WO2011070896A1 - Composition de caoutchouc et utilisations de celle-ci - Google Patents

Composition de caoutchouc et utilisations de celle-ci Download PDF

Info

Publication number
WO2011070896A1
WO2011070896A1 PCT/JP2010/070401 JP2010070401W WO2011070896A1 WO 2011070896 A1 WO2011070896 A1 WO 2011070896A1 JP 2010070401 W JP2010070401 W JP 2010070401W WO 2011070896 A1 WO2011070896 A1 WO 2011070896A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
rubber composition
water
composition according
tetrafluoroethylene
Prior art date
Application number
PCT/JP2010/070401
Other languages
English (en)
Japanese (ja)
Inventor
一如 月森
順良 成相
勤 犬山
真治 水野
Original Assignee
オムロン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by オムロン株式会社 filed Critical オムロン株式会社
Priority to CN201080054082.8A priority Critical patent/CN102639629B/zh
Priority to EP10835818.5A priority patent/EP2511333B1/fr
Priority to US13/512,629 priority patent/US8580892B2/en
Publication of WO2011070896A1 publication Critical patent/WO2011070896A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a rubber composition and its use, and more specifically, has sufficient resistance to deterioration and swelling due to a liquid such as a water-soluble coolant, and further has sufficient resistance to ozone. Rubber composition and its use.
  • the movable part is water soluble such as water soluble cutting oil such as limit switch used for detecting position of moving object or detection of operation limit, safety door switch for detecting that mechanical guard or cover is closed, etc.
  • water soluble cutting oil such as limit switch used for detecting position of moving object or detection of operation limit, safety door switch for detecting that mechanical guard or cover is closed, etc.
  • limit switch used for detecting position of moving object or detection of operation limit
  • safety door switch for detecting that mechanical guard or cover is closed, etc.
  • devices that are often used in environments exposed to coolants, solvents, chemicals, etc. (eg, machining sites).
  • the seal member may deteriorate or swell, so it is necessary to select the material of the seal member according to the use environment, and NBR, which is conventionally excellent in oil resistance and chemical resistance (Acrylonitrile-butadiene rubber), fluororubber, etc. have been used.
  • NBR which is conventionally excellent in oil resistance and chemical resistance (Acrylonitrile-butadiene rubber), fluororubber, etc.
  • an O-ring made of fluorine rubber is provided between a bearing and a housing to ensure sealing performance against chemicals
  • an O-ring made of nitrile rubber is provided to seal water.
  • Patent Document 2 discloses that a rubber composition comprising a highly saturated rubber having a specific iodine value, a functional group-containing lubricating oil and a functional group-containing thermosetting resin has ozone resistance.
  • Japanese patent publication Japanese Patent Application Laid-Open No. 2005-135780 (May 26, 2005)
  • Japanese Patent Publication Japanese Patent Application Laid-Open No. 9-67473 (released on March 11, 1997)
  • the constituent material used for the seal member is required to have sufficient resistance to both deterioration and swelling due to the coolant etc., and when used in an environment where ozone is present, ozone Tolerability is also required.
  • a water-soluble coolant is used in place of a non-water-soluble coolant which is flammable and has a large environmental load at the time of disposal.
  • a water-soluble coolant contains an amine compound and is alkaline to prevent rot, and a surfactant is mixed to mix water and a base oil.
  • Patent Document 1 Since the O-ring disclosed in Patent Document 1 uses a common fluororubber and a common NBR, it is difficult to obtain sufficient resistance to deterioration and swelling due to a water-soluble coolant. . Moreover, although the rubber composition disclosed in Patent Document 2 is considered to have ozone resistance, nothing is disclosed regarding resistance to deterioration and swelling due to a water-soluble coolant. Thus, there has been no knowledge as to whether a rubber composition of any composition will be able to satisfy the resistance to deterioration and swelling due to water-soluble coolant, and also sufficient ozone resistance.
  • the present invention has been made in view of the above problems, and its object is to have sufficient resistance to deterioration and swelling by a liquid such as a water-soluble coolant, and also to have sufficient resistance to ozone. It is an object of the present invention to provide a rubber composition that can be used and its use.
  • the inventors of the present invention conducted intensive studies on rubber compositions having sufficient resistance to deterioration of the seal member due to the water-soluble coolant, swelling and deterioration of the seal member due to the environmental gas containing ozone. It has been found that a rubber composition containing a rubber, a fluorine-based oil and a predetermined vulcanizing agent has the above-mentioned resistance, and the present invention has been completed.
  • the rubber composition according to the present invention is characterized by containing a fluororubber having no vinylidene fluoride structure, a nitrile rubber, a fluoro oil and a peroxide-based vulcanizing agent.
  • the fluorine rubber containing no vinylidene fluoride structure is contained as a repeating unit, swelling by a water-soluble coolant or the like can be suppressed and dehydrofluorination reaction by an amine contained in a water-soluble coolant or the like is possible. It is not affected by the resulting deterioration. Therefore, it is excellent in deterioration resistance and can suppress generation
  • nitrile rubber since it contains nitrile rubber, it is excellent in oil resistance, chemical resistance, and mechanical strength. Furthermore, a fluorine-based oil functions as a plasticizer for fluorine rubber and nitrile rubber, has poor compatibility with a water-soluble coolant, and has a relatively low molecular weight, and thus tends to be present on the surface of the rubber composition. Infiltration of the coolant into the rubber composition can be suppressed, and deterioration and swelling of the rubber composition can be further suppressed.
  • a peroxide-based vulcanizing agent is contained as a vulcanizing agent
  • the fluororubber and the nitrile rubber which can not be mixed with a conventional vulcanizing agent, can be sufficiently crosslinked, and the fluororubber is resistant to the fluororubber.
  • Deterioration resistance, swelling resistance and mechanical strength of the above nitrile rubber can be fully utilized. Therefore, it is possible to provide a rubber composition that is sufficiently resistant to deterioration and swelling due to a liquid such as a water-soluble coolant, oil, or chemical, particularly a water-soluble coolant.
  • the rubber composition according to the present invention is configured to contain a fluororubber having no vinylidene fluoride structure, a nitrile rubber, a fluoro oil and a peroxide-based vulcanizing agent.
  • FIG. 5 is a diagram showing a state where limit switches using a control O-ring are subjected to two cycles of tests 1 and 2; The results of observation of a member called C spring present inside the main body case after subjecting the control sample B shown in Table 3 to tests 1 and 2 for two cycles are shown.
  • the sample 1 using the rubber composition according to the present invention shown in Table 3 shows the appearance and the internal state after 3 cycles.
  • the rubber composition according to the present invention after leaving the rubber composition according to the present invention and the control nitrile rubber in the periphery of equipment of a machining line using a water-soluble cutting oil (ozone concentration: 0.05 ppm) for 1 month And the results of observing the appearance of nitrile rubber, and show the results of confirming the ozone resistance.
  • a to B indicating a range means that it is A or more and B or less.
  • the rubber composition according to the present invention contains a fluororubber having no vinylidene fluoride structure, a nitrile rubber, a fluoro oil and a peroxide-based vulcanizing agent.
  • the fluororubber is a synthetic rubber containing fluorine, and the fluororubber used in the present invention is a fluororubber having no vinylidene fluoride structure.
  • the vinylidene fluoride structure is a structure represented by the following formula A. -CF 2 -CH 2- (A)
  • Examples of fluororubber having no vinylidene fluoride structure include tetrafluoroethylene-propylene rubber and tetrafluoroethylene-vinylether rubber, and in view of availability, tetrafluoroethylene-propylene rubber and It is preferably at least one of tetrafluoroethylene-vinyl ether rubbers.
  • Fluorororubbers that do not have a vinylidene fluoride structure can not only suppress swelling of the rubber composition due to water-soluble coolant etc., but also dehydrofluorination reaction caused by amine-based additives contained in water-soluble coolant, engine oil etc. It is resistant to deterioration due to a liquid such as a water-soluble coolant, and can suppress a reduction in strength of the rubber composition. This is because, as described later, the vinylidene fluoride structure is susceptible to an attack of an amine or the like contained in a water-soluble coolant, an engine oil or the like, and becomes a deterioration point.
  • the fluorororubber which does not contain the above-mentioned vinylidene fluoride structure, for example, at least one of tetrafluoroethylene-propylene rubber and tetrafluoroethylene-vinylether rubber may be used alone or in combination. When combining, it can be used in any ratio.
  • a machine tool capable of using the rubber composition according to the present invention may be required to be used in a low temperature environment of 0 ° C. or more and less than 5 ° C.
  • a tetrafluoroethylene-propylene-based rubber is more preferably used because many rubbers which can be used even in such a low temperature environment are advantageous from the viewpoint of cost.
  • tetrafluoroethylene-propylene rubber refers to a copolymer of tetrafluoroethylene and propylene and / or a propylene derivative.
  • the degree of polymerization of the copolymer is not particularly limited.
  • the tetrafluoroethylene-propylene rubber is not particularly limited, and examples thereof include a copolymer containing a repeating unit represented by the general formula 1.
  • R is an electron donating substituent.
  • the electron donating substituent represented by R in General Formula 1 is not particularly limited, and examples thereof include (CH 3 ) 3 C—, (CH 3 ) 2 CH—, and CH 3 CH 2 —, CH 3 -, - O -, -S -, -N - R' and the like.
  • the R possessed by the repeating unit represented by General Formula 1 present in b molecules in one molecule may be the same in all repeating units or may be different from each other.
  • R ' represents an alkyl group.
  • the tetrafluoroethylene-propylene based fluororubber has a smaller deterioration point than the vinylidene fluoride-based fluororubber (FKM) which is a copolymer of vinylidene fluoride and hexafluoropropylene which are general fluororubbers.
  • FKM vinylidene fluoride-based fluororubber
  • HF hydrogen fluoride
  • FIG. 2A When an unsaturated bond, which is a degradation point, is generated and an addition reaction occurs between the unsaturated bond and an amine contained in a water-soluble coolant, engine oil or the like, cleavage occurs as shown in (c) of FIG. And cause cracking in the fluororubber.
  • the vinylidene fluoride structure represented by the formula A is contained in the fluororubber composition used in the present invention as in FKM, it may cause deterioration of the fluororubber composition as described above.
  • the rubber composition according to the present invention does not contain any fluorine-containing rubber having a vinylidene fluoride structure. Even when it is contained, the ratio of the number of vinylidene fluoride structures to the total number of repeating units of the fluororubber contained in the rubber composition is preferably 1% or less. If the above ratio is 1% or less, even when exposed to a water-soluble coolant, the effect on deterioration is extremely small in the entire rubber composition, and the problem of the present invention can be solved.
  • the “number of repeating units” means, for example, the sum of the number of tetrafluoroethylenes, the number of propylenes, and the number of propylene derivatives if the fluororubber is a tetrafluoroethylene-propylene rubber, and When the rubber is a tetrafluoroethylene-vinyl ether rubber, it refers to the sum of the number of tetrafluoroethylene, the number of vinyl ethers, and the number of vinyl ether derivatives.
  • a "propylene derivative” refers to the compound by which the hydrogen atom and / or the methyl group of a side chain of propylene were substituted by the other atom or the functional group.
  • a compound in which a methyl group of a propylene side chain is substituted with another atom or a functional group a compound in which a hydrogen atom of a methyl group in a propylene side chain is substituted with another functional group, a propylene main chain and / or The compound etc. by which the hydrogen atom of the side chain was substituted by the fluorine atom are included.
  • metal oxides such as magnesium oxide and zinc oxide as acid acceptors of HF (hydrogen fluoride) generated at the time of vulcanization It is not necessary to blend an acid acceptor such as metal oxide or metal hydroxide having high affinity with water like metal hydroxides such as calcium hydroxide and the like, and swelling by water is suppressed, in particular, Resistance to water-soluble coolant such as water-soluble cutting oil is improved.
  • tetrafluoroethylene-propylene rubber used in the present invention in addition to the copolymer containing a repeating unit represented by the general formula 1, for example, a copolymer of tetrafluoroethylene and perfluoropropylene can be mentioned.
  • the copolymer is difficult to use at a low temperature of about 5 ° C. or less, it does not have a vinylidene fluoride structure, and thus can exhibit excellent resistance to deterioration by a water-soluble coolant.
  • tetrafluoroethylene-vinyl ether rubber refers to a copolymer of tetrafluoroethylene and a vinyl ether and / or a derivative of vinyl ether.
  • the “derivative of vinyl ether” refers to a compound in which a hydrogen atom of a vinyl group contained in vinyl ether is substituted by another atom such as a fluorine atom.
  • the tetrafluoroethylene-vinyl ether rubber is not particularly limited, but is preferably a copolymer of tetrafluoroethylene and perfluorovinyl ether.
  • the vinyl ether and derivatives of vinyl ether are not particularly limited, and methyl vinyl ether, perfluoromethyl vinyl ether and the like can be used.
  • the ratio of tetrafluoroethylene in the molecules of tetrafluoroethylene-propylene rubber and tetrafluoroethylene-vinylether rubber is not particularly limited.
  • the nitrile rubber is a copolymer of acrylonitrile and 1,3-butadiene.
  • the nitrile rubber is used for the purpose of suppressing the deterioration of the mechanical strength of the rubber composition, and the hydrogenated nitrile rubber described later imparts ozone resistance to the rubber composition in addition thereto. Used for the purpose of
  • the ratio of acrylonitrile to 1,3-butadiene in the nitrile rubber is not particularly limited, but from the viewpoint of suppressing the swelling of the rubber composition in the environment exposed to the water-soluble coolant, the nitrile rubber has a so-called extreme height It is preferable that it is nitrile rubber. That is, the content of acrylonitrile group in one molecule of nitrile rubber is preferably 43 mol% or more and 60 mol% or less, and more preferably 43 mol% or more and 55 mol% or less.
  • the nitrile rubber in an environment exposed to ozone, ozone reacts with the double bond to form ozonite, and the ozonite finally becomes a hydroxide to break the bond. As a result, the rubber composition may be cracked. Therefore, in the rubber composition used under the environment, the nitrile rubber is preferably a hydrogenated nitrile rubber (HNBR). Hydrogenated nitrile rubber is one in which unstable unsaturated bonds in the polymer main chain of nitrile rubber are saturated by hydrogenation to improve chemical resistance, heat resistance, weather resistance, etc. It is a thing.
  • HNBR hydrogenated nitrile rubber
  • the ozone resistance of the rubber composition can be strengthened, and the deterioration of mechanical strength and the like can be reduced.
  • the hydrogenation of the nitrile rubber can be carried out by conventional known hydrogenation.
  • the proportion of double bonds in the hydrogenated nitrile rubber is preferably 10% or less when the number of all carbon-carbon bonds in the hydrogenated nitrile rubber is 100%.
  • the rubber composition according to the present invention is not necessarily used in an environment exposed to ozone. In such cases, the nitrile rubber does not necessarily have to be a hydrogenated nitrile rubber.
  • the rubber composition according to the present invention preferably has a weight ratio of fluororubber to nitrile rubber of 10:90 to 90:10 when the total weight of fluororubber and nitrile rubber is 100 parts by weight.
  • the inventors of the present invention found that the nitrile rubber is excellent in mechanical strength, but when the content is too large, the rubber composition tends to swell by a water-soluble coolant or the like, and the fluorine rubber resists deterioration by a water-soluble coolant or the like. However, if the content is too large, the mechanical strength of the rubber composition tends to weaken, and if too small, the rubber composition tends to swell due to a water-soluble coolant or the like.
  • the inventor examined the above weight ratio, and the weight ratio of the fluororubber and the nitrile rubber was 10:90 to 90 when the total weight of the fluororubber and the nitrile rubber was 100 parts by weight. It has been found that it is preferable that the ratio is 10 in order to maintain the strength of the rubber composition and prevent swelling.
  • the weight ratio is more preferably 30:70 to 70:30. Since the limit switch has the function of sliding contact between the movable part and the seal part, the mechanical strength and the swelling suppression property for preventing the liquid such as water-soluble coolant from intruding into the inside of the limit switch with respect to the rubber composition. In order to give
  • the above-mentioned fluorine-based oil functions as a plasticizer for fluorine rubber and nitrile rubber, has poor compatibility with a water-soluble coolant, and has a relatively low molecular weight, and thus tends to be present on the surface of the rubber composition. Deterioration and swelling of the rubber composition due to the coolant can be further suppressed.
  • the fluorine-containing oil for example perfluoropolyether (PFPE), CTFE oil (low polymer of chlorotrifluoroethylene), polytetrafluoroethylene (PTFE), fluoro ester (DOS, camphor acid C 7 fluoroalkyl ester, pyromellitic can be used trimellitate C 7 fluoroalkyl ester).
  • PFPE perfluoropolyether
  • CTFE oil low polymer of chlorotrifluoroethylene
  • PTFE polytetrafluoroethylene
  • DOS fluoro ester
  • camphor acid C 7 fluoroalkyl ester pyromellitic
  • trimellitate C 7 fluoroalkyl ester trimellitate C 7 fluoroalkyl ester
  • the content of the fluorine-based oil is too small, the low temperature properties deteriorate, and if it is too large, the mechanical strength and the processability decrease, so 1 to 10 with respect to 100 parts by weight of a rubber component consisting of fluorine rubber and nitrile rubber. It is preferable that it is a weight part.
  • the tetrafluoroethylene-propylene rubber and the tetrafluoroethylene-vinyl ether rubber do not cause dehydrofluorination reaction as described above, but have low vulcanization characteristics.
  • a peroxide-based vulcanizing agent By using a peroxide-based vulcanizing agent, the fluororubber and nitrile rubber used in the present invention can be simultaneously crosslinked.
  • the peroxide-based vulcanizing agent is not particularly limited, and examples thereof include alkyl, acyl, ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, and peroxyketal.
  • the curing agent include alkyl perester-based and percarbonate-based vulcanizing agents.
  • Each peroxide-based vulcanizing agent may be used alone or in combination.
  • the mixing ratio in the case of mixing and using may be arbitrary.
  • alkyl peroxide-based vulcanizing agents examples include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxy) -diisopropylbenzene. It can be used suitably.
  • acyl peroxide-based vulcanizing agent dicumyl peroxide, benzoyl peroxide or the like can be suitably used.
  • the content of the peroxide-based vulcanizing agent is preferably a content for satisfying the mechanical strength and the degree of swelling of the rubber composition targeted according to the use environment of the rubber composition of the present invention.
  • the content of peroxide-based vulcanizing agent is 0.1 to 20 parts by weight with respect to 100 parts by weight of a rubber component consisting of fluororubber and nitrile rubber. Is preferred. Since the limit switch has the function of sliding contact between the movable part and the seal part, the mechanical strength and the swelling suppression property for preventing the liquid such as water-soluble coolant from intruding into the inside of the limit switch with respect to the rubber composition. In order to give
  • a vulcanization acceleration auxiliary may be added to the rubber composition according to the present invention, if necessary.
  • the vulcanization acceleration coagent for example, polyallyl compounds such as triallyl isocyanate, triallyl cyanurate, etc., trimethylolpropane trimethacrylate, sodium stearate and the like can be suitably used.
  • the content of the vulcanization accelerating auxiliary is the mechanical strength and the degree of swelling of the rubber composition targeted according to the use environment of the rubber composition of the present invention It is preferable that it is content for satisfy
  • the content of the vulcanization acceleration auxiliary is 1 to 10 parts by weight with respect to 100 parts by weight of a rubber component consisting of fluororubber and nitrile rubber. Is preferred.
  • the limit switch is functionally in sliding contact with the movable part and the seal part, mechanical strength and swelling suppression are provided to prevent the liquid such as water-soluble coolant and the like from entering the inside of the limit switch with respect to the rubber composition. It is in order to have sex.
  • a filler to the rubber composition according to the present invention for reinforcement.
  • the filler for example, carbon black, talc, wollastonite, and mistron paper are suitable, and 20 to 70 parts by weight of these may be added to 100 parts by weight of a rubber component consisting of fluororubber and nitrile rubber. preferable.
  • acidic substances such as silica and clew are not preferable because they delay vulcanization.
  • dioctyl adipate As a plasticizer to the rubber composition concerning this invention.
  • DOA dioctyl adipate
  • the low temperature resistance can be improved while maintaining the swelling suppressing effect and mechanical strength of the rubber composition according to the present invention.
  • the high nitrile rubber having a high content of acrylonitrile group or the very high nitrile rubber is inferior in low-temperature resistance to nitrile rubber. Therefore, the addition of DOA is very effective.
  • tetrafluoroethylene-vinyl ether rubber is difficult to use in a low temperature environment of 0 ° C. or more and less than 5 ° C., the addition of DOA can improve the low temperature resistance, and the above-mentioned low temperature environment It can be used.
  • the addition amount of DOA is a compounding amount for satisfying the low temperature resistance characteristics while satisfying the mechanical strength and the degree of swelling of the rubber composition targeted according to the use environment of the rubber composition of the present invention.
  • the limit switch is functionally in contact with the movable portion and the seal portion, so that the rubber composition can be used under severe environments where the limit switch is used.
  • fluorine rubber and nitrile rubber are used to provide mechanical strength and swelling suppression ability to prevent liquid such as water-soluble coolant from invading the inside of the limit switch, and to satisfy low temperature resistance.
  • the amount is preferably 0 to 10 parts by weight with respect to 100 parts by weight of the rubber component.
  • rubber additives for example, an antiaging agent, a stabilizer, a releasing agent, etc.
  • an antiaging agent for example, an antiaging agent, a stabilizer, a releasing agent, etc.
  • the rubber composition according to the present invention is to achieve the suppression of deterioration of the rubber composition based on the hydrolysis reaction by the water-soluble coolant, the suppression of swelling of the rubber composition by the water-soluble coolant, and the impartation of ozone resistance to the rubber composition.
  • the present invention is obtained by examining components having a suppressing effect with respect to each deterioration factor, and finding an optimum combination of components, more preferably, uniquely finding the combination and blending balance. Finding such a combination and formulation balance is by no means easy.
  • the rubber composition according to the present invention can be used as a seal member of a movable part of an apparatus used under a severe environment exposed to a water-soluble coolant or the like, the rubber composition can be used under such a severe environment.
  • the combination and formulation balance there is no conventional knowledge on the combination and formulation balance that can impart sufficient mechanical strength and swelling suppression property.
  • the limit switch since the movable part and the seal part come into sliding contact in terms of function, high mechanical strength and high mechanical strength are provided to prevent the liquid such as the water-soluble coolant from invading the inside of the apparatus with respect to the rubber composition. It is required to provide high resistance to swelling, but the above combination which is compatible with high mechanical strength and high resistance to swelling, more preferably there is no conventional knowledge on the combination and formulation balance, It was very difficult to find
  • the oil resistance, cold resistance or heat resistance is linear according to the blending ratio of the components.
  • the rubber composition has the resistance to deterioration by the water-soluble coolant and the resistance against the deterioration by the composition containing fluorine rubber having no vinylidene fluoride structure, nitrile rubber, fluorine-based oil and peroxide-based vulcanizing agent.
  • the effect of significantly improving the swelling property can not be predicted even by combining the above-mentioned fluororubber, nitrile rubber, fluorocarbon oil and peroxide-based vulcanizing agent.
  • the component of the suitable rubber composition is intensively studied, and the fluororubber having no vinylidene fluoride structure is a nitrile
  • the fluororubber having no vinylidene fluoride structure is a nitrile
  • the rubber composition according to the present invention has excellent resistance to mechanical strength deterioration and swelling by a liquid such as a water-soluble coolant.
  • a liquid such as a water-soluble coolant.
  • it since it also has oil resistance, it can be used not only for water resistant coolant purpose but also for oil resistant purpose.
  • the method for producing the rubber composition according to the present invention is not particularly limited, and a conventionally known method can be used.
  • a conventionally known method can be used.
  • it is generally used after mixing fluoro rubber, nitrile rubber, fluoro oil and peroxide vulcanizing agent, other additives, etc. at a predetermined ratio and kneading with a roll, a closed-type kneader, etc.
  • it can be manufactured by being subjected to compression molding, injection molding or the like and vulcanization molding.
  • the shape of the fluororubber molded body can be any shape depending on the application, such as a ring shape, a sheet shape, a rod shape, and various complex block shapes.
  • a water-soluble coolant is a coolant which can be dissolved or emulsified in water, and usually, an amine compound is blended to be alkaline and a surfactant is blended to mix water and a base oil.
  • the water-soluble coolant include water-soluble cutting oil, engine oil, transmission oil, and brake oil, and also include steam generated in a factory line or the like.
  • the above water-soluble cutting oil is of emulsion type (mineral oil, fatty oil, etc. consisting of a component not soluble in water and surfactant, and when added to water, it becomes milky white in appearance), sosh bull type ( Water soluble components such as surfactants alone, or water soluble components and water insoluble components such as mineral oil and fatty oil, which become translucent or transparent in appearance when added to water), solution type It may be any of those which are composed of components soluble in water, and their appearance becomes clear when added to water and diluted.
  • emulsion type mineral oil, fatty oil, etc. consisting of a component not soluble in water and surfactant, and when added to water, it becomes milky white in appearance
  • sosh bull type Water soluble components such as surfactants alone, or water soluble components and water insoluble components such as mineral oil and fatty oil, which become translucent or transparent in appearance when added to water
  • solution type It may be any of those which are composed of components soluble in water, and their appearance becomes clear when added
  • the seal member according to the present invention contains the rubber composition according to the present invention, and the device according to the present invention comprises the seal member.
  • the shape of the seal member is not particularly limited, and may be changed as appropriate depending on the application. For example, O-rings, sheets, packings, gaskets and the like can be mentioned.
  • the seal member may appropriately contain components other than the rubber composition according to the present invention, as necessary.
  • a crosslinking agent, a crosslinking aid, a plasticizer, an antiaging agent, a filler, a coloring agent, a foaming agent, a processing aid and the like may be suitably contained.
  • the rubber composition according to the present invention is particularly used in an environment exposed to a water-soluble coolant or ozone since it is excellent in mechanical strength and swelling resistance.
  • a water-soluble coolant or ozone since it is excellent in mechanical strength and swelling resistance.
  • it is used for the sliding part of the device.
  • the seal member according to the present invention includes, for example, movable parts such as limit switches, safety door switches, robot arms and connectors, bent parts such as covering materials such as electric wires and cables, oil rings, door packings for machine tools, rubber boots And the like.
  • the device according to the present invention may be any device that may be used in an environment exposed to a water-soluble coolant or ozone.
  • machine tools in general such as limit switches, safety door switches, robot arms, connectors, bearings and the like.
  • FIG. 1 is a side view showing a part of a limit switch which is an example of a device having a seal member made of a rubber composition according to the present invention.
  • the limit switch 1 is connected to an outer end of a body case 2 in which a switching mechanism (not shown) is installed, a head 3 for operation connected to the upper part thereof, a rotary shaft 4 rotatably mounted on the head 3 and a rotary shaft 4
  • the lower end flat surface of the pressing member 8 biased downward by the spring 7 is pressed and abutted against the upper surface of the flat portion 4a which is formed of a fixed detection lever 5 and is cut and formed on a part of the rotating shaft 4.
  • the shaft 4 is held in a neutral position, and an actuator (plunger) 6 biased upward is received and supported on the lower surface of the flat portion 4a.
  • the seal member according to the present invention is formed in the annular groove 12 formed in the outer peripheral surface of the rotary shaft 4 in the sliding portion between the shaft insertion hole 9 formed in the head 3 and the rotary shaft 4
  • An O-ring 13 is fitted and mounted, and an O-ring 10 as a seal member is interposed also at the joint between the operation head 3 and the main body case 2.
  • the O-rings 10 and 13 as sealing members are constituted by the rubber composition according to the present invention, the O-rings 10 and 13 when exposed to a water-soluble coolant. Deterioration or swelling is sufficiently suppressed. As a result, entry of the water-soluble coolant into the sliding portion can be sufficiently suppressed, and the durability of the limit switch 1 can be improved.
  • hydrogenated nitrile rubber is used as the nitrile rubber, the generation of ozonite is suppressed even when the limit switch 1 is used in an environment where a large amount of ozone is present, so ozone by O-rings 10 and 13 is used. Deterioration can be sufficiently suppressed.
  • the rubber composition according to the present invention has a weight ratio of the fluororubber to the nitrile rubber of 10:90 to 90:10 when the total weight of the fluororubber and the nitrile rubber is 100 parts by weight. Is preferred.
  • the content of the fluororubber which does not contain a vinylidene fluoride structure and the content of the nitrile rubber are preferable ranges in achieving both the mechanical strength and the swelling suppression property of the rubber composition. There is. Therefore, while being able to suppress swelling by water-soluble coolant etc. more certainly, the practicality of a rubber composition is enough, excluding the influence of the deterioration resulting from the dehydrofluorination reaction by the amine contained in water-soluble coolant etc. Mechanical strength can be secured.
  • the fluororubber is preferably at least one of tetrafluoroethylene-propylene rubber and tetrafluoroethylene-vinylether rubber.
  • the fluororubber is a typical fluororubber having no vinylidene fluoride structure, a rubber composition having sufficient resistance to deterioration and swelling by a water-soluble coolant is provided at low cost. be able to.
  • the rubber composition according to the present invention may be a copolymer in which the tetrafluoroethylene-propylene rubber contains a repeating unit represented by the general formula 1.
  • the electron donating substituent is a methyl group.
  • the rubber composition is a copolymer of tetrafluoroethylene and propylene, so that the synthesis is easy and advantageous in cost.
  • the tetrafluoroethylene-vinyl ether rubber may be a copolymer of tetrafluoroethylene and perfluorovinyl ether.
  • the copolymer also has excellent deterioration resistance because it does not contain a vinylidene fluoride structure, and a dehydrofluorination reaction by an amine contained in a water-soluble coolant or the like does not occur. Therefore, it is possible to provide a rubber composition having sufficient resistance to deterioration and swelling due to a liquid such as a water-soluble coolant.
  • the tetrafluoroethylene-propylene rubber may be a copolymer of tetrafluoroethylene and perfluoropropylene.
  • the rubber composition described above has an electron withdrawing group in the side chain but does not contain a vinylidene fluoride structure and does not cause a dehydrofluorination reaction by an amine contained in a water-soluble coolant or the like. Have. Therefore, it is possible to provide a rubber composition having sufficient resistance to deterioration and swelling due to a liquid such as a water-soluble coolant.
  • the content of the acrylonitrile group in the nitrile rubber is preferably 43% by mole or more and 60% by mole or less. According to the above configuration, since the nitrile rubber is a so-called very high nitrile rubber, a rubber composition extremely excellent in oil resistance can be provided.
  • the nitrile rubber is preferably a hydrogenated nitrile rubber.
  • the hydrogenated nitrile rubber has a low content of carbon-carbon double bonds, so that the reaction between ozone and the double bonds hardly occurs. Therefore, deterioration of the rubber composition due to ozone can be significantly reduced, and a rubber composition capable of exhibiting sufficient ozone resistance even in an environment where ozone is present, such as a machining site, can be provided.
  • the fluorine-based oil is preferably a perfluoro-based oil.
  • the fluorine-based oil functions as a plasticizer for fluorine rubber and nitrile rubber, has poor compatibility with the water-soluble coolant, and has a relatively low molecular weight, so it is easily present on the surface of the rubber composition. Infiltration of the rubber composition can be suppressed. Therefore, according to the said structure, deterioration and swelling of a rubber composition can be suppressed further.
  • the seal member according to the present invention is characterized by containing the rubber composition according to the present invention.
  • An apparatus according to the present invention is characterized by including the seal member according to the present invention.
  • the rubber composition according to the present invention is sufficiently resistant to deterioration and swelling due to a liquid such as a water-soluble coolant and may further be sufficiently resistant to ozone.
  • the member can ensure sufficient sealing performance over a long period of time. Therefore, by applying the above-mentioned seal member to devices such as limit switches, safety door switches, cables, connectors, etc., even if these devices are exposed to the environment where the coolant is used or even the environment where a large amount of ozone exists, It is possible to sufficiently suppress the entry of water-soluble coolant or the like into a part or the like. Therefore, the durability of the device can be greatly improved, stable operation of the device can be enabled over a long period of time, and failure can be prevented.
  • Table 1 shows the results of measurement of the swelling ratio and the deterioration rate of mechanical strength which are the compounding and evaluation items of the components of the rubber composition in the examples and the comparative examples.
  • Example 1 the numerical values in the formulations of Examples and Comparative Examples mean parts by weight. After mixing each component by the composition shown in Table 1 and kneading with a roll, a closed-type kneader, etc., vulcanization molding is carried out by compression molding method, injection molding method, etc. according to commonly used crosslinking conditions, The rubber compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were produced.
  • FEPM is a copolymer of tetrafluoroethylene and propylene, and in the present example, one having a Mooney viscosity of about 100 is used.
  • HNBR1 and HNBR2 are both hydrogenated nitrile rubbers, HNBR1 is a so-called medium and high nitrile type, and HNBR2 is a so-called very high nitrile type hydrogenated nitrile rubber.
  • the content of acrylonitrile group in one molecule of hydrogenated nitrile rubber is 36 mol% of HNBR1 and 50 mol% of HNBR2.
  • Carbon is a reinforcing agent
  • 1,3,5-triarylisocyanurate is a co-crosslinking agent
  • bis (tert-butyldioxyisopropyl) benzene, dimethyldibutylperoxyhexine is a vulcanizing agent
  • sodium stearate is a vulcanization accelerating assistant
  • DOA is a plasticizer
  • perfluoropolyether is a fluorine-based oil.
  • test piece JIS No. 3 dumbbell piece of each rubber composition of the example and the comparative example of the composition shown in Table 1 was made of Glyton 1700 (liquid temperature 100 ° C., manufactured by Toho Chemical Industry Co., Ltd.) which is a water-soluble cutting oil. ) And the deterioration rate of the mechanical strength and the swelling rate were calculated according to the following formula.
  • Swelling percentage (%) ⁇ (weight of test piece after immersion ⁇ weight of test piece before immersion) / weight of test piece before immersion ⁇ ⁇ 100
  • the mechanical strength deterioration rate was measured for breaking strength (Tb) and elongation at break (Eb) according to JIS K6251 for test pieces not immersed in Grayton 1700, and it was 70 hours at Grayton 1700 (liquid temperature 100 ° C)
  • the breaking strength (Tb ') and the elongation at break (Eb') of the test pieces after immersion were measured, and the deterioration rate of mechanical strength was calculated according to the following equation.
  • Deterioration rate of mechanical strength (%) [ ⁇ (Tb ′ ⁇ Eb ′) ⁇ (Tb ⁇ Eb) ⁇ / (Tb ⁇ Eb)] ⁇ 100
  • the degradation rate of mechanical strength is preferably 10% or less
  • the swelling rate is preferably 10% or less.
  • Example 1 As shown in Table 1, in the rubber composition of Example 1, 30 parts by weight of FEPM and 70 parts by weight of extremely high nitrile type hydrogenated nitrile rubber (HNBR) were blended as 100 parts by weight of the rubber component, and further plasticized Fluorine-based oil is blended as an agent.
  • the swelling rate is 5.4% and the deterioration rate of mechanical strength is 0.5%, and both show good results, and the deterioration rate of mechanical strength is particularly small.
  • Example 2 Similar to Example 1, in the rubber composition of Example 2, 30 parts by weight of FEPM and 70 parts by weight of extremely high nitrile type HNBR were blended as 100 parts by weight of the rubber component, and further a fluorine-based oil was blended as a plasticizer. doing. In Example 2, the swelling rate is 5.5%, and the deterioration rate of mechanical strength shows good results, both being 6.1%. However, compared with Example 1, the blending amount of the fluorinated oil The rate of deterioration of mechanical strength is somewhat high, probably because
  • the rubber composition of Example 3 contains, as 100 parts by weight of the rubber component, 85 parts by weight of FEPM and 15 parts by weight of HNBR of very high nitrile type, and further contains a fluorine-based oil as a plasticizer.
  • the swelling rate is 7%, and the deterioration rate of mechanical strength is -4.2%, both showing good results.
  • the rubber composition of Comparative Example 1 does not contain nitrile rubber and fluorine-based oil. Therefore, the mechanical strength deterioration rate is considered to have exceeded 10%.
  • the rubber composition of Comparative Example 2 does not contain FEPM and a fluorinated oil. Therefore, it is considered that the swelling rate has become very large.
  • the rubber compositions of Examples 1 to 3 contain FEPM which does not contain a vinylidene fluoride structure as a rubber component, and an acid acceptor such as metal oxide or metal hydroxide having high affinity with water.
  • FEPM which does not contain a vinylidene fluoride structure as a rubber component
  • an acid acceptor such as metal oxide or metal hydroxide having high affinity with water.
  • the device provided with the seal member containing the rubber composition according to the present invention can maintain the seal performance well over a long period even when used in an environment where water-soluble cutting oil or the like is applied.
  • Example 4 Durability test using limit switch
  • vulcanization molding is performed by a compression molding method, an injection molding method, etc. according to the commonly used crosslinking conditions.
  • the rubber composition according to the present invention was produced.
  • Five lots of O-rings made of the rubber composition were prepared (described as samples 1 to 5 in Table 3), and attached to the limit switch 1 as O-rings 10 and 13 shown in FIG. 1, respectively.
  • As a control 5 lots of O-ring consisting only of nitrile rubber were used (described as samples A to E in Table 3).
  • test 1 In order to check the degree of penetration of water-soluble cutting oil into the switch and the degree of functionally harmful failure such as cracking or breakage, the switch 6 is turned on by pushing down and pushing up the actuator 6 in the water-soluble cutting oil. The operation of repeating off was performed 600,000 times (frequency: 240 times / minute) (this test is hereinafter referred to as “test 1”). Next, in order to confirm the water resistance of the limit switch 1, water in the switch after being submerged in 1 m of water for 30 minutes based on JIS C 4520 (section 8.18) and JIS C 0920 (section 4.8) The degree of invading was examined (this test is hereinafter referred to as "Test 2").
  • ⁇ indicates that the water-soluble cutting oil or water does not penetrate
  • x 1 indicates that the rubber composition is broken and the water-soluble cutting oil or water enters and the limit switch 1 Indicates a failure.
  • ⁇ * 2 the rubber composition was broken, water-soluble cutting oil or water infiltrated and the limit switch 1 failed, and a member called C spring inside the main body case 2 was broken. Indicates that.
  • the limit switch equipped with the O-ring containing the rubber composition according to the present invention shows no infiltration of water-soluble cutting oil and water even after 4 cycles, and no failure occurs.
  • the average number of cycles to failure occurrence of the limit switch equipped with the control O-ring made of nitrile rubber was 1.4 cycles.
  • FIG. 4 shows the limit switch subjected to test 1 and 2 for two cycles using the control O-ring (sample B in Table 3).
  • the crack has generate
  • the crack penetrated to the inner periphery of rubber
  • the limit switch is filled with a water-soluble coolant or water, and the limit switch has insulation resistance and pressure resistance. As a result of measuring, it was in an unusable state.
  • the insulation resistance was evaluated by measuring the resistance value at DV 500 V, and the withstand voltage was evaluated by applying a voltage of 1200 V for 1 minute and confirming that there was no leakage current of 10 mA or more.
  • FIG. 5 shows the results of observation of a member called C spring present inside the main body case 2 after subjecting the control sample B shown in Table 3 to tests 1 and 2 for two cycles.
  • the C spring shown in the photograph on the right side of FIG. 5 shows progress of fracture along the grain boundary as shown in the electron micrographs in the center and left side of FIG. It was shown.
  • FIG. 6 shows the appearance and the internal state of the sample 1 using the rubber composition according to the present invention shown in Table 3 after three cycles.
  • (a) and (d) of FIG. 6 in the limit switch using the rubber composition according to the present invention, no cracking of the rubber occurred and no abnormality was observed in the holding state of the rubber. .
  • the water-soluble coolant and the water did not infiltrate into the limit switch at all. Furthermore, as a result of measuring the insulation resistance of a limit switch and pressure
  • FIG. 7 shows the present invention after leaving the rubber composition according to the present invention and the control nitrile rubber around equipment of a machining line using an aqueous cutting oil (ozone concentration: 0.05 ppm) for 1 month. It shows the result of observing the appearance of the rubber composition and the nitrile rubber, and shows the result of confirming the ozone resistance.
  • ozone concentration 0.05 ppm
  • the rubber composition according to the present invention is sufficiently resistant to deterioration and swelling due to a water-soluble coolant, and may also be resistant to ozone. Therefore, the present invention can be widely applied to machine tools used in an environment exposed to water-soluble coolant and ozone.

Abstract

La présente invention concerne une composition de caoutchouc qui a une résistance à l'ozone suffisante et qui est suffisamment résistante à la dégradation et au gonflement causé par un liquide tel qu'un réfrigérant hydrosoluble. La présente invention concerne en outre des utilisations de la composition de caoutchouc. La composition de caoutchouc comprend : un fluoro-élastomère qui n'a pas de structure fluorure de vinylidène ; un caoutchouc nitrile ; une huile fluorée ; et un agent de vulcanisation à base de peroxyde.
PCT/JP2010/070401 2009-12-11 2010-11-16 Composition de caoutchouc et utilisations de celle-ci WO2011070896A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201080054082.8A CN102639629B (zh) 2009-12-11 2010-11-16 橡胶组合物及其利用
EP10835818.5A EP2511333B1 (fr) 2009-12-11 2010-11-16 Composition de caoutchouc et utilisations de celle-ci
US13/512,629 US8580892B2 (en) 2009-12-11 2010-11-16 Rubber composition and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009282234A JP5291608B2 (ja) 2009-12-11 2009-12-11 ゴム組成物およびその利用
JP2009-282234 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011070896A1 true WO2011070896A1 (fr) 2011-06-16

Family

ID=44145446

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/070401 WO2011070896A1 (fr) 2009-12-11 2010-11-16 Composition de caoutchouc et utilisations de celle-ci

Country Status (5)

Country Link
US (1) US8580892B2 (fr)
EP (1) EP2511333B1 (fr)
JP (1) JP5291608B2 (fr)
CN (1) CN102639629B (fr)
WO (1) WO2011070896A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321321A (zh) * 2011-08-31 2012-01-18 铜陵万通阀门有限公司 含氟橡胶阀体复合材料及其制备方法
CN102321322A (zh) * 2011-08-31 2012-01-18 铜陵万通阀门有限公司 一种含氟橡胶阀体复合材料及其制备方法
CN102352081A (zh) * 2011-08-31 2012-02-15 铜陵万通阀门有限公司 一种含氟橡胶复合胶料及其制备方法
CN102382403A (zh) * 2011-10-27 2012-03-21 安徽金源流体控制技术有限公司 橡胶阀体复合材料及其制备方法
CN102432962A (zh) * 2011-10-27 2012-05-02 安徽金源流体控制技术有限公司 一种橡胶阀体复合材料及其制备方法
CN104576110A (zh) * 2013-10-15 2015-04-29 欧姆龙株式会社 开关

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140191477A1 (en) * 2011-09-13 2014-07-10 Osamu Kobayashi Hydrogenated nitrile rubber composition
EP2955420A4 (fr) * 2013-02-18 2016-07-20 Eagle Ind Co Ltd Joint à lèvre pour pompe à eau
CN103467795A (zh) * 2013-09-18 2013-12-25 大连海事大学 一种水润滑橡胶轴承的制备方法
PL3102634T3 (pl) 2014-02-06 2020-11-16 Borealis Ag Miękkie i przezroczyste kopolimery odporne na uderzenia
CN104861226A (zh) * 2015-04-29 2015-08-26 洛阳市河之阳高分子材料有限公司 一种用于汽车防尘罩的聚丙烯材料及其制备方法
JP6628697B2 (ja) 2015-09-30 2020-01-15 パナソニック株式会社 非水電解質二次電池
JP6455420B2 (ja) * 2015-12-25 2019-01-23 オムロン株式会社 電子機器およびその製造方法
EP3255088B1 (fr) * 2016-06-07 2020-04-29 ARLANXEO Deutschland GmbH Utilisation de compositions vulcanisables et vulcanisats en contact avec un agent de refroidissement comprenant un wollastonite recouvert de silane
JP6846781B2 (ja) * 2017-05-31 2021-03-24 国立大学法人大阪大学 積層体及びその製造方法
CA3134255C (fr) * 2019-03-26 2023-08-29 Nippon Soda Co., Ltd. Composition de caoutchouc fluore contenant du polybutadiene epoxyde
CN115850887A (zh) * 2022-12-07 2023-03-28 江苏中煜橡塑科技有限公司 一种低成本低压缩永久变形氟橡胶组合物及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04126727A (ja) * 1989-06-23 1992-04-27 Nippon Valqua Ind Ltd 代替フロン用ゴム成形体およびその製造方法
JPH04268357A (ja) * 1991-02-25 1992-09-24 Asahi Chem Ind Co Ltd 低硬度フッ素ゴム加硫組成物
WO1993020148A1 (fr) * 1992-03-30 1993-10-14 Idemitsu Kosan Co., Ltd. Palier et composition de resine
JPH05296233A (ja) * 1992-04-16 1993-11-09 Ntn Corp ロール軸受の密封装置
JPH0967473A (ja) 1995-09-04 1997-03-11 Nippon Valqua Ind Ltd ゴム組成物および該組成物からなるゴム成形体
JP2000281856A (ja) * 1999-03-30 2000-10-10 Asahi Glass Co Ltd 架橋性弾性共重合体組成物
JP2002310171A (ja) * 2001-04-10 2002-10-23 Nsk Ltd 転がり軸受
JP2005135780A (ja) 2003-10-31 2005-05-26 Yamatake Corp リミットスイッチ

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62190241A (ja) * 1986-02-14 1987-08-20 Mitsubishi Cable Ind Ltd 耐熱耐油性ゴム組成物
JPH10110080A (ja) * 1996-10-08 1998-04-28 Tokai Rubber Ind Ltd 導電性フッ素系ゴム組成物
EP1130057B1 (fr) 1998-06-16 2004-03-24 Asahi Glass Company Ltd. Composition copolymere elastique pouvant etre reticulee
JP2000318042A (ja) 1999-05-17 2000-11-21 Takeshi Hiramatsu 加工性が改善されたゴムライニング材
US6905637B2 (en) * 2001-01-18 2005-06-14 General Electric Company Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom
US6572269B2 (en) 2000-11-30 2003-06-03 Nsk Ltd. Bearing apparatus
ITMI20012165A1 (it) 2001-10-18 2003-04-18 Ausimont Spa Perfluoroelastomeri
CA2436742A1 (fr) * 2003-06-26 2004-12-26 Bayer Inc. Melanges de polymeres contenant du caoutchouc nitrile
DE602007001540D1 (de) 2006-02-13 2009-08-27 Shinetsu Chemical Co Härtbare Fluorpolyether-Zusammensetzungen und in einem Stück geformete Harz/Gummi-Produkte
JP2007238928A (ja) 2006-02-13 2007-09-20 Shin Etsu Chem Co Ltd 硬化性フルオロポリエーテル組成物及びそれを用いたゴム硬化物と有機樹脂との一体成型品
US7608216B2 (en) * 2006-12-27 2009-10-27 Freudenberg-Nok General Partnership Methods for preparing articles from processable and dimensionally stable elastomer compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04126727A (ja) * 1989-06-23 1992-04-27 Nippon Valqua Ind Ltd 代替フロン用ゴム成形体およびその製造方法
JPH04268357A (ja) * 1991-02-25 1992-09-24 Asahi Chem Ind Co Ltd 低硬度フッ素ゴム加硫組成物
WO1993020148A1 (fr) * 1992-03-30 1993-10-14 Idemitsu Kosan Co., Ltd. Palier et composition de resine
JPH05296233A (ja) * 1992-04-16 1993-11-09 Ntn Corp ロール軸受の密封装置
JPH0967473A (ja) 1995-09-04 1997-03-11 Nippon Valqua Ind Ltd ゴム組成物および該組成物からなるゴム成形体
JP2000281856A (ja) * 1999-03-30 2000-10-10 Asahi Glass Co Ltd 架橋性弾性共重合体組成物
JP2002310171A (ja) * 2001-04-10 2002-10-23 Nsk Ltd 転がり軸受
JP2005135780A (ja) 2003-10-31 2005-05-26 Yamatake Corp リミットスイッチ

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102321321A (zh) * 2011-08-31 2012-01-18 铜陵万通阀门有限公司 含氟橡胶阀体复合材料及其制备方法
CN102321322A (zh) * 2011-08-31 2012-01-18 铜陵万通阀门有限公司 一种含氟橡胶阀体复合材料及其制备方法
CN102352081A (zh) * 2011-08-31 2012-02-15 铜陵万通阀门有限公司 一种含氟橡胶复合胶料及其制备方法
CN102382403A (zh) * 2011-10-27 2012-03-21 安徽金源流体控制技术有限公司 橡胶阀体复合材料及其制备方法
CN102432962A (zh) * 2011-10-27 2012-05-02 安徽金源流体控制技术有限公司 一种橡胶阀体复合材料及其制备方法
CN102432962B (zh) * 2011-10-27 2014-04-09 安徽金源流体控制技术有限公司 一种橡胶阀体复合材料及其制备方法
CN104576110A (zh) * 2013-10-15 2015-04-29 欧姆龙株式会社 开关

Also Published As

Publication number Publication date
US8580892B2 (en) 2013-11-12
EP2511333B1 (fr) 2017-10-18
EP2511333A1 (fr) 2012-10-17
EP2511333A4 (fr) 2015-08-26
CN102639629B (zh) 2014-01-01
CN102639629A (zh) 2012-08-15
JP5291608B2 (ja) 2013-09-18
US20120309881A1 (en) 2012-12-06
JP2011122105A (ja) 2011-06-23

Similar Documents

Publication Publication Date Title
WO2011070896A1 (fr) Composition de caoutchouc et utilisations de celle-ci
KR100854944B1 (ko) 수소화 니트릴 고무 조성물
KR101640953B1 (ko) 내크랙성 실재를 형성 가능한 불소고무 조성물 및 그 조성물로부터 얻어지는 내크랙성 실재
JP6288398B2 (ja) フッ素ゴム組成物
KR20140002779A (ko) 워터 펌프용 립 시일
JP5440605B2 (ja) シール材
TW200535189A (en) Perfluoroelastomer composition for use in vulcanization and method for making a molded perfluoroelastomer product
JP2011168630A (ja) 耐燃料透過性の良好な耐寒フッ素ゴム組成物
JP2004026897A (ja) タイヤ加硫用ブラダー用ゴム組成物及びタイヤ加硫用ブラダー
JP3950353B2 (ja) 低温フッ素系エラストマー組成物
JP4509516B2 (ja) フッ素ゴム系シール材用組成物及びフッ素ゴム系シール材
JP2005140196A (ja) 燃料電池用ガスケット
JP4651202B2 (ja) シール材用ゴム組成物を用いたシール材
JP3840230B2 (ja) ゴム組成物
JP4712960B2 (ja) シール材
JP2004307765A (ja) ふっ素ゴム系配合物
JP6134293B2 (ja) 封止材
JP2005344037A (ja) 水素化ｎｂｒゴム組成物
JP2016079200A (ja) フッ素ゴム組成物、及び該フッ素ゴム組成物を用いたシール材を具備するシール構造
JP2015013972A (ja) フッ素ゴム系シール材用組成物およびフッ素ゴム系シール材
JP2002194156A (ja) シール材用ゴム組成物およびそれを用いたシール材
JP5711870B2 (ja) 封止材
JP5698976B2 (ja) エラストマーの架橋ブレンドを含有する組成物に基づく物品
JP2007100109A (ja) 含フッ素共重合体ブレンド物架橋成形品
JPH038666B2 (fr)

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080054082.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10835818

Country of ref document: EP

Kind code of ref document: A1

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10835818

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2010835818

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2010835818

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13512629

Country of ref document: US