for a condensation reaction is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 5 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the hydrosilylation reaction, the organopolysiloxane (b-1) is preferably a diorganopolysiloxane containing at least 2 alkenyl groups in one molecule thereof as a crosslinkable reaction group. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and most preferably a vinyl group. When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the hydrosilylation reaction, an example of the crosslinking agent (b-2) is an organopolysiloxane containing silicon atom-bonded hydrogen atoms which has at least 2 hydrogen atoms bonded with a silicon atom in one molecule thereof. Further, examples of other groups bonded with a silicon atom are alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and an octyl group; alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group and an octenyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; and non-substituted or substituted hydrocarbon groups in which at least a portion of hydrogen atoms in these groups is substituted with a halogen atom, a cyano group or the like such as a chloromethyl group, a chloropropyl group, a 3,3,3-trifluoropropyl group and a cyanoethyl group, and among these, a methyl group and a phenyl group are preferable. Examples of the organopolysiloxane containing silicon atom-bonded hydrogen atoms which has at least 2 of hydrogen atoms bonded with a silicon atom in one molecule thereof are a dimethylpolysiloxane end-capped with hydrogen atoms, a dimethylsiloxane-methylhydrogensiloxane copolymer end-capped with trimethylsilyl groups, cyclic methylhydrogenpolysiloxane, organopolysiloxane comprising a siloxane unit represented by the formula (CHs)HSiO1^ and a siloxane unit represented by the formula SiO4/2, and a mixture of at least 2 of these. As a compounding amount of the organopolysiloxane containing silicon atom-bonded hydrogen atoms which has at least 2 hydrogen atoms bonded with a silicon atom in one molecule thereof, the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-1) is preferably within a range of 1 : 5 to 5 : 1, more preferably 1 : 3 to 2 : 1.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the hydrosilylation reaction, examples of the crosslinking catalyst (b-3) are platinum catalysts such as chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, platinum black, and platinum supported on silica; rhodium catalysts such as rhodium chloride and rhodium chloride complex; and palladium catalysts such as palladium chloride and palladium supported on carbon. Among these, platinum-based catalysts are preferable from the viewpoint of high reactivity thereof. A compounding amount of the crosslinking catalyst (b-3) is preferably 0.1 to 1,000 parts by weight based on 1,000,000 parts by weight of organopolysiloxane (b-1). Particularly, when it is a platinum- based catalyst, the amount is preferably 1 to 50 parts by weight based on 1,000,000 parts by weight of organopolysiloxane (b-1) as platinum metal.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by the hydrosilylation reaction, a curing retardant (b-4) is preferably further contained from the viewpoint that storage stability and handling workability of the crosslinkable silicone rubber are improved, and dispersibility to the fluororesin (A) is improved.
Examples of the curing retardant (b-4) are acetylene compounds such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-l-hexyn-3-ol and 2-phenyl-3-butyn-2-ol: enyne compounds such as 3-methyl-3-penten-l-yne and 3,5-dimethyl-3-hexen-l-yne; organosiloxane compounds having at least 5 % by weight of vinyl groups in one molecule thereof such as
1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl- 1 ^S^-tetrahexenylcyclotetrasiloxane, and methylvinylpolysiloxane end-capped with silanol groups; triazoles such as benzotriazole, phosphines, mercaptans, and hydrazines. An amount of these curing retardants (b-4) is not particularly limited, and is preferably 0.001 to 5 parts by weight based on 100 parts by weight of organopolysiloxane (b-1).
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a radical reaction with organic peroxide, the organopolysiloxane (b-1) is preferably diorganopolysiloxane containing at least 2 alkenyl groups in one molecule thereof as a crosslinkable reaction group. The organopolysiloxane (b-1) which does not contain a specific crosslinkable reaction group, for example, dimethylpolysiloxane end-capped with a trimethylsiloxy group can be also used depending on kind of an organic peroxide which is the crosslinking catalyst (b-3), but since crosslinking efficiency is high and many kinds of organic peroxides as the crosslinking catalyst (b-3) can be used, at least 2 of the above-mentioned alkenyl groups are preferably contained in one molecule thereof. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, most preferably a vinyl group.
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a radical reaction with an organic peroxide, examples of the crosslinking catalyst (b-3) are organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, orthomethylbenzoyl peroxide, para-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1 , 1 -bis(t-butylperoxy) -3,3, 5-trimethylcyclohexane , 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,2-bis(t-butylperoxy)~p-diisopropylbenzene, t-buiyl peracetate and t-butylcumyl peroxide. These may be used alone or a combination of at least 2 kinds may be also used. A compounding amount of the crosslinking catalyst (b-3) can be a catalyst amount, and is preferably 0.1 to 5 parts by weight based on 100 parts by weight of organopolysiloxane (b-1).
When the silicone rubber (B) is a crosslinked product which is obtained by crosslinking the crosslinkable silicone rubber composition by a radical reaction with an organic peroxide, it is not essential to compound the crosslinking agent (b-2) but the above-mentioned crosslinking agent (b-2) may be compounded if necessary.
Reinforcing fillers such as precipitated silica, fumed silica, fumed silica surface-treated for making the surface hydrophobic, and carbon black; non-reinforcing fillers such as quartz powder, diatom earth, calcium carbonate such as precipitated calcium carbonate and ground calcium carbonate may be compounded if necessary in the crosslinkable silicone rubber composition used in the present invention. Among these, reinforcing silica fillers such as fumed silica and fumed silica surface-treated for making the surface hydrophobic and/ or non reinforcing fillers such as quartz powder and diatom earth are preferably contained from the viewpoint that workability in handling and flame retardance of the silicone rubber (B), and dispersibility to the fluororesin (A) may be improved in some cases.
It is preferable that the reinforcing fillers and non-reinforcing fillers are previously compounded in the organopolysiloxane (b- 1 ) . An addition amount of the reinforcing silica fillers is preferably 1 to 100 parts by weight, more preferably 10 to 60 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
Further, an addition amount of the non-reinforcing fillers is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane (b-1).
When the reinforcing silica fillers are compounded in the organopolysiloxane (b-1), it is preferable that the surface of the reinforcing silica filler is made hydrophobic by simultaneously compounding with a hydroxyl group-containing low molecular weight diorganopolysiloxane, hexaorganodisilazane, and the like.
As the silicone rubber (B), the fine particles of crosslinked silicone rubber particles obtained by finely graining the crosslinked silicone rubber can be also used. Examples of the particle shape of the crosslinked silicone rubber particles are spherical shape and irregular shape, and spherical particles are preferable. A diameter of the particles is not specifically limited, and an average particle diameter is preferably 0.1 to 200 μm, particularly preferably 0.1 to 100 μm from the viewpoint that poor appearance is not caused by large particles. Further, crosslinked silicone rubber particles which contain a fluorine-containing organic group are preferable in order to improve affinity for the fluororesin (A).
As a process for preparing the crosslinked silicone rubber particles, for example, the following preparation processes are mentioned. The preparation processes 2 to 5 are preferable, and the preparation process 5 is particularly preferable from the viewpoint that the diameter and the shape of the obtained crosslinked silicone rubber particles are easily controlled.
(Preparation process 1) A process of grinding the crosslinked product of the crosslinkable silicone rubber composition.
(Preparation process 2) A process of crosslinking the crosslinkable silicone rubber composition to be a powder. (Preparation process 3) A process of crosslinking the crosslinkable silicone rubber composition in dispersed state in water. (Preparation process 4) A process of crosslinking the crosslinkable silicone rubber composition containing a surfactant to be a powder. (Preparation process 5) A process of crosslinking the crosslinkable silicone rubber composition in an aqueous solution of a surfactant in a dispersed state, and then removing water.
The crosslinkable silicone rubber composition obtained by these preparation processes is a crosslinked product obtained by crosslinking by a hydro silylation reaction, a condensation reaction and a radical reaction with an organic peroxide, and is preferably a crosslinked product obtained by crosslinking by the a hydrosilylation reaction or a condensation reaction. As the crosslinked silicone rubber particles, those which are commercially available as "TREPIL E POWDER" from Dow Corning Toray Co., Ltd. can be used. A mixing proportion of the fluororesin (A) and the silicone rubber (B) in the silicone-containing thermoplastic fluororesin composition of the present invention is preferably 99/ 1 to 30/70 in a weight ratio, more preferably 95/5 to 70/30. When the weight ratio of the silicone rubber (B) is less than 1 % by weight, flexibility tends to be lowered, and when it exceeds 70 % by weight, flame retardance tends to be lowered. Further, the silicone-containing thermoplastic fluororesin composition of the present invention is preferable from the viewpoint that the fluororesin (A) forms a continuous phase and the silicone rubber (B) forms a dispersion phase, thereby enabling moldability to be enhanced. Further, the silicone-containing thermoplastic fluororesin composition of the present invention may contain a co-continuous phase structure between the fluororesin (A) and the silicone rubber (B) in a part of a structure in which the fluororesin (A) forms a continuous phase and the silicone rubber (B) forms a dispersion phase as a preferred embodiment.
An average particle diameter of the crosslinked particles of the silicone rubber (B) is not specifically limited, and is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, further preferably 0.3 to 10 μm. When the average particle diameter is less than 0.01 μm, preparation of crosslinked particles tends to be difficult, and when it exceeds 30 μm, dispersibility of the silicone rubber becomes poor, and moldability tends to be lowered.
Further, the silicone-containing thermoplastic fluororesin composition of the present invention preferably contains the flame retardant (C) from the viewpoint of flame retardance.
The flame retardant (C) is not specifically limited, and those generally used may be optionally used. Examples are titanium oxide, cerium oxide, metal hydroxides such as magnesium hydroxide and aluminum hydroxide; a phosphoric acid flame retardant; and halogen flame retardants such as a bromine flame retardant and a chlorine flame retardant. Among these, titanium oxide and cerium oxide are preferable from the viewpoint that heat resistance of the silicone rubber can be improved. Further, flame retardant aids such as antimony trioxide and zinc borate, and fuming inhibitors such as molybdenum oxide may be used in combination. These flame retardants may be used alone or a plural number of these may be used in combination. Further, it is preferable from the viewpoint of handling workability that they are used as a mixture of flame retardants dispersed in the organopolysiloxane (b-1).
A compounding amount of the flame retardant (C) is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight based on 100 parts by weight of the total of the fluororesin (A) and the silicone rubber (B). When it is less than 0.01 part by weight, flame-retardant effect caused by the addition of the flame retardant (C) is not specifically observed, and when it exceeds 100 parts by weight, moldability and flexibility tend to be inferior. The silicone-containing thermoplastic fluororesin composition of the present invention preferably further contains the inorganic filler (D) from the viewpoint that char is formed at combustion and the flame retardance can be further improved.
The inorganic filler (D) is not specifically limited, and examples are reinforcing inorganic fillers such as talc, clay and barium sulfate. The inorganic filler (D) is preferably at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide, and hydrotalcite from the viewpoint that rigid char can be formed. Wollastonite is known as calcium metasilicate, and a high aspect ratio thereof is preferable. Typically, the aspect ratio is at least 2 : 1, preferably at least 3 : 1. Further, an average particle diameter of wollastonite is preferably 2 to 30 μm, more preferably 5 to 15 μm. Preferable wollastonite is supplied by NYCO (registered trademark) Minerals Inc., Willsboro NY or JFE Mineral Co., Ltd.
A compounding amount of the inorganic filler (D) is preferably 1 to 70 parts by weight, more preferably 3 to 15 parts by weight based on 100 parts by weight of the total of the fluororesin (A), the silicone rubber (B) and the flame retardant (C). When it is less than 1 part by weight, flame-retardant effect by addition of the inorganic filler (D) is not specifically observed, and when it exceeds 70 parts by weight, moldability and flexibility of the obtained molded article tend to be inferior.
The silicone-containing thermoplastic fluororesin composition of the present invention is characterized by having high flame retardance, but when it contains the flame retardant (C) or the inorganic filler (D), the flame retardance is further heightened. When both of them are contained together, the flame retardance can be further improved. As the index of the flame retardance, a peak of heat release rate (HRR) and a peak of released smoke rate (RSR) which are measured by a cone calorimeter can be used. The peak value of HRR of the silicone-containing thermoplastic fluororesin composition of the present invention can be at most 70 kW/m2, and the peak value of the RSR can be at most 6 /sec.
The preparation process of the silicone-containing thermoplastic fluororesin composition of the present invention comprises (1) a step of mixing the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the crosslinkable silicone rubber composition containing organopolysiloxane (b-1), and (2) a step of crosslinking the crosslinkable silicone rubber composition in a mixture of the fluorine-containing ethylenic polymer (a) and the crosslinkable silicone rubber composition.
Further, the process for preparing the silicone-containing thermoplastic fluororesin composition comprising (1) a step of preparing a mixture comprising the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, the organopolysiloxane (b-1) and the crosslinking catalyst (b-3) without containing the crosslinking agent (b-2), thereafter, (2) a step of adding the crosslinking agent (b-2), and (3) a step of crosslinking the organopolysiloxane (b-1) in the mixture is preferable from the viewpoint that an average particle diameter of the crosslinked particles of the silicone rubber (B) can be lowered.
Further, to the silicone-containing thermoplastic fluororesin composition of the present invention, other polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane, a pigment, a lubricant, a photostabilizer, a weather resistant stabilizer, an antistatic agent, an ultraviolet absorbent, an antioxidant, a mold releasing agent, a foaming agent, a perfume, an oil, a softening agent and the like can be added, within a range not affecting the effect of the present invention.
The silicone-containing thermoplastic fluororesin composition of the present invention can be molded using general molding processes and molding equipments. As the molding process, optional processes such as injection molding, extrusion molding, compression molding, blow molding, calender molding, and vacuum molding can be adopted, and the silicone-containing thermoplastic fluororesin composition of the present invention is molded into molded articles with an optional shape in accordance with its intended purpose.
Further, the present invention includes molded articles such as a sheet or a film, and an electric wire jacket which are formed from the silicone-containing thermoplastic fluororesin composition of the present invention, and includes a laminated structure having a layer comprising the silicone-containing thermoplastic fluororesin composition of the present invention, and a layer comprising other materials.
The above-mentioned electric wire jacket is generally used in a wire or a cable for electronic equipments such as a computer for imparting flame retardance and preventing mechanical damage, and it has a tube shape storing a copper wire and its covering material. Its molding process is not particularly limited and, for example, known processes such as a process of carrying out extrusion molding by a cross head and a single screw extruder are exemplified.
Since the electric wire jacket comprises the above-mentioned composition, it is excellent in moldability and flexibility, exhibits excellent heat resistance in particular, and can be also used suitably as a jacket for LCC (Limited Combustible Cable) which is required to have higher flame retardance than a conventional one. A thickness of the electric wire jacket of the present invention can be appropriately set in accordance with its use, and it has usually a thickness range from 0.2 to 1.0 mm. Since the electric wire jacket of the present invention has a thickness of the above-mentioned range, it is excellent in flexibility in particular.
The electric wire jacket of the present invention is obtained by molding the silicone-containing thermoplastic fluororesin composition of the present invention, and is excellent in properties such as flame retardance and flexibility. Although not specifically limited, the electric wire jacket of the present invention can be used, for example, for electric wires for wiring electronic equipments, a 600 V insulating electric wire for electric equipments, and communication cables such as a LAN cable. The above-mentioned LAN cable is a cable used for the Local Area Network.
A cable used for the LAN characterized by being equipped with the electric wire jacket of the present invention is also one of the present invention. An example of the cable used for the LAN is a plenum cable, and the above-mentioned LCC is suitable. A thickness of the cable jacket used for the LAN of the present invention can be optionally set, and the cable is usually molded to have a thinness of 0.2 to 1.0 mm. Since the cable used for the LAN of the present invention is equipped with the electric wire jacket of the present invention, it is excellent in flame retardance and flexibility.
The silicone-containing thermoplastic fluororesin composition of the present invention, and a molded article, a sheet, and a film comprising the composition can be used for automobile parts, mechanical parts, electrical and electronic parts, OA parts, daily- necessaries, building materials, sundries and the like, and the laminated structure can be used as food containers, fuel containers, a tube, a hose and the like.
EXAMPLES
The present invention is explained based on Examples, but the present invention is not limited only thereto. In Examples and Comparative Examples, "part" represents "part by weight". <Tensile strength and tensile elongation at break>
Using the pellets of the silicone-containing thermoplastic fluororesin compositions prepared in Examples and Comparative Examples, sheet-shaped test pieces having a thickness of 2 mm were prepared by compression-molding the pellets by a thermal pressing machine at 2800C for the fluororesins (a-1 and a-2), and at 200°C for the fluororesin (a-3) under the condition of 3.5 MPa, and dumbbell V-shaped test pieces described in ASTM-D638 were punched out from the sheets. Using the obtained dumbbell test pieces, tensile strength and tensile elongation at break at 23°C were measured under the condition of 50 mm/min according to ASTM-D638 using an Autograph (manufactured by Shimadzu Corporation). <Flame retardance>
Using the pellets of the silicone-containing thermoplastic fluororesin compositions prepared in Examples and Comparative Examples, sheet-shaped test pieces having a thickness of 2 mm were prepared by compression-molding the pellets by a thermal pressing machine at 2800C for the fluororesins (a-1 and a-2), and at 2000C for the fluororesin (a-3) under the condition of 3.5 MPa, and sheet-shaped test pieces having a thickness of 2 mm, a length of 50 mm and a width of 50 mm were cut out from the sheets. Using the obtained sheet-shaped test pieces, radiation heat of 50 kW/m2 was applied to the test pieces using a cone calorimeter (manufactured by Tokyo System Pack Co.), to carry out a combustion test according to ASTM-E 1354, and the peak value of HRR and the peak value of RSR were determined. In Examples and Comparative Examples, the following fluorine-containing ethylenic polymer (a-1), fluorine-containing ethylenic polymer (a-2), fluorine-containing ethylenic polymer (a-3), organopolysiloxane (b-1), crosslinking agent (b-2), crosslinking catalyst (b-3), flame retardant (C), inorganic filler (D-I), inorganic filler (D-2), and crosslinked silicone rubber particles (E) were used. <Fluorine-containing ethylenic polymer (a-l)>
A copolymer of TFE/ HFP/ perfluoro (propyl vinyl ether) (molar ratio = 91.9/7.7/0.4, a melting point of 2600C, the number of -COOH end groups = 550 per 1,000,000 carbon atoms) having a carboxyl group.
<Fluorine-containing ethylenic polymer (a-2)>
A copolymer of TFE/HFP/perfluoro(propyl vinyl ether) (molar ratio = 91.9/7.7/0.4, a melting point of 2600C, the number of carbonyl group-containing end groups = 0 per 1,000,000 carbon atoms).
<Fluorine-containing ethylenic polymer (a-3)>
A copolymer of TFE/ethylene/HFP/2,3,3,4,4,5,5-heρtafluoro-l-pentene (molar ratio = 38.9/45.9/ 14.8/0.4, a melting point of 172°C, the number of -OCOCH2CH2CH3 end groups = 411 per 1,000,000 carbon atoms) having a -OCOCH2CH2CH3 end group. <Organopolysiloxane (b-lA)>
A mixture of organopolysiloxane and silica obtained by kneading 100 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with dimethylvinylsilyl groups (an amount of vinyl group = 0.088 % by weight, weight average molecular weight of about 620,000), 32 parts by weight of fumed silica (AEROSIL 200: trade name), and 6.4 parts by weight of dimethylpolysiloxane end-capped with dimethylhydroxysilyl groups and having a viscosity of 40 Pa-s at 1700C for 2 hours, and then, compounding 60 parts by weight of quartz powder thereto. <Organopolysiloxane (b-lB)>
A mixture of organopolysiloxane and silica obtained by kneading 70 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with dimethylvinylsilyl groups (an amount of vinyl group = 0.088 % by weight, a weight average molecular weight of about 620,000), 30 parts by weight of a polydimethylsiloxane end-capped with dimethylvinylsilyl groups (an amount of vinyl group = 0.010 % by weight, a weight average molecular weight of about 620,000), 39 parts by weight of fumed silica (CABOCYL MS-75D: trade name), and 10.0 parts by weight of dimethylpolysiloxane end-capped with dimethylhydroxysilyl groups and having a viscosity of 40 Pa-s at 1700C for 2 hours. <Crosslinking agent (b-2)> A mixture comprising 100 parts by weight of a dimethylsiloxane-methylhydrogensiloxane copolymer (an amount of silicon atom-bonded hydrogen atom = 0.83 % by weight) end-capped with trimethylsilyl groups and having a viscosity of 12 mPa-s and 20 parts by weight of fumed silica (REOLOSIL DM-30: trade name, available from Tokuyama Corporation), which is surface-treated with dimethyldichloro silane . <Crosslinking catalyst (b-3)> Chloroplatinic acid < Curing retardant (b-4)>
A mixture comprising 0.5 part by weight of 2-phenyl-3-butyn-2-ol and 99.5 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with trimethylsilyl groups (an amount of vinyl group = 0.048 % by weight, a weight average molecular weight of about 620,000). < Flame retardant (C) >
A mixture comprising 100 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer end-capped with trimethylsilyl groups (an amount of vinyl group = 0.031 % by weight, a weight average molecular weight of about 620,000), 41 parts by weight of titanium oxide (Titanium Dioxide P-25 (trade name), available from Nippon Aerosil Co.) and 38 parts by weight of cerium oxide (CE OXIDE 2N5 HF (trade name), available from Rhodia Japan Ltd.). <Inorganic filler (D- 1)> Zinc oxide (ZINC OXIDE Second Grade available from Sakai
Chemical Industry Co., Ltd., an average particle diameter of 0.6 μm) <Inorganic filler (D-2)> Wollastonite (WOLLASTONITE C-8 available from JFE Mineral Co., Ltd.; an aspect ratio of 3 : 1, an average particle diameter of 9 μm)
<Inorganic filler (D-3)> Wollastonite (NYAD 1250 available from NYCO; an aspect ratio of 3 : 1 , an average particle diameter of 3 μm) <Crosslinked silicone rubber particles (E)>
Crosslinked fluoro silicone rubber particles with an average particle diameter of 0.5 μm which are prepared by the following process:
65.5 Parts by weight of dimethylpolysiloxane end-capped with diimethylhydroxysilyl groups and having a viscosity of 40 mPa-s, 30 parts by weight of ethylpolysilicate (SILICATE 40 available from Tama Chemicals Co., Ltd.) and 4.5 parts by weight of 3,3,3-trifluoropropyltrimethoxysilane were uniformly mixed to prepare liquid fluorosilicone rubber composition having condensation reactivity.
Then, the composition was emulsified in an aqueous solution comprising 8 parts by weight of polyoxyethylene lauryl ether and 40 parts by weight of pure water, and further uniformly emulsified by a colloid mill, thereafter, 140 parts by weight of pure water was added for dilution, to prepare an emulsion of the liquid fluorosilicone rubber composition.
Then, a catalyst for a condensation reaction prepared by dispersing 1 part by weight of tin octylate in an aqueous solution comprising 1 part by weight of polyoxyethylene lauryl ether and 10 parts by weight of pure water was mixed in the emulsion, and the solution was allowed to stand at room temperature for one day, to obtain the homogeneous aqueous suspension of crosslinked fluorosilicone rubber particles and then water was removed by a hot-air drier at 3000C to obtain the crosslinked fluorosilicone rubber particles.
EXAMPLE 1
A temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 2800C, and 65 g of the fluorine-containing ethylenic polymer (a-1) was charged at a screw rotational number of 10 rpm. After confirming that the resin was completely melted after 5 minutes, thereto was charged 16.25 g of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.3 part of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5), 0.01 part of the crosslinking catalyst (b-3), 4.8 parts of the curing retardant (b-4), and 7.6 parts of the flame retardant (C) with a rubber roll). The screw rotational number was immediately increased to 80 rpm, and the mixture was kneaded for 10 minutes. The melted mixture was taken out from the laboplastmill and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 16.4 MPa, and the tensile elongation at break was 212 %. COMPARATIVE EXAMPLE 1
Pellets were obtained in the same manner as in Example 1 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-1). The tensile strength of the pellets was 8.0 MPa, and the tensile elongation at break was as low as 57 %.
EXAMPLE 2
Pellets were obtained in the same manner as in Example 1 except that the fluorine-containing ethylenic polymer (a-3) was used in place of the fluorine-containing ethylenic polymer (a-1), and a kneading temperature was 2000C. The tensile strength of the pellets was 11.0
MPa, and the tensile elongation at break was 208 %.
EXAMPLE 3
The temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 2000C, and 65 g of the fluorine-containing ethylenic polymer (a-3) was charged at a screw rotational number of 10 rpm. After confirming that the resin was completely melted after 5 minutes, thereto were charged 16.25 g of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.01 part of the crosslinking catalyst (b-3), and 7.6 parts of the flame retardant (C) with a rubber roll). The screw rotational number was immediately raised to 80 rpm, and the mixture was kneaded for 5 minutes. Then, 0.049 g of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5) was added, and the mixture was further kneaded for 5 minutes. The melted mixture was taken out from the laboplastmill, and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 12.7 MPa, and the tensile elongation at break was 250 %.
COMPARATIVE EXAMPLE 2
Pellets were obtained in the same manner as in Example 3 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-3), and a kneading temperature was 2800C. The tensile strength of the pellets was 8.2 MPa, and the tensile elongation at break was as low as 70 %.
EXAMPLE 4
The temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 2800C, and 65 g of the fluorine-containing ethylenic polymer (a-1) was charged at a screw rotational number of 10 rpm. After confirming that the resin was completely melted after 5 minutes, thereto was charged 16.25 g of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.01 part of the crosslinking catalyst (b-3), 7.6 parts of the flame retardant (C), and 54 parts of the inorganic filler (D-I) with a rubber roll). The screw rotational number was immediately raised to 80 rpm, and the mixture was kneaded for 5 minutes. Then, 0.036 g of the crosslinking agent (b-2) (the number of silicon atom-bonded hydrogen atoms to the number of alkenyl groups in the organopolysiloxane (b-lA) was 1 : 1.5) was added, and the mixture was further kneaded for 5 minutes. The melted mixture was taken out from the laboplastmill and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 13.9 MPa and the tensile elongation at break was 250 %. Further, the peak value of HRR in the cone calorimeter combustion test was 36.3 kW/m2, and the peak value of RSR was 3.7/ sec.
EXAMPLE 5
Pellets were obtained in the same manner as in Example 4 except that a mixture of the fluorine-containing ethylenic polymer (a-1) and the fluorine-containing ethylenic polymer (a-2) (weight ratio = 1 : 1, the number of -COOH end groups = 275 per 1,000,000 carbon atoms) was used in place of the fluorine-containing ethylenic polymer (a-1). The tensile strength of the pellets was 11.5 MPa, and the tensile elongation at break was 135 %.
EXAMPLE 6 Pellets were obtained in the same manner as in Example 4 except that a mixture of the fluorine-containing ethylenic polymer (a-1) and the fluorine-containing ethylenic polymer (a-2) (weight ratio = 1 : 3, the number of -COOH end groups = 138 per 1,000,000 carbon atoms) was used in place of the fluorine-containing ethylenic polymer (a-1). The tensile strength of the pellets was 10.1 MPa, and the tensile elongation at break was 102 %.
COMPARATIVE EXAMPLE 3
Pellets were obtained in the same manner as in Example 4 except that the fluorine-containing ethylenic polymer (a-2) was used in place of the fluorine-containing ethylenic polymer (a-1). The tensile strength of the pellets was 8.4 MPa, and the tensile elongation at break was as low as 27 %.
EXAMPLE 7
Pellets were obtained in the same manner as in Example 4 except that the fluorine-containing ethylenic polymer (a-3) was used in place of the fluorine-containing ethylenic polymer (a-1) and a kneading temperature was 2000C. The tensile strength of the pellets was 17.8
MPa, and the tensile elongation at break was 275 %. Further, the peak value of HRR in the cone calorimeter combustion test was 57.3 kW/m2, and the peak value of RSR was 4.9/sec.
EXAMPLE 8
Pellets were obtained in the same manner as in Example 4 except that the inorganic filler (D-2) was used in place of the inorganic filler (D-I). The tensile strength of the pellets was 12.0 MPa, and the tensile elongation at break was 261 %. Further, the peak value of
HRR in the cone calorimeter combustion test was 28.1 kW/m2, and the peak value of RSR was 1.2 /sec.
EXAMPLE 9
Pellets were obtained in the same manner as in Example 7 except that the inorganic filler (D-2) was used in place of the inorganic filler (D-I). The tensile strength of the pellets was 17.4 MPa, and the tensile elongation at break was 321 %. Further, the peak value of HRR in the cone calorimeter combustion test was 55.9 kW/m2, and the peak value of RSR was 3.9 /sec.
EXAMPLE 10
Pellets were obtained in the same manner as in Example 4 except that a mixture of the inorganic filler (D-I) and the inorganic filler (D-2) (weight ratio = 1 : 1) was used in place of the inorganic filler (D-I). The tensile strength of the pellets was 14.9 MPa, and the tensile elongation at break was 296 %. Further, the peak value of HRR in the cone calorimeter combustion test was 39.1 kW/m2, and the peak value of RSR was 2.9 /sec.
EXAMPLE 11
Pellets were obtained in the same manner as in Example 7 except that a mixture of the inorganic filler (D-I) and the inorganic filler (D-2) (weight ratio = 1 : 1) was used in place of the inorganic filler (D-I). The tensile strength of the pellets was 18.2 MPa, and the tensile elongation at break was 342 %. Further, the peak value of HRR in the cone calorimeter combustion test was 64.0 kW/m2, and the peak value of RSR was 4.9 /sec. EXAMPLE 12
80 parts by weight of the fluorine-containing ethylenic polymer (a-1) and 20 parts by weight of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lA), 0.01 part of the crosslinking catalyst (b-3), 7.6 parts of the flame retardant (C), 27 parts of the inorganic filler (D-I), and 54 parts of the inorganic filler (D-2) with a rubber roll) were continuously fed in a 25 mm diameter twin screw extruder manufactured by Werner Pfleiderer Inc. Further, 0.038 part by weight of the crosslinking agent (b-2) was continuously fed from the intermediary part of a cylinder. The mixture was melt-kneaded under the conditions of a cylinder temperature of 3100C and a screw rotational number of 500 rpm to prepare the pellets of the silicone-containing thermoplastic fluororesin composition. The tensile strength of the pellets was 10.7 MPa, and the tensile elongation at break was 154 %. Further, the peak value of HRR in the cone calorimeter combustion test was 33.4 kW/m2, and the peak value of RSR was 4.1 /sec.
EXAMPLE 13
Pellets were obtained in the same manner as in Example 12 except that the fluorine-containing ethylenic polymer (a-3) was used in place of the fluorine-containing ethylenic polymer (a-1), the cylinder temperature was changed to 2700C in place of 3100C, and the screw rotational number was changed to 300 rpm in place of 500 rpm. The tensile strength of the pellets was 16.5 MPa, and the tensile elongation at break was 316 %. Further, the peak value of HRR in the cone calorimeter combustion test was 56.4 kW/m2 and the peak value of RSR was 5.1 /sec.
EXAMPLE 14 The temperature of a laboplastmill having an internal volume of 60 ml manufactured by Toyo Seiki Seisaku-Sho Ltd. was raised to 2600C, and 65 g of the fluorine-containing ethylenic polymer (a-3) was charged at a screw rotational number of 10 rpm. After confirming that the resin was completely melted after 5 minutes, 16.25 g of the crosslinked silicone rubber particles (E) was charged thereto. The screw rotational number was immediately raised to 80 rpm, and the mixture was kneaded for 10 minutes. The melted mixture was taken out from the laboplastmill, and naturally cooled to a room temperature. The solidified silicone-containing thermoplastic fluororesin composition was chopped with scissors for cutting the resin to obtain about 80 g of about 2 mm-square pellets. The tensile strength of the pellets was 14.2 MPa, and the tensile elongation at break was 258 %.
It was cleared by morphology observation with a scanning electron microscope (manufactured by JEOL, Ltd.) that the silicone-containing thermoplastic fluororesin compositions obtained in Examples 1 to 14 have a structure in which the fluororesin (A) forms a continuous phase, and the silicone rubber (B) forms a dispersion phase.
EXAMPLE 15 90 parts by weight of the fluorine-containing ethylenic polymer (a-1) and 10 parts by weight of a premixed silicone rubber (a kneaded product obtained by preliminarily kneading 100 parts of the organopolysiloxane (b-lB), 0.01 part of the crosslinking catalyst (b-3) and 104 parts of the inorganic filler (D-3) with a rubber roll) were continuously fed in a 25 mm diameter twin screw extruder manufactured by Werner Pfleiderer Inc. Further, 0.022 part by weight of the crosslinking agent (b-2) was continuously fed from the intermediary part of a cylinder. The mixture was melt-kneaded under the conditions of a cylinder temperature of 28O0C and a screw rotational number of 500 rpm to prepare the pellets of the silicone-containing thermoplastic fluororesin composition. The tensile strength of the pellets was 15.2 MPa, and the tensile elongation at break was 313 %. Further, the peak value of HRR in the cone calorimeter combustion test was 18.1 kW/m2, and the peak value of RSR was 3.1 /sec.
Cat.6 4-pair UTP cable was produced by using the pellets of the silicone-containing thermoplastic fluororesin composition as a material for a jacket. NEOFLON FEP NP-101 available from Daikin Industries, Ltd. was used as an insulating covering material and a cross web for a primary copper wire. For molding of the jacket, a 30 mm diameter single screw extruder of L/D=22, a die having an inner diameter of 15.0 mm and a tip having an outer diameter of 13.2 mm were used. A temperature profile of the extruder was C-I: 270°C, C-2: 2900C, C-3: 3000C, flange: 3000C, head: 300°C, and die: 3000C, and a screw rotational number was 10 rpm. The silicone-containing thermoplastic fluororesin composition was provided as a jacket on the 4-pair cable with a cross web, and a cable having a jacket thickness of 0.32 mm and a cable outer diameter of 4.72 mm was obtained. In molding this jacket, DDR (Draw Down Ratio) was 9.
Steiner Tunnel combustion test described in NFPA255 standard was carried out by using the obtained cable. Flame Spread Index (FSI) indicating flame propagation of the cable was 0, and Smoke
Developed Index (SDI) indicating smoke generation from the cable was
35. UL2424 standard, Appendix A which is a standard for LCC
(Limited Combustible Cable) defines that FSI shall not exceed 25, and
SDI shall not exceed 50. Accordingly, it was found that the cable of the present invention satisfies the requirements of UL2424 standard, and can be used as LCC.
INDUSTRIAL APPLICABILITY
The present invention can provide a silicone-containing thermoplastic fluororesin composition which comprises the fluororesin (A) comprising the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, thereby having excellent flame retardance, flexibility and mechanical properties, and enabling an obtained crosslinked product to be printed.

Claims

1. A silicone-containing thermoplastic fluororesin composition comprising a fluororesin (A) and a silicone rubber (B), wherein the fluororesin (A) comprises a fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, and the silicone rubber (B) is crosslinked at least in a part thereof.
2. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein a melting point of the fluorine-containing ethylenic polymer (a) is 120 to 3100C.
3. The silicone-containing thermoplastic fluororesin composition of Claim 1 , wherein the silicone rubber (B) is dynamically crosslinked in the presence of the fluororesin (A).
4. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein the fluororesin (A) is a copolymer of tetrafluoroethylene with a perfluoro ethylenically unsaturated compound represented by the following general formula (1):
Figure imgf000047_0001
wherein, Rf1 represents -CF3 and/ or -ORf2, and Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
5. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein the fiuororesin (A) is a copolymer comprising 20 to 80 % by mole of a tetrafluoroethylene unit and 80 to 20 % by mole of an ethylene unit, or a copolymer comprising 19 to 90 % by mole of a tetrafluoroethylene unit, 9 to 80 % by mole of an ethylene unit and 1 to 72 % by mole of a perfluoro ethylenically unsaturated compound unit represented by the following general formula (1):
CF2=CF-Rf1 (1)
wherein Rf1 represents -CF3 and/ or -ORf2, and Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.
6. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by a condensation reaction, a hydrosilylation reaction, or a radical reaction with an organic peroxide.
7. The silicone-containing thermoplastic fluororesin composition of Claim 6, wherein the silicone rubber (B) is a crosslinked product obtained by crosslinking the crosslinkable silicone rubber composition by the hydrosilylation reaction.
8. The silicone-containing thermoplastic fluororesin composition of Claim 1 , wherein the silicone rubber (B) is a crosslinked product of the crosslinkable silicone rubber composition comprising an organopolysiloxane (b-1).
9. The silicone-containing thermoplastic fluororesin composition of Claim 8, wherein the crosslinkable silicone rubber composition further comprises a crosslinking agent (b-2) and a crosslinking catalyst (b-3).
10. The silicone-containing thermoplastic fluororesin composition of Claim 9, wherein the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group, the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom, and the crosslinking catalyst (b-3) is a hydro silylation reaction catalyst.
11. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein the carbonyl group-containing end group in the fluororesin (A) is at least one group selected from the group consisting of a carboxyl group, a fluoride carbonyl group and a group represented by the general formula (2) :
-O-C(=O)-ORi (2)
wherein R1 is an alkyl group having 1 to 5 carbon atoms.
12. The silicone-containing thermoplastic fluororesin composition of Claim 1, wherein the number of carbonyl group-containing end groups in the fluororesin (A) is 100 to 1 ,000 based on 1,000,000 carbon atoms.
13. The silicone-containing thermoplastic fluororesin composition of Claim 1, further comprising a flame retardant (C).
14. The silicone-containing thermoplastic fluororesin composition of Claim 1 , further comprising an inorganic filler (D) .
15. The silicone-containing thermoplastic fluororesin composition of Claim 13, further comprising an inorganic filler (D).
16. The silicone-containing thermoplastic fluororesin composition of Claim 14, wherein the inorganic filler (D) is at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide, and hydrotalcite.
17. The silicone-containing thermoplastic fluororesin composition of Claim 15, wherein the inorganic filler (D) is at least one filler selected from the group consisting of wollastonite, zinc oxide, magnesium oxide, aluminum oxide and hydrotalcite.
18. A molded article, which is formed from the silicone-containing thermoplastic fluororesin composition of Claim 1.
19. An electric wire jacket, which is formed from the silicone-containing thermoplastic fluororesin composition of Claim 1.
20. A cable having the electric wire jacket of Claim 19.
21. A process for preparing a silicone-containing thermoplastic fluororesin composition comprising: (1) a step of mixing a fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group and a crosslinkable silicone rubber composition comprising an organopolysiloxane (b-1), and (2) a step of crosslinking the crosslinkable silicone rubber composition in a mixture of the fluorine-containing ethylenic polymer (a) and the crosslinkable silicone rubber composition.
22. The process for preparing a silicone-containing thermoplastic fluororesin composition of Claim 21, wherein the crosslinkable silicone rubber composition further comprises a crosslinking agent (b-2) and a crosslinking catalyst (b-3).
23. The process for preparing a silicone-containing thermoplastic fluororesin composition of Claim 22, wherein the organopolysiloxane (b-1) is a diorganopolysiloxane containing an alkenyl group, the crosslinking agent (b-2) is an organopolysiloxane containing a silicon atom-bonded hydrogen atom and the crosslinking catalyst (b-3) is a hydro silylation reaction catalyst.
24. The process for preparing a silicone-containing thermoplastic fluororesin composition of Claim 22, comprising:
(1) a step of preparing a mixture comprising the fluorine-containing ethylenic polymer (a) having a carbonyl group-containing end group, the organopolysiloxane (b-1), and the crosslinking catalyst (b-3), without containing the crosslinking agent (b-2), thereafter,
(2) a step of adding the crosslinking agent (b-2), and
(3) a step of crosslinking the organopolysiloxane (b-1) in the mixture.
25. The process for preparing a silicone-containing thermoplastic fluororesin composition of Claim 21 , wherein a dynamic crosslinking method of simultaneously carrying out the mixing and the crosslinking is used.
26. The process for preparing a silicone-containing thermoplastic fluororesin composition of Claim 21, wherein a twin screw extruder is used.
PCT/JP2007/059794 2006-05-19 2007-05-01 Silicone-containing thermoplastic fluororesin composition, article molded therefrom, and process for preparing silicone-containing thermoplastic fluororesin composition WO2007135875A1 (en)

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