WO2006040944A1 - Formulation de caoutchouc fluoré - Google Patents

Formulation de caoutchouc fluoré Download PDF

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Publication number
WO2006040944A1
WO2006040944A1 PCT/JP2005/018119 JP2005018119W WO2006040944A1 WO 2006040944 A1 WO2006040944 A1 WO 2006040944A1 JP 2005018119 W JP2005018119 W JP 2005018119W WO 2006040944 A1 WO2006040944 A1 WO 2006040944A1
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WIPO (PCT)
Prior art keywords
fluororubber
weight
parts
rubber composition
sealing material
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PCT/JP2005/018119
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English (en)
Japanese (ja)
Inventor
Kazuhisa Matsumoto
Yousuke Nishimura
Mitsuru Kishine
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to JP2006540875A priority Critical patent/JP4636025B2/ja
Publication of WO2006040944A1 publication Critical patent/WO2006040944A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1009—Fluorinated polymers, e.g. PTFE
    • 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

Definitions

  • the present invention relates to a fluororubber composition, a sealing material obtained by vulcanization molding the composition, and further a sheath material for an oxygen sensor.
  • An oxygen sensor (o) for detecting oxygen concentration which is one of the uses of the rubber yarn composition of the present invention.
  • oxygen sensors for automobiles are usually protected by metal or the like, they are attached to high-temperature exhaust pipes, etc., and the inside of the sensor is exposed to a high-temperature exhaust gas stream containing a large amount of oxidizing substances. It must be excellent in chemical properties.
  • Oxygen sensors for automobiles are often mounted on the underside of the vehicle body floor, such as those mounted downstream of a catalyst that purifies exhaust gas and those that require detection of catalyst deterioration.
  • the oxygen sensor for automobiles since the oxygen sensor for automobiles is subject to external impacts such as vibration shock from the engine and road surface, stone splashes, and water, it must have mechanical shock resistance, thermal shock resistance, waterproofness, etc. Is also required
  • An automobile oxygen sensor is usually cylindrical, and introduces the oxygen concentration detection element at the back of the cylinder to the outside by introducing the oxygen concentration reference air into the oxygen concentration detection section of the oxygen sensor.
  • Several lead wires are built in for removal. The lead wire is arranged so as to penetrate a sealing material called a bush in order to fix the lead wire from the oxygen sensor for automobiles without contacting each other.
  • This sealing material usually has a cylindrical shape as a basic shape.
  • the sealing material has a diameter after passing through a through-hole extending in the height direction of several cylindrical columns provided in advance. Perform caulking to increase pressure in the direction.
  • the radial direction means a direction of the force perpendicular to the center line in the height direction of the cylinder from the side surface of the cylinder.
  • this sealing material has elasticity so that it is compressed to some extent by caulking, to securely fix the lead wire, and to exhibit sealing properties such as waterproofness and airtightness. From the installation location, it is desirable to have characteristics such as heat resistance and impact resistance as well as the oxygen sensor body for automobiles. Therefore, as a sealing material, conventionally, a sealing material obtained by vulcanizing and molding a fluororubber composition having these characteristics and also having a fluoro rubber strength has been used.
  • the compression set is small so as to exhibit excellent sealing characteristics.
  • conventional fluororubber compositions it has been possible to reduce the compression set of the sealing material by increasing the crosslink density by increasing the amount of vulcanizing agent added.
  • the cracking property caused by was bad.
  • a sealing material made of a composition containing a certain fluorine-containing elastomer is disclosed (for example, see pamphlet of International Publication No. 03Z074625).
  • the processability of fluoroelastomers and fluoroelastomer yarns and composites in which the compression set of the sealant is not sufficient is poor in fluidity, so that the viscosity of the rubber cannot be measured. There was a problem that could't be done.
  • the present invention provides a fluororubber composition having both high temperature sealability, crackability, and processability, a seal material obtained by vulcanizing the composition, and a seal material for an oxygen sensor.
  • the present invention is a rubber composition having fluororubber and vulcanizing power, and the vulcanizing agent is 0.5 to 1.7 parts by weight with respect to 100 parts by weight of the fluororubber in the composition. And a rubber composition having a Mu-one viscosity (MLl + 20, 140 ° C.) force of 70 to 150 of the fluororubber in the composition.
  • MLl + 20, 140 ° C. Mu-one viscosity
  • the fluoro rubber has a mu-one viscosity (ML1 + 20, 140 ° C) force of 100 to 150.
  • the fluororubber is preferably a fluororubber containing a bilidene fluoride unit.
  • the fluororubber is a binary fluororubber composed of a bilidene fluoride unit and a hexafluoropropylene unit.
  • the compounding amount of the vulcanizing agent with respect to 100 parts by weight of fluororubber is X (parts by weight), and the compression set at 25% compression of P-24 ⁇ 0 ring at 280 ° CX for 72 hours is ⁇ (%). Sometimes 20 ⁇
  • the vulcanizing agent is preferably a polyhydroxy compound.
  • bituminous coal filler It is preferable to contain 5 to 30 parts by weight of a bituminous coal filler with respect to 100 parts by weight of the fluororubber.
  • the present invention also relates to a sealing material obtained by vulcanizing the rubber composition.
  • the present invention also relates to a sealing material for an oxygen sensor that is also the sealing material.
  • the present invention relates to a sealing material for an oxygen sensor obtained by vulcanizing a rubber composition comprising a fluororubber and a vulcanizing agent.
  • a sealing material for an oxygen sensor obtained by vulcanizing a rubber composition comprising a fluororubber and a vulcanizing agent.
  • the present invention relates to a sealing material for oxygen sensor whose 140 ° C) is 70 to 150.
  • the present invention is a rubber composition comprising a fluororubber and a vulcanizing agent
  • the vulcanizing agent is 0.5 to 1.7 parts by weight with respect to 100 parts by weight of the fluororubber in the composition, and the mu-one viscosity (ML1 + 20, 140) of the fluororubber in the composition.
  • ° C) relates to a rubber composition having a force of 0 to 150.
  • fluororubber examples include perfluorofluororubber and non-perfluorofluororubber.
  • Perfluorofluororubber includes tetrafluoroethylene (hereinafter referred to as TFE) Z perfluoro (alkyl butyl ether) (hereinafter referred to as PAVE) copolymer, TFEZ hexafluoropropylene. (Hereinafter referred to as HFP) ZPAVE copolymer and the like.
  • TFE tetrafluoroethylene
  • PAVE alkyl butyl ether
  • HFP TFEZ hexafluoropropylene
  • non-perfluorofluororubber examples include a bi-lidene fluoride (hereinafter referred to as VdF) polymer, a TFEZ propylene copolymer, and the like. Any combination can be used within a range without impairing the effects of the invention.
  • those exemplified as the perfluoro fluorororubber and the non-perfluorofluorororubber are main monomers, and those obtained by copolymerizing a crosslinking monomer, a modified monomer, and the like can also be suitably used.
  • a crosslinking monomer or the modifying monomer a known crosslinking monomer such as an iodine atom, bromine atom, or one containing a double bond, a transfer agent, a modified monomer such as a known ethylenically unsaturated compound, or the like may be used. it can.
  • VdF polymer examples include a VdFZHFP copolymer, a VdF / TFE ZHFP copolymer, a VdFZTFEZ propylene copolymer, a VdFZ ethylene ZHFP copolymer, and a VdFZTFEZPAVE copolymer.
  • VdFZPAVE copolymer examples include VdFZPAVE copolymer, VdF Z chlorofluoroethylene (hereinafter referred to as CTFE) copolymer, and the like.
  • VdF 25 to 85 mol% of VdF and at least one copolymerizable with VdF More preferably, it is a fluorine-containing copolymer having a strength of 75 to 15 mol% of other monomers, more preferably 50 to 80 mol% of VdF, and at least one other monomer copolymerizable with VdF. This is a fluorine-containing copolymer having a strength of 50 to 20 mol%.
  • At least one other monomer copolymerizable with VdF for example, TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, penta
  • fluorine-containing monomers such as fluoropropylene, trifluorobutene, tetrafluoroisobutene, PAVE, and fluorinated butyl
  • non-fluorine monomers such as ethylene, propylene, and alkyl butyl ether.
  • fluororubber from the viewpoint of heat resistance, compression set, workability, and cost, it is preferable to use a fluororubber containing VdF units.
  • VdF units and HFP More preferably, it is a binary fluororubber having a unit force.
  • the binary fluororubber be that the sum of VdF unit and HFP unit is 90 mole 0/0 or more than is preferred instrument 95 mol% or more it is more preferred instrument 100 mol% Particularly preferred.
  • Mu-one viscosity (ML1 + 20, 140.C) of the fluororubber in the rubber composition of the present invention is 70 to 150, and is a force of 80 to 150 S, preferably 90 to 150 The force S is more preferable, and it is more preferably 100 to 150. If the fluoro rubber has a Mu-viscosity of less than 70, it tends to be impossible to provide a good balance between compression set and cracking properties under high temperature and high compression conditions. Above this, molding tends to be difficult. In general, products whose mu-one viscosity is adjusted to 60 are sold and widely used, but fluorine that combines sealing, cracking and workability under high temperature and high compression conditions. This range is insufficient for constituting a rubber composition, and it is necessary to select the Mooney viscosity in the above-mentioned region which is not generally used.
  • Mu-one viscosity is a value obtained by measuring using a Mu-one viscosity measuring device (manufactured by MV2000E ALPHA TECHNOLOGIES) in accordance with JIS K 6300 (1994).
  • the measurement conditions are the values measured using a L-shaped rotor at 140 ° C with a preheating time of 1 minute and a measurement time of 20 minutes.
  • the fluorororubber in the rubber composition may be one type, or two or more types. It may be combined, but in the case of two or more types, it is only necessary that the mu-one viscosity of the combined fluororubber is within the above predetermined range. Specifically, for example, even when mu-viscosity 60 fluoro rubber and 160 fluoro-rubber are blended to obtain mu-viscosity 110, they are within the scope of the present invention.
  • the rubber composition of the present invention is obtained by blending a vulcanizing agent with the fluororubber. Also, vulcanization accelerators can be used with vulcanizing agents.
  • the vulcanizing agent and the vulcanization accelerator are used for vulcanizing the fluororubber.
  • the vulcanization means that the same or different polymer chains of fluororubber are cross-linked by a vulcanizing agent, and the fluororubber is improved in tensile strength by being cross-linked in this way. It can be set as the sealing material of this invention which has elasticity.
  • the vulcanization system used in the present invention may be appropriately selected depending on the type of cure site or the use of the obtained sealing material.
  • the vulcanization system any of a polyol vulcanization system, a peroxide vulcanization system and a polyamine vulcanization system can be adopted.
  • the vulcanized fluororubber vulcanized by a polyol vulcanization system has a carbon-oxygen bond at the cross-linking point, has a small compression set, a good moldability, and an excellent sealing property. If so, it is suitable for the sealing material of the present invention.
  • the vulcanized fluororubber vulcanized by the peroxide vulcanization system has a carbon-carbon bond at the crosslinking point
  • a polyol vulcanization system having a carbon-oxygen bond at the crosslinking point and a carbon-nitrogen double Excellent chemical resistance and steam resistance compared to polyamine vulcanization systems with bonds! / When you talk! There is a characteristic.
  • a vulcanized fluorororubber vulcanized by polyamine vulcanization has a carbon-nitrogen double bond at the cross-linking point and is characterized by excellent dynamic mechanical properties.
  • compression set which is the most important physical property of sealing materials, tends to be larger than vulcanized fluoro rubbers vulcanized using polyol vulcanization system or peroxide vulcanization system vulcanizing agent. .
  • vulcanizing agent in the present invention polyamine-based, polyol-based and peroxide-based vulcanizing agents generally known for fluoro rubbers can be used.
  • Examples of the polyamine vulcanizing agent include hexamethylenediamine amine carbamate, N, N'-dicinnamylidene 1,6 hexamethylenediamine, 4, 4'-bis (aminocyclohexenole) methane
  • examples include polyamine compounds such as rubamate. Of these, N, N'-dicinnamylidene 1, 6 hexamethylenediamine is preferred!
  • the polyol vulcanizing agent a compound conventionally known as a fluororubber vulcanizing agent can be used.
  • a polyhydroxy compound particularly, a polyhydroxy hydroxy compound having excellent heat resistance is also used.
  • Aromatic compounds are preferably used.
  • the polyhydroxy aromatic compound is not particularly limited.
  • 2, 2 bis (4 hydroxyphenol) propane hereinafter referred to as bisphenol A
  • Perfluoropropane hereinafter referred to as bisphenol AF
  • resorcin 1,3 dihydroxybenzene, 1,7 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 4,4'-dihydroxydiphenyl 4, 4 'dihydroxystilbene, 2, 6 dihydroxyanthracene, hydroquinone, catechol, 2, 2-bis (4-hydroxyphenol) butane (hereinafter referred to as bisphenol B), 4, 4-bis (4— Hydroxyphenol) Valeric acid, 2, 2 Bis (4 hydroxyphenol) Tetrafluorodiclopropane Propane, 4, 4, Dihydroxydiph Ninoles norephone, 4, 4, -dihydroxydiphenyl ketone, tri (4-hydroxyphenol) methane, 3, 3 ', 5, 5,
  • the peroxide vulcanizing agent may be a compound having a reaction activity with respect to a peroxide radical and a polymer radical.
  • triallyl cyanurate, triallyl isocyanurate (TAIC), triali norenore meranole, triarinore trimellitate N, N '—n-phenylene bismaleimide, dipro Pagyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1, 3, 5 tris (2, 3, 3, trifluoro 2-probe)) 1, 3, 5 ⁇ riadin— 2, 4, 6 ⁇ lion), tris (diallylamine) S triazine, triallyl phosphite, N, N diallyacrylamide, 1, 6 divinyldodecafluor hexane, Xaarylphosphoramide, N, N, N ', N' —tetraaryltetraphthalamide, N, N, N ′, N ′ —tetraarylmalonamide,
  • the resulting sealant has a small compression set, a good moldability, and an excellent sealing property, so that a polyhydroxy compound is a preferred heat resistance. Since bisphenol AF is more preferable, bisphenol AF is more preferable.
  • the amount of the vulcanizing agent is 0.5 to 1.7 parts by weight and preferably 0.6 to 1.5 parts by weight with respect to 100 parts by weight of the fluororubber. More preferably, it is 0.7 to 1.3 parts by weight. If the vulcanizing agent is less than 0.5 parts by weight, the crosslinking density tends to be low and the compression set tends to be large, and if it exceeds 1.7 parts by weight, the crosslinking density becomes too high. Tend to break easily.
  • a vulcanization accelerator is usually used in combination with the polyol vulcanizing agent.
  • the vulcanization reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.
  • the vulcanization accelerator for the polyol vulcanization system a compound having a property that it is difficult to add to the fluororubber main chain is preferred, and an organic compound is generally used.
  • an organic compound is generally used.
  • the onium compound examples thereof include an ammonium compound such as a quaternary ammonium salt, a phosphonium compound such as a quaternary phosphonium salt, and an oxo-um.
  • an ammonium compound such as a quaternary ammonium salt
  • a phosphonium compound such as a quaternary phosphonium salt
  • an oxo-um Compounds, sulfo-compounds, cyclic amines, monofunctional amine compounds, and the like. Among these, quaternary ammonium salts and quaternary phosphonium salts are preferred.
  • the quaternary ammonium salt is not particularly limited.
  • DBU-B is preferable from the viewpoint of vulcanizability and physical properties of the vulcanizate.
  • the quaternary phospho-um salt is not particularly limited, and examples thereof include tetrabutyl phospho-um chloride, benzyl triphenyl phospho-um chloride (hereinafter referred to as BTPPC), benzyl trimethyl phospho-um chloride, Examples thereof include benzyltributylphosphomethylene chloride, tributylarylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, and benzylphenol (dimethylamino) phosphonium chloride. Among these, vulcanizability and physical properties of vulcanizates In view of the above, benzyltriphenylphospho-muchloride (BTPPC) is preferred.
  • BTPPC benzyltriphenylphospho-muchloride
  • a vulcanization accelerator a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, chlorine-free disclosed in JP-A-11-147891 Vulcanization accelerators can also be used.
  • the peroxide vulcanization accelerator may be any organic peroxide compound that can easily generate a peroxide radical in the presence of heat or a redox system.
  • the blending amount of the vulcanization accelerator is 0.1 to 2.0 parts by weight, preferably S, and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the fluororubber. More preferred is 1 to 0.7 parts by weight. If the blending amount of the vulcanization accelerator is less than 0.1 parts by weight, the vulcanization speed will be slow and the productivity tends to deteriorate, and if it exceeds 2.0 parts by weight, the vulcanization speed will be too fast. Scorch and molding defects tend to occur.
  • a filler may be added to the rubber composition of the present invention. Any filler that is generally used for fluoro rubber can be used! ,.
  • Examples of the filler include thermal black, furnace black, channel black, bituminous coal filler (mineral black), talc, white carbon, clay, magnesium oxide, calcium oxide, titanium oxide, silicon oxide, and oxide.
  • Metal oxides such as aluminum, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate Silicates such as sodium silicate and aluminum silicate, sulfates such as aluminum sulfate, calcium sulfate and barium sulfate, synthetic hydrotalcite, metal sulfides such as molybdenum disulfide, iron sulfide and copper sulfide, diatomaceous earth, asbestos, ritbon (Sulfur Lead Z barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, Kotasu and the like.
  • the blending amount of the filler is usually 0 to L00 parts by weight, more preferably 0 to 50 parts by weight with respect to 100 parts by weight of the fluororubber, which varies depending on the type of filler. Filler strength S When the amount exceeds 100 parts by weight, the hardness increases, the workability deteriorates and the compression set tends to deteriorate. [0061] Further, in order to achieve both high sealing performance and high cracking performance, it is preferable to use a combination of bituminous coal filler and other fillers. In this case, the blending amount of the bituminous coal filler is preferably 5 to 30 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the fluororubber.
  • the compression set tends to be poor, and if it exceeds 30 parts by weight, the hardness of the molded product tends to be hard and the sealing property tends to be poor. Even if the hardness is adjusted by the ratio with other fillers, if the bituminous coal filler exceeds 30 parts by weight, it is preferable because the mechanical strength is lowered and it is easy to break during compression.
  • the rubber composition of the present invention may be added with a metal oxide or a metal hydroxide as an acid acceptor or a vulcanization acceleration aid.
  • Metal oxides are mainly used as acid acceptors, and are used in polyol vulcanization systems and polyamine vulcanization systems to neutralize acidic substances generated during vulcanization.
  • Metal hydroxides are mainly used as vulcanization accelerators, and in polyol vulcanization systems, react with calorific accelerators to activate dehydrofluorination and activate vulcanization accelerators. Thus, the vulcanization reaction can be promoted.
  • Examples of the metal oxide include magnesium oxide, lead oxide, calcium oxide, zinc oxide, iron oxide, titanium oxide, silicon oxide, and aluminum oxide. Of these, magnesium oxide and its surface-treated product are preferred as acid acceptors. In addition to this, synthetic acid and id mouth talcite can also be used as the acid acceptor. In addition, zinc oxide is used for improving heat resistance, iron oxide, titanium oxide, and silicon oxide are used as colorants and fillers, and aluminum oxide is used as a thermal conductivity imparting agent.
  • Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like. Among these, calcium hydroxide and its surface-treated product are preferable.
  • the addition amount of the metal oxide and the metal hydroxide is preferably 0 to 25 parts by weight, preferably 0 to 10 parts by weight, with respect to 100 parts by weight of the fluororubber. More preferred. If the amount of metal oxide exceeds 25 parts by weight, scorching tends to occur, and if the amount of metal hydroxide exceeds 25 parts by weight, compression set tends to deteriorate. [0068] Further, in the rubber composition of the present invention, a processing aid, a release agent, a colorant, a conductivity imparting agent, a thermal conductivity imparting agent, a surface non-sticking agent, as long as the effects of the present invention are not impaired. Compounding agents such as pressure-sensitive adhesives, adhesives' pressure-sensitive adhesives, flexibility-imparting agents, heat resistance improvers and flame retardants may be added.
  • the rubber composition of the present invention generally uses a fluororubber, a vulcanizing agent, and, if necessary, a vulcanization accelerator, a filler, a metal oxide, a metal hydroxide, and other compounding agents. It can be obtained by kneading using a rubber kneading apparatus.
  • a rubber kneading apparatus a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.
  • Vulcanizing agents, vulcanization accelerators, fillers, metal oxides, metal hydroxides, and other compounding agents must be uniformly dispersed in the rubber. It tends to cause a decrease in speed, a decrease in mechanical strength, a decrease in elongation, and a poor cracking property during compression.
  • the melting point of the vulcanizing agent 'vulcanization accelerator is often relatively high.
  • a method of kneading a product or other compounding agent at a relatively low temperature below this is preferable.
  • the mixture is allowed to stand at room temperature for 12 hours or more and then kneaded again. By doing so, dispersibility can be further improved.
  • the sealing material of the present invention is obtained by vulcanization molding of the rubber composition of the present invention using a general rubber molding machine.
  • a compression press As the rubber molding machine, a compression press, an injection molding machine, an injection molding machine or the like can be used. A rubber composition preformed into a predetermined shape using a roll, an extruder, or a pre-molding machine is used. Perform primary vulcanization by heating at ° C for about 1 to 60 minutes.
  • the method using a compression press is a molding method suitable for fluoro rubber having a higher viscosity than that of other methods, and is preferably used as a method for molding the sealing material of the present invention.
  • the sealing material formed by the primary vulcanization is subjected to secondary vulcanization using an air oven. It is desirable.
  • the secondary vulcanization is performed for the purpose of completing the above primary vulcanization reaction, decomposing the vulcanizing agent / vulcanization accelerator remaining without cross-linking reaction, and releasing the gas generated during vulcanization.
  • the mechanical properties such as tensile strength and compression set of the sealing material of the present invention can be improved.
  • the secondary vulcanization conditions usually vary depending on the vulcanization system.
  • the polyamine vulcanization system is 180-220 ° C for about 16-24 hours, and the polyol vulcanization system is 210-260 ° C for about 16-24 hours.
  • the peroxide vulcanization system is generally performed at 160 to 200 ° C for about 2 to 24 hours.
  • the sealing property and cracking property at high temperature and high compression are characteristic, and secondary vulcanization at higher temperature is preferable.
  • the compounding amount of the vulcanizing agent with respect to 100 parts by weight of the fluororubber in the rubber composition of the present invention is X (parts by weight), 25% compression of 24-24' ⁇ ring, 280 ° CX compression at 72 hours It is preferable to satisfy 20% + ⁇ 70 when the permanent strain is Y (%). It is more preferable to satisfy 20% + ⁇ 68, more preferably 20% + ⁇ 68. Also, the lower limit of 20 ⁇ + ⁇ is not particularly limited, but it is preferable to satisfy 1 ⁇ 20 ⁇ + ⁇ . It is more preferable to satisfy 30 ⁇ 2 ⁇ + ⁇ . If 20 ⁇ + ⁇ exceeds 70, even if the amount of vulcanizing agent is adjusted, it tends to be difficult to achieve both compression set and crackability.
  • the sealing material of the present invention has a sealing property and a cracking property under high temperature and high compression as described above. Therefore, it is possible to apply pressure such as caulking for the purpose of ensuring the sealing performance, and it can be suitably used for applications that require the sealing performance to be maintained for long periods of use at high temperatures.
  • the present invention relates to a sealing material for an oxygen sensor obtained by vulcanizing a rubber composition comprising a fluororubber and a vulcanizing agent.
  • ML1 + 20, 140 ° C relates to an oxygen sensor sealing material having a temperature of 70 to 150.
  • the fluorororubber and the vulcanizing agent those described above can be preferably used. Further, the Mooney viscosity of the fluoro rubber, the measuring method of Mooney viscosity, the vulcanization conditions, and the like are the same as described above.
  • the blending amount of the vulcanizing agent is not particularly limited, but the above blending amount can be employed.
  • the use of the sealing material of the present invention is not particularly limited.
  • an engine body of a car engine a main motion system, a valve system, a lubricant / cooling system, a fuel system, an intake / exhaust system; Transmission system; Chassis steering system; Brake system; Heat-resistant, oil-resistant, fuel oil-resistant, anti-freezing liquid resistance for engine cooling, steam-resistant, such as basic electrical parts of control equipment, control system electrical parts, electrical equipment parts
  • Sealing materials such as gaskets that require high performance and non-contact type and contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.).
  • the sealing material used in the engine body of the automobile engine is not particularly limited.
  • gaskets such as cylinder head gasket, cylinder head cover gasket, oil pan packing, general gasket, O-ring, packing, timing Examples include sealing materials such as belt cover gaskets.
  • the seal material used in the main motion system of the automobile engine is not particularly limited, and examples thereof include a shaft seal such as a crankshaft seal and a camshaft seal.
  • the seal material used in the valve train of an automobile engine is not particularly limited, and examples thereof include a valve stem oil seal of an engine valve.
  • the lubricant used for the automotive engine's cooling system is particularly limited.
  • a seal gasket for an engine oil cooler can be mentioned.
  • the seal material used in the engine fuel system for automobiles is not particularly limited.
  • a fuel pump connector for example, a fuel tank filler seal, a tank knocker, etc., a fuel tube connector O-link Injector / cushion ring of fuel injector, injector seal ring, injector O-ring, etc.
  • the sealing material used for the intake and exhaust system of the automobile engine is not particularly limited.
  • the intake manifold seal packing of the hold, the exhaust hold packing, and the throttle throttle Examples include body packing and turbocharged turbine shaft seals.
  • the seal material used in the transmission system of the automobile engine is not particularly limited.
  • a transmission-related bearing seal for example, a transmission-related bearing seal, an oil seal, an O-ring, a knock, etc., an O-ring of an automatic transmission. , Knockins and the like.
  • the seal material used in the brake system of the automobile engine is not particularly limited.
  • a seal such as an oilless nole, an O-ring, a knocker, a piston cup (rubber cup) of a master cylinder, etc. Parseal, boots, etc.
  • the seal material used in the electrical equipment for the automobile engine is not particularly limited, and examples thereof include an O-ring and a packing of a car air conditioner.
  • the sealing material of the present invention is particularly suitable for an oxygen sensor, and further suitable for an automotive oxygen sensor.
  • the obtained fluororubber is sheeted by passing it through a kneading roll machine (roll gap: approx. Using an L-shaped rotor, the measurement was conducted at 140 ° C with a preheating time of 1 minute and a measurement time of 20 minutes in accordance with JIS K 6300 (1994).
  • RI detector manufactured by Tosoichi Co., Ltd.
  • 19 F-NMR (Bruker AC300P type) was used for measurement. However, the TFE-containing polymer was measured using 19 F-NMR (FX100 model manufactured by JEOL Ltd.).
  • the P-24 ⁇ O-rings obtained in the examples and comparative examples were charged into a compression device and a spacer preheated to 280 ° C, and the compression rate was 50%, 280 ° C for 1 hour. After holding, it was taken out from the compression device and visually checked for cracks. A total of 10 O-links were examined, and the crack rate was calculated from the following formula.
  • P-21 Solid solution in which bisphenol AF and BTPPC are mixed at a weight ratio of 2: 1, melted at 180 ° C for 1-2 hours, and cooled and crushed
  • MA-150 Highly active acid magnesium from Kyowa Chemical Industry Co., Ltd.
  • CALDIC2000 Calcium hydroxide manufactured by Omi Chemical Co., Ltd.
  • the polymerization vessel having an internal volume of 1.8 liters with an electromagnetic induction stirrer, pure water 720 g, 10 weight 0/0 par full O b octanoic acid ammonium - ⁇ anhydrous solution 290 g, and Jechiru malonate 0. 6 g was charged and the inside of the system was sufficiently replaced with nitrogen gas, and then the pressure was reduced. This operation was repeated three times, and VdF20g and HFP51g were charged under reduced pressure, and the temperature was raised to 80 ° C with stirring. Next, persulfate ammonium salt (APS) O. 02g dissolved in pure water 0.6g was added to nitrogen. Polymerization was started by press-fitting with gas.
  • APS persulfate ammonium salt
  • the polymerization pressure was set to 2 MPa, and VdFZHFP mixed monomer (78Z22 (mol%)) was continuously fed to carry out the polymerization with stirring in order to compensate for the pressure drop during the polymerization. By the end of the polymerization, 215 g of monomer was fed into the tank.
  • Production Example 1 Internal volume with the same electromagnetic induction stirrer 1. Charge a water tank of 83 liters with 977 g of pure water and 10.2 g of an aqueous dispersion of polymer particles produced in Production Example 1, and nitrogen gas in the system Then, the pressure was reduced. This operation was repeated three times. Under reduced pressure, 142 g of VdF and 449 g of HFP were charged, and the temperature was raised to 80 ° C. with stirring. Next, APSO.08g dissolved in 1.45g of methyl malonate and 15g of pure water was injected with nitrogen gas to start the polymerization, and the polymerization was continued under the conditions of (a) and (b). Stirring was stopped and the monomer was released to stop the polymerization.
  • the weight of the obtained emulsion was 1376 g, and the polymer concentration was 26.4 wt%.
  • Fluoro rubber was polymerized in the same manner as in Production Example 2, except that 1.80 g of methyl malonate and 0.09 g of APS were used.
  • the polymerization time is 2.7 hours, the weight of the obtained emulsion 1380 g, the polymer concentration was 26.7 by weight 0/0.
  • the fluororubber was 368 g, the weight average molecular weight Mw measured by GPC was 460,000, the number average molecular weight Mn was 200,000, and MwZMn was 2.3.
  • Fluorine rubber was polymerized in the same manner as in Production Example 2 except that 2.0 g of jetty malonate and 0.09 g of APS were used.
  • the polymerization time is 2.9 hours, the weight of the obtained emulsion 1372 g, the polymer concentration 26. was 4 by weight 0/0.
  • the fluororubber was 362 g, the weight average molecular weight Mw measured by GPC was 400,000, the number average molecular weight Mn was 170,000, and MwZMn was 2.4. 19 F
  • Fluorine rubber was polymerized in the same manner as in Production Example 2 except that 280 g of decyl malonate and 0.12 g of APS were used.
  • the polymerization time was 2.5 hours, the weight of the obtained emulsion was 1364 g, and the polymer concentration was 26.5% by weight.
  • the fluororubber was 361 g, the weight average molecular weight Mw measured by GPC was 290,000, the number average molecular weight Mn was 130,000, and MwZMn was 2.2. 19 F
  • VdFZHFPZTFE 56Z28Zl6 (mol 0/0) is 15k gf / cm 2 G.
  • VdFZHFPZTFE 66. 5/16/17. 5 ( mol 0/0) as internal pressure 15kgfZc m 2 G
  • isopentane as a chain transfer agent was equally divided into 5 parts with respect to the reaction yield, and a total amount of 2.5 cm 3 was charged. After 326 minutes from the start, the supply is stopped, the autoclave is cooled, the unreacted monomer is released, and the solid content concentration is 20 to 25% by mass. A clear aqueous dispersion was obtained.
  • the kneaded rubber is cooled and finally sheeted by using a kneading roll machine equipped with two 12 inch diameter rolls, and consists of fluoro rubber, vulcanizing agent and vulcanization accelerator.
  • the composition (S-1) was taken out.
  • Composition (S-1), thermal black (N-990 Cancarb), bituminous coal filler (32 5BA Keystone Filler & Mfg), highly active magnesium oxide (MA-150, manufactured by Kyowa Chemical Industry Co., Ltd.) ), Calcium hydroxide (CALDIC2000 manufactured by Omi Chemical Co., Ltd.) was added so as to have the mixing ratio shown in Table 2, and using a kneading roll machine equipped with two 8-inch rolls in a normal manner, It knead
  • the unvulcanized rubber sheet (G-1) was subjected to primary vulcanization with a 100-ton compression press at a gauge pressure of 60kgfZcm 2 at 170 ° C for 10 minutes to obtain a vulcanized sheet (width: about 140mm, Length: approx. 110mm, thickness: approx. 2mm) and a ⁇ -24 'ring (inner diameter: 23.7mm, thickness 3.5mm, exercise O-ring) were molded. Further, the obtained vulcanized sheet and P-24 ⁇ 0 ring were subjected to secondary vulcanization at 260 ° C for 5 hours and at 300 ° C for 2 hours. [0121] Examples 2 to 4 and Comparative Examples 1 to 3
  • a vulcanized sheet and a P-24 ⁇ O ring were obtained in the same manner as in Example 1 except that the fluororubbers obtained in Production Examples 2 to 6 were used and the blending conditions shown in Table 2 were used.
  • X is the compounding amount (parts by weight) of the vulcanizing agent with respect to 100 parts by weight of fluororubber
  • Y is 25% compression of P-24 ⁇ O ring
  • Z is the crack rate (%) at 50% compression, 280 ° CX for 1 hour of P-24 ⁇ 0 ring.
  • the rubber composition of the present invention is a rubber composition comprising a fluoro rubber and a vulcanizing agent, and the vulcanizing agent is 0.5 to 1.7 parts by weight with respect to 100 parts by weight of the fluoro rubber in the composition.
  • the Mooney viscosity (MLl + 20, 140 ° C) of the fluororubber in the composition is 70 to 150, so that the sealing material obtained by vulcanization molding has high temperature sealing properties.
  • the rubber composition also has good processability.
  • the sealing material comprising the rubber composition of the present invention is one that retains its sealing performance when used for a long time at high temperatures.

Abstract

La présente invention décrit une formulation de caoutchouc fluoré présentant des propriétés d'étanchéité à haute température, tout en conservant une résistance au fendillement et une facilité de mise en œuvre satisfaisantes. La présente invention décrit également un matériau pour joint d’étanchéité obtenu par moulage par vulcanisation d’une telle formulation de caoutchouc fluoré. La présente invention décrit en outre un matériau pour joint d’étanchéité destiné à des capteurs à oxygène. Plus spécifiquement, la présente invention décrit une formulation de caoutchouc composée d’un caoutchouc fluoré et d’un agent de vulcanisation, telle qu’entre 0,5 et 1,7 parts en masse d’agent de vulcanisation sont incluses pour 100 parts en masse de caoutchouc fluoré, et telle que la viscosité Mooney (ML1 +20, 140 °C) dudit caoutchouc fluoré soit comprise entre 70 et 150.
PCT/JP2005/018119 2004-10-08 2005-09-30 Formulation de caoutchouc fluoré WO2006040944A1 (fr)

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CN100465243C (zh) * 2007-09-20 2009-03-04 北京联合大学 一种生产密封材料的离心造粒方法及其产品与用途
JP2011522921A (ja) * 2008-07-18 2011-08-04 ダイキン工業株式会社 含フッ素エラストマー組成物およびそれからなる成形品
WO2012026557A1 (fr) 2010-08-25 2012-03-01 ダイキン工業株式会社 Élément de joint
JP2013539807A (ja) * 2010-10-15 2013-10-28 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． フルオロエラストマー
US8609774B2 (en) 2010-08-25 2013-12-17 Daikin Industries, Ltd. Belt
US8754161B2 (en) 2010-08-25 2014-06-17 Daikin Industries, Ltd. Complex-shaped fluororubber formed product
US9006328B2 (en) 2010-08-25 2015-04-14 Daikin Industries, Ltd. Fluororubber composition
US9045614B2 (en) 2010-08-25 2015-06-02 Daikin Industries, Ltd. Fluororubber composition
CN114437476A (zh) * 2022-03-11 2022-05-06 江苏中煜橡塑科技有限公司 一种抗挤压变形的氟橡胶密封圈及制备方法
WO2022210044A1 (fr) * 2021-04-02 2022-10-06 ダイキン工業株式会社 Composition pour réticulation de caoutchouc fluoré et article moulé
WO2022220018A1 (fr) * 2021-04-15 2022-10-20 ダイキン工業株式会社 Composition de réticulation de caoutchouc fluoré, produit moulé et élément d'étanchéité

Families Citing this family (1)

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WO2012026549A1 (fr) 2010-08-25 2012-03-01 ダイキン工業株式会社 Tuyau souple

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WO2003074625A1 (fr) * 2002-03-05 2003-09-12 Daikin Industries, Ltd. Materiau d'etancheite

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JP2001192482A (ja) * 2000-01-13 2001-07-17 Nok Corp フッ素ゴム加硫成形品の製造法
JP2002132081A (ja) * 2000-10-23 2002-05-09 Canon Inc 定着用ローラおよび定着装置
JP2003119455A (ja) * 2001-10-10 2003-04-23 Mitsubishi Cable Ind Ltd フッ素ゴムシール
WO2003074625A1 (fr) * 2002-03-05 2003-09-12 Daikin Industries, Ltd. Materiau d'etancheite

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100465243C (zh) * 2007-09-20 2009-03-04 北京联合大学 一种生产密封材料的离心造粒方法及其产品与用途
JP2011522921A (ja) * 2008-07-18 2011-08-04 ダイキン工業株式会社 含フッ素エラストマー組成物およびそれからなる成形品
WO2012026557A1 (fr) 2010-08-25 2012-03-01 ダイキン工業株式会社 Élément de joint
US8609774B2 (en) 2010-08-25 2013-12-17 Daikin Industries, Ltd. Belt
US8754161B2 (en) 2010-08-25 2014-06-17 Daikin Industries, Ltd. Complex-shaped fluororubber formed product
US9006328B2 (en) 2010-08-25 2015-04-14 Daikin Industries, Ltd. Fluororubber composition
US9045614B2 (en) 2010-08-25 2015-06-02 Daikin Industries, Ltd. Fluororubber composition
US9068653B2 (en) 2010-08-25 2015-06-30 Daikin Industries, Ltd. Sealing material
JP2013539807A (ja) * 2010-10-15 2013-10-28 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． フルオロエラストマー
WO2022210044A1 (fr) * 2021-04-02 2022-10-06 ダイキン工業株式会社 Composition pour réticulation de caoutchouc fluoré et article moulé
WO2022220018A1 (fr) * 2021-04-15 2022-10-20 ダイキン工業株式会社 Composition de réticulation de caoutchouc fluoré, produit moulé et élément d'étanchéité
CN114437476A (zh) * 2022-03-11 2022-05-06 江苏中煜橡塑科技有限公司 一种抗挤压变形的氟橡胶密封圈及制备方法

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