Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16J—PISTONS; CYLINDERS; SEALINGS
  • F16J15/00—Sealings
  • F16J15/02—Sealings between relatively-stationary surfaces
  • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
  • F16J15/064—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces the packing combining the sealing function with other functions
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16J—PISTONS; CYLINDERS; SEALINGS
  • F16J15/00—Sealings
  • F16J15/02—Sealings between relatively-stationary surfaces
  • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
  • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
  • F16J15/102—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/083—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds
• • 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
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0642—Copolymers containing at least three different monomers

Definitions

• the present invention relates to a rubber composition and a vulcanized molded product using the same.
• rubber materials such as nitrile rubber (NBR), fluororubber (FKM), and acrylic rubber (ACM) have been made of various rubber molded products (for example, sealing parts, electrical insulators, anti-vibration rubber, sound-proof rubber, etc. It is widely used as a material for general industrial rubber, etc.).
• NBR nitrile rubber
• FKM fluororubber
• ACM acrylic rubber
• these materials have a problem that they cannot exhibit sufficient rubber properties in a low temperature environment (for example, ⁇ 40 ° C. or lower), and there is a demand for the use of a rubber material having excellent cold resistance.
• EPDM ethylene / propylene / diene ternary copolymer
• Ethylene-butene-diene ternary copolymer is attracting attention as a rubber material to replace EPDM.
• Patent Document 1 describes a rubber composition containing an ethylene-butene-diene ternary copolymer (EBENB) as an ethylene-butene-diene ternary copolymer and a filler such as carbon black, silicic acid, and silicate. It is disclosed that the sealing component for high-pressure hydrogen equipment manufactured by using the above is excellent in low-temperature sealing property and blister resistance.
• Patent Document 2 by using a rubber composition containing EBENB, carbon black, a hardness adjusting agent, and a cross-linking agent, the rubber composition has a hardness equivalent to that of a conventional rubber product using EPDM, and is a low-temperature seal. It is disclosed that a rubber molded product having excellent properties can be obtained.
• Patent Documents 1 and 2 teach that, for example, by using a rubber composition containing EBENB and carbon black, an excellent low-temperature sealing property can be imparted to a rubber molded product (seal part), but electricity No mention is made of insulation and kneading processability. Therefore, it is desired to develop a rubber composition which can impart both low-temperature sealing property and electrical insulating property to the sealing component and has excellent kneading processability. In addition, since the sealing product is partially permanently deformed (distorted) after long-term use and the sealing performance is deteriorated, good compression permanent strain characteristics are also obtained when the rubber composition is applied to the sealing application. desired.
• the present invention provides a rubber composition suitable for producing a vulcanized molded product having excellent kneading processability, good compression set characteristics, low temperature characteristics and excellent electrical insulation properties.
• the rubber composition according to the embodiment of the present invention is crosslinked with an ethylene-butene-diene ternary copolymer, silica having a CTAB specific surface area of 30 m 2 / g or more and 150 m 2 / g or less, and a silane coupling agent.
• the content of the silica with respect to 100 parts by weight of the ethylene-butene-diene ternary copolymer containing the agent is 25 parts by weight or more and 90 parts by weight or less.
• the ethylene-butene-diene ternary copolymer is an ethylene-butene-ethylidene norbornene ternary copolymer.
• the iodine value of the ethylene-butene-diene ternary copolymer is 3 or more and 20 or less.
• the content of the silane coupling agent with respect to 100 parts by weight of the ethylene-butene-diene ternary copolymer is 0.5 parts by weight or more and 3.0 parts by weight or less.
• the cross-linking agent is an organic peroxide.
• the vulcanized molded product according to the embodiment of the present invention is obtained by vulcanizing the rubber composition.
• the value of TR-70 measured in accordance with JIS K6261: 2006 is ⁇ 40 ° C. or lower.
• the volume resistivity measured in accordance with JIS K6271-1: 2015 is 1 ⁇ 10 12 ⁇ ⁇ cm or more.
• the compression set is 20% or less measured under the conditions of 130 ° C. and 70 hours in accordance with JIS K6262: 2013.
• the vulcanized molded product is a sealing part.
• a rubber composition suitable for producing a vulcanized molded product having excellent kneading processability, good compression set characteristics, low temperature characteristics and excellent electrical insulation properties.
• the rubber composition according to the present embodiment includes an ethylene-butene-diene ternary copolymer as a rubber component (hereinafter, also referred to as "EBDM"), silica as a filler, a silane coupling agent, and a cross-linking agent. And contains.
• EBDM ethylene-butene-diene ternary copolymer
• silica as a filler
• silane coupling agent e.g., ethylene-butene-diene ternary copolymer
• a cross-linking agent e.g., ethylene-butene-diene ternary copolymer
• the silica used has a CTAB specific surface area of 30 m 2 / g or more and 150 m 2 / g or less, and the content of silica in the rubber composition with respect to 100 parts by weight of the ethylene-butene-diene ternary copolymer is , 25 parts by weight or more and 90 parts by weight
• the EBDM-containing rubber composition according to the present embodiment by blending silica having a predetermined CTAB specific surface area within a predetermined content range, it is excellent in kneading processability and has both low temperature characteristics and electrical insulation.
• a rubber composition suitable for producing an excellent vulcanized molded product can be obtained.
• the silane coupling agent good compression set characteristics are imparted to the obtained vulcanized molded product.
• the sealing component as an example of the usage form of such a vulcanized molded product exhibits excellent sealing performance in a low temperature environment.
• the rubber composition contains EBDM as a main component (rubber component) for the vulcanized molded product.
• EBDM ethylene-butene-diene ternary copolymer
• an ethylene-butene-ethylidene norbornene ternary copolymer (hereinafter, also referred to as "EBENB) is preferable.
• EBENB ethylene-butene-ethylidene norbornene ternary copolymer
• the characteristics of rubber materials such as EBENB and EPDM have a great influence on the material cost and production efficiency of the entire rubber composition (or vulcanized molded product).
• EBDM is superior in flexibility to EPDM, it is excellent in cold resistance (low temperature characteristics), and is also excellent in processability such as kneading property, dispersibility, and moldability, and thus production efficiency is greatly improved. It is possible to reduce the cost in the production process.
• the low temperature characteristics are excellent as compared with the conventional rubber composition using EPDM, and from the viewpoint of material cost and production efficiency. Therefore, the production cost of the vulcanized molded product can be reduced.
• EBENB any of ethylene and butene obtained by copolymerizing various diene components can be used.
• EBENB is not particularly limited as long as it is a copolymer of ethylene and butene with various diene components.
• a copolymer produced by synthesizing each monomer component may be used, or various commercially available products such as "EBT K-9330M” manufactured by Mitsui Chemicals, Inc. may be used as they are.
• the iodine value (g / 100 g) of EBDM is preferably 3 or more and 20 or less, and more preferably 5 or more and 18 or less.
• the iodine value is in the range of 3 or more and 20 or less, excellent heat aging resistance and weather resistance are imparted to the vulcanized molded product, and deterioration of the vulcanized molded product can be prevented.
• a stable molecular state of EBDM can be maintained even in a low temperature environment, and low temperature characteristics can be improved.
• EBDM Compared with EPDM, EBDM has a smaller polymer viscosity represented by Mooney viscosity ML 1 + 4 (100 ° C.) and is also excellent in processability (for example, kneadability, moldability, etc.). Therefore, by using EBDM instead of EPDM, productivity such as molding efficiency can be improved and production cost can be reduced.
• the Mooney viscosity ML 1 + 4 (100 ° C.) of such EBDM is preferably 10 or more and 45 or less, and more preferably 15 or more and 35 or less.
• Mooney viscosity ML 1 + 4 (100 ° C.) When the Mooney viscosity ML 1 + 4 (100 ° C.) is 10 or more, it is possible to prevent the compression set from becoming too large in the vulcanized molded product, and it is possible to impart an appropriate tensile strength. Further, when the Mooney viscosity ML 1 + 4 (100 ° C.) is 45 or less, it is possible to prevent the rubber composition from being deteriorated in processability.
• the Mooney viscosity ML 1 + 4 (100 ° C.) can be measured in accordance with the provisions of JIS K6300-1: 2013.
• the content of the ethylene component in the EBDM is preferably 60 mol% or more and 80 mol% or less, and more preferably 65 mol% or more and 75 mol% or less.
• the glass transition temperature Tg of EBDM shows the minimum value, and the cold resistance is improved.
• the EBDM constituting the rubber component may be used alone or in combination of two or more. Further, as another rubber component, ethylene / propylene / diene ternary copolymer (EPDM) or the like can also be used in combination.
• EPDM ethylene / propylene / diene ternary copolymer
• the rubber composition contains silica having a CTAB (cetyltrimethylammonium bromide) specific surface area of 30 m 2 / g or more and 150 m 2 / g or less.
• CTAB cetyltrimethylammonium bromide
• the CTAB specific surface area of silica is in the range of 30 m 2 / g or more and 150 m 2 / g or less
• the rubber composition adheres to the roll surface of the kneader, particularly the roll kneader, in the kneading step of the rubber composition. This is suppressed and the kneading processability is improved. As a result, workability in the kneading process is improved, and productivity can be improved.
• silica having a CTAB specific surface area of 150 m 2 / g or less the dispersibility of silica is improved and the compression set characteristics are improved.
• the CTAB specific surface area of silica is preferably in the range of 30 m 2 / g or more and 100 m 2 / g or less, and by using silica having such a CTAB specific surface area range, the compression set of permanent strain characteristics is further improved. To do.
• silica commercially available, for example, manufactured by Tosoh Silica Corporation of "Nipsil E74P" (CTAB specific surface area: 33m 2 / g), Evonik Co. "Carplex (registered trademark) # 101" (CTAB specific surface area: 50 m 2 / g), Ebonic's "Ultrasil® 360” (CTAB specific surface area: 55 m 2 / g), Ebonic's "Carplex® # 1120” (CTAB specific surface area: 85 m 2 / g), "Nipsil ER” (CTAB specific surface area: 115 m 2 / g) manufactured by Toso Silica and "Carplex (registered trademark) # 67" (CTAB specific surface area: 140 m 2 / g) manufactured by Ebonic can be used. It can.
• One type of silica may be used alone, or two or more types may be used in combination.
• the content of silica contained in the rubber composition is preferably 30 parts by weight or more and 90 parts by weight or less, and more preferably 30 parts by weight or more and 70 parts by weight or less with respect to 100 parts by weight of EBDM.
• the rubber composition exhibits excellent kneading processability, and the vulcanized molded product is provided with excellent low temperature characteristics.
• a rubber composition capable of producing a vulcanized molded product having excellent kneading processability and excellent low temperature characteristics. can be provided.
• the silica content is preferably 30 parts by weight or more and 70 parts by weight or less, and by strictly controlling the silica content according to a desired hardness, the compression set of permanent strain characteristics is further improved.
• the rubber composition may further contain a filler other than silica.
• a filler other than silica is used in combination, if the silica content is within the above range, the type and blending amount of the other filler can be arbitrarily determined according to the purpose. it can.
• carbon black, calcium carbonate, clay, talc, etc. which are generally used as reinforcing materials to be added to the rubber composition, may be appropriately added so as to obtain desired physical characteristics.
• a filler showing conductivity such as carbon black is combined for coloring, the vulcanized molded product is appropriately adjusted within a range showing desired electrical insulation.
• the rubber composition according to this embodiment further contains a silane coupling agent.
• the silane coupling agent include vinyl group-containing alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane, ⁇ -aminopropyltriethoxysilane, and ⁇ -aminopropyltrimethoxysilane. , N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane and other amino group-containing alkoxysilanes.
• the silane coupling agent may be used alone or in combination of two or more.
• the blending amount of the silane coupling agent is not particularly limited, but is 0.5 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of EBDM, and 0.5 parts by weight or more and 1.5 parts by weight. The following is preferable.
• a cross-linking agent for forming a cross-linking of EBDM is further contained.
• an organic peroxide is mainly preferable.
• the organic peroxide include dialkyl peroxides, peroxyketals, diacyl peroxides, peroxyesters and the like. Specifically, tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tert-).
• the cross-linking agent may be used alone or in combination of two or more.
• the blending amount of the cross-linking agent is preferably 0.5 parts by weight or more and 10 parts by weight or less, and more preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of EBDM.
• amount of the cross-linking agent is in the range of 0.5 parts by weight or more and 10 parts by weight or less, it is possible to prevent the rubber composition from foaming during vulcanization of EBDM and the vulcanization molding cannot be performed, and the cross-linking density is good. Therefore, it becomes easy to manufacture a vulcanized molded product having sufficient physical characteristics.
• a commercially available product may be used as it is, or a master batch containing the above-mentioned organic peroxide may be used.
• a masterbatch is preferable because it can improve kneadability and dispersibility when preparing a rubber composition.
• the rubber composition according to the present embodiment may further contain a cross-linking accelerator, if necessary.
• a cross-linking accelerator triallyl isocyanurate (TAIC), triallyl cyanate (TAC), liquid polybutadiene, N, N'-m-phenylenedimaleimide, trimethylolpropane trimethacrylate and the like can be used.
• the cross-linking agent may be used alone or in combination of two or more.
• the amount of the cross-linking accelerator to be blended is not particularly limited, but is preferably 0.5 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of EBDM.
• the rubber composition according to the present embodiment may further contain a plasticizer, if necessary.
• the plasticizer include process oils containing aliphatic hydrocarbons as a main component, for example, "Diana Process Oil PW-380" manufactured by Idemitsu Kosan Co., Ltd. and "Diana Process Oil PW-220” manufactured by Idemitsu Kosan Co., Ltd. ..
• the plasticizer may be used alone or in combination of two or more.
• the process oil has a smaller molecule than the paraffin wax having a similar chemical structure, it is more preferable in that it exerts a unique effect that cannot be achieved when the paraffin wax is blended.
• the blending amount of the plasticizer is not particularly limited, but is preferably 1.0 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of EBDM.
• the rubber composition according to the present embodiment may further contain a lubricant, if necessary.
• the lubricant has a melting point of 50 ° C. to 100 ° C., which is near the surface temperature of the kneader, and a fatty acid-based lubricant is mainly preferable.
• the fatty acid-based lubricant include fatty acid amide, fatty acid zinc, and fatty acid ester.
• the fatty acid amide include saturated fatty acid amide and unsaturated fatty acid amide, and depending on the structure, monoamide, substituted amide, bisamide, and methylolamide may be used.
• Examples of zinc fatty acid include zinc saturated fatty acid, zinc unsaturated fatty acid, derivatives thereof, and mixtures thereof.
• fatty acid esters examples include lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid.
• non-zinc lubricants and organosilicone lubricants can also be applied.
• the blending amount of the lubricant is not particularly limited, but is preferably 0.5 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of EBDM.
• a rubber compounding agent generally used in the rubber industry such as an antacid and an antioxidant may be appropriately added to the rubber composition, if necessary.
• the total amount of each rubber compounding agent is preferably 300 parts by weight or less with respect to 100 parts by weight of EBDM.
• the method for producing the rubber composition according to the present embodiment is not particularly limited, but the EBDM, silica, silane coupling agent and cross-linking agent described above, and any of the above-mentioned blending agents, if necessary, are blended.
• the rubber composition is kneaded by using a kneader such as a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, a kneader, or a high-shear mixer. Can be manufactured. Pre-kneading may be performed before kneading, if necessary.
• a vulcanized molded product can be produced by vulcanization molding of the rubber composition according to the present embodiment.
• Vulcanization molding of the rubber composition is generally carried out by pressure vulcanization at about 150 to 230 ° C. for about 0.5 to 30 minutes using an injection molding machine, a compression molding machine or the like.
• secondary vulcanization may be performed as necessary in order to reliably vulcanize the inside of the vulcanized molded product.
• Secondary vulcanization can generally be carried out by oven heating at about 150-250 ° C. for about 0.5-24 hours.
• the vulcanized molded product obtained by vulcanizing the rubber composition according to the present embodiment exhibits excellent low temperature characteristics even at ⁇ 40 ° C. or lower, and in a low temperature environment (for example, ⁇ 40 ° C. to ⁇ 60 ° C.). ) Is suitable for use.
• the low temperature characteristics of such a vulcanized molded product for example, the value of TR-70 measured in accordance with JIS K6261: 2006 is preferably ⁇ 40 ° C. or lower.
• the vulcanized molded product obtained by vulcanizing the rubber composition according to the present embodiment exhibits excellent electrical insulation.
• the electrical insulation of such a vulcanized molded product for example, the volume resistivity measured in accordance with JIS K6271-1: 2015 is preferably 1 ⁇ 10 12 ⁇ ⁇ cm or more.
• the vulcanized molded product obtained by vulcanizing the rubber composition according to the present embodiment has good compression set characteristics.
• the compression set characteristics of such a vulcanized molded product for example, the compression set rate measured at 130 ° C. and 70 hours in accordance with JIS K6262: 2013 is preferably 20% or less. More preferably, it is less than%.
• the vulcanized molded product according to the present embodiment exhibits good compression set characteristics, and is also excellent in low temperature characteristics and electrical insulation properties, and is therefore suitable for use as, for example, a sealing component or an insulator.
• a sealing component when the vulcanized molded product is a sealing component, such a sealing component exhibits excellent sealing performance in a low temperature environment.
• a sealing component that requires sealing property and electrical insulation property in a low temperature environment it is suitable for use as a gasket for electromobility (e-M Firmbility).
• the shape of the vulcanized molded product is not particularly limited, and various shapes can be made according to the application.
• the shape of the sealing part includes an O-ring, a gasket, a packing, a sheet, and the like.
• the vulcanized molded product is not limited to the above-mentioned seal parts, but is also suitable as other industrial seal parts such as an insulating seal and a seal for cold regions.
• EBDM iodine value: 16 (g / 100), product name "EBT K-9330M”, manufactured by Mitsui Kagaku Co., Ltd.
• silica A product name "Nipsil E74P”, manufactured by Toso Silane Co., Ltd.
• Silane coupling agent trade name "A171”, manufactured by Momentive
• cross-linking agent trade name "Park Mill D”, manufactured by Nihon Kasei Co., Ltd.
• lubricant trade name "Diamid 0-200T", 1 part by weight (manufactured by Nihon Kasei Co., Ltd.) was kneaded with an open roll kneader to prepare a rubber composition.
• the obtained rubber composition was subjected to pressure vulcanization (primary vulcanization) at 180 ° C. for 10 minutes and open vulcanization (secondary vulcanization) at 150 ° C. for 24 hours using a sheet mold for testing.
• a sheet-shaped vulcanized molded product having a thickness of 2 mm was produced as a piece.
• the temperature of the obtained vulcanized molded product test piece was measured in TR-70 in accordance with JIS K6261: 2006.
• TR-70 is a temperature at which the shrinkage rate becomes 70% when the test piece is stretched by 50%, frozen, and then heated to recover the elastic modulus.
• Example 2 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that the blending amount of silica A was 60 parts by weight, and the above measurement and evaluation were performed. The results are shown in Table 1.
• Example 3 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that the blending amount of silica A was 90 parts by weight, and the above measurement and evaluation were performed. The results are shown in Table 1.
• Example 4 The rubber composition and its vulcanized molded product were prepared in the same manner as in Example 1 except that silica B (trade name: "Carplex (registered trademark) # 101", manufactured by Evonik Industries, Inc.) was used instead of silica A. It was prepared and the above measurements and evaluations were performed. The results are shown in Table 1.
• silica B trade name: "Carplex (registered trademark) # 101", manufactured by Evonik Industries, Inc.
• Example 5 A rubber composition and a vulcanized molded product thereof were produced in the same manner as in Example 1 except that silica C (trade name: "Ultrasil (registered trademark) 360", manufactured by Evonik Industries, Inc.) was used instead of silica A. Then, the above measurement and evaluation were carried out. The results are shown in Table 1.
• silica C trade name: "Ultrasil (registered trademark) 360", manufactured by Evonik Industries, Inc.
• Example 6 A rubber composition and a vulcanized molded product thereof in the same manner as in Example 1 except that silica D (trade name: "Carplex (registered trademark) # 1120", manufactured by Evonik Industries, Inc.) was used instead of silica A. was prepared and the above measurement and evaluation were performed. The results are shown in Table 1.
• silica D trade name: "Carplex (registered trademark) # 1120", manufactured by Evonik Industries, Inc.
• Example 7 A rubber composition and a vulcanized molded product thereof were produced in the same manner as in Example 1 except that silica E (trade name: "Nipsil ER", manufactured by Tosoh Silica Co., Ltd.) was used instead of silica A. , The above measurements and evaluations were performed. The results are shown in Table 1.
• Example 8 The rubber composition and its vulcanized molded product were prepared in the same manner as in Example 1 except that silica F (trade name: "Carplex (registered trademark) # 67", manufactured by Evonik Industries, Inc.) was used instead of silica A. It was prepared and the above measurements and evaluations were performed. The results are shown in Table 1.
• silica F trade name: "Carplex (registered trademark) # 67", manufactured by Evonik Industries, Inc.
• Example 1 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that the blending amount of silica A was 20 parts by weight, and the above measurement and evaluation were performed. The results are shown in Table 1.
• Example 2 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that the blending amount of silica A was 100 parts by weight, and the above measurement and evaluation were performed. The results are shown in Table 1.
• Example 3 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that 30 parts by weight of silica G (trade name: "Nippil LP", manufactured by Evonik Industries, Inc.) was blended in place of silica A. The above measurements and evaluations were carried out. The results are shown in Table 1.
• Example 4 The rubber composition and its vulcanization molding were carried out in the same manner as in Example 1 except that 20 parts by weight of silica H (trade name: "Ultrasil (registered trademark) 9500GR", manufactured by Evonik Industries, Inc.) was blended in place of silica A. A product was prepared and the above measurement and evaluation were performed. The results are shown in Table 1.
• silica H trade name: "Ultrasil (registered trademark) 9500GR", manufactured by Evonik Industries, Inc.
• Example 6 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that the silane coupling agent was not contained, and the above measurement and evaluation were performed. The results are shown in Table 1.
• Example 7 A rubber composition and a vulcanized molded product thereof were prepared in the same manner as in Example 1 except that EPDM (trade name: "EP33", manufactured by JSR Corporation) was blended in place of EBDM, and the above measurement and the above measurement were performed. Evaluation was performed. The results are shown in Table 1.
• EPDM trade name: "EP33", manufactured by JSR Corporation
• -EBDM Ethylene butene-diene ternary copolymer (iodine value: 16 (g / 100), trade name "EBT K-9330M”, manufactured by Mitsui Chemicals, Inc.)
• EPDM Ethylene-propylene-diene ternary copolymer (trade name "EP33”, manufactured by JSR Corporation)
• -Silica A Product name "Nipsil E74P”, manufactured by Tosoh Silica Co., Ltd. (CTAB specific surface area: 33 m 2 / g)
• -Silica B Product name "Carplex (registered trademark) # 101", manufactured by Evonik Industries, Inc.
• CTAB specific surface area: 50 m 2 / g) -Silica C Product name "Ultrasil (registered trademark) 360", manufactured by Evonik Industries, Inc.
• D Product name "Carplex (registered trademark) # 1120", manufactured by Evonik Industries, Inc.
• E Product name "Nipsil ER", manufactured by Tosoh Silica Co., Ltd.
• CTAB specific surface area: 115 m 2 / g) -Silica F Product name "Carplex (registered trademark) # 67", manufactured by Evonik Industries, Inc.
• CTAB specific surface area: 140 m 2 / g) -Silica G Product name "Nipsil LP", manufactured by Tosoh Silica Co., Ltd.
• CTAB specific surface area: 154 m 2 / g) -Silica H Product name "Ultrasil (registered trademark) 9500GR", manufactured by Evonik Industries, Inc.
• Lubricants Product name “Diamid 0-200T”, manufactured by Nihon Kasei Co., Ltd.
• Carbon black Semi-super abrasion resistance (ISAF: Intermediate Super Abrasion Furnace) Carbon black (trade name "Show Black N220", manufactured by Cabot Japan) Further, the value of each of the above components in the above table 1 represents "part by weight”.
• silica having a CTAB specific surface area of 30 m 2 / g or more and 150 m 2 / g or less is in the range of 25 parts by weight or more and 90 parts by weight or less with respect to 100 parts by weight of EBDM.
• Examples 1 to 8 in which the rubber composition was not adhered to the surface of the kneader stable kneading was possible, and the kneading processability was excellent.
• TR-70 is ⁇ 40 ° C. or lower and the volume resistivity is 1 ⁇ 10 12 ⁇ ⁇ cm or more, low temperature characteristics.
• the vulcanized molded products produced by using the rubber compositions of Examples 1 to 8 show good compressive permanent strain characteristics because the compression permanent strain rate is 20% or less, and in particular, Examples 1 to 8 In Nos. 2, 4 to 6, excellent compression set characteristics were exhibited.
• Comparative Example 1 in which the content of silica having a CTAB specific surface area of 30 m 2 / g or more and 150 m 2 / g or less is less than 30 parts by weight with respect to 100 parts by weight of EBDM, the rubber composition adheres to the surface of the kneader. However, kneading could not be continued and the kneading workability was inferior.
• Comparative Example 2 in which the content of silica having a CTAB specific surface area of 30 m 2 / g or more and 150 m 2 / g or less exceeds 90 parts by weight with respect to 100 parts by weight of EBDM, vulcanization produced using a rubber composition
• the TR-70 indicated by the molded product was over ⁇ 40 ° C., which was inferior in low temperature characteristics.
• silica having a specific surface area of 30 m 2 / g or more and 150 m 2 / g or less is blended in a range of 25 parts by weight or more and 90 parts by weight or less with respect to 100 parts by weight of EBDM. It can be seen that a rubber composition suitable for producing a vulcanized molded product having excellent kneading processability, good compression set characteristics, and excellent low temperature characteristics and electrical insulation properties can be provided. Therefore, for example, when the vulcanized molded product is a sealing part, such a sealing part can exhibit excellent sealing performance in a low temperature environment, and is particularly suitable for use as a gasket for e-M Firmbility. is there.

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