Classifications

• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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

Definitions

• the present invention relates to a fluoroelastomer composition and a method for producing a crosslinked product.
• Fluoroelastomers especially fluoroelastomers that do not have hydrogen atoms bonded to carbon atoms, such as perfluoroelastomers, are excellent in mechanical properties, chemical resistance, and heat resistance.
• perfluoroelastomers In aviation, general equipment, chemical plants, industrial equipment, robot parts, etc., they are used as O-rings, gaskets, seal parts, valves and the like. Since the fluoroelastomer has the highest heat resistance among rubber-based materials, it is suitable for use in a high-temperature environment as a drilling member represented by oil drilling or a member around a furnace. However, improvement of the heat resistance of fluoroelastomers is being studied so that it can be used even at higher temperatures.
• a method for improving the heat resistance of a crosslinked product of fluoroelastomer a method of changing the composition of the fluoroelastomer composition or a method of changing the method of crosslinking the fluoroelastomer composition is known.
• a crosslinking method of a fluoroelastomer composition for improving the heat resistance of a crosslinked product of a fluoroelastomer a perfluoroelastomer having an iodine atom as a crosslinking site at a polymer chain terminal is used as a crosslinking aid in the presence of a peroxide.
• Patent Document 1 A method of crosslinking using triallyl isocyanurate (hereinafter also referred to as “TAIC”) (Patent Document 1), a method of crosslinking using 1,6-divinylperfluorohexane (Patent Document 2), and fluorine.
• Patent Documents 3 and 4 A method of crosslinking using an aromatic compound contained therein (Patent Documents 3 and 4) is known.
• metal oxides such as zinc oxide and magnesium oxide, basic phosphorus Acid acceptors such as lead acid are used in the processing of crosslinked products.
• a fluoroelastomer composition containing a peroxide-crosslinkable fluoroelastomer, zinc oxide, a metal oxide other than basic metal hydroxide or zinc oxide, and an organic peroxide is known (Patent Document 5). .
• the present invention provides a fluoroelastomer composition having the following configurations [1] to [12] and a method for producing a crosslinked product.
• a fluoroelastomer composition comprising a fluoroelastomer and a metal oxide, wherein the metal oxide has an average particle size of 75 nm or less.
• the metal oxide is hydrophobized with one or more hydrophobizing agents selected from the group consisting of siloxane hydrophobizing agents, silazane hydrophobizing agents, and silane hydrophobizing agents.
• hydrophobizing agents selected from the group consisting of siloxane hydrophobizing agents, silazane hydrophobizing agents, and silane hydrophobizing agents.
• the fluoroelastomer is a fluoroelastomer having no hydrogen atom bonded to a carbon atom.
• a method for producing a crosslinked product characterized in that a crosslinked product is obtained by performing secondary crosslinking at a high temperature of 360 ° C. or lower.
• the fluoroelastomer composition of the present invention can be suitably used in the method for producing a crosslinked product of the present invention. According to the method for producing a crosslinked product of the present invention, a crosslinked fluoroelastomer product having extremely excellent heat resistance can be obtained.
• “Fluoromonomer” means a monomer containing a fluorine atom.
• the “perfluoromonomer” means a monomer in which all hydrogen atoms bonded to carbon atoms in the monomer are replaced with fluorine atoms.
• the “structural unit” means a portion derived from a monomer formed by polymerization of the monomer.
• the structural unit may be a unit directly formed by a polymerization reaction of monomers, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
• “Main chain” refers to a portion having the maximum number of carbon atoms in a carbon chain formed by polymerization of monomers.
• “Side chain” means a moiety bonded to a main chain formed by polymerization of monomers.
• the fluoroelastomer composition of the present invention contains a fluoroelastomer and a specific metal oxide.
• a fluoroelastomer is a copolymer having rubber elasticity containing a constitutional unit based on a fluoromonomer.
• the fluorine atom may be bonded to the carbon atom constituting the main chain, or may be bonded to the carbon atom constituting the side chain.
• the fluorine content in the fluoroelastomer is preferably 40 to 75% by mass, more preferably 45 to 75% by mass, and still more preferably 50 to 75% by mass. When the fluorine content in the fluoroelastomer is within the above range, a crosslinked product excellent in mechanical properties, chemical resistance, and heat resistance is easily obtained.
• the fluorine content in the fluoroelastomer is the ratio of the total mass of all fluorine atoms in the total mass of the fluoroelastomer.
• fluoroelastomer a fluoroelastomer having no CH described later is preferable.
• fluoroelastomers not having CH CF elastomers described later, CX elastomers described below, and CG elastomers described below are more preferable, CF elastomers and CX elastomers are more preferable, and the chemical resistance and heat resistance of the crosslinked product are excellent. Therefore, CF elastomer is particularly preferable.
• the fluoroelastomer having no CH is a fluoroelastomer having no hydrogen atom bonded to a carbon atom.
• the content of hydrogen atoms in the fluoroelastomer not having CH is 0.1% by mass or less.
• the fluoroelastomer which does not have CH has at least one of an iodine atom and a bromine atom. The iodine atom and bromine atom function as a crosslinking point.
• the iodine atom and bromine atom that function as a crosslinking point may be present at at least one of the end of the main chain and the side chain, and the end of the main chain and the end of the branched carbon chain when the fluoroelastomer has a branched structure ( Hereinafter, they are collectively referred to as “the end of the polymer chain”).
• iodine atoms and bromine atoms that function as crosslinking points are referred to as “iodine atoms and the like”.
• the “CF elastomer” is a perfluoromonomer having a carbon atom and a fluorine atom and may contain an etheric oxygen atom, but does not contain an atom other than the carbon atom, the fluorine atom and the etheric oxygen atom. (Hereinafter also referred to as “monomer CF”). In addition, you may have an iodine atom etc. only in the terminal of a polymer chain.
• monomer CF perfluoroolefin and perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”) are preferable.
• PAVE perfluoroolefin and perfluoro (alkyl vinyl ether)
• the CF elastomer a copolymer having a structural unit based on perfluoroolefin and PAVE is used. preferable.
• Perfluoroolefin is a monomer in which all of the hydrogen atoms bonded to the carbon atoms of the alkene having a carbon-carbon double bond are replaced with fluorine atoms.
• the perfluoroolefin include tetrafluoroethylene (hereinafter also referred to as “TFE”) and hexafluoropropylene (hereinafter also referred to as “HFP”).
• TFE tetrafluoroethylene
• HFP hexafluoropropylene
• perfluoroolefins other than TFE and HFP are referred to as “other perfluoroolefins”.
• One perfluoroolefin may be used, or two or more perfluoroolefins may be used.
• PAVE is preferably a compound of the following formula (1) (hereinafter also referred to as “compound (1)”).
• CF 2 CFO (R f11 O) n (R f12 O) m R f1 (1)
• R f11 represents a linear or branched perfluoroalkylene group having 2 to 6 carbon atoms
• R f12 represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms different from R f11.
• An alkylene group, m and n are each independently an integer of 0 to 10
• R f1 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms.
• Specific examples are perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (methoxyethyl vinyl ether), perfluoro (ethoxyethyl vinyl ether), perfluoro (propoxypropyl vinyl ether).
• Perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether) are preferable.
• R f11 in the above formula (1) is CF 2 CF 2
• R f12 is CF 2
• R f1 is a linear or branched perfluoro having 1 to 4 carbon atoms.
• examples thereof include an alkyl group, n is 0 to 3, m is 0 to 4, and (n + m) is 1 to 7.
• Specific examples include CF 2 ⁇ CFO— (CF 2 CF 2 O) — (CF 2 O) 4 —CF 3 , CF 2 ⁇ CFO— (CF 2 CF 2 O) — (CF 2 O) 2 —CF 3.
• CF 2 ⁇ CFO— (CF 2 CF 2 O) 2 —CF 2 CF 3 , CF 2 ⁇ CFO— (CF 2 O) —CF 3 , CF 2 ⁇ CFO— (CF 2 O) 2 —CF 3 CF 2 ⁇ CFO— (CF 2 CF 2 O) — (CF 2 O) 4 —CF 3 , CF 2 ⁇ CFO— (CF 2 CF 2 O) — (CF 2 O) 2 —CF 3 , CF 2 CFO- (CF 2 CF 2 O) 2 -CF 2 CF 3 is preferred.
• PAVE may use 1 type and may use 2 or more types.
• CF elastomers examples include TFE / PAVE copolymers, HFP / PAVE copolymers, and TFE / PAVE / HFP copolymers that may have iodine atoms only at the ends of the polymer chains.
• a TFE / PAVE copolymer which may have an iodine atom or the like only at the chain end is preferred.
• the CF elastomer may have a structural unit based on another monomer CF in addition to the structural unit based on perfluoroolefin or PAVE.
• Examples of the other monomer CF include a compound represented by the following formula (2) (hereinafter also referred to as “compound (2)”).
• R f2 is a linear or branched perfluoroalkylene group or one or more etheric oxygen atoms in a linear or branched perfluoroalkylene group having 1 to 25 carbon atoms, having 1 to 25 carbon atoms It is a group containing. ]
• the CF elastomer When the CF elastomer has a structural unit based on the compound (2), it becomes a fluoroelastomer having a branched chain structure, and the average number of polymer chain ends per molecule exceeds 2. Therefore, the number of iodine atoms or the like functioning as a crosslinking point is increased, and the structural unit based on the compound (2) is compared with a fluoroelastomer having a straight chain having no branched chain and having 2 terminal groups of the polymer chain.
• the CF elastomer has excellent crosslinking reactivity.
• the content of the structural unit based on PAVE is 100 as the sum of the structural unit based on perfluoroolefin and the structural unit based on PAVE.
• the molar ratio is preferably 20 to 70, more preferably 25 to 50, and particularly preferably 30 to 45.
• the CF elastomer has a structural unit based on another monomer CF in addition to the structural unit based on perfluoroolefin or PAVE
• the content of the structural unit based on the other monomer CF is the entire structural unit constituting the CF elastomer.
• the molar ratio is preferably 0.01 to 5, more preferably 0.01 to 3, and particularly preferably 0.05 to 1.
• the total content of iodine atoms and bromine atoms in the CF elastomer is preferably from 0.1 to 30 ⁇ mol / g, more preferably from 0.2 to 20 ⁇ mol / g, as the molar amount per gram of the CF elastomer.
• a fluoroelastomer composition containing a CF elastomer in which the total content of iodine atoms and bromine atoms in the CF elastomer is within this range is excellent in crosslinking reactivity.
• TFE / PAVE copolymer or TFE / PAVE / others may have an iodine atom only at the end of the main chain in that the number of crosslinking reaction points can be controlled and rubber characteristics are easily developed.
• the monomer CF copolymer is particularly preferred.
• CF elastomers include TFE / PAVE copolymer, HFP / PAVE copolymer, TFE / HFP / PAVE copolymer, TFE / other perfluoroolefin copolymers, HFP / other perfluoroolefin copolymers.
• examples thereof include polymers, TFE / HFP / other perfluoroolefin copolymers, and the like.
• the “CX elastomer” includes one or more atoms selected from an iodine atom, a bromine atom and a chlorine atom in addition to a carbon atom and a fluorine atom, and may include an etheric oxygen atom. It is a fluoroelastomer containing a structural unit based on a fluoromonomer containing no atoms (hereinafter also referred to as “monomer CX”). The CX elastomer preferably includes a structural unit based on the monomer CF in addition to the structural unit based on the monomer CX.
• CF 2 CFCl
• CF 2 CFBr
• CF 2 CFI
• CF 2 CFOCF 2 CF 2 Cl
• CF 2 CFOCF 2 CF 2 Br
• CF 2 CFBr
• CF 2 CFOCF 2 CF 2 Br
• the CX elastomer is a fluoroelastomer having an iodine atom or the like that functions as a crosslinking point in the side chain when it has a structural unit based on the monomer CX having an iodine atom or a bromine atom.
• a fluoroelastomer having an iodine atom or the like at the end of the polymer chain is used.
• the CX elastomer is a copolymer having a perfluoroolefin and a structural unit based on PAVE
• the total of the structural unit based on PAVE when the total of the structural unit based on perfluoroolefin and the structural unit based on PAVE is 100
• the preferred content is the same as the preferred content in the CF elastomer.
• the CX elastomer has a structural unit based on the other monomer CF in addition to the structural unit based on perfluoroolefin or PAVE
• the total monomer unit constituting the CX elastomer is assumed to be 100.
• the preferable content of the structural unit based on it is the same as the preferable content in the CF elastomer.
• the content of the structural unit based on the monomer CX in the CX elastomer is preferably 0.01 to 5 and preferably 0.01 to 3 in terms of molar ratio, where the total of all the structural units in the CX elastomer is 100. More preferably, 0.05 to 1 is particularly preferable.
• the “CG elastomer” includes one or more groups selected from the group consisting of nitrile groups, aminocarbonyl groups, carboxyl groups, and ester groups in addition to carbon atoms and fluorine atoms, and etheric oxygen atoms.
• a fluoroelastomer comprising a structural unit based on a perfluoromonomer that does not contain other atoms and other groups (hereinafter also referred to as “monomer CG”).
• the CG elastomer may include at least one of a structural unit based on the monomer CF and a structural unit based on the monomer CX in addition to the structural unit based on the monomer CG.
• the CG elastomer preferably includes a structural unit based on the monomer CF in addition to the structural unit based on the monomer CG.
• a fluoroelastomer having an iodine atom or the like at the end of the polymer chain is preferable.
• G is a nitrile group, aminocarbonyl group, carboxy group, or ester group
• n is an integer of 1 to 10.
• the ester group is a group represented by —C ( ⁇ O) O—R G
• R G is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms.
• perfluoro 8-cyano-5-methyl-3,6-dioxa-1-octene
• the CG elastomer is a copolymer having a perfluoroolefin and a structural unit based on PAVE
• the total of the structural unit based on PAVE when the total of the structural unit based on perfluoroolefin and the structural unit based on PAVE is 100
• the preferred content is the same as the preferred content in the CF elastomer.
• the CG elastomer has a structural unit based on the other monomer CF in addition to the structural unit based on perfluoroolefin or PAVE, the total of all the structural units constituting the CG elastomer is assumed to be 100.
• the preferable content of the structural unit based on it is the same as the preferable content in the CF elastomer.
• the preferable content of the structural unit based on the monomer CX is preferably the content in the CX elastomer when the total of all the structural units constituting the CG elastomer is 100. It is the same.
• the content of the structural unit based on the monomer CG in the CG elastomer is preferably 0.01 to 5 and preferably 0.01 to 3 in terms of molar ratio when the total of all the structural units in the CG elastomer is 100. More preferably, 0.05 to 1 is particularly preferable.
• the fluoroelastomer in the present invention may be a fluoroelastomer having a hydrogen atom bonded to a carbon atom (hereinafter also referred to as “CH elastomer”).
• the CH elastomer includes a structural unit based on a monomer having a hydrogen atom bonded to a carbon atom or a fluoromonomer having a hydrogen atom bonded to a carbon atom (hereinafter also referred to as “monomer CH”).
• the CH elastomer may further include a structural unit based on one or more monomers selected from the monomer CF, the monomer CX, and the monomer CG.
• the CH elastomer preferably contains a structural unit based on the monomer CF in addition to the structural unit based on the monomer CH.
• the hydrogen atom content in the CH elastomer is more than 0.1% by mass.
• the monomer CH examples include vinyl fluoride, vinylidene fluoride (hereinafter also referred to as “VdF”), trifluoroethylene, tetrafluoropropene such as 2,3,3,3-tetrafluoro-1-propene, A pentafluoropropene is mentioned.
• CH elastomer examples include TFE / propylene copolymer, TFE / propylene / VdF copolymer, TFE / propylene / vinyl fluoride copolymer, TFE / propylene / trifluoroethylene copolymer, TFE / propylene / Pentafluoropropene copolymer, TFE / propylene / chlorotrifluoroethylene copolymer, TFE / propylene / ethylidene norbornene copolymer, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / HFP / PAVE Copolymer, VdF / chlorotrifluoroethylene copolymer, VdF / tetrafluoropropene copolymer, HFP / ethylene copolymer, VdF / TFE / PAVE copolymer, VdF
• the Mooney viscosity of the fluoroelastomer is preferably 50 to 250, more preferably 50 to 200, and particularly preferably 50 to 150.
• Mooney viscosity is a measure of molecular weight. When Mooney viscosity is large, that is, when the molecular weight is high, the physical properties of the crosslinked product are good, but the fluidity is low and the processability tends to be poor. On the other hand, when the Mooney viscosity is small, that is, the molecular weight is low, the fluidity is high and the processability is good, but the physical properties of the crosslinked product tend to be poor. When the Mooney viscosity of the fluoroelastomer is in the above range, the processability is excellent, and the crosslinked product is excellent in rubber properties.
• Mooney viscosity is measured according to JIS K6300 using a large rotor with a diameter of 38.1 mm and a thickness of 5.54 mm at 100 ° C. with a preheating time of 1 minute and a rotor rotation time of 4 minutes.
• Storage elastic modulus can also be used as a measure of molecular weight.
• the storage elastic modulus of the fluoroelastomer is preferably 50 to 700 kPa, more preferably 300 to 650 kPa, and particularly preferably 400 to 600 kPa.
• the storage elastic modulus is large, that is, the molecular weight is high, the physical properties of the crosslinked product are good, but the fluidity tends to be low and the processability tends to be poor.
• the storage elastic modulus is small, that is, the molecular weight is low, the fluidity is high and the processability is good, but the physical properties of the crosslinked product tend to be poor.
• the storage elastic modulus of the fluoroelastomer is in the above range, the processability is excellent, and the crosslinked product is excellent in rubber properties.
• the storage elastic modulus is measured at a temperature of 100 ° C., an amplitude of 0.5 degrees, and a vibration frequency of 50 times / minute according to ASTM D5289 and ASTM D6204 using a dynamic viscoelasticity measuring apparatus (RPA2000 manufactured by Alpha Technologies).
• the fluoroelastomer composition of the present invention contains a metal oxide that exhibits a function as an acid acceptor, and the metal oxide has an average particle size of 75 nm or less.
• the metal oxide is added to the fluoroelastomer composition as an acid acceptor for reacting with a hydrogen halide generated by thermal decomposition of the polymer to stabilize the fluoroelastomer.
• the present inventor has found that a crosslinked product that is remarkably excellent in heat resistance can be obtained by setting the average particle size to 75 nm or less.
• the average particle diameter of the metal oxide is preferably 5 to 60 nm, more preferably 5 to 50 nm, and further preferably 10 to 40 nm.
• the average particle diameter in this invention is an average particle diameter by the specific surface area conversion method.
• the metal oxides that have been used so far include monovalent or divalent metal oxides such as zinc oxide, magnesium oxide, sodium oxide, calcium oxide, barium oxide, lead oxide, and copper oxide. These metal oxides can also be used in the present invention. Of these, zinc oxide and magnesium oxide are preferable, and zinc oxide is more preferable.
• the content of the metal oxide in the fluoroelastomer composition of the present invention is preferably 1 to 20 parts by mass, more preferably 1.5 to 15 parts by mass, and more preferably 1.5 to 10 parts by mass with respect to 100 parts by mass of the fluoroelastomer. Part by mass is more preferable. If the content of the metal oxide in the fluoroelastomer composition of the present invention is not less than the lower limit of the above range, the fluoroelastomer composition is excellent in heat resistance, and if it is not more than the upper limit of the above range, the metal oxide is contained. The effect of improving the physical properties according to the amount is sufficiently obtained, and the dispersibility of the metal oxide in the fluoroelastomer is good.
• the metal oxide in the fluoroelastomer composition of the present invention is preferably zinc oxide having an average particle size of 5 to 60 nm, more preferably zinc oxide having an average particle size of 5 to 50 nm, from the viewpoint of availability. More preferred is zinc oxide having a diameter of 10 to 40 nm.
• the metal oxide in the present invention preferably has a hydrophobic particle surface.
• the particle surface is hydrophobized with one or more hydrophobizing agents selected from the group consisting of siloxane hydrophobizing agents, silazane hydrophobizing agents, and silane hydrophobizing agents. More preferably.
• Siloxane hydrophobizing agents include methylhydrogenpolysiloxane, dimethyldisiloxane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, methylhydrogendisiloxane, dimethyl Examples thereof include polysiloxane and amino-modified siloxane.
• silazane hydrophobizing agent examples include hexamethyldisilazane, trimethyldisilazane, tetramethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, diphenyltetramethyldisilazane, divinyltetramethyldisilazane, and the like.
• silane hydrophobic treatment agent examples include 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and the like.
• the hydrophobizing agent a siloxane-based hydrophobizing agent is more preferable, and methyl hydrogen polysiloxane (hydrogen dimethicone) is particularly preferable.
• the particle surface may be surface-treated with the hydrophobizing agent and silica.
• the fluoroelastomer composition of the present invention preferably further contains a crosslinking agent.
• a known crosslinking agent can be used.
• the fluoroelastomer has an iodine atom or the like, it is preferable to use an organic peroxide as a crosslinking agent.
• the organic peroxide increases the reaction probability of the crosslinking point, and contributes to the improvement of the mechanical properties, chemical resistance, and heat resistance of the crosslinked product.
• a fluoroelastomer has a nitrile group, it is preferable to use an organotin compound.
• the organic peroxide only needs to generate radicals easily by heating.
• those having a 1-minute half-life temperature are preferably 80 to 220 ° C., and diisopropyl peroxydicarbonate, 1,1-bis (tert-hexylperoxy).
• the content of the organic peroxide in the fluoroelastomer composition is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and more preferably 0.5 to 3 parts per 100 parts by mass of the fluoroelastomer. Part by mass is particularly preferred. If the content is at least the lower limit of the above range, the fluoroelastomer composition is excellent in cross-linking reactivity, and if the content is not more than the upper limit of the above range, the organic peroxide has excellent cross-linking efficiency and decomposes. The amount of product generated is suppressed.
• the fluoroelastomer composition of the present invention preferably further contains a crosslinking aid.
• a crosslinking aid As the crosslinking aid, triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, trimethallyl isocyanurate, 1,3 , 5-triacryloylhexahydro-1,3,5-triazine, m-phenylenediamine bismaleimide, p-quinonedioxime, p, p'-dibenzoylquinonedioxime; polymethylvinylsiloxane, polymethylphenylvinylsiloxane Vinyl group-containing siloxane oligomers such as bisolefin-containing compounds; fluorine-containing aromatic compounds having two or more vinyl groups or allyl groups bonded to an
• the fluoroelastomer composition of the present invention preferably contains one or more crosslinking aids selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, bisolefin-containing compounds, and the above-mentioned fluorine-containing aromatic compounds.
• the fluorine-containing aromatic compound as the crosslinking aid is a compound having two or more groups represented by the following formula (3), and includes two or more groups represented by the following formula (3). Examples thereof include compounds bonded to a fluorine aromatic ring. [Wherein, s is 0 or 1, and R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or a fluorine atom. ]
• the fluorine-containing aromatic compound is preferably a fluorine-containing aromatic compound in which two or more hydrogen atoms of the aromatic ring are substituted with a group represented by the above formula (3).
• the aromatic ring include a benzene ring, a condensed ring containing a benzene ring (a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, etc.), an aromatic ring containing biphenyl, and the like.
• R 1 to R 4 is a fluorine atom or bonded to the aromatic ring.
• the bis-containing olefin compound includes a linear or branched alkylene group which may be substituted with a fluorine atom, or one or more etheric oxygen atoms in a linear or branched alkylene group which may be substituted with a fluorine atom.
• bonded is mentioned.
• R 41 R 42 C CR 43 ⁇ (4)
• R 41 , R 42 and R 43 each independently represents a hydrogen atom or a linear or branched alkyl group.
• crosslinking aid triallyl isocyanurate and the above-mentioned fluorine-containing aromatic compound are preferable. Of these, the fluorine-containing aromatic compound is particularly preferable because of excellent heat resistance.
• a crosslinking aid may be used individually by 1 type, and may use 2 or more types together.
• the content of the crosslinking aid in the fluoroelastomer composition is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluoroelastomer. Part is particularly preferred.
• the fluoroelastomer composition is excellent in crosslinking reactivity, and the resulting crosslinked product is excellent in chemical resistance, heat resistance, and rubber physical properties including compression set.
• the fluoroelastomer composition of the present invention may contain additives other than those described above.
• additives include acid acceptors, processing aids, scorch retarders, pigments, fillers, reinforcing materials, and the like.
• the acid acceptor examples include a monovalent or divalent metal hydroxide and hydrotalcite, in addition to a metal oxide having an average particle diameter exceeding 75 nm. Specific examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and hydrotalcite.
• the acid acceptor may be used alone or in combination of two or more.
• the content of the acid acceptor in the fluoroelastomer composition is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the fluoroelastomer as the total of the above-described metal oxide having an average particle diameter of 75 nm or less. 5 to 15 parts by mass is more preferable, and 1.5 to 10 parts by mass is particularly preferable.
• processing aids can be used.
• processing aids that exhibit a function as a lubricant include fatty acid metal salts such as sodium stearate and calcium stearate, synthetic waxes such as polyethylene wax, and fatty acid esters such as glycerin monooleate.
• Processing aids may be used alone or in combination of two or more.
• the content of the processing aid in the fluoroelastomer composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and more preferably 0.2 to 3 parts per 100 parts by weight of the fluoroelastomer. Part by mass is particularly preferred. When the content of the processing aid in the fluoroelastomer composition is within the above range, the molding processability is excellent, and the obtained cross-linked product is excellent in heat resistance.
• Scorch retarders include phenolic hydroxyl group-containing compounds such as bisphenol A, bisphenol AF, phenol, ethyl p-hydroxybenzoate, quinones such as hydroquinone and hydroquinone monomethyl ether, 2,4-bis (3-isopropylphenyl) -4-methyl-1-pentene, 2- (3-isopropylphenyl) -4- (4-isopropylphenyl) -4-methyl-1-pentene, 2,4-bis (4-methylphenyl) -4-methyl And ⁇ -methylstyrene dimers such as -1-pentene.
• a scorch retarder may be used alone or in combination of two or more.
• the content of the scorch retarder in the fluoroelastomer composition is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 2 parts per 100 parts by mass of the fluoroelastomer. Part by mass is particularly preferred.
• pigments As pigments, fillers, and reinforcing materials, carbon black, titanium oxide, silicon dioxide, clay, talc, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, TFE / ethylene copolymer, TFE / Vinylidene fluoride copolymer.
• the reinforcing material includes carbon black such as furnace black, channel black, acetylene black, thermal black, Austin black, mineral black and the like.
• carbon black such as furnace black, channel black, acetylene black, thermal black, Austin black, mineral black and the like.
• Austin Black or mineral black which is a pulverized carbon of high caking property called bituminous coal or subbituminous coal, in combination with other carbon black because the compression set of the molded product can be improved.
• the amount of Austin black and mineral black added is preferably 20 to 100% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 70% by mass with respect to the total amount of carbon black.
• the content of other additives in the fluoroelastomer composition is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the fluoroelastomer. 30 parts by mass is particularly preferred.
• the fluoroelastomer composition of this invention can be manufactured by mix
• the fluoroelastomer in the present invention can be produced by radical polymerization of a desired monomer mixture by an ordinary method.
• the radical polymerization method include known polymerization methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.
• an emulsion polymerization method using a water-soluble radical polymerization initiator is preferable.
• Emulsion polymerization is suitable for the production of high molecular weight fluoroelastomers.
• a fluoroelastomer is produced by polymerizing a monomer mixture in the presence of a radical polymerization initiator, an aqueous medium, an emulsifier, and optionally a chain transfer agent.
• the polymerization temperature is preferably 0 to 100 ° C, more preferably 10 to 90 ° C.
• the polymerization time is preferably 6 to 24 hours, and more preferably 6 to 12 hours.
• the polymerization pressure is preferably from 0.1 to 20 MPa, more preferably from 0.3 to 10 MPa. Within this range, the monomer conversion is good, the polymer yield is high, and the productivity is excellent.
• radical polymerization initiator As a radical polymerization initiator, the well-known radical polymerization initiator used for manufacture of a perfluoroelastomer is mentioned.
• the radical polymerization initiator may be appropriately selected according to the polymerization method. In the case of polymerization in an aqueous medium such as an emulsion polymerization method, a water-soluble radical polymerization initiator is preferred. In the case of solution polymerization, an organic peroxide initiator or an azo initiator is preferable. Examples of the water-soluble radical polymerization initiator include organic initiators such as persulfates such as ammonium persulfate, hydrogen peroxide, disuccinic acid peroxide, and azobisisobutylamidine dihydrochloride.
• a redox initiator comprising a combination of persulfuric acid or hydrogen peroxide and a reducing agent such as sodium bisulfite or sodium thiosulfate, or a smaller amount of iron, ferrous salt, sulfuric acid in the redox initiator. It is also preferable to use an inorganic initiator coexisting with silver or the like.
• the radical polymerization initiator may be added all at once at the start of polymerization, or may be added continuously or intermittently. From the viewpoint of the uniformity of the polymerization reaction and the controllability of the molecular weight distribution of the resulting perfluoroelastomer, it is preferably added continuously or intermittently.
• the amount of the radical polymerization initiator is preferably 0.01 to 3% by mass, more preferably 0.1 to 1% by mass, based on the total mass of all monomers.
• Examples of the aqueous medium include water and a mixture of water and a water-soluble organic solvent.
• Examples of the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• Examples of the emulsifier include emulsifiers conventionally used for emulsion polymerization. Anionic emulsifiers are more preferred because the resulting latex is excellent in mechanical and chemical stability.
• Examples of the anionic emulsifier include an anionic hydrocarbon emulsifier and an anionic fluorine-containing emulsifier.
• Examples of the anionic hydrocarbon emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate.
• Examples of the anionic fluorinated emulsifier include anionic fluorinated sulfonic acid and the like, and examples thereof include perfluorooctane sulfonic acid and C 6 F 13 CH 2 CH 2 SO 3 H.
• a method for introducing an iodine atom or the like that functions as a crosslinking point a method for introducing a chain transfer agent having an iodine atom or the like, a method for introducing a perfluoromonomer containing an iodine atom or the like by copolymerization Is mentioned.
• the iodine atom or the like that functions as a crosslinking point is present at the end of the polymer chain, the iodine atom or the like is introduced by producing a fluoroelastomer in the presence of a chain transfer agent having an iodine atom or the like. It is preferable.
• the atom functioning as a crosslinking point is more preferably an iodine atom.
• a chain transfer agent is preferable in that the molecular weight of the fluoroelastomer can be appropriately controlled.
• a compound having an iodine atom or the like is preferable. Examples thereof include a diiodo compound having two iodine atoms and a monoiodo monobromo compound having one iodine atom and one bromine atom.
• a chain transfer agent having an iodine atom or the like for the production of a fluoroelastomer having an iodine atom or the like at the end of the polymer chain.
• a compound represented by the following formula (5) or the following formula (6) hereinafter also referred to as “compound (5)” or “compound (6)” is preferable.
• R f5 and R f6 are each independently a linear or branched fluoroalkylene group having 1 to 12 carbon atoms, or a carbon atom having 2 or more carbon atoms having one or more etheric oxygen atoms between carbon atoms. 12 linear or branched fluoroalkylene groups (also referred to as “oxafluoroalkylene groups”). ]
• R f5 and R f6 are preferably a C 3-12 fluoroalkylene group or an oxafluoroalkylene group, and more preferably a C 3-12 perfluoroalkylene group.
• the compound (5) include diiododifluoromethane, 1,2-diiodoperfluoroethane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodoperfluoro Examples include pentane, 1,6-diiodoperfluorohexane, 1,7-diiodoperfluoroheptane, 1,8-diiodoperfluorooctane, 1,4-diiodoperfluorobutane, 1,6- Diiodoperfluorohexane is preferred.
• the compound (6) include 1-iodo-4-bromoper
• the chain transfer agent may be added at the start of radical polymerization, or may be added sequentially as the polymerization proceeds.
• a chain transfer agent having an iodine atom or the like is used, it is preferably added at the start of radical polymerization.
• the amount of chain transfer agent used is preferably 0.01 to 5 mol%, more preferably 0.05 to 1 mol%, based on the total number of moles of all monomers.
• a pH buffer may be used.
• the pH buffering agent include inorganic salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen carbonate, and hydrates thereof.
• Formulation method It does not specifically limit as a compounding method, A well-known method is employable. A method of kneading the essential component or the essential component and the optional component using a kneader such as an open roll, a Banbury mixer, a kneader or the like is preferable. Moreover, the method of kneading
• the fluoroelastomer composition of the present invention contains a crosslinking agent and a crosslinking aid, it is preferable to knead the crosslinking aid with the fluoroelastomer and then knead the crosslinking agent.
• the kneader is preferably water-cooled and maintained in a temperature range of 20 to 120 ° C.
• the kneading temperature is more preferably 40 to 60 ° C.
• the kneading time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes.
• a crosslinked product is obtained by primary crosslinking at a temperature of 200 ° C. or lower.
• the cross-linked product obtained by the primary cross-linking may be handled as a molded product as it is, but at the cross-linking temperature in the primary cross-linking, a longer time may be required for sufficient cross-linking. Therefore, the crosslinking may be further advanced by heating the crosslinked product obtained by the primary crosslinking in an oven or the like using electricity, hot air, steam or the like as a heat source.
• the amount of those contained in the molded body is reduced.
• the cross-linked product obtained by the primary cross-linking is further heated at a temperature higher than the temperature of the primary cross-linking and not higher than 360 ° C. to obtain a cross-linked product.
• the fluoroelastomer composition may be molded into the shape of the desired crosslinked product, and then primary crosslinked to form a crosslinked product.
• the fluoroelastomer composition may be subjected to primary crosslinking and simultaneously molded into the desired crosslinked product shape to form a crosslinked product.
• a molding method of the fluoroelastomer composition a known molding method such as extrusion molding, injection molding, transfer molding or press molding can be employed.
• the fluoroelastomer composition of the present invention is subjected to primary crosslinking at a temperature of 200 ° C. or lower to obtain a molded product, and then the molded product is further higher than the temperature of the primary crosslinking, and 360 Secondary cross-linking is performed at a temperature of °C or lower to obtain a cross-linked product.
• the fluoroelastomer composition of the present invention is crosslinked at a temperature of 200 ° C. or lower to obtain a molded product.
• the crosslinking temperature in primary crosslinking is preferably set according to the type of fluoroelastomer and organic peroxide used.
• the crosslinking temperature in the primary crosslinking is 200 ° C. or less, preferably 190 ° C. or less, and more preferably 170 or less. If the crosslinking temperature in the primary crosslinking is not more than the above upper limit value, the crosslinking of the surface of the fluoroelastomer composition at the portion where the heating device and the fluoroelastomer composition are in contact with each other does not proceed rapidly, and the molding becomes easy.
• the crosslinking temperature in primary crosslinking is preferably 130 ° C. or higher. If the crosslinking temperature in the primary crosslinking is not less than the lower limit, the crosslinking of the fluoroelastomer composition proceeds sufficiently and the crosslinking does not take a long time.
• the crosslinking temperature in the primary crosslinking is a temperature lower than the fatty acid metal salt, the fatty acid metal salt is concentrated on a part of the crosslinked product, and It may cause the occurrence. Since the generation of white foreign matters becomes a defect in appearance and function, the crosslinking temperature in the primary crosslinking is preferably higher than the melting point of the fatty acid metal salt contained in the fluoroelastomer composition.
• the heating time for primary crosslinking is preferably 5 to 40 minutes, more preferably 10 to 30 minutes.
• the heating temperature in the secondary cross-linking is sufficiently higher than the cross-linking temperature in the primary cross-linking and 360 ° C. or lower because the cross-linking of the fluoroelastomer composition can sufficiently proceed and the residue contained in the cross-linked product can be decomposed and volatilized. It is preferable that The heating temperature in the secondary crosslinking is preferably 150 to 360 ° C, more preferably 200 ° C to 340 ° C, further preferably 250 to 340 ° C, and particularly preferably 260 to 340 ° C.
• the heating time in the secondary crosslinking is preferably 1 to 48 hours, and more preferably 2 to 24 hours.
• the cross-linked product is a thick cross-linked product
• the cross-linked product obtained by the primary cross-linking is immediately put into a heating apparatus adjusted to the heating temperature of the secondary cross-linking in the secondary cross-linking
• the surface and the inside of the cross-linked product are Due to the temperature difference, cracks and cracks may be caused by differences in the heat shrinkage rate.
• a method of gradually raising the temperature also referred to as “step temperature raising method” is used for raising the temperature from a low temperature of about room temperature to about 50 ° C. to the heating temperature for secondary crosslinking.
• the heating time in the above-mentioned secondary crosslinking does not include the time for raising the temperature to such a secondary crosslinking heating temperature.
• Secondary cross-linking can be performed in air or under an inert gas that does not react with the fluoroelastomer.
• the secondary cross-linking is preferably performed under an inert gas.
• the inert gas is not particularly limited as long as it does not react with the fluoroelastomer, and specific examples thereof include nitrogen and argon, and nitrogen is preferable.
• the heating device used for secondary crosslinking is preferably an inert gas oven.
• cross-linking is preferably performed at a temperature of 260 to 340 ° C. in an inert gas atmosphere.
• the thick cross-linked product means a cross-linked product having a thickness of 5 mm or more at the thinnest part of the cross-linked product.
• the crosslinked product obtained from the fluoroelastomer composition of the present invention comprises a composition containing a crosslinked fluoroelastomer and a metal oxide having an average particle size of 75 nm or less.
• This cross-linked product may contain an additive blended in the fluoroelastomer composition.
• a crosslinked product containing these additives can be obtained from a fluoroelastomer composition containing additives such as pigments and fillers.
• Cross-linked fluoroelastomers are elastic bodies.
• a crosslinked product is a molded object shape
• the present inventors have found that a crosslinked product having excellent heat resistance can be obtained by reducing the average particle size of the metal oxide in the fluoroelastomer composition. Since the average particle diameter of the metal oxide is small, the dispersibility of the metal oxide in the fluoroelastomer composition is improved, so that the cross-linked product obtained by cross-linking the fluoroelastomer composition of the present invention is heat resistant. Is considered to have improved.
• the heat resistance is further improved by further improving the dispersibility of the metal oxide in the fluoroelastomer composition.
• Glass-transition temperature Glass transition temperature (Tg) was increased to 135 ° C. at a heating rate of 10 ° C./min using DSC Q-100 manufactured by TA Instrument, cooled at a cooling rate of 20 ° C./min, and again at a heating rate of 10 ° C. The temperature at the inflection point of the obtained DSC curve was defined as Tg.
• Tm melting point
• DSC Q-100 manufactured by TA Instrument was used, the temperature was increased to 135 ° C. at a temperature increase rate of 10 ° C./min, cooled at a cooling rate of 20 ° C./min, and again the temperature increase rate of 10 ° C./min.
• Tm melting point
• the solid obtained by filtration was separated by filtration and washed twice with ion-exchanged water to obtain 30.1 g (yield 53.0%) of the fluorinated aromatic compound (X) as a white solid.
• the physicochemical properties of the obtained fluorine-containing aromatic compound (X) are as shown below, and it is confirmed that the fluorine-containing aromatic compound has two or more groups represented by the above formula (3). did.
• Compression set (%) (original thickness of test piece ⁇ thickness 30 minutes after removing test piece from compression device) ⁇ (thickness of test piece ⁇ thickness of spacer) ⁇ 100
• FFKM Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (product name: AFLAS (registered trademark) Premium PM-3000, manufactured by Asahi Glass Co., Ltd.)
• FEPM Tetrafluoroethylene / propylene copolymer (Asahi Glass Co., Ltd., product name: AFLAS (registered trademark) 600S)
• FKM Tetrafluoroethylene / 6-fluoropropylene / vinylidene fluoride copolymer (manufactured by Daikin Industrial Co., Ltd., product name: DAIEL (registered trademark) G-901)
• Crosslinking aid 1 Triallyl isocyanurate Silica 60% diluted product, product name: TAIC WH-60 (manufactured by Nippon Kasei Co., Ltd.)
• Crosslinking aid 2 Fluorine-containing aromatic compound
• Crosslinking aid 3 triallyl isocyanurate, product name: TAIC (manufactured by Nippon Kasei Co., Ltd.)
• Carbon black 1 manufactured by Cancarb Limited, product name: Thermax (registered trademark) N990 Carbon black 2: manufactured by Coal Fillers Incorporated, product name: Austin Black 325
• Acid acceptor 1 FINEX (registered trademark) -30 (manufactured by Sakai Chemical Industry Co., Ltd.) ⁇ Zinc oxide, average particle size: 35 nm, no surface treatment>
• Acid acceptor 2 FINEX (registered trademark) -30S-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.) ⁇ Zinc oxide, average particle size: 35 nm, hydrophobized hydrogen dimethicone>
• Acid acceptor 3 FINEX (registered trademark) -33W-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.) ⁇ Zinc oxide, average particle size: 35 nm, hydrophobized hydrogen dimethicone treatment + silica treatment>
• Acid acceptor 4 FINEX (registered trademark) -50 (manufactured by Sakai Chemical Industry Co., Ltd.) ⁇ Zinc oxide, average particle size: 20 nm, no surface treatment> Acid acceptor 5
• the obtained cross-linked product was evaluated for tensile strength, tensile elongation, hardness, heat aging test, and compression set in a P-26 size O-ring test piece.
• the evaluation results are shown in Table 1.
• “crack” means that the cross-linked product after secondary cross-linking is broken and the thickness cannot be measured, or even if the thickness is measured, partial cracking has occurred.
• Examples 6 to 8 According to Table 2, the compounding ingredients were kneaded with an open roll for 10 minutes to prepare a fluoroelastomer composition. Next, the obtained fluoroelastomer composition was subjected to crosslinking under the following crosslinking conditions.
• Primary cross-linking set in a mold heated to 150 ° C., and held at 150 ° C. for 20 minutes using a hot press.
• Secondary crosslinking ⁇ Condition 2> Heating from 40 ° C. to 120 ° C. at a heating rate of 80 ° C./hour in an oven in a nitrogen atmosphere, then heating from 120 ° C. to 200 ° C.
• the resulting crosslinked product was evaluated for tensile strength, tensile elongation, hardness, heat aging test, compression set with a P-26 size O-ring test piece, and compression set with a DISK-like test piece.
• the evaluation results are shown in Table 2.
• “crack” in the compression set of Table 2 has the same meaning as “crack” in the compression set of Table 1.
• Example 1 in which secondary crosslinking was performed at a crosslinking temperature of 300 ° C. in a nitrogen atmosphere that is an inert gas, in a DISK-shaped test piece of ⁇ 29 ⁇ 12.5 mm size that is a thick crosslinked product There was no breakage, and a crosslinked product having good heat resistance was obtained.
• the crosslinked product produced by the method for producing a crosslinked product of the present invention can be used in various applications such as a sealing material, a wire coating material, a diaphragm, a hose, a belt, and a vibration isolating rubber, a semiconductor field, a plasma field, a solar cell field, Automotive field, aircraft field, rocket and ship field, chemical plant field, analytical / physical and chemical machine field, food plant equipment field, nuclear power plant equipment field, oil field drilling field, chemical field such as plant, pharmaceutical field such as pharmaceutical, developing machine Photography field such as printing machinery, painting field such as painting equipment, analysis / physical machinery field, food plant equipment field, nuclear power plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, Fuel cell field, electronic parts field,

Landscapes

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

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=59225301

Family Applications (1)

Country Status (3)

Cited By (2)

Citations (8)

Family Cites Families (1)

• 2016
  • 2016-12-27 WO PCT/JP2016/088965 patent/WO2017115812A1/ja active Application Filing
  • 2016-12-27 JP JP2017559220A patent/JPWO2017115812A1/ja active Pending
  • 2016-12-27 TW TW105143337A patent/TW201736484A/zh unknown

Patent Citations (8)

Also Published As

Similar Documents

Legal Events