WO2019124462A1 - Composition de caoutchouc et article moulé en caoutchouc - Google Patents

Composition de caoutchouc et article moulé en caoutchouc Download PDF

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WO2019124462A1
WO2019124462A1 PCT/JP2018/046871 JP2018046871W WO2019124462A1 WO 2019124462 A1 WO2019124462 A1 WO 2019124462A1 JP 2018046871 W JP2018046871 W JP 2018046871W WO 2019124462 A1 WO2019124462 A1 WO 2019124462A1
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Prior art keywords
mass
parts
rubber
rubber composition
molded article
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PCT/JP2018/046871
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English (en)
Japanese (ja)
Inventor
和志 坂手
太賀 國井
義彦 山口
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内山工業株式会社
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Priority to DE112018006565.0T priority Critical patent/DE112018006565T5/de
Priority to CN201880081318.3A priority patent/CN111479867A/zh
Priority to JP2019560544A priority patent/JP7244086B2/ja
Publication of WO2019124462A1 publication Critical patent/WO2019124462A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • 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
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252—Clays
    • 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
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252—Clays
    • C09K2200/026—Kaolin
    • 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
    • C09K2200/0607—Rubber or rubber derivatives
    • C09K2200/0612—Butadiene-acrylonitrile rubber

Definitions

  • the present invention relates to a rubber composition and a rubber molded article obtained by crosslinking the same.
  • Rubber molded articles are used in a wide range of applications, taking advantage of their elastic properties. Above all, they are suitably used for automotive parts such as gaskets for sealing fluid and seals for bearings used for axles.
  • the rubber molded article of patent document 1 As a rubber molded article used for a bearing, the rubber molded article of patent document 1 is mentioned, for example.
  • Patent Document 1 100 parts by mass of nitrile rubber (A), 1 to 30 parts by mass of conductive carbon black (B) having a DBP oil absorption of 150 mL / 100 g or more and 1000 mL / 100 g or less, and silylated clay (C) 5 A rubber composition containing ⁇ 60 parts by weight is described. And since a rubber molded article obtained by vulcanizing this rubber composition is excellent in conductivity and weatherability, it is supposed to be suitably used as a seal for bearings.
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a rubber molded article excellent in heat resistance and low temperature resistance. Another object of the present invention is to provide a rubber composition for obtaining such a rubber molded article.
  • the above-mentioned subjects are 100 parts by mass of nitrile rubber (A), 5 to 100 parts by mass of carbon black (B), 5 to 75 parts by mass of calcined kaolin (C), 5 to 75 parts by mass of diatomaceous earth (D), and plasticizer (E) And 5) containing 1 to 30 parts by mass, the acrylonitrile unit content of the nitrile rubber (A) is 25 to 30% by mass, and the heating loss ratio of the plasticizer (E) after leaving at 150 ° C. for 24 hours is 5
  • the problem is solved by providing a rubber composition characterized in that it is not more than mass%.
  • the rubber composition further contain 0.1 to 10 parts by mass of an antioxidant (F). Moreover, it is preferable that the said rubber composition contains dithio carbamate and microcrystalline wax as an antiaging agent (F).
  • the rubber composition preferably further contains 0.5 to 10 parts by mass of paraffin wax (G) having a melting point of 45 to 100 ° C.
  • a rubber molded article obtained by vulcanizing the above rubber composition is a preferred embodiment of the present invention.
  • a seal or a gasket made of the above-mentioned rubber molded article is also a preferred embodiment of the present invention.
  • a rubber molded article excellent in heat resistance and low temperature resistance can be provided.
  • the rubber composition for obtaining such a rubber molded article can be provided.
  • the present invention comprises 100 parts by mass of nitrile rubber (A), 5 to 100 parts by mass of carbon black (B), 5 to 75 parts by mass of calcined kaolin (C), 5 to 75 parts by mass of diatomaceous earth (D), and a plasticizer (E) And 5) containing 1 to 30 parts by mass, the acrylonitrile unit content of the nitrile rubber (A) is 25 to 30% by mass, and the heating loss ratio of the plasticizer (E) after leaving at 150 ° C. for 24 hours is 5 It is the rubber composition characterized by being below mass%.
  • Nirile rubber (A) As a nitrile rubber (A) used by this invention, the copolymer of an acrylonitrile and a 1, 3- butadiene is mentioned. Hydrogenation to the double bond remaining in the 1,3-butadiene unit after polymerization is optional. Non-hydrogenated nitrile rubber and hydrogenated nitrile rubber can be properly used properly.
  • the content of acrylonitrile units of the nitrile rubber (A) is 25 to 30% by mass. From the viewpoint of the balance between heat resistance and low temperature resistance, it is important that the content of the acrylonitrile unit is in the above range.
  • the content of the acrylonitrile unit is preferably 26% by mass or more.
  • the content of acrylonitrile units is preferably 29% by mass or less.
  • the nitrile rubber (A) used in the present invention may contain a structural unit derived from another copolymerizable monomer as long as the effect of the present invention is not impaired.
  • it may contain a functional group such as a carboxyl group or a carboxylic acid anhydride group.
  • the copolymerization amount of such other monomers is usually 10 mol% or less, preferably 5 mol% or less, and more preferably 2 mol% or less.
  • the Mooney viscosity (ML 1 +4 , 100 ° C.) of the nitrile rubber (A) is preferably 10 to 120. From the viewpoint of the moldability of the rubber composition, the Mooney viscosity is preferably 10 or more, and more preferably 20 or more. On the other hand, the Mooney viscosity is preferably 120 or less, more preferably 100 or less, from the viewpoint of the strength of the rubber molded article.
  • a nitrile rubber (A) may be used individually by 1 type, and may mix and use 2 or more types.
  • the content of the acrylonitrile unit in the mixed nitrile rubber and the Mooney viscosity are taken as an average value taking into consideration the blending ratio of the nitrile rubber.
  • Carbon black (B) The type of carbon black (B) used in the present invention is not particularly limited, and SAF, ISAF, HAF, FEF, GPF, MAF, SRF, FT, MT, etc. can be used, and in terms of the balance between performance and cost. FEF, FT, MT, SRF, MAF are preferred. As carbon black (B), two or more types of carbon black can be used in combination.
  • the content of carbon black (B) is 5 to 100 parts by mass with respect to 100 parts by mass of nitrile rubber (A). When the content of the carbon black (B) is less than 5 parts by mass, the tensile strength of the rubber molded article is insufficient.
  • the content of carbon black (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. On the other hand, when the content of carbon black (B) exceeds 100 parts by mass, the formability is deteriorated.
  • the content of carbon black (B) is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.
  • the average primary particle size of the carbon black (B) is not particularly limited, and is usually 5 to 200 nm.
  • the average primary particle diameter of the carbon black (B) is preferably 40 nm or less, and preferably 30 nm or less, from the viewpoint that the tensile strength of the rubber molded product can be improved even if the compounding amount to the rubber composition is small. It is more preferable that
  • the rubber composition of the present invention comprises calcined kaolin (C) and diatomaceous earth (D).
  • kaolin is a natural clay mineral containing hydrous aluminum silicate (composition formula: Al 2 Si 2 O 5 (OH) 4 ) as a main component. And after baking kaolin refines this clay mineral, baking water is removed at high temperature.
  • diatomaceous earth is a deposit composed of fossil shells of diatoms, which is a kind of single cell algae, and is mainly composed of silicon dioxide (SiO 2 ).
  • the rubber molded product obtained by blending only the calcined kaolin (C) among the calcined kaolin (C) and the diatomaceous earth (D) is heated and thereby the hardness is excessively increased and the elongation is decreased. .
  • the glass transition point is too high. Therefore, the content of each of the calcined kaolin (C) and the diatomaceous earth (D) in the rubber molding is important.
  • the content of the calcined kaolin (C) is 5 to 75 parts by mass with respect to 100 parts by mass of the nitrile rubber (A).
  • the content of the calcined kaolin (C) is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.
  • the content of the calcined kaolin (C) is preferably 70 parts by mass or less, and more preferably 60 parts by mass or less.
  • the content of diatomaceous earth (D) is 5 to 75 parts by mass with respect to 100 parts by mass of nitrile rubber (A).
  • the content of diatomaceous earth (D) is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.
  • the content of diatomaceous earth (D) is preferably 70 parts by mass or less, and more preferably 60 parts by mass or less.
  • the total amount of the calcined kaolin (C) and the diatomaceous earth (D) is preferably 100 parts by mass or less and more preferably 80 parts by mass or less with respect to 100 parts by mass of the nitrile rubber (A).
  • the mass ratio [(C) / (D)] of calcined kaolin (C) to diatomaceous earth (D) is usually 90/10 to 10/90, preferably 80/20. 20 to 80, more preferably 70/30 to 30/70.
  • the calcined kaolin (C) may be surface-treated with a fatty acid, a surfactant, a silane coupling agent or the like. Further, the diatomaceous earth (D) may be similarly surface-treated with a fatty acid, a surfactant, a silane coupling agent or the like.
  • the rubber composition of the present invention contains a plasticizer (E).
  • a plasticizer (E) having a heating loss ratio of 5% by mass or less after standing at 150 ° C. for 24 hours.
  • the heating loss ratio is preferably 4% by mass or less, more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.
  • the heating loss ratio in the present specification is a value obtained by subtracting the mass of the rubber composition after heating from the mass of the rubber composition before heating divided by the mass of the rubber composition before heating and expressed as a percentage. It is a representation. The details of the method for measuring the heating loss rate are as described in the examples below.
  • the type of the plasticizer (E) used in the present invention is not particularly limited as long as the heating loss ratio is as described above, and a plasticizer generally used in a rubber composition is used.
  • a plasticizer generally used in a rubber composition is used.
  • phthalic acid derivatives tetrahydrophthalic acid derivatives, adipic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-acid derivatives, maleic acid derivatives, fumaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, citric acid Derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, sulfonic acid derivatives, phosphoric acid derivatives, glutaric acid derivatives, glycol derivatives, glycerin derivatives, paraffin derivatives, epoxy derivatives, polymeric plasticizers (polyesters, polyethers, etc.), etc. Can be mentioned.
  • These plasticizers
  • the content of the plasticizer (E) is 1 to 30 parts by mass with respect to 100 parts by mass of the nitrile rubber (A). When the content of the plasticizer (E) is less than 1 part by mass, the effect of blending the plasticizer (E) becomes insufficient.
  • the content of the plasticizer (E) is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more. On the other hand, when content of a plasticizer (E) exceeds 30 mass parts, there exists a possibility that a plasticizer (E) may bleed.
  • the content of the plasticizer (E) is preferably 25 parts by mass or less, and more preferably 20 parts by mass or less.
  • the rubber composition further contains an antiaging agent (F).
  • the antiaging agent (F) include dithiocarbamates, microcrystalline waxes, naphthylamines, diphenylamines, p-phenylenediamines, quinolines, hydroquinones, phenols, and ion-containings.
  • the antiaging agent (F) contains both dithiocarbamate and microcrystalline wax.
  • microcrystalline wax is a wax mainly extracted from the vacuum distillation residue of crude oil, and branched hydrocarbon (isoparaffin) and saturated cyclic hydrocarbon (cycloparaffin) compared to paraffin wax (G) described later.
  • dithiocarbamates include nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate.
  • the content of the antiaging agent (F) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the nitrile rubber (A). If the content of the antiaging agent (F) is less than 0.1 parts by mass, the ozone resistance of the rubber molded product may be insufficient.
  • the content of the antiaging agent (F) is more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more. On the other hand, when the content of the antiaging agent (F) exceeds 10 parts by mass, bloom may occur.
  • the content of the antioxidant (F) is more preferably 8 parts by mass or less.
  • the mass ratio of dithiocarbamate (X) to microcrystalline wax (Y) in the antiaging agent (F) [(X) / (Y)] is usually 90/10 to 10/90, preferably 80/20 to 20/80, more preferably 70/30 to 30/70.
  • paraffin wax (G) In the present invention, it is preferable that the rubber composition further contains a paraffin wax (G) from the viewpoint of further improving the ozone resistance of the rubber molded article.
  • paraffin wax (G) refers to one obtained by separating and extracting a hydrocarbon with good crystallinity from a vacuum distillation distillate of crude oil, which contains a linear hydrocarbon (normal paraffin) as a main component.
  • paraffin wax (G) is usually added to a rubber composition in order to improve kneadability and mold releasability at the time of production of a rubber molded article. For these reasons, paraffin wax (G) and the microcrystalline wax (anti-aging agent) described above are clearly distinguished by those skilled in the art.
  • the melting point of paraffin wax (G) is preferably 45 to 100.degree. By using paraffin wax (G) having a melting point in this range, the ozone resistance of the rubber molded article can be further improved.
  • the melting point is more preferably 48 ° C. or more, further preferably 50 ° C. or more. On the other hand, the melting point is more preferably 90 ° C. or less, still more preferably 80 ° C. or less.
  • the content of paraffin wax (G) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of nitrile rubber (A). When the content of the paraffin wax (G) is in this range, the ozone resistance of the rubber molded article can be further improved.
  • the content of the paraffin wax (G) is more preferably 0.7 parts by mass or more. On the other hand, the content of paraffin wax (G) is more preferably 5 parts by mass or less.
  • the above rubber composition contains components other than nitrile rubber (A), carbon black (B), calcined kaolin (C), diatomaceous earth (D) and plasticizer (E) within the range that the effects of the present invention are not inhibited. You may include it.
  • a vulcanizing agent in addition to the anti-aging agent (F) described above, a vulcanizing agent, a vulcanizing aid, a vulcanization accelerator, a vulcanization retarder, an adhesive, an acid acceptor, a coloring agent, a filler, processing
  • Various additives such as auxiliary agents, coupling agents and lubricants can be mentioned.
  • the method for producing the rubber molded article of the present invention is not particularly limited, preferred production methods include nitrile rubber (A), carbon black (B), calcined kaolin (C), diatomaceous earth (D), plasticizer (E) and The method includes a kneading step of kneading a vulcanizing agent to obtain a rubber composition, a molding step of molding the rubber composition, and a vulcanization step of vulcanizing the rubber composition.
  • the method of mixing the above-mentioned components in the kneading step is not particularly limited, and kneading can be performed using an open roll, a kneader, a Banbury mixer, an intermixer, an extruder, or the like. Above all, it is preferable to knead using a Banbury mixer, an intermixer or a kneader.
  • the temperature during kneading is preferably 20 to 140.degree.
  • the rubber composition of the present invention is obtained by molding the rubber composition thus obtained in a molding step and subsequently vulcanizing in a vulcanization step.
  • injection molding, extrusion molding, compression molding, roll molding and the like can be mentioned. Among them, injection molding and compression molding are preferable. At this time, it may be vulcanized after being molded in advance, or may be vulcanized simultaneously with molding.
  • the vulcanization temperature is preferably 150 to 230 ° C. in general.
  • the vulcanization time is usually 0.1 to 60 minutes.
  • a heating method for vulcanization a general method used for vulcanization of rubber such as compression heating, steam heating, oven heating, hot air heating and the like is used.
  • the method of vulcanization is not particularly limited, and examples thereof include sulfur vulcanization and peroxide vulcanization.
  • Sulfur or a sulfur-containing compound is used as a vulcanizing agent at the time of sulfur vulcanization.
  • an organic peroxide is used as a vulcanizing agent at the time of peroxide vulcanization.
  • the amount of the vulcanizing agent used at this time is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the nitrile rubber (A).
  • the rubber molded article of the present invention is suitably used for a seal or a gasket mounted on an automobile.
  • the seal may, for example, be a bearing seal, an oil seal or a shaft seal.
  • the gasket include a gasket for a cylinder head cover, a gasket for an oil pan, and the like.
  • Nitrile rubber (A1) JSR Corporation “N241” (Acrylonitrile unit content: 29%, Mooney viscosity (ML 1 + 4 , 100 ° C.): 56) ⁇ Nitrile rubber (A2) JSR Corporation “N 240 S” (Acrylonitrile unit content: 26%, Mooney viscosity (ML 1 + 4 , 100 ° C.): 56) ⁇ Nitrile rubber (A3) Nippon Zeon Co., Ltd. “Nipol DN 2850” (Acrylonitrile unit content: 28%, Mooney viscosity (ML 1 + 4 , 100 ° C.): 50)
  • Anti-aging agent (F1) Alkyl diphenylamine (brand name "NOCRACK ODA” made by Ouchi Emerging Chemical Industry Co., Ltd.)
  • Anti-aging agent (F2) Dibutyl dithiocarbamate nickel (trade name "NOCLAK NBC” manufactured by Ouchi Shinko Chemical Co., Ltd.)
  • Anti-aging agent (F3) Microcrystalline wax made by Ouchi Emerging Chemical Industry Co., Ltd.
  • Paraffin wax 135" (melting point: 58 ° C, oil content: 0.3% by mass, penetration: 13 (25 ° C), 21 (35 ° C), viscosity: 3.9 mm 2 / s / 100 ° C., Saybolt color: +30, density: 0.911 g / cm 3 (25 ° C.), 0.775 g / cm 3 (70 ° C.), flash point: 234 ° C., average molecular weight: 389 (gas chromatography method))
  • Example 1 (Production of rubber sheet) The mixture having the composition shown below was kneaded using an open roll at a temperature of 20 to 100 ° C. for 10 to 30 minutes to obtain a rubber composition. Then, using this rubber composition, an unvulcanized rubber sheet having a thickness of 2 mm was produced (hereinafter, may be simply referred to as an unvulcanized rubber sheet).
  • Nitrile rubber 100 parts by mass Carbon black (B1): 50 parts by mass Calcined kaolin (C): 25 parts by mass Diatomaceous earth (D): 25 parts by mass Plasticizer (E1): 15 parts by mass Anti-aging agent (F1): 2 parts by mass Anti-aging agent (F2): 1 part by mass Anti-aging agent (F3): 1 part by mass Active zinc flower: 5 parts by mass Stearic acid: 1 part by mass Sulfur: 1.5 parts by mass Vulcanization accelerator (DM): 1 part by mass Curing accelerator (TT): 1 part by mass
  • the obtained unvulcanized rubber sheet was press-cured at 120 ° C. for 10 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm (hereinafter sometimes referred to simply as a vulcanized rubber sheet).
  • Three sheets of this vulcanized rubber sheet were stacked, and measurement was performed at 23 ° C. and 50% relative humidity using a type A durometer, and the peak value was read. As a result, the A hardness was 71.
  • tensile strength (MPa) and elongation (%) were measured at a tensile speed of 500 mm / min at a temperature of 23 ° C. and a relative humidity of 50%. As a result, the tensile strength was 12.9 MPa and the elongation was 360%.
  • the tensile test was performed according to JIS K6251, and the measurement of hardness was performed according to JIS K6253.
  • Thermal aging test The vulcanized rubber sheet was heated at 170 ° C. for 70 hours. After heating, three sheets of this vulcanized rubber sheet were stacked, and measurement was performed at 23 ° C. and 50% relative humidity using a type A durometer, and the peak value was read. Further, using the vulcanized rubber sheet after the heating, the tensile strength (MPa) and the elongation (%) were measured at a tensile speed of 500 mm / min at 23 ° C. and a relative humidity of 50%. The heat aging test was conducted in accordance with JIS K6257.
  • the heat aging characteristic was evaluated by calculating the change of the value with respect to the said normal-state physical property.
  • the hardness change was +5 points.
  • the hardness change is a value obtained by subtracting the A hardness before heating from the A hardness after heating.
  • the tensile strength change rate was + 4%.
  • the rate of change in tensile strength is the value obtained by subtracting the value of tensile strength before heating from the value of tensile strength after heating divided by the value of tensile strength before heating and expressed as a percentage. is there. When this value is positive, it shows that tensile strength rose by heating, and when negative, it shows that tensile strength fell.
  • the rate of change in elongation was calculated by the same calculation method, the rate of change in elongation was -33%. The results are shown in Table 1.
  • Measurement condition 1 Static extension ratio 20%, Temperature 40 ° C, Humidity 10%, Leave for 4 hours under atmosphere of ozone concentration 50 pphm
  • Measurement condition 2 Static extension ratio 5%, Temperature 23 ° C, Humidity 10%, Ozone concentration For 48 hours in an atmosphere of 200 pphm
  • Measurement condition 3 For 48 hours in an atmosphere of a static elongation of 5%, a temperature of 23 ° C., a humidity of 65%, and an ozone concentration of 200 pphm
  • the glass transition temperature (° C.) of the rubber molded article is shown in Table 1.
  • the glass transition temperature (° C.) shown in Table 1 is a glass transition start temperature measured at a temperature rising rate of 10 ° C./minute using a differential scanning calorimeter (DSC). The lower the glass transition temperature (° C.), the better the low temperature resistance.
  • Heating loss rate of plasticizer (E) The rubber composition obtained in the above "preparation of rubber sheet” was placed in an oven at 150 ° C., and left for 24 hours to determine the heating loss ratio of the plasticizer (E).
  • the heating loss ratio was represented by a value obtained by subtracting the mass of the rubber composition after heating from the mass of the rubber composition before heating divided by the mass of the rubber composition before heating.
  • the heating loss ratio of the plasticizer (E) was 2%.
  • Examples 2 to 15 and Comparative Examples 1 to 4 A rubber composition was obtained in the same manner as in Example 1 except that in the above-mentioned "Production of Vulcanized Rubber Sheet", the types and amounts of the components were changed as shown in Tables 1 to 3. And evaluation similar to Example 1 was performed using the obtained rubber composition. The results are shown in Tables 1 to 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

Cette invention concerne une composition de caoutchouc qui est caractérisée en ce qu'elle contient 100 parties en poids de caoutchouc nitrile (A), 5-100 parties en poids de noir de carbone (B), 5-75 parties en poids de kaolin cuit (C), 5-75 parties en poids de terre à diatomées (D), et 1-30 parties en poids de plastifiant (E), où le caoutchouc nitrile (A) a une teneur en motifs acrylonitrile de 25-30 % en poids, et le plastifiant (E) a une perte après chauffage n'excédant pas 5 % en poids, après 24 heures à 150 °C. La présente invention permet d'obtenir un article moulé en caoutchouc ayant une excellente résistance à la chaleur et une excellente résistance à basses températures.Une composition de caoutchouc permettant d'obtenir ledit article moulé en caoutchouc est en outre décrite.
PCT/JP2018/046871 2017-12-20 2018-12-19 Composition de caoutchouc et article moulé en caoutchouc WO2019124462A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE112018006565.0T DE112018006565T5 (de) 2017-12-20 2018-12-19 Kautschukzusammensetzung und kautschukformartikel
CN201880081318.3A CN111479867A (zh) 2017-12-20 2018-12-19 橡胶组合物及橡胶成型品
JP2019560544A JP7244086B2 (ja) 2017-12-20 2018-12-19 ゴム組成物及びゴム成形品

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