WO2010076876A1 - Composition d’elastomere perfluore, et article reticule moule obtenu par reticulation et moulage de ladite composition - Google Patents

Composition d’elastomere perfluore, et article reticule moule obtenu par reticulation et moulage de ladite composition Download PDF

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Publication number
WO2010076876A1
WO2010076876A1 PCT/JP2009/071523 JP2009071523W WO2010076876A1 WO 2010076876 A1 WO2010076876 A1 WO 2010076876A1 JP 2009071523 W JP2009071523 W JP 2009071523W WO 2010076876 A1 WO2010076876 A1 WO 2010076876A1
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Prior art keywords
molded article
perfluoroelastomer
crosslinked molded
crosslinking
mole
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PCT/JP2009/071523
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English (en)
Inventor
Daisuke Ota
Junpei Terada
Tatsuya Morikawa
Meiten Koh
William Brock Alexander
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Daikin Industries, Ltd.
Greene, Tweed Of Delaware, Inc.
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Application filed by Daikin Industries, Ltd., Greene, Tweed Of Delaware, Inc. filed Critical Daikin Industries, Ltd.
Publication of WO2010076876A1 publication Critical patent/WO2010076876A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • the present invention relates to a crosslinked molded article obtained by crosslinking and molding a perfluoroelastomer composition and further relates to a perfluoroelastomer composition.
  • Fluorine-containing elastomers particularly perfluoroelastomers predominantly comprising a tetrafluoroethylene (TFE) unit are widely used as a sealing material, etc. to be used under harsh environment because of excellent chemical resistance, solvent resistance and heat resistance thereof.
  • TFE tetrafluoroethylene
  • WO 01 /23470 discloses a perfluoroelastomer composition, in which fluorine-containing resin fine particles are finely dispersed in a perfluoroelastomer, and an elastomer molded article obtained by crosslinking and molding the composition.
  • a copolymer of TFE unit and perfluoro(alkyl vinyl ether) (PAVE) unit is described as a perfluoroelastomer. Since fluorine-containing resin fine particles are contained as a filler, there is room for improvement from the viewpoint that steps for producing a molded article are complicated, and in the case of use of the crosslinked molded article as a sealing material for semiconductor manufacturing equipment, generation of particles occurs.
  • JP2003-137930A discloses a perfluoroelastomer having iodine atom and /or bromine atom in its chain and/ or its end which is obtained by polymerizing TFE, perfluoro vinyl ether such as
  • carbon black and zinc oxide are blended as a filler in order to impart excellent mechanical characteristics.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • JP2002-507640A discloses a perfluoroelastomer composition
  • a perfluoroelastomer composition comprising perfluoro olefin, perfluoro vinyl ether, perfluoroelastomer comprising a component having vulcanizable site being capable of undergoing peroxide vulcanization reaction and a peroxide vulcanization agent, and a molded article obtained therefrom.
  • TFE is raised as the perfluoro olefin
  • PAVE and perfluoro alkoxy vinyl ether are raised as perfluoro vinyl ether.
  • carbon black and zinc oxide are blended as a filler.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • JP2003-526705A discloses a crosslinkable perfluoroelastomer composition
  • a crosslinkable perfluoroelastomer composition comprising a perfluoro olefin, a perfluoro vinyl ether, a perfluoroelastomer comprising a component having cure site being capable of undergoing peroxide curing reaction, an additive selected from the group consisting of organic onium, phosphate, phosphine oxide, amine oxide, alkylamine, polycyclic salt and polycyclic amine salt, a peroxide curing agent and a coagent.
  • TFE is raised as the perfluoro olefin
  • PAVE and perfluoro alkoxy vinyl ether are raised as the perfluoro vinyl ether.
  • carbon black and zinc oxide are blended.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • JP2005-220161A describes a crosslinkable perfluoroelastomer composition comprising a crosslinkable perfluoroelastomer and a fluorine-containing solvent.
  • the crosslinkable perfluoroelastomer comprises TFE, PAVE or perfluoro alkoxy vinyl ether and a cure site-containing monomer having at least one bromine group or iodine group.
  • a PFA resin powder is contained as a filler in the crosslinkable perfluoroelastomer composition of JP2005-220161A, there is room for improvement from the viewpoint of complicated production step of a molded article and generation of particles in the case of use of the crosslinked molded article as a sealing material for semiconductor manufacturing equipment.
  • JP2002-265733A and JP2000-53835A disclose crosslinkable perfluoroelastomer compositions comprising a TFE/ PAVE copolymer having iodine atom and/ or bromine atom, an organic peroxide and a co-crosslinking agent.
  • hydrotalcite is blended as an acid acceptor.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing a molded article cannot be detected.
  • WO 02/48200 and JP2004-532902A disclose a process for preparing a perfluoroelastomer molded article comprising a copolymer of TFE, perfluoro vinyl ether such as PAVE or perfluoro alkoxy vinyl ether, and a monomer having cure site such as nitrile-containing fluorinated olefin or nitrile-containing fluorinated vinyl ether and a curing agent.
  • This perfluoroelastomer molded article is semi-transparent or transparent, has hypochromic color or is colorless, and has good tensile properties and compression set.
  • a monomer having nitrile cure site is necessary as an essential component.
  • JP2005-290011A discloses a process for preparing fluorinated iodoalkylnitrile to be used as a chain transfer agent for preparing a perfluoroelastomer, and describes a perfluoroelastomer prepared by using
  • carbon black is blended.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • U.S. Patent No. 4,983,697 discloses a TFE/PMVE copolymer.
  • This copolymer has nitrile group and iodine atom as a cure site, and there are described peroxide as a crosslinking agent and triallyl isocyanurate as a co-crosslinking agent.
  • peroxide as a crosslinking agent
  • triallyl isocyanurate as a co-crosslinking agent.
  • carbon black is blended.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • U.S. Patent No. 5,447,993 and JP9-512569A disclose TFE/ PMVE copolymers. Those copolymers have nitrile group and iodine atom as a cure site, and peroxide is raised as a crosslinking agent and triallyl isocyanurate is raised as a co-crosslinking agent. In a crosslinked molded article, carbon black is blended. As a result, the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected. In addition, there is room for improvement from the viewpoint that particles are generated in the case of use of the crosslinked molded article as a sealing material for semiconductor manufacturing equipment.
  • JP4-505633A discloses a perfluoroelastomer comprising a TFE unit, a PAVE unit and a monomer having bromine atom and iodine atom as a cure site.
  • a composition prepared from the perfluoroelastomer of JP4-505633A is excellent in curability and mold-release property.
  • carbon black for improvement in mechanical strength.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing a molded article cannot be detected.
  • JP9-500163A discloses a perfluoroelastomer composition comprising a peroxide-crosslinkable perfluoroelastomer and containing neither extracted metal nor metallic compound substantially, and a crosslinked article obtained by molding the composition.
  • the composition and the crosslinked article obtained therefrom are usefully used for applications requiring high purity, but carbon black is blended for improving mechanical strength, an organic peroxide dispersed in an inactive carrier is used and proton sponge is blended as an acid acceptor.
  • the obtained molded article is not transparent, and therefore, contaminants and foreign matters which are possibly mixed in a step for producing the molded article cannot be detected.
  • the present inventors have made studies with respect to technique of not using a filler, a processing aid or the like other than a crosslinking agent being essential for crosslinking reaction in order to prevent generation of particles and outgas (gas generated from a molded sealing material), for applications, especially in the case of using a crosslinked molded article as a sealing material for semiconductor and liquid crystal manufacturing equipment, and have found that there is room for improvement in tensile strength when a filler such as carbon black is not blended in the case of a perfluoroelastomer having iodine and/ or bromine to be subjected to peroxide crosslinking.
  • the crosslinked molded article is transparent and has satisfactory mechanical properties.
  • the present invention relates to a crosslinked molded article obtained by crosslinking and molding a perfluoroelastomer composition consisting of:
  • the perfluoro vinyl ether unit (a) is a unit represented by the formula (1): — CF 2 - CF
  • Rf is a perfluoroalkyl group having 1 to 10 carbon atoms.
  • the perfluoro vinyl ether unit (a) is a perfluoro (methyl vinyl ether) unit.
  • a metal content of the crosslinked molded article is not more than 100 ppm.
  • a haze value of the crosslinked molded article is not more than 50 %. It is preferable that a tensile strength of the crosslinked molded article is not less than 8 MPa.
  • the crosslinked molded article is a sealing material.
  • the crosslinked molded article is a sealing material for semiconductor manufacturing equipment.
  • the present invention also relates to a perfluoroelastomer composition consisting of:
  • (C) a compound having at least two double bonds in its molecule.
  • the total amount of the organic peroxide (B) and the compound (C) having at least two double bonds in its molecule is from 0.5 to 3.0 parts by mass based on 100 parts by mass of the perfluoroelastomer (A) .
  • the crosslinked molded article of the present invention obtained by crosslinking and molding the perfluoroelastomer composition consists of (A) the perfluoroelastomer having iodine atom and /or bromine atom and comprising the perfluoro vinyl ether (hereinafter also referred to as PVE) unit (a) and the tetrafluoroethylene (hereinafter also referred to as TFE) unit (b), (B) the organic peroxide, and (C) the compound having at least two double bonds in its molecule.
  • PVE perfluoro vinyl ether
  • TFE tetrafluoroethylene
  • the content of PVE unit (a) in the perfluoroelastomer (A) is not less than 20 % by mole, more preferably not less than 22 % by mole in the perfluoroelastomer (A) from the viewpoint that properties of the elastic rubber are not lost, and properties thereof do not become akin to properties of a resin.
  • the content of PVE unit (a) is preferably not more than 35 % by mole in the perfluoroelastomer (A) from the viewpoint of excellent mechanical strength of the crosslinked molded article.
  • a preferable PVE unit is one represented by the formula (1): -CF 2 - CF- (1
  • Examples of the PVE unit (a) are, for instance, perfluoro (methyl vinyl ether) (hereinafter also referred to as PMVE), perfluoro(propyl vinyl ether) and the like.
  • PMVE perfluoro (methyl vinyl ether)
  • PMVE perfluoro(propyl vinyl ether)
  • a glass transition temperature of a cured article can be decreased, properties of an elastic rubber are maintained and mechanical strength is excellent.
  • PVE unit (a) examples of other PVE unit (a) are ones represented by
  • CF 2 CFOCF 2 CFCF 3 OCF 2 CF 2 CF 3 .
  • the content of TFE unit (b) in the perfluoroelastomer (A) is preferably not less than 65 % by mole in the perfluoroelastomer (A) from the viewpoint of excellent tensile strength of the crosslinked molded article. Also the content of TFE unit (b) is not more than 80 % by mole, more preferably not more than 78 % by mole in the perfluoroelastomer (A) from the viewpoint that properties of the elastic rubber are not lost, and properties thereof do not become akin to properties of a resin.
  • the perfluoroelastomer (A) has iodine atom and/ or bromine atom.
  • Preferable as a process for preparing the perfluoroelastomer (A) having iodine atom and/ or bromine atom is a known iodine transfer polymerization method from the viewpoint that an obtained polymer has a narrow molecular weight distribution, control of the molecular weight is easy, iodine atom can be introduced to a polymer end, and the polymer end can be used as a cure site.
  • an iodine and/ or bromine compound preferably a diiodine and/ or dibromine compound, further preferably diiodine compound in an aqueous medium under pressure while stirring in the presence of a radical polymerization initiator in a substantially oxygen-free atmosphere.
  • iodine or bromine compound to be used are compounds represented by the formula (2): R 2 I ⁇ Br y (2) wherein each of x and y is 0 or an integer of 1 to 4, and 1 ⁇ x + y ⁇ 4 is to be satisfied; R 2 is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 3 carbon atoms, and may contain an oxygen atom.
  • an iodine or bromine compound to be used is an iodine compound represented by the general formula: Rf 1 I x .
  • Rf 1 is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, and a perfluoroalkyl group having 4 to 8 carbon atoms is preferable. If the number of carbon atoms exceeds 16, reactivity tends to be lowered.
  • Rf 1 I x x represents the number of bonds of Rf 1 , and is an integer of not less than 1 and not more than 4, preferably an integer of not less than 2 and not more than 3. Even if x exceeds 4, the compound can be used, but is not preferable from the viewpoint of synthesis cost. It is most preferable that x is 2, from the viewpoint that the obtained polymer has fewer branches.
  • the carbon-iodine bond of this iodine compound is a relatively weak bond, and is subject to fission in the form of radical in the presence of radical releasing source. Since reactivity of the released radical is high, a monomer undergoes addition growth reaction, and then, by removing iodine from the iodine compound, the reaction is ceased. In the thus obtained fluorine-containing elastomer, in which iodine is bonded to the carbon at an end of its molecule, the end iodine becomes an effective cure site, and crosslinking can be efficiently conducted.
  • Examples of the iodine compound represented by the general formula: Rf 1 ⁇ I x are, for instance, monoiodoperfluoromethane, monoiodoperfluoroethane , monoiodoperfluoropropane , monoiodoperfluorobutane (for example, 2 -iodoperfluoro butane, l-iodoperfluoro(l, 1-dimethylethane)), monoiodoperfluoropentane (for example, l-iodoperfluoro(4-methylbutane)), 1-iodoperfluoro-n-octane, monoiodoperfluorocyc Io butane,
  • the hydrocarbon group of Rf 1 may contain a functional group such as an ether linkage-formable oxygen atom, a thioether linkage-formable sulfur atom or carboxyl group, and examples of compounds having such a functional group are 2-iodoperfluoroethylperfluorovinylether, 2-iodoperfluoroethylperfiuoroisopropylether,
  • 1,4-diiodoperfluoro-n-butane and 1,6-diiodoperfluoro-n-hexane are preferable from the viewpoint of easy synthesis, reactivity, economical efficiency and stability, and 1,4-diiodoperfluoro-n-butane is preferable from the viewpoint that it is a liquid at room temperature and handling thereof is easy.
  • Example of other method of preparing the perfluoroelastomer (A) having iodine atom or bromine atom is a method of copolymerizing a perfluoroelastomer with an iodine- or bromine-containing monomer.
  • Examples of a monomer having iodine atom or bromine atom are iodine- or bromine-containing monomers represented by the general formula (3):
  • CY 1 2 CY 1 -Rf 2 (CHR 3 )nX 1 (3)
  • Y 1 is hydrogen atom, fluorine atom or -CH3
  • Rf 2 is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group
  • R 3 is hydrogen atom or -CH3
  • X 1 is iodine atom or bromine atom
  • n is 0 or 1, monomers represented by the general formula (4):
  • CF 2 CFO(CF2CF(CF 3 )O) m (CF2)n-X 2 (4) wherein m is 0 or an integer of 1 to 5; n is an integer of 1 to 3; X 2 is bromine atom or iodine atom, and monomers represented by the general formula (5):
  • CH 2 CH(CF 2 )nI (5) wherein n is an integer of 1 to 10.
  • iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-l-hexene) and perfluoro(5-iodo-3-oxa-l-pentene) disclosed in JP5-63482B and
  • CH 2 CH(CF 2 J 4 I
  • CH 2 CH(CF 2 ) 6 I.
  • iodine- or bromine-containing monomers can increase an amount of iodine /bromine to be introduced to the perfluoroelastomer by reaction using the above-mentioned iodine and/ or bromine compounds.
  • the perfluoroelastomer (A) to be used in the present invention can be prepared by usual polymerization method such as an emulsion polymerization method, a suspension polymerization method or a solution polymerization method.
  • Polymerization conditions such as a polymerization temperature and time may be optionally decided depending on kind of monomers and an intended elastomer.
  • An emulsifying agent, a molecular weight regulator, a pH regulator and the like may be added.
  • the molecular weight regulator may be added batchwise at an initial stage of the polymerization or may be added continuously or intermittently.
  • various emulsifying agents can be used for the emulsion polymerization.
  • desirable emulsifying agents are salts of carboxylic acid having a fluorocarbon chain or a fluoropolyether chain.
  • use of a reactive emulsifying agent is desirable.
  • an oil soluble radical polymerization initiator or a water soluble radical polymerization initiator as a polymerization initiator.
  • a water soluble radical polymerization initiator are, for instance, ammonium persulfate (APS), potassium persulfate (KPS), and the like.
  • Examples of a pH regulator for a polymerization system are electrolytic substances having buffer capacity such as phosphate, carbonate and borate or sodium hydroxide, potassium hydroxide and ammonium hydroxide.
  • Examples of a molecular weight regulator are iodine compounds and bromine compounds exemplified above.
  • a method of coagulation by acid treatment by mixing a polymerization reaction mixture and hydrochloric acid, nitric acid or the like and a method of coagulation by freezing a polymerization reaction mixture and then thawing it. Further a method of coagulation by an ultrasonic wave or a method of coagulation by a mechanical force can be adopted.
  • Example of other method of separating a polymerization product from a polymerization reaction mixture is a method of coagulation by adding, for example, a metallic salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum chloride, magnesium sulfate, barium sulfate, or aluminum sulfate.
  • a metallic salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum chloride, magnesium sulfate, barium sulfate, or aluminum sulfate.
  • a method without using a metal-containing compound such as metallic salt is preferred, and the above-mentioned method of coagulation by acid treatment or by freezing and then thawing is preferred.
  • the content of iodine atoms and/ or bromine atoms in the perfluoroelastomer (A) is preferably not less than 0.05 % by mass, more preferably not less than 0.10 % by mass, further preferably not less than 0.15 % by mass, from the viewpoint of satisfactory compression set of a molded article produced using the perfluoroelastomer.
  • the content of iodine atoms and/ or bromine atoms is preferably not more than 1.5 % by mass, more preferably not more than 1.2 % by mass, further preferably not more than 1.0 % by mass, from the viewpoint of reduction of an amount of expensive iodine /bromine compounds to be used and satisfactory tensile properties of a molded article produced using the perfluoroelastomer.
  • the perfluoroelastomer (A) of the present invention does not comprise a monomer having cure site such as a nitrile-containing fluorinated olefin or a nitrile-containing fluorinated vinyl ether.
  • the organic peroxide (B) may be generally an organic peroxide which easily generates radical in the presence of heat or a reducing agent. Examples thereof are, for instance,
  • dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are preferred.
  • kind and amount of the organic peroxide are selected generally in consideration of an amount of active -O-O-, a decomposition temperature, etc.
  • organic peroxides having a ten-hour half-life temperature of 100° to 140 0 C for example, t-butyl peroxybenzoate, dicumyl peroxide,
  • the amount of the organic peroxide (B) is preferably not less than 0.1 part by mass, more preferably not less than 0.2 part by mass, further preferably not less than 0.3 part by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint of improvement in a degree of crosslinking of the obtained perfluoroelastomer composition.
  • the amount of the organic peroxide (B) is preferably not more than 2.5 parts by mass, more preferably not more than 2 parts by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint that the amount of the organic peroxide (B) which is difficult to be kneaded can be decreased.
  • the composition of the present invention comprises the compound (C) having at least two double bonds in its molecule which is a crosslinking agent.
  • triallyl cyanurate triallyl isocyanurate (TAIC), TAIC prepolymer, trimethallyl isocyanurate, triacryl formal, triallyl trimellitate, N,N'-n-phenylenebismaleimide, diallyl phthalate, tetraallyl terephthalateamide, triallyl phosphate, bismaleimide, fluorinated triallylisocyanurate( 1 ,3,5-tris(2,3,3-trifluoro-2-propenyl)- 1 ,3,5-triazine- 2,4,6-trion), tris(diallylamine)-S-triazine, triallyl phosphite, N,N-diallyl acrylamide, hexaallyl phosphoramide, N,N,N',N'-tetraallyl tetraphthalamide, N,N,N',N'-tetraallyl malonamide, trivinyl isocyanur
  • the amount of the compound (C) having at least two double bonds in its molecule is preferably not less than 0.1 part by mass, more preferably not less than 0.2 part by mass, further preferably not less than 0.3 part by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint of improvement in a degree of crosslinking of the obtained perfluoroelastomer composition.
  • the amount of the compound (C) having at least two double bonds in its molecule is preferably not more than 2.5 parts by mass, more preferably not more than 2 parts by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint that the amount of the compound (C) having at least two double bonds in its molecule which is difficult to be kneaded can be decreased.
  • the total amount of the organic peroxide (B) and the compound (C) having at least two double bonds in its molecule is preferably not less than 0.5 part by mass, more preferably not less than 0.8 part by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint of improvement in a degree of crosslinking of the obtained perfluoroelastomer composition.
  • the total amount of the organic peroxide (B) and the compound (C) having at least two double bonds in its molecule is preferably not more than 3.0 parts by mass, more preferably not more than 2.5 parts by mass, further preferably not more than 2.0 parts by mass based on 100 parts by mass of the perfluoroelastomer (A), from the viewpoint that the amounts of the organic peroxide (B) and the compound (C) which are difficult to be kneaded can be decreased.
  • the perfluoroelastomer composition to be used for the crosslinked molded article of the present invention can be prepared by mixing each of the above-mentioned components with usual elastomer processing equipment, for example, an open roll, a Banbury mixer or a kneader. In addition, the composition can be prepared also by a method of using an internal mixer.
  • the crosslinked molded article of the present invention does not contain additives which can be generating sources of particles and outgas. Examples of such additives are, for instance, a filler, a processing aid, a plasticizer, a coloring agent, an antioxidant, a crosslinking accelerator, an acid acceptor, and the like.
  • Examples of a filler are inorganic fillers and organic fillers.
  • Examples of an organic filler are imide fillers having an imide structure such as polyimide, polyamide imide and polyether imide; ketone engineering plasties such as polyether ether ketone (PEEK) and polyether ketone (PEK) and engineering plasties such as polyarylate, polysulfone, polyether sulfone, polyphenylene sulfide, and polyoxybenzoate.
  • fluoro polymers such as polytetrafluoroethylene (PTFE), copolymers (PFA) of perfluoro olefins and perfluoro (alkyl vinyl ethers), tetrafluoroethylene/hexafluoro propylene copolymer, polyvinylidene fluoride, polyvinyl fluoride and polychlorotrifluoroethylene powder.
  • PTFE polytetrafluoroethylene
  • PFA copolymers
  • alkyl vinyl ethers alkyl vinyl ethers
  • tetrafluoroethylene/hexafluoro propylene copolymer polyvinylidene fluoride
  • polyvinyl fluoride polyvinyl fluoride
  • polychlorotrifluoroethylene powder polychlorotrifluoroethylene powder
  • an inorganic filler examples include metallic oxide fillers such as aluminum oxide, silicon oxide, yttrium oxide and titanium oxide; metallic carbides such as silicon carbide and aluminum carbide; metallic nitride fillers such as silicon nitride and aluminum nitride; fluoride fillers such as aluminum fluoride and carbon fluoride; and generally used fillers such as barium sulfate, carbon black, silica, clay, talc and calcium carbonate.
  • processing aids are higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic amide; higher fatty acid ester such as ethyl oleate; higher fatty acid amines such as stearylamine and oleylamine; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as vaseline and paraffin; silicone oil, silicone polymer, low molecular weight polyethylene, phthalic acid esters, phosphoric esters, rosin, (halogenated) dialkylamine, (halogenated) dialkylsulfone, surfactants, and the like.
  • higher fatty acids such as stearic acid, oleic acid, palm
  • plasticizer examples include, for instance, phthalic acid derivatives and sebacic acid derivatives. Also there are fluorine-containing oils such as perfluoro polyether.
  • coloring agents are condensation azo pigments, isoindolenone pigments, quinacridone pigments, dike to pyrro Io pyrrole pigments, and anthraquinone pigments.
  • coloring agents there are carbon black, barium sulfate, titanium oxide, zinc oxide, silica, magnesium carbonate, calcium carbonate, clay, and the like.
  • antioxidants are amine, phenol, sulfur and phosphorus compounds, and nonlimiting examples thereof are triphenyl phosphite and polyphenylene sulfide resin.
  • Compounds having anti-oxidation effect against plasma are those used as an organic pigment and an antioxidant.
  • Examples of a crosslinking accelerator are inorganic oxides, inorganic nitrides and carbon materials. Specifically there are compounds having adsorptivity of water and alcohol and compounds having a base site. Examples of compounds having adsorptivity of water and alcohol are, for instance, molecular sieves, magnesium sulfate, sodium sulfate, activated carbon and mesoporous silica.
  • Examples of compounds having a base site are, for instance, (1) alkali metal, alkali earth metal and oxides thereof, (2) silica, alumina, carbon and activated carbon which contain an alkali metal, alkali earth metal or oxide thereof, (3) inorganic nitrides such as silicon nitride (Si3N4) and AlN, and (4) silica, alumina, carbon and activated carbon having amine functional group on their surfaces.
  • Examples of the compounds of (1) to (4) are magnesium oxide, aluminum oxide, sodium oxide, zinc oxide, silver oxide, aluminum oxide, titanium oxide, tin oxide, hydro talcite, xonotlite, wollastonite, talc, attapulgite, bentonite, zeolite, clay, pyrophyllite, and selenite.
  • organic salts such as quaternary ammonium salts and phosphonium salts are exemplified as a crosslinking accelerator.
  • an acid acceptor examples include magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, hydro talcite, proton sponge (l,8-bis-(dimethylamino)naphthalene, available from Aldrich), and octadecylamine.
  • a pre-molded article For producing a pre-molded article from the above-mentioned composition, usual methods may be employed, such as a method of heating and compressing in a metal mold, a method of putting in a heated metal mold under pressure and a method of extruding with an extruder.
  • a crosslinked molded article can be obtained by steam crosslinking after the extrusion.
  • crosslinking conditions are not limited particularly, and the crosslinking can be carried out under usual crosslinking conditions for perfluoroelastomers.
  • a crosslinked article can be obtained by charging the above-mentioned perfluoroelastomer composition in a metal mold, carrying out press-crosslinking by holding under pressure at 120° to 250°C (preferably 140° to 180°C) for 1 to 120 minutes, and subsequently carrying out oven-crosslinking by holding in the air or in an inert gas in an oven at 120° to 320°C (preferably 140° to 240 0 C, more preferably 160° to 220 0 C) for 0 to 48 hours (preferably 2 to 12 hours).
  • 120° to 250°C preferably 140° to 180°C
  • oven-crosslinking by holding in the air or in an inert gas in an oven at 120° to 320°C (preferably 140° to 240 0 C, more preferably 160° to 220 0 C) for 0 to 48 hours (preferably 2 to 12 hours).
  • a metal content of the crosslinked molded article produced by crosslinking and molding the perfluoroelastomer composition is preferably not more than 100 ppm, more preferably not more than 50 ppm, further preferably not more than 30 ppm, from the viewpoint of prevention of contamination of semiconductor manufacturing equipment due to elution of a minute amount of metal.
  • a haze value of the crosslinked molded article produced by crosslinking and molding the perfluoroelastomer composition is preferably not more than 50 %, more preferably not more than 40 %, further preferably not more than 30 %, from the viewpoint that contaminants and foreign matters which are possibly mixed in a step for producing the molded article can be detected.
  • the tensile strength of the crosslinked molded article produced by crosslinking and molding the perfluoroelastomer composition is preferably not less than 8 MPa, more preferably not less than 9 MPa, further preferably not less than 10 MPa.
  • the tensile strength can be measured according to JIS K6251.
  • the crosslinked molded article of the present invention is excellent in chemical resistance, mechanical strength and heat resistance, and is suitable, for example, as a sealing material for semiconductor equipment.
  • the sealing material are O-ring, square ring, gasket, packing, oil seal, bearing seal, lip seal, etc.
  • the semiconductor manufacturing equipment is not limited particularly to equipment for producing semiconductors and encompasses whole manufacturing equipment used in the field of semiconductors where a high degree of cleanness is required, such as equipment for manufacturing a liquid crystal panel and a plasma panel. Examples of the semiconductor manufacturing equipment are as follows.
  • 1,000 g out of the obtained aqueous dispersion was diluted with 1,000 g of pure water, and the diluted dispersion was slowly added with stirring to 8,000 g of 3.5 % by mass aqueous solution of hydrochloric acid. After completion of the addition, the solution was stirred for 5 minutes, and then coagulated polymer was filtered off, and the obtained polymer was poured into 5,000 g of pure water, followed by stirring for five minutes and was filtered off again. Then washing with water and filtering off were repeated, and when a pH value of the washing water after the washing became 6 or more, the polymer was taken out.
  • this polymer was one comprising the monomer units of TFE /PMVE having a percent by mole ratio of 75.9/24.1.
  • a Mooney viscosity of this polymer (ML1+20, 140 0 C) was 86. Iodine content in the polymer was 0.16 % by mass. The polymer was not melted sufficiently at 100 0 C, and a Mooney viscosity could not be measured. The results of evaluation are shown in Tables 1 and 2. 3. Evaluation of crosslinked molded article The obtained perfluoroelastomer A, triallyl isocyanurate
  • a vulcanization curve of this perfluoroelastomer composition was obtained at 160 0 C according to JIS K6300-2 using a rubber processability analyzer RPA2000 (available from Alfa Technologies Japan LLC), and induction time (TlO), 90 % vulcanization time (T90), maximum torque and minimum torque were determined. Evaluation results are shown in Table 2.
  • this perfluoroelastomer composition was subjected to press-crosslinking at 160 0 C for ten minutes and further heating at
  • Hardness (Shore A) of a molded article is measured according to JIS K6253. (Specific gravity)
  • Specific gravity of a molded article is measured according to JIS K6268.
  • Compression set of a sample of crosslinked O-ring is measured at 20 % compression at 200 0 C for five hours according to JIS
  • Haze value of a 2 mm thick sheet of crosslinked molded article is measured using a haze meter (Haze Guard II available from Kabushiki Kaisha Toyo Seiki Seisakusho) according to ASTM D 1003. (Metal content)
  • ND means that no metal component is detected.
  • TFE/ PMVE (% by mole) 75.9/24.1 70.4/29.6 68.1/31.9 66.7/33.3 63.3/36.7 Iodine content (% by mass) 0.16 0.24 0.24 0.24 0.22
  • Blending amount (part by mass) Perfluoroelastomer A 100 Perfluoroelastomer B 100 Perfluoroelastomer C 100 Perfluoroelastomer D 100 Perfluoroelastomer E 100 Triallyl isocyanurate 0.5 0.5 0.5 0.5 0.5 0.5 PERHEXA 25B 0.5 0.5 0.5 0.5 0.5 ⁇ en
  • a tensile strength can be significantly improved by increasing a TFE unit content of a copolymer comprising a TFE unit and a PAVE unit.
  • the crosslinked molded article obtained by crosslinking and molding the perfluoroelastomer composition comprises the perfluoroelastomer forming the crosslinked molded article and the crosslinking agents and contains no additives, it is transparent, has satisfactory mechanical properties and can be expected especially to be a sealing material for semiconductor manufacturing equipment.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un article réticulé moulé obtenu par réticulation et moulage d'une composition d'élastomère perfluoré qui ne comprend aucun additif générant un dégagement gazeux ou des particules telles que du noir de carbone, de l'oxyde de zinc ou de l'éponge à protons, et qui permet d'améliorer sensiblement la résistance à la traction de l'article moulé. Cet article est transparent et possède des propriétés mécaniques satisfaisantes. Il est obtenu en réticulant et en moulant une composition d'élastomère perfluoré comprenant (A) un élastomère perfluoré portant des atomes d'iode et/ou de brome et comprenant 20 à 35 % en mole d'un motif d’éther perfluorovinylique (a) et 65 à 80 % en mole d'un motif de tétrafluoroéthylène (b), (B) un peroxyde organique, et (C) un composé avec au moins deux doubles liaisons par molécule.
PCT/JP2009/071523 2008-12-29 2009-12-17 Composition d’elastomere perfluore, et article reticule moule obtenu par reticulation et moulage de ladite composition WO2010076876A1 (fr)

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Cited By (7)

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US9018309B2 (en) 2010-09-24 2015-04-28 Greene, Tweed Technologies, Inc. Fluorine-containing elastomer compositions suitable for high temperature applications
US9365712B2 (en) 2010-09-24 2016-06-14 Greene, Tweed Technologies, Inc. Fluorine-containing elastomer compositions suitable for high temperature applications
US9982091B2 (en) 2014-03-06 2018-05-29 3M Innovative Properties Company Highly fluorinated elastomers
US10513626B2 (en) 2013-06-26 2019-12-24 3M Innovative Properties Company Stain resistant microsphere articles
US10557031B2 (en) 2015-10-23 2020-02-11 3M Innovative Properties Company Composition including amorphous fluoropolymer and fluoroplastic particles and methods of making the same
JPWO2020184427A1 (fr) * 2019-03-08 2020-09-17
US11111326B2 (en) 2013-12-11 2021-09-07 3M Innovative Properties Company Highly fluorinated elastomers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9018309B2 (en) 2010-09-24 2015-04-28 Greene, Tweed Technologies, Inc. Fluorine-containing elastomer compositions suitable for high temperature applications
US9365712B2 (en) 2010-09-24 2016-06-14 Greene, Tweed Technologies, Inc. Fluorine-containing elastomer compositions suitable for high temperature applications
US10513626B2 (en) 2013-06-26 2019-12-24 3M Innovative Properties Company Stain resistant microsphere articles
US11111326B2 (en) 2013-12-11 2021-09-07 3M Innovative Properties Company Highly fluorinated elastomers
US9982091B2 (en) 2014-03-06 2018-05-29 3M Innovative Properties Company Highly fluorinated elastomers
US10557031B2 (en) 2015-10-23 2020-02-11 3M Innovative Properties Company Composition including amorphous fluoropolymer and fluoroplastic particles and methods of making the same
JPWO2020184427A1 (fr) * 2019-03-08 2020-09-17
EP3936534A4 (fr) * 2019-03-08 2022-11-23 Agc Inc. Composition à base d'un copolymère contenant du fluor, caoutchouc réticulé et son procédé de production
JP7400805B2 (ja) 2019-03-08 2023-12-19 Ａｇｃ株式会社 含フッ素共重合体組成物、架橋ゴムおよびその製造方法

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