WO2023189908A1 - Rubber composition, vulcanizate, and vulcanized molded object - Google Patents

Rubber composition, vulcanizate, and vulcanized molded object Download PDF

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Publication number
WO2023189908A1
WO2023189908A1 PCT/JP2023/011135 JP2023011135W WO2023189908A1 WO 2023189908 A1 WO2023189908 A1 WO 2023189908A1 JP 2023011135 W JP2023011135 W JP 2023011135W WO 2023189908 A1 WO2023189908 A1 WO 2023189908A1
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Prior art keywords
rubber
rubber composition
mass
parts
chloroprene
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PCT/JP2023/011135
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French (fr)
Japanese (ja)
Inventor
友貴 坂井
聖耶 富澤
敦典 近藤
貴史 砂田
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デンカ株式会社
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Publication of WO2023189908A1 publication Critical patent/WO2023189908A1/en

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    • 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
    • C08K3/06—Sulfur
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • 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

Definitions

  • the present invention relates to a rubber composition, a vulcanizate, and a vulcanized molded product.
  • Rubber compositions containing chloroprene rubber have excellent mechanical strength, weather resistance, chemical resistance, heat resistance, cold resistance, and oil resistance, so they are used in power transmission belts and conveyor belts for general industry, air springs for automobiles, Widely used as material for anti-vibration rubber, hoses, wipers, immersion products, sealing parts, adhesives, boots, rubberized cloth, rubber rolls, etc.
  • Patent Document 1 discloses that the rubber is composed of sulfur-modified chloroprene rubber, a vulcanization accelerator, zinc oxide, and magnesium oxide, the amount of the vulcanization accelerator is 0.1 to 5 parts by weight, and the amount of zinc oxide is The invention relates to a sulfur-modified chloroprene rubber composition in which the blending amounts of magnesium oxide and magnesium oxide are specified by a predetermined relational expression between the respective blending amounts and Mooney scorch time.
  • Patent Document 2 discloses an invention relating to a copolymer of a chloroprene monomer and an unsaturated nitrile compound, which has a Mooney viscosity ML (1+4) at 100°C of 20 to 80 and has a functional group with a specific structure. has been done.
  • Patent Document 3 describes 30 to 93 mass % of chloroprene rubber, 5 to 50 mass % of soft polyvinyl chloride obtained by plasticizing polyvinyl chloride with a plasticizer, and 2 to 20 mass % of acrylonitrile butadiene rubber.
  • An invention relating to a blend rubber containing the following is disclosed.
  • the present invention has been made in view of these circumstances, and provides a rubber composition capable of obtaining a vulcanizate with an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance. It provides:
  • a rubber composition containing a chloroprene-based rubber and a nitrile-butadiene-based rubber, in which the rubber composition contains 5 parts by mass of the chloroprene-based rubber when the rubber contained in the rubber composition is 100 parts by mass.
  • the chloroprene rubber contains 0.1 to 95 parts by mass of unsaturated nitrile monomer units and 5 to 95 parts by mass of the nitrile butadiene rubber, and the chloroprene rubber contains 0.1 to 95 parts by mass of unsaturated nitrile monomer units when the chloroprene rubber is 100 mass %.
  • a rubber composition is provided in which the nitrile-butadiene-based rubber contains 5 to 60% by mass of acrylonitrile monomer units when the nitrile-butadiene-based rubber is 100% by mass.
  • the present inventor has found that a specific amount of chloroprene-based rubber and nitrile-butadiene-based rubber is blended into a rubber composition, and that the chloroprene-based rubber contains unsaturated nitrile monomer units in the chloroprene-based rubber.
  • the acrylonitrile monomer unit content in the nitrile-butadiene rubber within a specific numerical range, it has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and flex fatigue resistance. It was discovered that a rubber composition can be obtained from which a vulcanizate can be obtained, leading to the completion of the present invention.
  • the rubber composition described above is one in which the unsaturated nitrile monomer unit is an acrylonitrile monomer unit.
  • the rubber composition has an amount of unsaturated nitrile monomer units contained in the chloroprene rubber of X parts by mass, based on 100 parts by mass of the rubber contained in the rubber composition, and The rubber composition described above, where X ⁇ 2.5+Y is 5.0 to 55.0, where Y is the amount of acrylonitrile monomer units contained in the butadiene rubber.
  • the rubber composition described above contains at least one compound selected from the group consisting of:
  • the rubber composition described above contains 0.1 to 10 parts by mass of an organic peroxide based on 100 parts by mass of rubber contained in the rubber composition.
  • the rubber composition described above contains 0.1 to 5 parts by mass of a compound having a cyclohexene structure and a molecular weight of 100 to 1000, based on 100 parts by mass of the rubber contained in the rubber composition. It is.
  • the rubber composition described above contains 0.1 to 10 parts by mass of a maleimide compound based on 100 parts by mass of rubber contained in the rubber composition.
  • the volume change rate ⁇ V of the vulcanizate of the rubber composition is less than 20%, as measured using IRM903 oil in accordance with JIS K 6258, and as determined by Gehman torsion test in accordance with JIS K 6261.
  • the T10 of the vulcanizate of the rubber composition is less than -15°C.
  • a vulcanizate of the rubber composition described above there is provided a vulcanized molded article using the rubber composition described above.
  • a vulcanizate with an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance can be obtained. Furthermore, the obtained vulcanizates and vulcanized molded bodies can be used as various members requiring these properties.
  • the vulcanizate and vulcanized molded product according to an embodiment of the present invention can be used, for example, in power transmission belts and conveyor belts for general industry, air springs for automobiles, anti-vibration rubber, hoses, wipers, and immersion products. It can be suitably used as a material for seal parts, adhesives, boots, rubberized cloth, rubber rolls, etc.
  • the vulcanizate and vulcanized molded article according to an embodiment of the present invention are characterized by the content of each monomer unit in each rubber contained in the rubber composition, the blending amount of each rubber, and the content of each monomer unit in each rubber contained in the rubber composition.
  • the types and blending amounts of components other than rubber the balance of these properties can be adjusted to a higher degree. Therefore, by adjusting these, a vulcanized product and a vulcanized molded product having characteristics that meet the requirements of each member can be obtained.
  • the rubber composition according to the present invention is a rubber composition containing chloroprene rubber and nitrile butadiene rubber.
  • the rubber composition according to the present invention will be explained in detail.
  • Examples of the chloroprene-based polymer include chloroprene homopolymers, chloroprene copolymers (copolymers of chloroprene and a monomer copolymerizable with chloroprene), and the like.
  • the polymer structure of the chloroprene polymer is not particularly limited.
  • 2-chloro-1,3-butadiene may contain a small amount of 1-chloro-1,3-butadiene as an impurity.
  • 2-chloro-1,3-butadiene containing such a small amount of 1-chloro-1,3-butadiene can also be used as the chloroprene monomer in this embodiment.
  • the chloroprene rubber according to the present invention includes a chloroprene rubber containing unsaturated nitrile monomer units.
  • the chloroprene rubber containing unsaturated nitrile monomer units according to the present invention contains 0.1 to 25 mass % of unsaturated nitrile monomer units when the chloroprene rubber containing unsaturated nitrile monomer units is 100 mass %. %, and can be contained in an amount of 0.1% by mass or more and less than 25% by mass.
  • the content of unsaturated nitrile monomer units in the chloroprene rubber containing unsaturated nitrile monomer units according to an embodiment of the present invention is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 mass %, and may be within a range between any two of the numerical values exemplified here, or the lower limit may be any of the numerical values illustrated here, and the upper limit may be less than 25% by mass.
  • the resulting vulcanizate and vulcanized molded product will have sufficient cold resistance.
  • the resulting vulcanizate and vulcanized molded product will have sufficient oil resistance.
  • the unsaturated nitrile monomer unit examples include an acrylonitrile monomer unit, a methacrylonitrile monomer unit, an ethacrylonitrile monomer unit, a phenyl acrylonitrile monomer unit, and the like. Unsaturated nitriles can be used alone or in combination of two or more.
  • the unsaturated nitrile monomer unit may contain an acrylonitrile monomer unit from the viewpoint of easily obtaining excellent moldability and from the viewpoint of easily obtaining excellent mechanical properties and oil resistance in the vulcanized molded product. preferable.
  • the content of unsaturated nitrile monomer units contained in the chloroprene rubber can be calculated from the content of nitrogen atoms in the chloroprene rubber. Specifically, the content of nitrogen atoms in 100 mg of chloroprene rubber was measured using an elemental analyzer (Sumigraph 220F, manufactured by Sumika Analysis Center Co., Ltd.), and the content of structures derived from unsaturated nitrile monomers was determined. can be calculated. Elemental analysis measurements can be performed under the following conditions.
  • the electric furnace temperature is set to 900°C for the reactor, 600°C for the reduction furnace, 70°C for the column, and 100°C for the detector, oxygen at 0.2 mL/min as the combustion gas, and helium at 80 mL/min as the carrier gas.
  • a calibration curve can be created using aspartic acid (10.52%), which has a known nitrogen content, as a standard substance.
  • the chloroprene-based rubber according to an embodiment of the present invention preferably contains 60 to 100% by mass of chloroprene monomer units when the chloroprene-based rubber is 100% by mass.
  • the content of chloroprene monomer units in the chloroprene rubber is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 99, 100% by mass, and any two of the values exemplified here. It may be within the range between.
  • the chloroprene rubber according to one embodiment of the present invention may also have monomer units other than chloroprene monomer and unsaturated nitrile monomer.
  • the monomer units other than chloroprene monomer and unsaturated nitrile monomer are not particularly limited as long as they can be copolymerized with chloroprene monomer or chloroprene monomer and unsaturated nitrile monomer.
  • (meth)acrylic acid esters (methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), hydroxyalkyl (meth)acrylate (2-hydroxymethyl (meth)acrylate) , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.), 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene , sulfur, etc.
  • the chloroprene-based rubber according to an embodiment of the present invention shall contain 0 to 20% by mass of monomer units other than chloroprene monomer and unsaturated nitrile monomer when the chloroprene-based rubber is 100% by mass. I can do it.
  • the content of monomer units other than chloroprene monomer and unsaturated nitrile monomer in the rubber is, for example, 0, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20% by mass. Yes, it may be within the range between any two of the numerical values exemplified here.
  • the chloroprene rubber according to one embodiment of the present invention may be composed only of chloroprene monomer units and unsaturated nitrile monomer units.
  • chloroprene rubber in the rubber composition according to the present invention, one type of chloroprene rubber can be used alone or two or more types can be used in combination.
  • the chloroprene rubber according to one embodiment of the present invention can also be a rubber obtained by mixing a chloroprene rubber containing an unsaturated nitrile monomer unit and another chloroprene rubber (for example, a homopolymer of chloroprene).
  • the chloroprene rubber according to one embodiment of the present invention may consist only of chloroprene rubber containing one or more unsaturated nitrile monomer units.
  • the total of each component contained in the two or more types of chloroprene rubber contained in the rubber composition is within the above numerical range.
  • the total content of unsaturated nitrile monomer units is preferably from 0.1 to 25% by mass.
  • the chloroprene polymer contained in the chloroprene rubber according to the present invention is a sulfur-modified chloroprene polymer, a mercaptan-modified chloroprene polymer, a xanthogen-modified chloroprene polymer, a dithiocarbonate-based chloroprene polymer, and a trithiocarbonate-based polymer. It may be a chloroprene-based polymer, a carbamate-based chloroprene-based polymer, or the like.
  • the method for producing chloroprene-based rubber according to one embodiment of the present invention is not particularly limited, but may include an emulsion polymerization step of emulsion polymerization of raw material monomers containing chloroprene monomers. can be obtained by In the emulsion polymerization step according to one embodiment of the present invention, monomers including chloroprene monomers and unsaturated nitrile monomers are emulsion polymerized using appropriate emulsifiers, dispersants, catalysts, chain transfer agents, etc. A latex containing a chloroprene polymer containing chloroprene monomer units can be obtained by adding a polymerization terminator when the desired final conversion rate is reached.
  • unreacted monomers can be removed from the polymerization solution obtained by the emulsion polymerization step.
  • the method is not particularly limited, and includes, for example, a steam stripping method. Thereafter, the pH is adjusted, and a chloroprene rubber containing a chloroprene polymer can be obtained through conventional steps such as freezing and coagulation, washing with water, and drying with hot air.
  • the polymerization initiator used in emulsion polymerization is not particularly limited, and any known polymerization initiator commonly used in emulsion polymerization of chloroprene can be used.
  • the polymerization initiator include organic peroxides such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide.
  • the emulsifier used in emulsion polymerization is not particularly limited, and known emulsifiers commonly used in emulsion polymerization of chloroprene can be used.
  • emulsifiers include alkali metal salts of saturated or unsaturated fatty acids having 6 to 22 carbon atoms, alkali metal salts of rosin acid or disproportionated rosin acids (e.g. potassium rosin acid), formalin condensates of ⁇ -naphthalenesulfonic acid.
  • alkali metal salts eg, sodium salts
  • the molecular weight regulator used in emulsion polymerization is not particularly limited, and known molecular weight regulators commonly used in emulsion polymerization of chloroprene can be used, such as mercaptan compounds, xanthogen compounds, dithiocarbonate compounds, etc. compounds, trithiocarbonate compounds, and carbamate compounds.
  • molecular weight regulator for the chloroprene rubber according to one embodiment of the present invention xanthogen compounds, dithiocarbonate compounds, trithiocarbonate compounds, and carbamate compounds can be suitably used.
  • the polymerization temperature and the final conversion rate of monomers are not particularly limited, but the polymerization temperature may be, for example, 0 to 50°C or 10 to 50°C.
  • the polymerization may be carried out such that the final conversion of monomer is in the range of 40 to 95% by weight.
  • a polymerization terminator that stops the polymerization reaction may be added to terminate the polymerization.
  • the polymerization terminator is not particularly limited, and any known polymerization terminator commonly used in emulsion polymerization of chloroprene can be used.
  • Examples of the polymerization terminator include phenothiazine (thiodiphenylamine), 4-t-butylcatechol, 2,2-methylenebis-4-methyl-6-t-butylphenol, and the like.
  • the chloroprene rubber according to an embodiment of the present invention can be produced by, for example, removing unreacted monomers by a steam stripping method, adjusting the pH of the latex, freezing and coagulating the rubber by conventional methods, washing with water, drying with hot air, etc. It can be obtained through the process of
  • Chloroprene-based rubbers are classified into mercaptan-modified types, xanthogen-modified types, sulfur-modified types, dithiocarbonate-based types, trithiocarbonate-based types, and carbamate-based types depending on the type of molecular weight modifier.
  • nitrile butadiene rubber refers to a rubber containing a nitrile butadiene polymer having acrylonitrile and 1,3-butadiene as monomer units.
  • the nitrile-butadiene-based rubber includes a rubber containing a nitrile-butadiene-based polymer having acrylonitrile and 1,3-butadiene as monomer units (hereinafter also referred to as nitrile rubber) and a rubber containing a nitrile-butadiene-based polymer having acrylonitrile and 1,3-butadiene as monomer units; It includes a rubber containing a hydrogenated nitrile-butadiene-based polymer (hereinafter also referred to as hydrogenated nitrile rubber) obtained by hydrogenating at least a portion of the nitrile-butadiene-based polymer as a mer unit.
  • hydrogenated nitrile rubber obtained by hydrogenating at least a portion of the nitrile-
  • the nitrile butadiene rubber according to the present invention contains at least one of nitrile rubber and hydrogenated nitrile rubber, and can also contain nitrile rubber and hydrogenated nitrile rubber.
  • the nitrile butadiene rubber according to one embodiment of the present invention preferably includes nitrile rubber or hydrogenated nitrile rubber.
  • the type of nitrile butadiene rubber to be blended into the rubber composition can be selected depending on the desired properties of the rubber composition, vulcanizate, and vulcanized product.For example, cost reduction, oil resistance, and If a balance of cold resistance is important, nitrile rubber can be selected. Further, as an example, when the balance between oil resistance and cold resistance, ozone resistance, and heat resistance are important, hydrogenated nitrile rubber can be selected.
  • the nitrile butadiene rubber according to the present invention contains 5 to 60% by mass of acrylonitrile monomer units when the nitrile butadiene rubber is 100% by mass.
  • the acrylonitrile monomer unit content in the nitrile butadiene rubber according to one embodiment of the present invention is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass. Yes, it may be within the range between any two of the numerical values exemplified here.
  • a rubber composition can be obtained that provides a vulcanizate and a vulcanized molded product with an excellent balance of oil resistance and cold resistance.
  • one type of nitrile butadiene rubber can be used alone or two or more types can be used in combination.
  • the rubber composition according to an embodiment of the present invention contains two or more types of nitrile butadiene rubber, the total content of acrylonitrile monomer units contained in the two or more types of nitrile butadiene rubber contained in the rubber composition.
  • the ratio is 5 to 60% by weight.
  • hydrogenated nitrile rubber When hydrogenated nitrile rubber is used as the nitrile butadiene rubber, it is possible to use a hydrogenated nitrile rubber whose iodine number, which is an indicator of the amount of double bonds present in the polymer, is 5 to 60 mg/100 mg.
  • the iodine value of hydrogenated nitrile rubber is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 mg/100 mg, and between any two of the values exemplified here. may be within the range of
  • the rubber composition according to the present invention contains 5 to 95 parts by mass of chloroprene rubber and 5 to 95 parts by mass of nitrile butadiene rubber, when the rubber contained in the rubber composition is 100 parts by mass. Contains.
  • the rubber composition according to one embodiment of the present invention contains, for example, 5, 10, 15, 20, 25, 30, 35, 40 parts of chloroprene rubber when the rubber contained in the rubber composition is 100 parts by mass. , 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to one embodiment of the present invention contains, for example, 5, 10, 15, 20, 25, 30, 35, 40 parts of nitrile butadiene rubber when the rubber contained in the rubber composition is 100 parts by mass. , 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to the present invention has a balance of oil resistance, cold resistance, heat resistance, ozone resistance, and flex fatigue resistance by adjusting the blending amount of chloroprene rubber and nitrile butadiene rubber within the above numerical range.
  • An excellent vulcanizate can be obtained.
  • the vulcanizate and vulcanized molded product according to an embodiment of the present invention can further improve these properties by adjusting the content of each monomer unit in each rubber in addition to the amount of rubber compounded. The balance can be adjusted.
  • the amount of unsaturated nitrile monomer units contained in the chloroprene rubber is X parts by mass, when the rubber contained in the rubber composition is 100 parts by mass.
  • X x 2.5 + Y can be from 5.0 to 55.0, and is more than 8.0 and less than 55.0. It is preferably from 10.0 to 50.0.
  • X ⁇ 2.5+Y is 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 55 .0, and may be within a range between any two of the numerical values exemplified here.
  • the obtained vulcanizate has oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, especially oil resistance and cold resistance. The balance can be adjusted to a higher level.
  • the rubber composition according to the present invention can contain sulfur and a vulcanization accelerator.
  • the rubber composition according to one embodiment of the present invention can contain 5.0 parts by mass or less of sulfur and a vulcanization accelerator, based on 100 parts by mass of rubber contained in the rubber composition.
  • the content of sulfur and vulcanization accelerator is, for example, 0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5. , 4.0, 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the type of vulcanization accelerator is not particularly limited as long as it does not impair the effects of the present invention.
  • the vulcanization accelerator is preferably a vulcanization accelerator that can be used for vulcanization of chloroprene rubber and/or nitrile butadiene rubber, and is preferably a vulcanization accelerator that can be used for chloroprene rubber. More preferred.
  • One or more vulcanization accelerators can be freely selected and used.
  • the rubber composition according to the present invention contains sulfur, a thiourea compound, a thiuram compound, a thiazole compound, a sulfenamide compound, a dithiocarbamate compound, a guanidine compound, a xanthate compound, an imidazole compound, and 3- It preferably contains at least one compound selected from the group consisting of methylthiazolidine-2-thione, including sulfur, thiourea compounds, thiuram compounds, thiazole compounds, sulfenamide compounds, dithiocarbamate compounds, and 3-methyl. More preferably, it contains at least one compound selected from the group consisting of thiazolidine-2-thione.
  • thiourea-based compounds examples include thiourea-based compounds such as ethylenethiourea, diethylthiourea (N,N'-diethylthiourea), trimethylthiourea, diphenylthiourea (N,N'-diphenylthiourea), and 1,3-trimethylene-2-thiourea. can be mentioned.
  • thiuram-based compounds include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, and the like.
  • TMTD tetramethylthiuram disulfide
  • TMTD tetraethylthiuram disulfide
  • tetrabutylthiuram disulfide tetrakis(2-ethylhexyl)thiuram disulfide
  • tetramethylthiuram monosulfide dipentamethylenethiuram tetrasulfide, and the like.
  • thiazole compounds include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, cyclohexylamine salt of 2-mercaptobenzothiazole, and 2-(4'-morpholinodithio)benzo
  • Examples include thiazole, N-cyclohexylbenzothiazole-2-sulfenamide, and the like.
  • sulfenamide compounds include N-cyclohexylbenzothiazole-2-sulfenamide.
  • dithiocarbamic acid compounds include sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, copper dimethyldithiocarbamate, and zinc dimethyldithiocarbamate.
  • Examples include diiron, tellurium diethyldithiocarbamate, and the like. These can be used alone or in combination of two or more.
  • Examples of the guanidine-based compound include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatecholborate, and the like.
  • Examples of the xanthate compounds include zinc butylxanthate, zinc isopropylxanthate, and the like.
  • Examples of imidazole compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole.
  • the rubber composition according to the present invention may be free of sulfur and vulcanization accelerator. As shown below, the rubber composition according to the present invention can also contain an organic peroxide.
  • the rubber composition according to the present invention preferably contains at least one of sulfur and a vulcanization accelerator, or preferably contains an organic peroxide. Whether at least one of sulfur and a vulcanization accelerator or an organic peroxide is blended into the rubber composition depends on the desired characteristics of the rubber composition, vulcanizate, and vulcanized molded product. For example, if heat resistance and bending fatigue resistance are important, it may be selected to include at least one of sulfur and a vulcanization accelerator. Further, as an example, when heat resistance is important, organic peroxides can be selected.
  • the rubber composition according to the present invention can contain an organic peroxide.
  • organic peroxides include dicumyl peroxide, benzoyl peroxide, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumyl peroxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di(4 -t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butylperoxyneohepta Noate, t-
  • dicumyl peroxide 1,4-bis[(t-butylperoxy)isopropyl]benzene
  • t-butyl ⁇ -cumyl peroxide 2,5-dimethyl-2,5-bis(t-butylperoxy) oxy)hexane
  • 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3
  • 1,4-bis[(t-butylperoxy)hexane-3. oxy)isopropyl]benzene 1,4-bis[(t-butylperoxy)hexane-3. oxy)isopropyl]benzene.
  • the rubber composition according to the present invention contains 0.1 to 10 parts by mass of an organic peroxide based on 100 parts by mass of rubber, from the viewpoint of ensuring processing safety and obtaining a good vulcanizate. be able to.
  • the amount of organic peroxide added is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 1, 2, 3, 4, 5, 6, 7, 8 , 9, and 10, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to the present invention may also be one that does not contain an organic peroxide.
  • the rubber composition according to one embodiment of the present invention may contain a compound having a cyclohexene structure.
  • a compound having a cyclohexene structure can have one or more cyclohexene structures in the molecule, and may have two or more cyclohexene structures in the molecule.
  • Compounds having a cyclohexene structure can be used alone or in combination of two or more.
  • the rubber composition according to one embodiment of the present invention can further improve ozone resistance by containing a compound having a cyclohexene structure. From the viewpoint of further improving ozone resistance, the rubber composition according to one embodiment of the present invention more preferably contains an organic peroxide and a compound having a cyclohexene structure.
  • the compound having a cyclohexene structure preferably has a molecular weight of 100 to 1000.
  • the molecular weight of the compound having a cyclohexene structure is, for example, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, and is within the range between any two of the numerical values exemplified here. Good too.
  • a rubber composition according to an embodiment of the present invention may contain 0.1 to 5.0 parts by mass of a compound having a cyclohexene structure based on 100 parts by mass of rubber.
  • the amount of the compound having a cyclohexene structure added is, for example, 0.1, 0.2, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3. 5, 4.0, 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to one embodiment of the present invention may contain a maleimide compound.
  • Maleimide compounds can be used alone or in combination of two or more.
  • the maleimide compound can contribute to the vulcanization of the rubber composition as a co-crosslinking agent.
  • maleimide compounds include N,N'-o-phenylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-(4,4 '-diphenylmethane)bismaleimide, 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl ) hexane. N,N'-m-phenylene bismaleimide
  • a rubber composition according to an embodiment of the present invention contains 0.1 to 10 parts by mass of a maleimide compound based on 100 parts by mass of rubber.
  • the content of the maleimide compound is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, It may be within the range between any two of the numerical values exemplified here.
  • vulcanization of the resulting rubber composition proceeds more fully, and a vulcanized molded product with good mechanical properties and heat resistance can be obtained.
  • the content of the maleimide compound to be below the above upper limit, the rubber elasticity of the obtained vulcanized product can be sufficiently maintained, and a decrease in bending fatigue resistance can be suppressed.
  • the rubber composition according to one embodiment of the present invention may contain an anti-aging agent and/or an antioxidant.
  • Anti-aging agents and antioxidants include ozone anti-aging agents, phenolic anti-aging agents, amine anti-aging agents, acrylate anti-aging agents, imidazole anti-aging agents, metal carbamates, wax, and phosphorus anti-aging agents. and sulfur-based anti-aging agents.
  • the rubber composition according to one embodiment of the present invention preferably contains an ozone anti-aging agent, and more preferably contains an anti-aging agent having a p-phenylenediamine structure.
  • the rubber composition according to one embodiment of the present invention preferably contains at least one of sulfur and a vulcanization accelerator, and an ozone anti-aging agent, More preferably, it contains at least one of sulfur and a vulcanization accelerator, and an anti-aging agent having a p-phenylenediamine structure.
  • the rubber composition according to the present invention can contain 0.1 to 10 parts by mass of an anti-aging agent and an antioxidant, based on 100 parts by mass of rubber contained in the rubber composition.
  • the amount of anti-aging agent and antioxidant added is, for example, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, It may be within the range between any two of the numerical values exemplified here.
  • the rubber composition according to one embodiment of the present invention can contain a metal oxide.
  • metal oxides include zinc oxide, magnesium oxide, lead oxide, trilead tetroxide, iron trioxide, titanium dioxide, and calcium oxide.
  • the metal oxide preferably contains at least one of zinc oxide, magnesium oxide, and hydrotalcite compounds, and can also contain zinc oxide and magnesium oxide.
  • Metal oxides can be used alone or in combination of two or more.
  • zinc oxide when zinc oxide is added to the rubber composition according to an embodiment of the present invention, the zinc oxide can function as a vulcanizing agent.
  • magnesium oxide can function as an acid acceptor.
  • the rubber composition according to one embodiment of the present invention can include a metal oxide that functions as a vulcanizing agent and a metal oxide that functions as an acid acceptor.
  • the rubber composition according to the present invention may contain 0.1 to 20 parts by mass of a metal oxide based on 00 parts by mass of rubber.
  • the content of the metal oxide is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
  • the amount may be 13, 14, 15, 16, 17, 18, 19, or 20 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to the present invention can contain a filler.
  • Fillers and reinforcing materials include furnace carbon blacks such as SAF, ISAF, HAF, EPC, XCF, FEF, GPF, HMF, and SRF, modified carbon blacks such as hydrophilic carbon black, channel black, soot black, FT, Examples include thermal carbon such as MT, acetylene black, Ketjenblack, silica, clay, talc, and calcium carbonate. These can be used alone or in combination of two or more.
  • the rubber composition according to one embodiment of the present invention may contain 20 to 90 parts by mass of filler/reinforcing material, and may contain 35 to 80 parts by mass, when the rubber contained in the rubber composition is 100 parts by mass. It is preferable.
  • the content of the filler/reinforcing material is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass, and the It may be within a range between any two values.
  • the rubber composition according to one embodiment of the present invention can be cured by containing the filler content within the above numerical range.
  • the rubber composition according to the present invention may further contain a lubricant/processing aid.
  • Lubricants and processing aids are mainly added to improve processability, such as making it easier for the rubber composition to peel off from rolls, molds, extruder screws, etc.
  • Examples of lubricants and processing aids include fatty acids such as stearic acid, paraffin processing aids such as polyethylene, fatty acid amides, vaseline, factice, and the like. These can be used alone or in combination of two or more.
  • the rubber composition according to the present invention can contain 15 parts by mass or less of a lubricant/processing aid, and can also contain 10 parts by mass or less, when the rubber contained in the rubber composition is 100 parts by mass.
  • the content of the lubricant/processing aid is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by mass, where It may be within the range between any two of the illustrated numerical values.
  • the rubber composition according to the present invention can also be free of lubricants and processing aids.
  • the rubber composition according to the present invention may contain components such as an antioxidant, an antioxidant, a silane coupling agent, a co-crosslinking agent, a stabilizer, a flame retardant, and a vulcanization retarder. , may further be included within a range that does not impede the effects of the present invention.
  • the content of soft polyvinyl chloride is preferably less than 5 parts by mass when the rubber contained in the rubber composition is 100 parts by mass. It can be made without containing.
  • the rubber composition according to one embodiment of the present invention can be obtained by kneading chloroprene rubber, nitrile butadiene rubber, and other necessary components at a temperature below the vulcanization temperature. I can do it.
  • the device for kneading the raw material components include conventionally known kneading devices such as a mixer, a Banbury mixer, a kneader mixer, and an open roll.
  • the vulcanizate of the rubber composition has the following characteristics.
  • a rubber composition according to an embodiment of the present invention is obtained by immersing a vulcanized product of the rubber composition in a test oil (automotive high lubricating oil, ASTM No. 3, IRM 903 oil) at 130°C for 72 hours.
  • the volume change rate ⁇ V calculated based on JIS K 6258 is preferably less than 20%, more preferably less than 16%.
  • the volume change rate ⁇ V is, for example, less than 0, 5, 10, 15%, or 20%, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to an embodiment of the present invention preferably has a T10 of a vulcanizate of the rubber composition of less than -15°C, as determined by a Gehman torsion test based on JIS K 6261, and a T10 of less than -22°C. It is more preferable that it is less than T10 is, for example, less than -40, -35, -30, -25, -20°C, and -15°C, and may be within a range between any two of the numerical values exemplified here.
  • the rubber composition according to one embodiment of the present invention has a volume change rate ⁇ V of the vulcanizate of the rubber composition measured using IRM903 oil based on JIS K 6258 of less than 20%, and JIS K 6261 Based on this, it is more preferable that the T10 of the vulcanizate of the rubber composition determined by the Gehman torsion test is less than -15°C.
  • the content of each monomer unit in each rubber contained in the rubber composition, the blending amount of each rubber, and the amount contained in the rubber composition so that the oil resistance and cold resistance of the rubber composition are within the above numerical range.
  • the rubber composition according to one embodiment of the present invention has an elongation at break measured in accordance with JIS K 6251 of the vulcanizate of the rubber composition as EB 0 , and the vulcanizate of the rubber composition is heated at 130°C. After heating for 72 hours at It is preferably -30% or more, and more preferably -30% or more.
  • the change ⁇ EB in elongation at cutting before and after the heat resistance test is, for example, -40, -35, -30, -25, -20, -15, -10, -5, and 0%, and any of the values exemplified here or within a range between the two.
  • the rubber composition according to one embodiment of the present invention is statically tested under the conditions of a test temperature of 40° C., an ozone concentration of 50 pphm, and an elongation rate of 20% based on JIS K 6259-1.
  • a test temperature 40° C.
  • an ozone concentration of 50 pphm 50 pphm
  • an elongation rate of 20% based on JIS K 6259-1 the time required for cracks to occur on the surface or side surfaces is preferably 1 hour or more, more preferably 10 hours or more.
  • the time it takes for cracks to occur on the surface or side surfaces is, for example, 1, 5, 10, 15, 20, 25, 30 hours, even if it is within the range between any two of the numerical values exemplified here. good.
  • a rubber composition according to an embodiment of the present invention was subjected to a dematcher bending fatigue test on a vulcanized product of the rubber composition based on JIS K 6260, and was measured under conditions of a stroke of 58 mm and a speed of 300 ⁇ 10 rpm.
  • the number of times the bending test is performed at the time a crack occurs is preferably 100 times or more, and preferably 3000 times or more.
  • the number of bending tests at the time a crack occurs is, for example, 100, 1000, 5000, 10,000, 100,000, or 1 million times, and even if it is within the range between any two of the numerical values exemplified here. good.
  • the vulcanized product of the rubber composition can be a vulcanized product or a vulcanized molded product obtained by press vulcanization at 170°C for 20 minutes based on JIS K 6299. can be produced by the method described in Examples.
  • the oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance of the vulcanized product of the rubber composition are determined by the content of each monomer unit in each rubber contained in the rubber composition, and the content of each monomer unit in each rubber contained in the rubber composition. It can be controlled by adjusting the amount of rubber compounded, and the types and amounts of components other than rubber contained in the rubber composition.
  • the unvulcanized molded product according to this embodiment uses the rubber composition according to this embodiment, and the rubber composition according to this embodiment (unvulcanized product) It is a molded article (molded product) in a sulfur state).
  • the method for producing an unvulcanized molded body according to the present embodiment includes a step of molding the rubber composition (unvulcanized state) according to the present embodiment.
  • the unvulcanized molded article according to this embodiment is made of the rubber composition (in an unvulcanized state) according to this embodiment.
  • the vulcanizate according to this embodiment is a vulcanizate of the rubber composition according to this embodiment.
  • the method for producing a vulcanizate according to the present embodiment includes a step of vulcanizing the rubber composition according to the present embodiment.
  • the vulcanized molded article according to this embodiment is a vulcanized molded article of the rubber composition according to this embodiment.
  • the vulcanized molded article according to this embodiment uses the vulcanized product according to this embodiment, and is a molded article (molded article) of the vulcanized product according to this embodiment.
  • the vulcanized molded article according to this embodiment is made of the vulcanized product according to this embodiment.
  • the vulcanized molded article according to this embodiment can be obtained by molding a vulcanizate obtained by vulcanizing the rubber composition (unvulcanized state) according to this embodiment, and It can also be obtained by vulcanizing a molded article obtained by molding the rubber composition (in an unvulcanized state).
  • the vulcanized molded article according to this embodiment can be obtained by vulcanizing the rubber composition according to this embodiment after or during molding.
  • the method for producing a vulcanized molded body according to this embodiment includes a step of molding a vulcanized product according to this embodiment, or a step of vulcanizing an unvulcanized molded body according to this embodiment.
  • the vulcanizate and vulcanized molded article according to one embodiment of the present invention preferably have the oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance described above.
  • the unvulcanized molded product, vulcanized product, and vulcanized molded product according to the present embodiment can be used as rubber parts in various industrial fields such as buildings, structures, ships, railways, coal mines, and automobiles.
  • the vulcanizate made from the rubber composition according to one embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, and therefore can be used in various applications where these properties are required. It can be used as a member.
  • the rubber composition according to one embodiment of the present invention can be used as rubber parts in various industrial fields such as buildings, structures, ships, railways, coal mines, and automobiles, and can be used as rubber parts for automobiles (for example, sealing materials for automobiles). It can be used as rubber parts for hose materials, rubber molds, gaskets, rubber rolls, industrial cables, industrial conveyor belts, sponges, etc.
  • Rubber parts for automobiles include gaskets, oil seals, and packing, and are parts that prevent liquid and gas leaks and dirt and foreign matter such as rainwater and dust from entering machines and equipment.
  • gaskets used for fixed applications, and oil seals and packings used for moving parts.
  • various materials are used depending on the purpose for soft gaskets such as O-rings and rubber sheets.
  • Packing is also used in rotating parts such as the shafts of pumps and motors, moving parts of valves, reciprocating parts such as pistons, coupling parts of couplers, and water stop parts of water faucets.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture seals that
  • hose material The hose material is a bendable pipe, and specifically includes water, oil, air, steam, and hydraulic high/low pressure hoses.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture hose materials that
  • Rubber-type products include anti-vibration rubber, damping materials, and boots.
  • Anti-vibration rubber and damping materials are rubber that prevent the transmission and spread of vibrations, and specifically, torsional rubber that prevents noise by absorbing vibrations when the engine of automobiles and various other vehicles is running. Includes dampers, engine mounts, muffler hangers, etc.
  • the rubber composition of the present invention can increase the tensile strength of vibration-proof rubber and damping materials. As a result, it is possible to produce vibration-proof rubber and damping materials that can be used in applications subject to high loads, which have been difficult to achieve with conventional rubber compositions.
  • the boot is a bellows-shaped member whose outer diameter gradually increases from one end to the other, and specifically, boots for constant velocity joint covers for protecting drive parts such as automobile drive systems; There are boots for ball joint covers (dust cover boots), boots for rack and pinion gears, etc.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture boots that
  • Gaskets, oil seals, and packing are parts that prevent liquid and gas leaks and dirt and foreign matter such as rainwater and dust from entering machines and equipment, and are specifically used for fixed purposes.
  • gaskets, oil seals and packing used for moving parts.
  • various materials are used depending on the purpose for soft gaskets such as O-rings and rubber sheets.
  • Packing is also used in rotating parts such as the shafts of pumps and motors, moving parts of valves, reciprocating parts such as pistons, coupling parts of couplers, and water stop parts of water faucets.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture seals that
  • Rubber rolls are manufactured by adhesively covering a metal core such as an iron core with rubber, and are generally manufactured by spirally wrapping a rubber sheet around a metal iron core. Rubber rolls are made of rubber materials such as NBR, EPDM, and CR, depending on the characteristics required for various uses such as paper manufacturing, various metal manufacturing, film manufacturing, printing, general industry, agricultural machinery such as hulling, and food processing. It is used. CR has good mechanical strength that can withstand the friction of conveyed objects, so it is used in a wide range of rubber roll applications. On the other hand, rubber rolls used in environments where oil adheres, such as during the production of industrial materials and products for steel manufacturing and paper manufacturing, have insufficient oil resistance, and improvements are needed.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture rubber rolls that
  • Industrial cables are linear members for transmitting electrical and optical signals.
  • a cable is made of a good conductor such as copper or copper alloy or an optical fiber coated with an insulating coating layer, and a wide variety of industrial cables are manufactured depending on its structure and installation location.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture industrial cables based on
  • Industrial conveyor belts are available in rubber, resin, and metal belts, and are selected to suit a wide variety of uses. Among these, rubber conveyor belts are inexpensive and widely used, but when used in environments where there is a lot of friction and collision with conveyed objects, they tend to deteriorate and break.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture industrial conveyor belts.
  • the rubber composition of the present invention can increase the tensile strength of sponge. Additionally, since chlorine-based rubber is used, it is possible to improve the flame retardancy of the sponge.
  • a vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to produce sponges with excellent flame retardant properties. Furthermore, the hardness of the resulting sponge can be adjusted as appropriate by adjusting the content of the foaming agent.
  • Examples of methods for molding the rubber composition (unvulcanized state) and vulcanizate according to this embodiment include press molding, extrusion molding, calendar molding, and the like.
  • the temperature at which the rubber composition is vulcanized may be appropriately set according to the composition of the rubber composition, and may be 140 to 220°C or 160 to 190°C.
  • the vulcanization time for vulcanizing the rubber composition may be appropriately set depending on the composition of the rubber composition, the shape of the unvulcanized molded article, etc., and may be 10 to 60 minutes.
  • emulsion polymerization was performed at a polymerization temperature of 40° C. under a nitrogen stream.
  • the above-mentioned chloroprene should be added in portions starting 20 seconds after the start of polymerization, and the flow rate should be adjusted using a solenoid valve based on the change in heat value of the refrigerant during the 10 seconds after the start of polymerization, and the flow rate should be readjusted every 10 seconds thereafter. performed continuously.
  • the above-mentioned polymerization rate [%] of the chloroprene latex was calculated from the dry mass when the chloroprene latex was air-dried. Specifically, it was calculated using the following formula (A).
  • solid content concentration is the solid content concentration [mass %] after heating 2 g of sampled chloroprene latex at 130°C and removing volatile components such as solvent (water), volatile chemicals, and raw materials. It is.
  • the “total amount charged” is the total amount [g] of raw materials, reagents, and solvent (water) charged into the polymerization reactor from the start of polymerization to a certain time.
  • Evaporation residue is the mass [g] of chemicals that remain as a solid content with the polymer without volatilizing under the condition of 130° C., among the chemicals and raw materials charged up to a certain time from the start of polymerization.
  • the “amount of monomer charged” is the total amount [g] of the monomer initially charged into the polymerization reactor and the amount of monomer added in portions up to a certain time from the start of polymerization.
  • the “monomer” here is the total amount of chloroprene and acrylonitrile.
  • Polymerization rate ⁇ [(total charged amount x solid content concentration/100) - evaporation residue]/monomer charged amount ⁇ x 100...(A)
  • the content of acrylonitrile monomer units contained in the chloroprene rubber A-2 was calculated from the content of nitrogen atoms in the chloroprene-acrylonitrile copolymer rubber. Specifically, the content of nitrogen atoms in 100 mg of chloroprene rubber A-2 was measured using an elemental analyzer (Sumigraph 220F, manufactured by Sumika Analysis Center Co., Ltd.), and the content of nitrogen atoms in the monomer unit of acrylonitrile was determined. The content was calculated. The content of acrylonitrile monomer units was 10.0% by mass.
  • the above elemental analysis was performed as follows.
  • the electric furnace temperature was set at 900°C for the reactor, 600°C for the reduction furnace, 70°C for the column, and 100°C for the detector.
  • Oxygen gas was used as the combustion gas at 0.2 mL/min
  • helium gas was used as the carrier gas at 80 mL/min. It flowed.
  • a calibration curve was created using aspartic acid (10.52%), which has a known nitrogen content, as a standard substance.
  • the content of acrylonitrile monomer units in the chloroprene rubber A-2 obtained by the above production method was 10.0% by mass.
  • Rubber compositions of Examples and Comparative Examples were obtained by mixing the components as shown in Tables 1 to 6 and kneading them with an 8-inch open roll.
  • Chloroprene rubber ⁇ Chloroprene rubber A-1 to A-4 mentioned above ⁇ Mercaptan-modified chloroprene rubber, manufactured by Denka Corporation, S-40V (unsaturated nitrile monomer unit content 0%)
  • Nitrile butadiene rubber ⁇ Nitrile rubber, manufactured by JSR Corporation, JSR N220S (acrylonitrile monomer unit content 41.5%) ⁇ Nitrile rubber, manufactured by JSR Corporation, JSR N230S (acrylonitrile monomer unit content 35%) ⁇ Nitrile rubber, manufactured by JSR Corporation, JSR N240S (acrylonitrile monomer unit content 26%) ⁇ Nitrile rubber, manufactured by JSR Corporation, JSR N250S (acrylonitrile monomer unit content 19.5%) ⁇ Hydrogenated nitrile rubber, manufactured by Nippon Zeon Co., Ltd., Zetpol2020 (acrylonitrile monomer unit content 36.2%, iodine value 28
  • ⁇ Preparation of vulcanized molded body> The obtained rubber composition was press-vulcanized in accordance with JIS K 6299 at 170° C. for 20 minutes to produce a sheet-like vulcanized product having a thickness of 2 mm.
  • test piece was obtained by punching out a test piece measuring 25 mm in length and 20 mm in width from the above-mentioned sheet-like vulcanized product. The obtained test piece was immersed in test oil (automotive high lubricant oil, ASTM No. 3, IRM 903 oil) at 130°C for 72 hours.
  • test oil automotive high lubricant oil, ASTM No. 3, IRM 903 oil
  • the volume change rate ⁇ V was calculated in accordance with JIS K 6258.
  • the obtained volume change rate was evaluated using the following evaluation criteria. A: Less than 8% B: 8% or more, less than 12% C: 12% or more, less than 16% D: 16% or more, less than 20% E: 20% or more
  • T10 The temperature (T10) at which the 180° torsional modulus becomes 10 times the 180° torsional modulus at room temperature was determined for the above-mentioned vulcanized product.
  • the obtained T10 was evaluated based on the following criteria. A: Less than -36°C B: -36°C or more, less than -29°C C: -29°C or more, less than -22°C D: -22°C or more, less than -15°C E: -15°C or more
  • the obtained sheet was formed into a dumbbell-shaped No. 3 test piece, and the elongation at break EB 0 was measured based on JIS K 6251.
  • the vulcanized molded product was heated at 130° C. for 72 hours, and then the elongation at break EB i was measured again based on JIS K 6251.
  • the change ⁇ EB in elongation at break before and after the heat resistance test was calculated from the elongation at break EB 0 before heating and the elongation at break EBi after heating.
  • the obtained ⁇ EB was evaluated based on the following criteria.
  • ⁇ EB (EB i -EB 0 ) ⁇ EB 0 ⁇ 100
  • a dematcher bending fatigue test was conducted based on JIS K 6260. Under the conditions of a stroke of 58 mm and a speed of 300 ⁇ 10 rpm, the number of bending tests at the time when a crack occurred was measured to evaluate durability and fatigue properties. Measurements were performed up to 2 million times. The number of bending tests at the time a crack occurred was evaluated using the following evaluation criteria. S: 1 million times or more A: 9000 times or more, less than 1 million times B: 6000 times or more, less than 9000 times C: 3000 times or more, less than 6000 times D: 100 times or more, less than 3000 times E: Less than 100 times

Abstract

Provided is a rubber composition capable of giving vulcanizates having an excellent balance among oil resistance, freeze resistance, heat resistance, ozone resistance, and flex fatigue resistance. This rubber composition comprises a chloroprene-based rubber and a nitrile-butadiene-based rubber, wherein, when the amount of the rubbers contained in the rubber composition is taken as 100 parts by mass, the chloroprene-based rubber and the nitrile-butadiene-based rubber are contained in amounts of 5-95 parts by mass and 5-95 parts by mass, respectively, and wherein the chloroprene-based rubber comprises a chloroprene-based rubber that contains units of an unsaturated nitrile monomer in an amount of 0.1-25 mass% and the nitrile-butadiene-based rubber contains acrylonitrile monomer units in an amount of 5-60 mass% with respect to the nitrile-butadiene-based rubber, which is taken as 100 mass%.

Description

ゴム組成物、加硫物、及び加硫成形体Rubber composition, vulcanizate, and vulcanized molded product
本発明は、ゴム組成物、加硫物、及び加硫成形体に関する。 The present invention relates to a rubber composition, a vulcanizate, and a vulcanized molded product.
クロロプレン系ゴムを含むゴム組成物は、優れた機械的強度・耐候性・耐薬品性・耐熱性・耐寒性・耐油性を有するため、一般産業用の伝動ベルトやコンベアベルト、自動車用空気バネ、防振ゴム、ホース、ワイパー、浸漬製品、シール部品、接着剤、ブーツ、ゴム引布、ゴムロールなどの材料として広く使用されている。 Rubber compositions containing chloroprene rubber have excellent mechanical strength, weather resistance, chemical resistance, heat resistance, cold resistance, and oil resistance, so they are used in power transmission belts and conveyor belts for general industry, air springs for automobiles, Widely used as material for anti-vibration rubber, hoses, wipers, immersion products, sealing parts, adhesives, boots, rubberized cloth, rubber rolls, etc.
例えば、特許文献１には、硫黄変性クロロプレンゴム、加硫促進剤、酸化亜鉛及び酸化マグネシウムからなり、上記加硫促進剤の配合量が０．１～５重量部であり、酸化亜鉛の配合量及び酸化マグネシウムの配合量が、それぞれの配合量とムーニースコーチ時間との予め求めた関係式により特定される、硫黄変性クロロプレンゴム組成物に係る発明が開示されている。
また、特許文献２には、ムーニー粘度ＭＬ（１＋４）１００℃が２０～８０であり、特定の構造の官能基を有する、クロロプレン単量体と不飽和ニトリル化合物の共重合体に係る発明が開示されている。 For example, Patent Document 1 discloses that the rubber is composed of sulfur-modified chloroprene rubber, a vulcanization accelerator, zinc oxide, and magnesium oxide, the amount of the vulcanization accelerator is 0.1 to 5 parts by weight, and the amount of zinc oxide is The invention relates to a sulfur-modified chloroprene rubber composition in which the blending amounts of magnesium oxide and magnesium oxide are specified by a predetermined relational expression between the respective blending amounts and Mooney scorch time.
Further, Patent Document 2 discloses an invention relating to a copolymer of a chloroprene monomer and an unsaturated nitrile compound, which has a Mooney viscosity ML (1+4) at 100°C of 20 to 80 and has a functional group with a specific structure. has been done.
また、特許文献３には、クロロプレンゴム３０～９３質量％と、ポリ塩化ビニルを可塑剤により可塑化して得られる軟質ポリ塩化ビニル５～５０質量％と、アクリロニトリルブタジエンゴム２～２０質量％と、を含有するブレンドゴムに係る発明が開示されている。 Further, Patent Document 3 describes 30 to 93 mass % of chloroprene rubber, 5 to 50 mass % of soft polyvinyl chloride obtained by plasticizing polyvinyl chloride with a plasticizer, and 2 to 20 mass % of acrylonitrile butadiene rubber. An invention relating to a blend rubber containing the following is disclosed.
特開平１１－２０９５２２号公報Japanese Patent Application Publication No. 11-209522 ＷＯ２０２０／０４４８９９WO2020/044899 ＷＯ２０１４／１５７６０２WO2014/157602
しかしながら、従来のクロロプレン系ゴムを含むゴム組成物を用いた場合、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れた加硫物を得ることは困難であった。 However, when using conventional rubber compositions containing chloroprene rubber, it has been difficult to obtain vulcanizates with an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and flex fatigue resistance. .
本発明は、このような事情に鑑みてなされたものであり、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れた加硫物を得ることができるゴム組成物を提供するものである。 The present invention has been made in view of these circumstances, and provides a rubber composition capable of obtaining a vulcanizate with an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance. It provides:
本発明によれば、クロロプレン系ゴム及びニトリルブタジエン系ゴムを含むゴム組成物であって、前記ゴム組成物は、前記ゴム組成物に含まれるゴムを１００質量部としたとき、前記クロロプレン系ゴム５～９５質量部と、前記ニトリルブタジエン系ゴム５～９５質量部を含有し、前記クロロプレン系ゴムは、前記クロロプレン系ゴムを１００質量％としたとき、不飽和ニトリル単量体単位を０．１～２５質量％含有し、前記ニトリルブタジエン系ゴムは、前記ニトリルブタジエン系ゴムを１００質量％としたとき、アクリロニトリル単量体単位を５～６０質量％含有する、ゴム組成物が提供される。 According to the present invention, there is provided a rubber composition containing a chloroprene-based rubber and a nitrile-butadiene-based rubber, in which the rubber composition contains 5 parts by mass of the chloroprene-based rubber when the rubber contained in the rubber composition is 100 parts by mass. The chloroprene rubber contains 0.1 to 95 parts by mass of unsaturated nitrile monomer units and 5 to 95 parts by mass of the nitrile butadiene rubber, and the chloroprene rubber contains 0.1 to 95 parts by mass of unsaturated nitrile monomer units when the chloroprene rubber is 100 mass %. A rubber composition is provided in which the nitrile-butadiene-based rubber contains 5 to 60% by mass of acrylonitrile monomer units when the nitrile-butadiene-based rubber is 100% by mass.
本発明者は、鋭意検討を行ったところ、ゴム組成物に、クロロプレン系ゴム及びニトリルブタジエン系ゴムを特定の量配合し、さらに、クロロプレン系ゴム中に不飽和ニトリル単量体単位含有クロロプレン系ゴムを配合し、ニトリルブタジエン系ゴム中のアクリロニトリル単量体単位含有率を特定の数値範囲内とすることによって、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れた加硫物を得ることができるゴム組成物となることを見出し、本発明の完成に至った。 After intensive studies, the present inventor has found that a specific amount of chloroprene-based rubber and nitrile-butadiene-based rubber is blended into a rubber composition, and that the chloroprene-based rubber contains unsaturated nitrile monomer units in the chloroprene-based rubber. By blending the acrylonitrile monomer unit content in the nitrile-butadiene rubber within a specific numerical range, it has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and flex fatigue resistance. It was discovered that a rubber composition can be obtained from which a vulcanizate can be obtained, leading to the completion of the present invention.
以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
好ましくは、前記不飽和ニトリル単量体単位がアクリロニトリル単量体単位である、前記記載のゴム組成物である。
好ましくは、前記ゴム組成物は、前記ゴム組成物に含まれるゴムを１００質量部としたときの、前記クロロプレン系ゴム中に含まれる不飽和ニトリル単量体単位の量をＸ質量部、前記ニトリルブタジエン系ゴムに含まれるアクリロニトリル単量体単位の量をＹ質量部としたとき、Ｘ×２．５＋Ｙが、５．０～５５．０である、前記記載のゴム組成物である。
好ましくは、硫黄、チオウレア系化合物、チウラム系化合物、チアゾール系化合物、スルフェンアミド系化合物、ジチオカルバミン酸系化合物、グアニジン系化合物、キサントゲン酸塩系化合物、イミダゾール系化合物及び３－メチルチアゾリジン－２－チオンからなる群より選ばれる少なくとも一種の化合物を含む、前記記載のゴム組成物である。
好ましくは、前記ゴム組成物に含まれるゴムを１００質量部としたとき、有機過酸化物を０．１～１０質量部含有する前記記載のゴム組成物である。
好ましくは、前記ゴム組成物に含まれるゴムを１００質量部としたとき、シクロヘキセン構造を有し、分子量が１００～１０００である化合物を０．１～５質量部含有する、前記記載のゴム組成物である。
好ましくは、前記ゴム組成物に含まれるゴムを１００質量部としたとき、マレイミド系化合物を０．１～１０質量部含有する前記記載のゴム組成物である。
好ましくは、ＪＩＳ　Ｋ　６２５８に基づき、ＩＲＭ９０３オイルを用いて測定される、前記ゴム組成物の加硫物の体積変化率ΔＶが、２０％未満であり、ＪＩＳ　Ｋ　６２６１に基づき、ゲーマンねじり試験により求めた、前記ゴム組成物の加硫物のＴ１０が－１５℃未満である。 Various embodiments of the present invention will be illustrated below. The embodiments shown below can be combined with each other.
Preferably, the rubber composition described above is one in which the unsaturated nitrile monomer unit is an acrylonitrile monomer unit.
Preferably, the rubber composition has an amount of unsaturated nitrile monomer units contained in the chloroprene rubber of X parts by mass, based on 100 parts by mass of the rubber contained in the rubber composition, and The rubber composition described above, where X×2.5+Y is 5.0 to 55.0, where Y is the amount of acrylonitrile monomer units contained in the butadiene rubber.
Preferably, sulfur, thiourea compounds, thiuram compounds, thiazole compounds, sulfenamide compounds, dithiocarbamate compounds, guanidine compounds, xanthate compounds, imidazole compounds, and 3-methylthiazolidine-2-thione The rubber composition described above contains at least one compound selected from the group consisting of:
Preferably, the rubber composition described above contains 0.1 to 10 parts by mass of an organic peroxide based on 100 parts by mass of rubber contained in the rubber composition.
Preferably, the rubber composition described above contains 0.1 to 5 parts by mass of a compound having a cyclohexene structure and a molecular weight of 100 to 1000, based on 100 parts by mass of the rubber contained in the rubber composition. It is.
Preferably, the rubber composition described above contains 0.1 to 10 parts by mass of a maleimide compound based on 100 parts by mass of rubber contained in the rubber composition.
Preferably, the volume change rate ΔV of the vulcanizate of the rubber composition is less than 20%, as measured using IRM903 oil in accordance with JIS K 6258, and as determined by Gehman torsion test in accordance with JIS K 6261. Further, the T10 of the vulcanizate of the rubber composition is less than -15°C.
本発明の別の観点によれば、前記記載のゴム組成物の加硫物が提供される。
また、本発明の別の観点によれば、前記記載のゴム組成物を用いた加硫成形体が提供される。 According to another aspect of the present invention, there is provided a vulcanizate of the rubber composition described above.
According to another aspect of the present invention, there is provided a vulcanized molded article using the rubber composition described above.
本発明に係るゴム組成物によれば、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れた加硫物を得ることができる。さらに、得られた加硫物及び加硫成形体は、これらの特性が必要とされる様々な部材として用いることができる。具体的には、本発明の一実施形態に係る加硫物及び加硫成形体は、例えば、一般産業用の伝動ベルトやコンベアベルト、自動車用空気バネ、防振ゴム、ホース、ワイパー、浸漬製品、シール部品、接着剤、ブーツ、ゴム引布、ゴムロールなどの材料として、好適に用いることができる。本発明の一実施形態に係る加硫物及び加硫成形体は、ゴム組成物に含まれる各ゴム中の各単量体単位の含有率、及び各ゴムの配合量、並びにゴム組成物に含まれるゴム以外の成分の種類及び配合量等を調整することによって、さらに高度にこれらの特性のパランスを調整可能である。したがって、これらを調整することによって、各部材の要求に適合した特性を有する加硫物及び加硫成形体とすることもできる。 According to the rubber composition of the present invention, a vulcanizate with an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance can be obtained. Furthermore, the obtained vulcanizates and vulcanized molded bodies can be used as various members requiring these properties. Specifically, the vulcanizate and vulcanized molded product according to an embodiment of the present invention can be used, for example, in power transmission belts and conveyor belts for general industry, air springs for automobiles, anti-vibration rubber, hoses, wipers, and immersion products. It can be suitably used as a material for seal parts, adhesives, boots, rubberized cloth, rubber rolls, etc. The vulcanizate and vulcanized molded article according to an embodiment of the present invention are characterized by the content of each monomer unit in each rubber contained in the rubber composition, the blending amount of each rubber, and the content of each monomer unit in each rubber contained in the rubber composition. By adjusting the types and blending amounts of components other than rubber, the balance of these properties can be adjusted to a higher degree. Therefore, by adjusting these, a vulcanized product and a vulcanized molded product having characteristics that meet the requirements of each member can be obtained.
以下、本発明の実施形態を例示して本発明について詳細な説明をする。本発明は、これらの記載によりなんら限定されるものではない。以下に示す本発明の実施形態の各特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, the present invention will be described in detail by illustrating embodiments of the present invention. The present invention is not limited in any way by these descriptions. Features of the embodiments of the present invention described below can be combined with each other. Further, the invention is established independently for each characteristic matter.
１．ゴム組成物
本発明に係るゴム組成物は、クロロプレン系ゴム及びニトリルブタジエン系ゴムを含むゴム組成物である。以下、本発明に係るゴム組成物について、詳述する。 1. Rubber Composition The rubber composition according to the present invention is a rubber composition containing chloroprene rubber and nitrile butadiene rubber. Hereinafter, the rubber composition according to the present invention will be explained in detail.
１．１　クロロプレン系ゴム
本発明において、クロロプレン系ゴムとは、クロロプレン（２－クロロ－１，３－ブタジエン）を単量体単位（単量体単位＝構造単位）として有するクロロプレン系重合体を含むゴムを示す。クロロプレン系重合体としては、クロロプレンの単独重合体、クロロプレンの共重合体（クロロプレンと、クロロプレンに共重合可能な単量体との共重合体）等が挙げられる。クロロプレン系重合体のポリマー構造は、特に限定されるものではない。 1.1 Chloroprene-based rubber In the present invention, chloroprene-based rubber includes chloroprene-based polymers having chloroprene (2-chloro-1,3-butadiene) as a monomer unit (monomer unit = structural unit). Showing rubber. Examples of the chloroprene-based polymer include chloroprene homopolymers, chloroprene copolymers (copolymers of chloroprene and a monomer copolymerizable with chloroprene), and the like. The polymer structure of the chloroprene polymer is not particularly limited.
なお、市販品の２－クロロ－１，３ブタジエンには不純物として少量の１－クロロ－１，３－ブタジエンが含まれる場合がある。このような少量の１－クロロ－１，３－ブタジエンを含む２－クロロ－１，３ブタジエンを、本実施形態のクロロプレン単量体として用いることもできる。 Note that commercially available 2-chloro-1,3-butadiene may contain a small amount of 1-chloro-1,3-butadiene as an impurity. 2-chloro-1,3-butadiene containing such a small amount of 1-chloro-1,3-butadiene can also be used as the chloroprene monomer in this embodiment.
本発明に係るクロロプレン系ゴムは、不飽和ニトリル単量体単位含有クロロプレン系ゴムを含む。
本発明に係る不飽和ニトリル単量体単位含有クロロプレン系ゴムは、不飽和ニトリル単量体単位含有クロロプレン系ゴムを１００質量％としたとき、不飽和ニトリル単量体単位を０．１～２５質量％含有し、０．１質量％以上、２５質量％未満含有することができる。本発明の一実施形態に係る不飽和ニトリル単量体単位含有クロロプレン系ゴムにおける不飽和ニトリル単量体単位の含有率は、例えば、０．１、０．２、０．３、０．５、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよく、また例示した数値の何れかを下限とし上限を２５質量％未満としてもよい。不飽和ニトリル単量体単位の含有率を上記上限以下とすることにより、得られる加硫物及び加硫成形体は充分な耐寒性を有するものとなる。また、不飽和ニトリル単量体単位の含有率を上記下限以上とすることにより、得られる加硫物及び加硫成形体は十分な耐油性を有するものとなる。 The chloroprene rubber according to the present invention includes a chloroprene rubber containing unsaturated nitrile monomer units.
The chloroprene rubber containing unsaturated nitrile monomer units according to the present invention contains 0.1 to 25 mass % of unsaturated nitrile monomer units when the chloroprene rubber containing unsaturated nitrile monomer units is 100 mass %. %, and can be contained in an amount of 0.1% by mass or more and less than 25% by mass. The content of unsaturated nitrile monomer units in the chloroprene rubber containing unsaturated nitrile monomer units according to an embodiment of the present invention is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 mass %, and may be within a range between any two of the numerical values exemplified here, or the lower limit may be any of the numerical values illustrated here, and the upper limit may be less than 25% by mass. By controlling the content of unsaturated nitrile monomer units to be below the above upper limit, the resulting vulcanizate and vulcanized molded product will have sufficient cold resistance. Furthermore, by setting the content of unsaturated nitrile monomer units to the above lower limit or more, the resulting vulcanizate and vulcanized molded product will have sufficient oil resistance.
不飽和ニトリル単量体単位としては、アクリロニトリル単量体単位、メタクリロニトリル単量体単位、エタクリロニトリル単量体単位、フェニルアクリロニトリル単量体単位等が挙げられる。不飽和ニトリルは、１種単独で又は２種以上を組み合わせて用いることができる。不飽和ニトリル単量体単位は、優れた成形性が得られやすい観点、並びに、加硫成形体において優れた機械的特性及び耐油性が得られやすい観点から、アクリロニトリル単量体単位を含むことが好ましい。 Examples of the unsaturated nitrile monomer unit include an acrylonitrile monomer unit, a methacrylonitrile monomer unit, an ethacrylonitrile monomer unit, a phenyl acrylonitrile monomer unit, and the like. Unsaturated nitriles can be used alone or in combination of two or more. The unsaturated nitrile monomer unit may contain an acrylonitrile monomer unit from the viewpoint of easily obtaining excellent moldability and from the viewpoint of easily obtaining excellent mechanical properties and oil resistance in the vulcanized molded product. preferable.
クロロプレン系ゴムに含まれる不飽和ニトリル単量体単位の含有量は、クロロプレン系ゴム中の窒素原子の含有量から算出することができる。具体的には、元素分析装置（スミグラフ２２０Ｆ：株式会社住化分析センター製）を用いて１００ｍｇのクロロプレン系ゴムにおける窒素原子の含有量を測定し、不飽和ニトリル単量体由来の構造の含有量を算出できる。元素分析の測定は次の条件で行うことができる。例えば、電気炉温度として反応炉９００℃、還元炉６００℃、カラム温度７０℃、検出器温度１００℃に設定し、燃焼用ガスとして酸素を０．２ｍＬ／ｍｉｎ、キャリアーガスとしてヘリウムを８０ｍＬ／ｍｉｎフローする。検量線は、窒素含有量が既知のアスパラギン酸（１０．５２％）を標準物質として用いて作成できる。 The content of unsaturated nitrile monomer units contained in the chloroprene rubber can be calculated from the content of nitrogen atoms in the chloroprene rubber. Specifically, the content of nitrogen atoms in 100 mg of chloroprene rubber was measured using an elemental analyzer (Sumigraph 220F, manufactured by Sumika Analysis Center Co., Ltd.), and the content of structures derived from unsaturated nitrile monomers was determined. can be calculated. Elemental analysis measurements can be performed under the following conditions. For example, the electric furnace temperature is set to 900°C for the reactor, 600°C for the reduction furnace, 70°C for the column, and 100°C for the detector, oxygen at 0.2 mL/min as the combustion gas, and helium at 80 mL/min as the carrier gas. Flow. A calibration curve can be created using aspartic acid (10.52%), which has a known nitrogen content, as a standard substance.
本発明の一実施形態に係るクロロプレン系ゴムは、クロロプレン系ゴムを１００質量％としたとき、クロロプレン単量体単位を６０～１００質量％含むことが好ましい。クロロプレン系ゴムにおけるクロロプレン単量体単位の含有率は、例えば、６０、６５、７０、７５、８０、８５、９０、９５、９９、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。クロロプレン単量体単位の含有率を上記数値範囲内とすることにより、機械的特性及び耐寒性のバランスに優れる加硫物及び加硫成形体を得ることができるゴム組成物とできる。 The chloroprene-based rubber according to an embodiment of the present invention preferably contains 60 to 100% by mass of chloroprene monomer units when the chloroprene-based rubber is 100% by mass. The content of chloroprene monomer units in the chloroprene rubber is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 99, 100% by mass, and any two of the values exemplified here. It may be within the range between. By controlling the content of the chloroprene monomer unit within the above-mentioned numerical range, a rubber composition can be obtained from which a vulcanizate and a vulcanized molded product with an excellent balance of mechanical properties and cold resistance can be obtained.
本発明の一実施形態に係るクロロプレン系ゴムは、クロロプレン単量体及び不飽和ニトリル単量体以外の単量体単位を有するものとすることもできる。クロロプレン単量体及び不飽和ニトリル単量体以外の単量体単位としては、クロロプレン単量体、又は、クロロプレン単量体及び不飽和ニトリル単量体と共重合可能であれば特に制限はないが、（メタ）アクリル酸のエステル類（（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル等）、ヒドロキシアルキル（メタ）アクリレート（２－ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等）、２，３－ジクロロ－１，３－ブタジエン、１－クロロ－１，３－ブタジエン、ブタジエン、イソプレン、エチレン、スチレン、硫黄等が挙げられる。 The chloroprene rubber according to one embodiment of the present invention may also have monomer units other than chloroprene monomer and unsaturated nitrile monomer. The monomer units other than chloroprene monomer and unsaturated nitrile monomer are not particularly limited as long as they can be copolymerized with chloroprene monomer or chloroprene monomer and unsaturated nitrile monomer. , (meth)acrylic acid esters (methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), hydroxyalkyl (meth)acrylate (2-hydroxymethyl (meth)acrylate) , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.), 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene , sulfur, etc.
本発明の一実施形態に係るクロロプレン系ゴムは、クロロプレン系ゴムを１００質量％としたとき、クロロプレン単量体及び不飽和ニトリル単量体以外の単量体単位を０～２０質量％含むものとすることができる。ゴムおけるクロロプレン単量体及び不飽和ニトリル単量体以外の単量体単位の含有率は、例えば、０、２、４、６、８、１０、１２、１４、１６、１８、２０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。クロロプレン単量体及び不飽和ニトリル単量体以外の単量体の共重合量をこの範囲に調整することで、得られるゴム組成物の特性を損なわずに、これら単量体を共重合させたことによる効果を発現することができる。
また、本発明の一実施形態に係るクロロプレン系ゴムは、クロロプレン単量体単位及び不飽和ニトリル単量体単位のみからなるものとすることもできる。 The chloroprene-based rubber according to an embodiment of the present invention shall contain 0 to 20% by mass of monomer units other than chloroprene monomer and unsaturated nitrile monomer when the chloroprene-based rubber is 100% by mass. I can do it. The content of monomer units other than chloroprene monomer and unsaturated nitrile monomer in the rubber is, for example, 0, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20% by mass. Yes, it may be within the range between any two of the numerical values exemplified here. By adjusting the amount of copolymerization of monomers other than chloroprene monomer and unsaturated nitrile monomer within this range, these monomers were copolymerized without impairing the properties of the resulting rubber composition. It is possible to express the effect of this.
Furthermore, the chloroprene rubber according to one embodiment of the present invention may be composed only of chloroprene monomer units and unsaturated nitrile monomer units.
本発明に係るゴム組成物は、クロロプレン系ゴムを、１種単独で又は２種以上を組み合わせて用いることができる。本発明の一実施形態に係るクロロプレン系ゴムは、不飽和ニトリル単量体単位含有クロロプレン系ゴム及びそれ以外のクロロプレン系ゴム（例えば、クロロプレンの単独重合体）を混合したゴムとすることもできる。また、本発明の一実施形態に係るクロロプレン系ゴムは、１又は複数の、不飽和ニトリル単量体単位含有クロロプレン系ゴムのみからなるものとすることできる。
本発明の一実施形態に係るゴム組成物は、２種以上のクロロプレン系ゴムを含む場合、ゴム組成物に含まれる２種以上のクロロプレン系ゴムに含まれる各成分の合計が、上記数値範囲内であることが好ましく、例えば、不飽和ニトリル単量体単位の合計含有率が０．１～２５質量％であることが好ましい。 In the rubber composition according to the present invention, one type of chloroprene rubber can be used alone or two or more types can be used in combination. The chloroprene rubber according to one embodiment of the present invention can also be a rubber obtained by mixing a chloroprene rubber containing an unsaturated nitrile monomer unit and another chloroprene rubber (for example, a homopolymer of chloroprene). Furthermore, the chloroprene rubber according to one embodiment of the present invention may consist only of chloroprene rubber containing one or more unsaturated nitrile monomer units.
When the rubber composition according to one embodiment of the present invention contains two or more types of chloroprene rubber, the total of each component contained in the two or more types of chloroprene rubber contained in the rubber composition is within the above numerical range. For example, the total content of unsaturated nitrile monomer units is preferably from 0.1 to 25% by mass.
本発明に係るクロロプレン系ゴムに含まれるクロロプレン系重合体は、硫黄変性クロロプレン重合体、メルカプタン変性クロロプレン系重合体、キサントゲン変性クロロプレン系重合体、ジチオカルボナート系クロロプレン系重合体、トリチオカルボナート系クロロプレン系重合体、カルバメート系クロロプレン系重合体などであってよい。 The chloroprene polymer contained in the chloroprene rubber according to the present invention is a sulfur-modified chloroprene polymer, a mercaptan-modified chloroprene polymer, a xanthogen-modified chloroprene polymer, a dithiocarbonate-based chloroprene polymer, and a trithiocarbonate-based polymer. It may be a chloroprene-based polymer, a carbamate-based chloroprene-based polymer, or the like.
１．２　クロロプレン系ゴムの製造方法
本発明の一実施形態に係るクロロプレン系ゴムの製造方法は特に限定されないが、クロロプレン単量体を含む原料単量体を乳化重合する乳化重合工程を含む製造方法によって得ることができる。
本発明の一実施形態に係る乳化重合工程では、クロロプレン単量体及び不飽和ニトリル単量体を含む単量体を、乳化剤や分散剤や触媒や連鎖移動剤等を適宜に用いて乳化重合させ、目的とする最終転化率に達した際に重合停止剤を添加してクロロプレン単量体単位を含むクロロプレン系重合体を含むラテックスを得ることができる。
次に、乳化重合工程により得られた重合液から、未反応単量体の除去を行うことができる。その方法は、特に限定されるものではなく、例えば、スチームストリッピング法が挙げられる。
その後、ｐＨを調整し、常法の凍結凝固、水洗、熱風乾燥などの工程を経て、クロロプレン系重合体を含むクロロプレン系ゴムを得ることができる。 1.2 Method for producing chloroprene-based rubber The method for producing chloroprene-based rubber according to one embodiment of the present invention is not particularly limited, but may include an emulsion polymerization step of emulsion polymerization of raw material monomers containing chloroprene monomers. can be obtained by
In the emulsion polymerization step according to one embodiment of the present invention, monomers including chloroprene monomers and unsaturated nitrile monomers are emulsion polymerized using appropriate emulsifiers, dispersants, catalysts, chain transfer agents, etc. A latex containing a chloroprene polymer containing chloroprene monomer units can be obtained by adding a polymerization terminator when the desired final conversion rate is reached.
Next, unreacted monomers can be removed from the polymerization solution obtained by the emulsion polymerization step. The method is not particularly limited, and includes, for example, a steam stripping method.
Thereafter, the pH is adjusted, and a chloroprene rubber containing a chloroprene polymer can be obtained through conventional steps such as freezing and coagulation, washing with water, and drying with hot air.
乳化重合する場合に用いる重合開始剤としては、特に制限はなく、クロロプレンの乳化重合に一般に用いられる公知の重合開始剤を用いることができる。重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、過酸化水素、ｔ－ブチルハイドロパーオキサイド等の有機過酸化物などが挙げられる。 The polymerization initiator used in emulsion polymerization is not particularly limited, and any known polymerization initiator commonly used in emulsion polymerization of chloroprene can be used. Examples of the polymerization initiator include organic peroxides such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide.
乳化重合する場合に用いる乳化剤としては、特に制限はなく、クロロプレンの乳化重合に一般に用いられる公知の乳化剤を用いることができる。乳化剤としては、炭素数が６～２２の飽和又は不飽和の脂肪酸のアルカリ金属塩、ロジン酸又は不均化ロジン酸のアルカリ金属塩（例えばロジン酸カリウム）、β－ナフタレンスルホン酸のホルマリン縮合物のアルカリ金属塩（例えばナトリウム塩）等が挙げられる。 The emulsifier used in emulsion polymerization is not particularly limited, and known emulsifiers commonly used in emulsion polymerization of chloroprene can be used. Examples of emulsifiers include alkali metal salts of saturated or unsaturated fatty acids having 6 to 22 carbon atoms, alkali metal salts of rosin acid or disproportionated rosin acids (e.g. potassium rosin acid), formalin condensates of β-naphthalenesulfonic acid. Examples include alkali metal salts (eg, sodium salts) of .
乳化重合する場合に用いる分子量調整剤としては、特に制限はなく、クロロプレンの乳化重合に一般に用いられる公知の分子量調整剤を用いることができ、例えば、メルカプタン系化合物、キサントゲン系化合物、ジチオカルボナート系化合物、トリチオカルボナート系化合物及びカルバメート系化合物がある。本発明の一実施形態に係るクロロプレン系ゴムの分子量調整剤としては、キサントゲン系化合物、ジチオカルボナート系化合物、トリチオカルボナート系化合物及びカルバメート系化合物を好適に使用できる。 The molecular weight regulator used in emulsion polymerization is not particularly limited, and known molecular weight regulators commonly used in emulsion polymerization of chloroprene can be used, such as mercaptan compounds, xanthogen compounds, dithiocarbonate compounds, etc. compounds, trithiocarbonate compounds, and carbamate compounds. As the molecular weight regulator for the chloroprene rubber according to one embodiment of the present invention, xanthogen compounds, dithiocarbonate compounds, trithiocarbonate compounds, and carbamate compounds can be suitably used.
重合温度及び単量体の最終転化率は特に制限するものではないが、重合温度は、例えば０～５０℃又は１０～５０℃であってよい。単量体の最終転化率が４０～９５質量％の範囲に入るように重合を行ってよい。最終転化率を調整するためには、所望する転化率になった時に、重合反応を停止させる重合停止剤を添加して重合を停止させればよい。 The polymerization temperature and the final conversion rate of monomers are not particularly limited, but the polymerization temperature may be, for example, 0 to 50°C or 10 to 50°C. The polymerization may be carried out such that the final conversion of monomer is in the range of 40 to 95% by weight. In order to adjust the final conversion rate, when the desired conversion rate is reached, a polymerization terminator that stops the polymerization reaction may be added to terminate the polymerization.
重合停止剤としては、特に制限はなく、クロロプレンの乳化重合に一般に用いられる公知の重合停止剤を用いることができる。重合停止剤としては、フェノチアジン（チオジフェニルアミン）、４－ｔ－ブチルカテコール、２，２－メチレンビス－４－メチル－６－ｔ－ブチルフェノール等が挙げられる。 The polymerization terminator is not particularly limited, and any known polymerization terminator commonly used in emulsion polymerization of chloroprene can be used. Examples of the polymerization terminator include phenothiazine (thiodiphenylamine), 4-t-butylcatechol, 2,2-methylenebis-4-methyl-6-t-butylphenol, and the like.
本発明の一実施形態に係るクロロプレン系ゴムは、例えば、スチームストリッピング法によって未反応の単量体を除去した後、上記ラテックスのｐＨを調整し、常法の凍結凝固、水洗、熱風乾燥等の工程を経て得ることができる。 The chloroprene rubber according to an embodiment of the present invention can be produced by, for example, removing unreacted monomers by a steam stripping method, adjusting the pH of the latex, freezing and coagulating the rubber by conventional methods, washing with water, drying with hot air, etc. It can be obtained through the process of
クロロプレン系ゴムは、分子量調整剤の種類によりメルカプタン変性タイプ、キサントゲン変性タイプ、硫黄変性タイプ、ジチオカルボナート系タイプ、トリチオカルボナート系タイプ及びカルバメート系タイプに分類される。 Chloroprene-based rubbers are classified into mercaptan-modified types, xanthogen-modified types, sulfur-modified types, dithiocarbonate-based types, trithiocarbonate-based types, and carbamate-based types depending on the type of molecular weight modifier.
１．４　ニトリルブタジエン系ゴム
本発明において、ニトリルブタジエン系ゴムとは、アクリロニトリルと１，３－ブタジエンを単量体単位として有するニトリルブタジエン系重合体を含むゴムを示す。本発明において、ニトリルブタジエン系ゴムは、アクリロニトリルと１，３－ブタジエンを単量体単位として有するニトリルブタジエン系重合体を含むゴム（以下、ニトリルゴムとも称する）及びアクリロニトリルと１，３－ブタジエンを単量体単位として有するニトリルブタジエン系重合体の少なくとも一部を水素化した水素化ニトリルブタジエン系重合体を含むゴム（以下、水素化ニトリルゴムとも称する）を含む。 1.4 Nitrile Butadiene Rubber In the present invention, nitrile butadiene rubber refers to a rubber containing a nitrile butadiene polymer having acrylonitrile and 1,3-butadiene as monomer units. In the present invention, the nitrile-butadiene-based rubber includes a rubber containing a nitrile-butadiene-based polymer having acrylonitrile and 1,3-butadiene as monomer units (hereinafter also referred to as nitrile rubber) and a rubber containing a nitrile-butadiene-based polymer having acrylonitrile and 1,3-butadiene as monomer units; It includes a rubber containing a hydrogenated nitrile-butadiene-based polymer (hereinafter also referred to as hydrogenated nitrile rubber) obtained by hydrogenating at least a portion of the nitrile-butadiene-based polymer as a mer unit.
本発明に係るニトリルブタジエン系ゴムは、ニトリルゴム及び水素化ニトリルゴムのうち、少なくとも１種を含み、ニトリルゴム及び水素化ニトリルゴムを含むこともできる。本発明の一実施形態に係るニトリルブタジエン系ゴムは、ニトリルゴム又は水素化ニトリルゴムを含むことが好ましい。ゴム組成物に配合するニトリルブタジエン系ゴムの種類は、所望されるゴム組成物、加硫物及び加硫成形体の特性に応じて選択することができ、一例として、コスト低減や、耐油性及び耐寒性のバランスを重視する場合、ニトリルゴムを選択することができる。また、一例として、耐油性及び耐寒性のバランス、耐オゾン性、耐熱性を重視する場合、水素化ニトリルゴムを選択することができる。 The nitrile butadiene rubber according to the present invention contains at least one of nitrile rubber and hydrogenated nitrile rubber, and can also contain nitrile rubber and hydrogenated nitrile rubber. The nitrile butadiene rubber according to one embodiment of the present invention preferably includes nitrile rubber or hydrogenated nitrile rubber. The type of nitrile butadiene rubber to be blended into the rubber composition can be selected depending on the desired properties of the rubber composition, vulcanizate, and vulcanized product.For example, cost reduction, oil resistance, and If a balance of cold resistance is important, nitrile rubber can be selected. Further, as an example, when the balance between oil resistance and cold resistance, ozone resistance, and heat resistance are important, hydrogenated nitrile rubber can be selected.
本発明に係るニトリルブタジエン系ゴムは、ニトリルブタジエン系ゴムを１００質量％としたとき、アクリロニトリル単量体単位を５～６０質量％含有する。本発明の一実施形態に係るニトリルブタジエン系ゴムにおけるアクリロニトリル単量体単位含有率は、例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。ニトリルブタジエン系ゴムにおけるアクリロニトリル単量体単位含有率を上記数値範囲内とすることにより、耐油性及び耐寒性のバランスに優れる加硫物及び加硫成形体を得ることができるゴム組成物となる。 The nitrile butadiene rubber according to the present invention contains 5 to 60% by mass of acrylonitrile monomer units when the nitrile butadiene rubber is 100% by mass. The acrylonitrile monomer unit content in the nitrile butadiene rubber according to one embodiment of the present invention is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass. Yes, it may be within the range between any two of the numerical values exemplified here. By controlling the acrylonitrile monomer unit content in the nitrile-butadiene rubber to be within the above numerical range, a rubber composition can be obtained that provides a vulcanizate and a vulcanized molded product with an excellent balance of oil resistance and cold resistance.
本発明に係るゴム組成物は、ニトリルブタジエン系ゴムを、１種単独で又は２種以上を組み合わせて用いることができる。
本発明の一実施形態に係るゴム組成物が、２種以上のニトリルブタジエン系ゴムを含む場合、ゴム組成物に含まれる２種以上のニトリルブタジエン系ゴムに含まれるアクリロニトリル単量体単位の合計含有率が５～６０質量％であることが好ましい。 In the rubber composition according to the present invention, one type of nitrile butadiene rubber can be used alone or two or more types can be used in combination.
When the rubber composition according to an embodiment of the present invention contains two or more types of nitrile butadiene rubber, the total content of acrylonitrile monomer units contained in the two or more types of nitrile butadiene rubber contained in the rubber composition. Preferably, the ratio is 5 to 60% by weight.
ニトリルブタジエン系ゴムとして、水素化ニトリルゴムを用いる場合、重合体中に存在する二重結合の量の指標となるヨウ素価が、５～６０ｍｇ／１００ｍｇである水素化ニトリルゴムを用いることができる。水素化ニトリルゴムのヨウ素価は、例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０ｍｇ／１００ｍｇであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 When hydrogenated nitrile rubber is used as the nitrile butadiene rubber, it is possible to use a hydrogenated nitrile rubber whose iodine number, which is an indicator of the amount of double bonds present in the polymer, is 5 to 60 mg/100 mg. The iodine value of hydrogenated nitrile rubber is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 mg/100 mg, and between any two of the values exemplified here. may be within the range of
１．４　ゴムの配合量
本発明に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、クロロプレン系ゴム５～９５質量部と、ニトリルブタジエン系ゴム５～９５質量部を含有する。 1.4 Amount of rubber compounded The rubber composition according to the present invention contains 5 to 95 parts by mass of chloroprene rubber and 5 to 95 parts by mass of nitrile butadiene rubber, when the rubber contained in the rubber composition is 100 parts by mass. Contains.
本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、クロロプレン系ゴムを、例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、９５質量部含むことができ、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The rubber composition according to one embodiment of the present invention contains, for example, 5, 10, 15, 20, 25, 30, 35, 40 parts of chloroprene rubber when the rubber contained in the rubber composition is 100 parts by mass. , 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 parts by mass, and may be within a range between any two of the numerical values exemplified here.
本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、ニトリルブタジエン系ゴムを例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、９５質量部含むことができ、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The rubber composition according to one embodiment of the present invention contains, for example, 5, 10, 15, 20, 25, 30, 35, 40 parts of nitrile butadiene rubber when the rubber contained in the rubber composition is 100 parts by mass. , 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 parts by mass, and may be within a range between any two of the numerical values exemplified here.
本発明に係るゴム組成物は、クロロプレン系ゴム及びニトリルブタジエン系ゴムの配合量を上記数値範囲内とすることにより、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れた加硫物を得ることができる。また、本発明の一実施形態に係る加硫物及び加硫成形体は、ゴムの配合量に加え、各ゴム中の各単量体単位の含有率を調整することによってさらに高度にこれらの特性のパランスを調整可能である。 The rubber composition according to the present invention has a balance of oil resistance, cold resistance, heat resistance, ozone resistance, and flex fatigue resistance by adjusting the blending amount of chloroprene rubber and nitrile butadiene rubber within the above numerical range. An excellent vulcanizate can be obtained. In addition, the vulcanizate and vulcanized molded product according to an embodiment of the present invention can further improve these properties by adjusting the content of each monomer unit in each rubber in addition to the amount of rubber compounded. The balance can be adjusted.
本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたときの、クロロプレン系ゴム中に含まれる不飽和ニトリル単量体単位の量をＸ質量部、ニトリルブタジエン系ゴムに含まれるアクリロニトリル単量体単位の量をＹ質量部としたとき、Ｘ×２．５＋Ｙを、５．０～５５．０とでき、８．０超、５５．０以下であることが好ましく、１０．０～５０．０であることがより好ましい。Ｘ×２．５＋Ｙは、例えば、５．０、１０．０、１５．０、２０．０、２５．０、３０．０、３５．０、４０．０、４５．０、５０．０、５５．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。Ｘ×２．５＋Ｙの値を上記数値範囲内とすることにより、得られる加硫物の耐油性、耐寒性、耐熱性、耐オゾン性，及び耐屈曲疲労性、特には、耐油性、耐寒性のバランスをより高度に調整することができる。 In the rubber composition according to an embodiment of the present invention, the amount of unsaturated nitrile monomer units contained in the chloroprene rubber is X parts by mass, when the rubber contained in the rubber composition is 100 parts by mass. When the amount of acrylonitrile monomer units contained in the nitrile butadiene rubber is Y parts by mass, X x 2.5 + Y can be from 5.0 to 55.0, and is more than 8.0 and less than 55.0. It is preferably from 10.0 to 50.0. For example, X×2.5+Y is 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 55 .0, and may be within a range between any two of the numerical values exemplified here. By setting the value of X x 2.5 + Y within the above numerical range, the obtained vulcanizate has oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, especially oil resistance and cold resistance. The balance can be adjusted to a higher level.
１．５　硫黄・加硫促進剤
本発明に係るゴム組成物は、硫黄及び加硫促進剤を含むことができる。本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、硫黄及び加硫促進剤を５．０質量部以下含むことができる。硫黄及び加硫促進剤の含有量は、例えば、０、０.１、０．３、０．５、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 1.5 Sulfur/Vulcanization Accelerator The rubber composition according to the present invention can contain sulfur and a vulcanization accelerator. The rubber composition according to one embodiment of the present invention can contain 5.0 parts by mass or less of sulfur and a vulcanization accelerator, based on 100 parts by mass of rubber contained in the rubber composition. The content of sulfur and vulcanization accelerator is, for example, 0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5. , 4.0, 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified here.
加硫促進剤の種類は、本発明の効果を損なわなければ特に限定されない。加硫促進剤は、クロロプレン系ゴム及び／又はニトリルブタジエン系ゴムの加硫に用いることができる加硫促進剤であることが好ましく、クロロプレン系ゴムに用いることができる加硫促進剤であることがより好ましい。加硫促進剤は、１種又は２種以上自由に選択して用いることができる。
本発明に係るゴム組成物は、硫黄、チオウレア系化合物、チウラム系化合物、チアゾール系化合物、スルフェンアミド系化合物、ジチオカルバミン酸系化合物、グアニジン系化合物、キサントゲン酸塩系化合物、イミダゾール系化合物及び３－メチルチアゾリジン－２－チオンからなる群より選ばれる少なくとも一種の化合物を含むことが好ましく、硫黄、チオウレア系化合物、チウラム系化合物、チアゾール系化合物、スルフェンアミド系化合物、ジチオカルバミン酸系化合物及び３－メチルチアゾリジン－２－チオンからなる群より選ばれる少なくとも一種の化合物を含むことがより好ましい。 The type of vulcanization accelerator is not particularly limited as long as it does not impair the effects of the present invention. The vulcanization accelerator is preferably a vulcanization accelerator that can be used for vulcanization of chloroprene rubber and/or nitrile butadiene rubber, and is preferably a vulcanization accelerator that can be used for chloroprene rubber. More preferred. One or more vulcanization accelerators can be freely selected and used.
The rubber composition according to the present invention contains sulfur, a thiourea compound, a thiuram compound, a thiazole compound, a sulfenamide compound, a dithiocarbamate compound, a guanidine compound, a xanthate compound, an imidazole compound, and 3- It preferably contains at least one compound selected from the group consisting of methylthiazolidine-2-thione, including sulfur, thiourea compounds, thiuram compounds, thiazole compounds, sulfenamide compounds, dithiocarbamate compounds, and 3-methyl. More preferably, it contains at least one compound selected from the group consisting of thiazolidine-2-thione.
チオウレア系化合物としては、エチレンチオウレア、ジエチルチオウレア（Ｎ，Ｎ'－ジエチルチオウレア）、トリメチルチオウレア、ジフェニルチオウレア（Ｎ，Ｎ'－ジフェニルチオウレア）、１、３－トリメチレン－２－チオウレア等のチオウレア系化合物が挙げられる。
チウラム系化合物としては、テトラメチルチウラムジスルフィド（ＴＭＴＤ）、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラキス（２－エチルヘキシル）チウラムジスルフィド、テトラメチルチウラムモノスルフィド、ジペンタメチレンチウラムテトラスルフィド等が挙げられる。
チアゾール系化合物としては、２－メルカプトベンゾチアゾール、ジ－２－ベンゾチアゾリルジスルフィド、２－メルカプトベンゾチアゾール亜鉛塩、２－メルカプトベンゾチアゾールのシクロヘキシルアミン塩、２－（４'－モルホリノジチオ）ベンゾチアゾール、Ｎ－シクロヘキシルベンゾチアゾール－２－スルフェンアミド等が挙げられる。
スルフェンアミド系化合物としては、Ｎ－シクロヘキシルベンゾチアゾール－２－スルフェンアミド等が挙げられる。
ジチオカルバミン酸系化合物としては、ジブチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、Ｎ－エチル－Ｎ－フェニルジチオカルバミン酸亜鉛、Ｎ－ペンタメチレンジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸銅、ジメチルジチオカルバミン酸第二鉄、ジエチルジチオカルバミン酸テルル等が挙げられる。
これらは、それぞれ１種単独で又は２種以上を組み合わせて用いることができる。
グアニジン系化合物としては、１，３－ジフェニルグアニジン、１，３－ジ－ｏ－トリルグアニジン、１－ｏ－トリルビグアニド、ジカテコールボレートのジ－ｏ－トリルグアニジン塩等が挙げられる。
キサントゲン酸塩系化合物としては、ブチルキサントゲン酸亜鉛、イソプロピルキサントゲン酸亜鉛等が挙げられる。
イミダゾール系化合物としては、２－メルカプトベンゾイミダゾール、２－メルカプトメチルベンゾイミダゾール及び２－メルカプトベンゾイミダゾールの亜鉛塩を挙げることができる。 Examples of thiourea-based compounds include thiourea-based compounds such as ethylenethiourea, diethylthiourea (N,N'-diethylthiourea), trimethylthiourea, diphenylthiourea (N,N'-diphenylthiourea), and 1,3-trimethylene-2-thiourea. can be mentioned.
Examples of thiuram-based compounds include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, and the like.
Examples of thiazole compounds include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, cyclohexylamine salt of 2-mercaptobenzothiazole, and 2-(4'-morpholinodithio)benzo Examples include thiazole, N-cyclohexylbenzothiazole-2-sulfenamide, and the like.
Examples of sulfenamide compounds include N-cyclohexylbenzothiazole-2-sulfenamide.
Examples of dithiocarbamic acid compounds include sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, copper dimethyldithiocarbamate, and zinc dimethyldithiocarbamate. Examples include diiron, tellurium diethyldithiocarbamate, and the like.
These can be used alone or in combination of two or more.
Examples of the guanidine-based compound include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatecholborate, and the like.
Examples of the xanthate compounds include zinc butylxanthate, zinc isopropylxanthate, and the like.
Examples of imidazole compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole.
また、本発明に係るゴム組成物は、硫黄及び加硫促進剤を含まないものとすることもできる。
以下に示すように、本発明に係るゴム組成物は、有機過酸化物を含むこともできる。
本発明に係るゴム組成物は、硫黄及び加硫促進剤のうち少なくとも１つを含むか、又は、有機過酸化物を含むことが好ましい。
ゴム組成物に硫黄及び加硫促進剤のうち少なくとも１つを配合するか、又は、有機過酸化物を配合するかは、所望されるゴム組成物、加硫物及び加硫成形体の特性に応じて選択することができ、一例として、耐熱性及び耐屈曲疲労性を重視する場合、硫黄及び加硫促進剤のうち少なくとも１つを配合すことを選択することができる。また、一例として、耐熱性を重視する場合、有機過酸化物を選択することができる。 Furthermore, the rubber composition according to the present invention may be free of sulfur and vulcanization accelerator.
As shown below, the rubber composition according to the present invention can also contain an organic peroxide.
The rubber composition according to the present invention preferably contains at least one of sulfur and a vulcanization accelerator, or preferably contains an organic peroxide.
Whether at least one of sulfur and a vulcanization accelerator or an organic peroxide is blended into the rubber composition depends on the desired characteristics of the rubber composition, vulcanizate, and vulcanized molded product. For example, if heat resistance and bending fatigue resistance are important, it may be selected to include at least one of sulfur and a vulcanization accelerator. Further, as an example, when heat resistance is important, organic peroxides can be selected.
１．６　有機過酸化物
本発明に係るゴム組成物は、有機過酸化物を含むことができる。
有機過酸化物としては、例えば、ジクミルパーオキサイド、ベンゾイルパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）－３，５，５－トリメチルシクロヘキサン、ジイソブチリルパーオキサイド、クミルパーオキシネオデカノエート、ジ－ｎ－プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、ジ（４－ｔ－ブチルシクロへキシル）パーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、ｔ－ヘキシルパーオキシネオデカノエート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ブチルパーオキシネオヘプタノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジ（３，５，５－トリメチルヘキサノイル）パーオキサイド、ジラウロイルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジコハク酸パーオキサイド、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキサイド、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジベンゾイルパーオキサイド、１，１－ジ（ｔ－ブチルパーオキシ）－２－メチルシクロヘキサン、１，１－ジ（ｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ジ（４，４－ジ－（ｔ－ブチルパーオキシ）シクロへキシル）プロパン、ｔ－ヘキシルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシマレイン酸、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルパーオキシラウレート、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ２－エチルヘキシルモノカーボネート、ｔ－ヘキシルパーオキシベンゾエート、２，５－ジ－メチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシアセテート、２，２－ジ－（ｔ－ブチルパーオキシ）ブタン、ｔ－ブチルパーオキシベンゾエート、ｎ－ブチル４，４－ジ－（ｔ－ブチルパーオキシ）バレレート、１，４－ビス［（ｔ－ブチルパーオキシ）イソプロピル］ベンゼン、ジ－ｔ－ヘキシルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｐ－メンタンヒドロパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルペルオキシ）ヘキシン－３、ジイソプロピルベンゼンヒドロパーオキサイド　、１，１，３，３－テトラメチルブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、ｔ－ブチルヒドロパーオキサイドなどがある。この中でも、ジクミルパーオキサイド、１，４－ビス［（ｔ－ブチルパーオキシ）イソプロピル］ベンゼン、ｔ－ブチルα－クミルペルオキシド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ビス（ｔ－ブチルペルオキシ）ヘキシン－３から選ばれる少なくとも１種であることが好ましく、特に好ましくは１，４－ビス［（ｔ－ブチルパーオキシ）イソプロピル］ベンゼンである。 1.6 Organic Peroxide The rubber composition according to the present invention can contain an organic peroxide.
Examples of organic peroxides include dicumyl peroxide, benzoyl peroxide, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumyl peroxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di(4 -t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneohepta Noate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, Di(4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1, 1-di(t-butylperoxy)-2-methylcyclohexane, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy) Cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-Butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl Monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy) Butane, t-butylperoxybenzoate, n-butyl 4,4-di-(t-butylperoxy)valerate, 1,4-bis[(t-butylperoxy)isopropyl]benzene, di-t-hexylperoxy oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc. . Among these, dicumyl peroxide, 1,4-bis[(t-butylperoxy)isopropyl]benzene, t-butyl α-cumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) oxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3, and particularly preferably 1,4-bis[(t-butylperoxy)hexane-3. oxy)isopropyl]benzene.
本発明に係るゴム組成物は、加工安全性が確保され、良好な加硫物を得ることができる観点から、ゴム１００質量部に対して、有機過酸化物を０．１～１０質量部含むことができる。有機過酸化物の添加量は、例えば、０．１、０．２、０．３、０．４、０．５、１．０、１、２、３、４、５、６、７、８、９、１０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、本発明に係るゴム組成物は、有機過酸化物を含まないものとすることもできる。 The rubber composition according to the present invention contains 0.1 to 10 parts by mass of an organic peroxide based on 100 parts by mass of rubber, from the viewpoint of ensuring processing safety and obtaining a good vulcanizate. be able to. The amount of organic peroxide added is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 1, 2, 3, 4, 5, 6, 7, 8 , 9, and 10, and may be within a range between any two of the numerical values exemplified here. Note that the rubber composition according to the present invention may also be one that does not contain an organic peroxide.
１．７　シクロヘキセン構造を有する化合物
本発明の一実施形態に係るゴム組成物は、シクロヘキセン構造を有する化合物を含むことができる。シクロヘキセン構造を有する化合物は、分子内にシクロヘキセン構造を１つ以上有するものとでき、分子内に２つ以上のシクロヘキセン構造を有していてもよい。シクロヘキセン構造を有する化合物は１種単独で又は２種以上を組み合わせて用いることができる。シクロヘキセン構造を有する化合物の具体例としては、３，９－ジ（３－シクロヘキセン－１－イル）－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、ベンジル［（３－シクロヘキセン－１－イリデン）メチル］エーテルを挙げることができる。
本発明の一実施形態に係るゴム組成物は、シクロヘキセン構造を有する化合物を含むことにより、耐オゾン性をより向上させることができる。耐オゾン性をより向上させるという観点から、本発明の一実施形態に係るゴム組成物は、有機過酸化物及びシクロヘキセン構造を有する化合物を含むことがより好ましい。 1.7 Compound Having Cyclohexene Structure The rubber composition according to one embodiment of the present invention may contain a compound having a cyclohexene structure. A compound having a cyclohexene structure can have one or more cyclohexene structures in the molecule, and may have two or more cyclohexene structures in the molecule. Compounds having a cyclohexene structure can be used alone or in combination of two or more. Specific examples of compounds having a cyclohexene structure include 3,9-di(3-cyclohexen-1-yl)-2,4,8,10-tetraoxaspiro[5.5]undecane, benzyl[(3-cyclohexene -1-ylidene)methyl] ether.
The rubber composition according to one embodiment of the present invention can further improve ozone resistance by containing a compound having a cyclohexene structure. From the viewpoint of further improving ozone resistance, the rubber composition according to one embodiment of the present invention more preferably contains an organic peroxide and a compound having a cyclohexene structure.
シクロヘキセン構造を有する化合物は、分子量が１００～１０００であることが好ましい。シクロヘキセン構造を有する化合物の分子量は、例えば、１００、２００、３００、４００、５００、６００、７００、８００、９００、１０００であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The compound having a cyclohexene structure preferably has a molecular weight of 100 to 1000. The molecular weight of the compound having a cyclohexene structure is, for example, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, and is within the range between any two of the numerical values exemplified here. Good too.
本発明の一実施形態に係るゴム組成物は、ゴム１００質量部に対して、シクロヘキセン構造を有する化合物を０．１～５．０質量部含有するものとできる。シクロヘキセン構造を有する化合物の添加量は、例えば、０．１、０．２、０．３、０．５、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 A rubber composition according to an embodiment of the present invention may contain 0.1 to 5.0 parts by mass of a compound having a cyclohexene structure based on 100 parts by mass of rubber. The amount of the compound having a cyclohexene structure added is, for example, 0.1, 0.2, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3. 5, 4.0, 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified here.
１．８　マレイミド系化合物
本発明の一実施形態に係るゴム組成物は、マレイミド系化合物を含有することができる。マレイミド系化合物は１種単独で又は２種以上を組み合わせて用いることができる。 1.8 Maleimide Compound The rubber composition according to one embodiment of the present invention may contain a maleimide compound. Maleimide compounds can be used alone or in combination of two or more.
マレイミド系化合物は、共架橋剤として、ゴム組成物の加硫に寄与することができる。マレイミド系化合物としては、例えば、Ｎ，Ｎ'－ｏ－フェニレンビスマレイミド、Ｎ，Ｎ'－ｍ－フェニレンビスマレイミド、Ｎ，Ｎ'－ｐ－フェニレンビスマレイミド、Ｎ，Ｎ'－（４，４'－ジフェニルメタン）ビスマレイミド、２，２－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、ビスフェノール　Ａ　ジフェニルエーテルビスマレイミド、３，３'－ジメチル－５，５'－ジエチル－４，４'－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、１，６'－ビスマレイミド－（２，２，４－トリメチル）ヘキサンを挙げることができる。得られる加硫物及び加硫成形体の耐熱性が向上するという観点から、特に好ましくはＮ，Ｎ'－ｍ－フェニレンビスマレイミド（別名ｍ－フェニレンジマレイミド）を用いるとよい。 The maleimide compound can contribute to the vulcanization of the rubber composition as a co-crosslinking agent. Examples of maleimide compounds include N,N'-o-phenylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-(4,4 '-diphenylmethane)bismaleimide, 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl ) hexane. N,N'-m-phenylene bismaleimide (also known as m-phenylene dimaleimide) is particularly preferably used from the viewpoint of improving the heat resistance of the resulting vulcanizate and vulcanized molded product.
本発明の一実施形態に係るゴム組成物は、ゴム１００質量部に対してマレイミド系化合物を０．１～１０質量部含有する。マレイミド系化合物の含有量は、例えば、０．１、０．２、０．３、０．５、１、２、３、４、５、６、７、８、９、１０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。マレイミド系化合物の含有量を上記下限以上とすることで、得られるゴム組成物の加硫がより十分に進行し、機械的特性や耐熱性が良好な加硫成形体を得ることができる。また、マレイミド系化合物の含有量を上記上限以下とすることで、得られる加硫成形体のゴム弾性を十分に維持することができ、耐屈曲疲労性の低下を抑制することができる。 A rubber composition according to an embodiment of the present invention contains 0.1 to 10 parts by mass of a maleimide compound based on 100 parts by mass of rubber. The content of the maleimide compound is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, It may be within the range between any two of the numerical values exemplified here. By setting the content of the maleimide compound to the above-mentioned lower limit or more, vulcanization of the resulting rubber composition proceeds more fully, and a vulcanized molded product with good mechanical properties and heat resistance can be obtained. Moreover, by controlling the content of the maleimide compound to be below the above upper limit, the rubber elasticity of the obtained vulcanized product can be sufficiently maintained, and a decrease in bending fatigue resistance can be suppressed.
１．９　老化防止剤
本発明の一実施形態に係るゴム組成物は、老化防止剤及び／又は酸化防止剤を含むことができる。
老化防止剤及び酸化防止剤としては、オゾン老化防止剤、フェノール系老化防止剤、アミン系老化防止剤、アクリレート系老化防止剤、イミダゾール系老化防止剤、カルバミン酸金属塩、ワックス、リン系老化防止剤、硫黄系老化防止剤などを挙げることができる。
本発明の一実施形態に係るゴム組成物は、オゾン老化防止剤を含むことが好ましく、ｐ－フェニレンジアミン構造を有する老化防止剤を含むことがより好ましい。また、本発明の一実施形態に係るゴム組成物は、耐オゾン性を更に向上させる観点から、硫黄及び加硫促進剤のうちの少なくとも１つ、並びに、オゾン老化防止剤を含むことが好ましく、硫黄及び加硫促進剤のうちの少なくとも１つ、並びに、ｐ－フェニレンジアミン構造を有する老化防止剤を含むことがより好ましい。 1.9 Anti-aging agent The rubber composition according to one embodiment of the present invention may contain an anti-aging agent and/or an antioxidant.
Anti-aging agents and antioxidants include ozone anti-aging agents, phenolic anti-aging agents, amine anti-aging agents, acrylate anti-aging agents, imidazole anti-aging agents, metal carbamates, wax, and phosphorus anti-aging agents. and sulfur-based anti-aging agents.
The rubber composition according to one embodiment of the present invention preferably contains an ozone anti-aging agent, and more preferably contains an anti-aging agent having a p-phenylenediamine structure. Further, from the viewpoint of further improving ozone resistance, the rubber composition according to one embodiment of the present invention preferably contains at least one of sulfur and a vulcanization accelerator, and an ozone anti-aging agent, More preferably, it contains at least one of sulfur and a vulcanization accelerator, and an anti-aging agent having a p-phenylenediamine structure.
本発明に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、老化防止剤及び酸化防止剤を０．１～１０質量部含むことができる。老化防止剤及び酸化防止剤の添加量は、例えば、０．１、０．２、０．５、１、２、３、４、５、６、７、８、９、１０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The rubber composition according to the present invention can contain 0.1 to 10 parts by mass of an anti-aging agent and an antioxidant, based on 100 parts by mass of rubber contained in the rubber composition. The amount of anti-aging agent and antioxidant added is, for example, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, It may be within the range between any two of the numerical values exemplified here.
１．１０　金属酸化物
本発明の一実施形態に係るゴム組成物は、金属酸化物を含むことができる。
金属酸化物としては、例えば、酸化亜鉛、酸化マグネシウム、酸化鉛、四酸化三鉛、三酸化鉄、二酸化チタン、酸化カルシウム等を挙げることができる。金属酸化物は、酸化亜鉛、酸化マグネシウム、及びハイドロタルサイト類化合物のうち少なくとも一つを含むことが好ましく、酸化亜鉛及び酸化マグネシウムを含むこともできる。金属酸化物は１種単独で又は２種以上を組み合わせて用いることができる。一例として、本発明の一実施形態に係るゴム組成物に酸化亜鉛を添加した場合、酸化亜鉛は、加硫剤として機能できる。また、本発明の一実施形態に係るゴム組成物に酸化マグネシウムを添加した場合、酸化マグネシウムは、受酸剤として機能できる。本発明の一実施形態に係るゴム組成物は、加硫剤として機能する金属酸化物及び受酸剤として機能する金属酸化物を含むことができる。 1.10 Metal Oxide The rubber composition according to one embodiment of the present invention can contain a metal oxide.
Examples of metal oxides include zinc oxide, magnesium oxide, lead oxide, trilead tetroxide, iron trioxide, titanium dioxide, and calcium oxide. The metal oxide preferably contains at least one of zinc oxide, magnesium oxide, and hydrotalcite compounds, and can also contain zinc oxide and magnesium oxide. Metal oxides can be used alone or in combination of two or more. As an example, when zinc oxide is added to the rubber composition according to an embodiment of the present invention, the zinc oxide can function as a vulcanizing agent. Further, when magnesium oxide is added to the rubber composition according to an embodiment of the present invention, the magnesium oxide can function as an acid acceptor. The rubber composition according to one embodiment of the present invention can include a metal oxide that functions as a vulcanizing agent and a metal oxide that functions as an acid acceptor.
本発明に係るゴム組成物は、ゴムを００質量部に対し、金属酸化物を、０．１～２０質量部含有することができる。金属酸化物の含有率は、例えば、０．１、０．２、０．３、０．５、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The rubber composition according to the present invention may contain 0.1 to 20 parts by mass of a metal oxide based on 00 parts by mass of rubber. The content of the metal oxide is, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, The amount may be 13, 14, 15, 16, 17, 18, 19, or 20 parts by mass, and may be within a range between any two of the numerical values exemplified here.
１．１１　充填材（補強材）
本発明に係るゴム組成物は、充填材を含むことができる。
充填材・補強材としては、ＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＥＰＣ、ＸＣＦ、ＦＥＦ、ＧＰＦ、ＨＭＦ、ＳＲＦなどのファーネスカーボンブラック、親水性カーボンブラックなどの改質カーボンブラック、チャンネルブラック、油煙ブラック、ＦＴ、ＭＴなどのサーマルカーボン、アセチレンブラック、ケッチェンブラック、シリカ、クレー、タルク、炭酸カルシウムを挙げることができる。これらは、１種単独で又は２種以上を組み合わせて用いることができる。 1.11 Filler (reinforcement material)
The rubber composition according to the present invention can contain a filler.
Fillers and reinforcing materials include furnace carbon blacks such as SAF, ISAF, HAF, EPC, XCF, FEF, GPF, HMF, and SRF, modified carbon blacks such as hydrophilic carbon black, channel black, soot black, FT, Examples include thermal carbon such as MT, acetylene black, Ketjenblack, silica, clay, talc, and calcium carbonate. These can be used alone or in combination of two or more.
本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、充填材・補強材を２０～９０質量部含むことができ、３５～８０質量部含むことが好ましい。充填材・補強材の含有量は、例えば、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
本発明の一実施形態に係るゴム組成物は、充填材の含有率を上記数値範囲内含有することにより、加硫 The rubber composition according to one embodiment of the present invention may contain 20 to 90 parts by mass of filler/reinforcing material, and may contain 35 to 80 parts by mass, when the rubber contained in the rubber composition is 100 parts by mass. It is preferable. The content of the filler/reinforcing material is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass, and the It may be within a range between any two values.
The rubber composition according to one embodiment of the present invention can be cured by containing the filler content within the above numerical range.
１．１２　滑剤・加工助剤
本発明に係るゴム組成物は、さらに滑剤・加工助剤を含むこともできる。滑剤・加工助剤は、主に、ゴム組成物がロールや成形金型、押出機のスクリューなどから剥離しやすくなるようにするなど、加工性を向上させるために添加する。滑剤・加工助剤としては、ステアリン酸等の脂肪酸、ポリエチレン等のパラフィン系加工助剤、脂肪酸アミド、ワセリン、ファクチス等が挙げられる。これらは、１種単独で又は２種以上を組み合わせて用いることができる。本発明に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、滑剤・加工助剤を１５質量部以下含むことができ、１０質量部以下とすることもできる。滑剤・加工助剤の含有量は、例えば、０、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。本発明に係るゴム組成物は、滑剤・加工助剤を含まないこともできる。 1.12 Lubricant/Processing Aid The rubber composition according to the present invention may further contain a lubricant/processing aid. Lubricants and processing aids are mainly added to improve processability, such as making it easier for the rubber composition to peel off from rolls, molds, extruder screws, etc. Examples of lubricants and processing aids include fatty acids such as stearic acid, paraffin processing aids such as polyethylene, fatty acid amides, vaseline, factice, and the like. These can be used alone or in combination of two or more. The rubber composition according to the present invention can contain 15 parts by mass or less of a lubricant/processing aid, and can also contain 10 parts by mass or less, when the rubber contained in the rubber composition is 100 parts by mass. The content of the lubricant/processing aid is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by mass, where It may be within the range between any two of the illustrated numerical values. The rubber composition according to the present invention can also be free of lubricants and processing aids.
１．１１　その他
本発明に係るゴム組成物は、上記した成分に加え、老化防止剤、酸化防止剤、シランカップリング剤、共架橋剤、安定剤、難燃剤、加硫遅延剤等の成分を、本発明の効果を阻害しない範囲でさらに含むことができる。
本発明の一実施形態に係るゴム組成物は、ゴム組成物に含まれるゴムを１００質量部としたとき、軟質ポリ塩化ビニルの含有量が５質量部未満であることが好ましく、軟質ポリ塩化ビニルを含まないものとできる。 1.11 In addition to the above-mentioned components, the rubber composition according to the present invention may contain components such as an antioxidant, an antioxidant, a silane coupling agent, a co-crosslinking agent, a stabilizer, a flame retardant, and a vulcanization retarder. , may further be included within a range that does not impede the effects of the present invention.
In the rubber composition according to an embodiment of the present invention, the content of soft polyvinyl chloride is preferably less than 5 parts by mass when the rubber contained in the rubber composition is 100 parts by mass. It can be made without containing.
２．ゴム組成物の製造方法
本発明の一実施形態に係るゴム組成物は、クロロプレン系ゴム及びニトリルブタジエン系ゴム、及び必要とされるその他の成分を加硫温度以下の温度で混練することで得ることができる。原料成分を混練する装置としては、従来公知のミキサー、バンバリーミキサー、ニーダーミキサー、オープンロールなどの混練装置を挙げることができる。 2. Method for producing rubber composition The rubber composition according to one embodiment of the present invention can be obtained by kneading chloroprene rubber, nitrile butadiene rubber, and other necessary components at a temperature below the vulcanization temperature. I can do it. Examples of the device for kneading the raw material components include conventionally known kneading devices such as a mixer, a Banbury mixer, a kneader mixer, and an open roll.
３．ゴム組成物の特性
本発明の一実施形態に係るゴム組成物は、該ゴム組成物の加硫物が以下の特性を有することが好ましい。 3. Characteristics of Rubber Composition In the rubber composition according to one embodiment of the present invention, it is preferable that the vulcanizate of the rubber composition has the following characteristics.
（耐油性）
本発明の一実施形態に係るゴム組成物は、該ゴム組成物の加硫物を、１３０℃の試験油（自動車用高潤滑油、ＡＳＴＭ　Ｎｏ．３、ＩＲＭ　９０３　ｏｉｌ）に７２時間浸漬した前後の、ＪＩＳ　Ｋ　６２５８に基づき算出される体積変化率ΔＶが、２０％未満であることが好ましく、１６％未満であることがより好ましい。体積変化率ΔＶは、例えば、０、５、１０、１５％、２０％未満であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 (Oil resistance)
A rubber composition according to an embodiment of the present invention is obtained by immersing a vulcanized product of the rubber composition in a test oil (automotive high lubricating oil, ASTM No. 3, IRM 903 oil) at 130°C for 72 hours. The volume change rate ΔV calculated based on JIS K 6258 is preferably less than 20%, more preferably less than 16%. The volume change rate ΔV is, for example, less than 0, 5, 10, 15%, or 20%, and may be within a range between any two of the numerical values exemplified here.
（耐寒性）
本発明の一実施形態に係るゴム組成物は、ＪＩＳ　Ｋ　６２６１に基づき、ゲーマンねじり試験により求めた、該ゴム組成物の加硫物のＴ１０が－１５℃未満であることが好ましく、－２２℃未満であることがより好ましい。Ｔ１０は、例えば、－４０、－３５、－３０、－２５、－２０℃、－１５℃未満であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 (cold resistance)
The rubber composition according to an embodiment of the present invention preferably has a T10 of a vulcanizate of the rubber composition of less than -15°C, as determined by a Gehman torsion test based on JIS K 6261, and a T10 of less than -22°C. It is more preferable that it is less than T10 is, for example, less than -40, -35, -30, -25, -20°C, and -15°C, and may be within a range between any two of the numerical values exemplified here.
本発明の一実施形態に係るゴム組成物は、ＪＩＳ　Ｋ　６２５８に基づき、ＩＲＭ９０３オイルを用いて測定されるゴム組成物の加硫物の体積変化率ΔＶが、２０％未満であり、ＪＩＳ　Ｋ　６２６１に基づき、ゲーマンねじり試験により求めたゴム組成物の加硫物のＴ１０が－１５℃未満であることがより好ましい。ゴム組成物の耐油性及び耐寒性が上記数値範囲となるよう、ゴム組成物に含まれる各ゴム中の各単量体単位の含有率、及び各ゴムの配合量、並びにゴム組成物に含まれるゴム以外の成分の種類及び配合量等を調整することによって、得られるゴム組成物は、該ゴム組成物の加硫物の耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスにより優れたものとなる。 The rubber composition according to one embodiment of the present invention has a volume change rate ΔV of the vulcanizate of the rubber composition measured using IRM903 oil based on JIS K 6258 of less than 20%, and JIS K 6261 Based on this, it is more preferable that the T10 of the vulcanizate of the rubber composition determined by the Gehman torsion test is less than -15°C. The content of each monomer unit in each rubber contained in the rubber composition, the blending amount of each rubber, and the amount contained in the rubber composition so that the oil resistance and cold resistance of the rubber composition are within the above numerical range. By adjusting the types and blending amounts of components other than rubber, the resulting rubber composition can improve the oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance of the vulcanized product of the rubber composition. Better balance.
（耐熱性（加熱後の切断時伸びの変化））
本発明の一実施形態に係るゴム組成物は、該ゴム組成物の加硫物の、ＪＩＳ　Ｋ　６２５１に基づき測定した切断時伸びをＥＢ０とし、該ゴム組成物の加硫物を、１３０℃で７２時間加熱後、再度、ＪＩＳ　Ｋ　６２５１に基づき、を測定した切断時伸びをＥＢｉとしたとき、下記式で算出される耐熱試験前後の切断時伸びの変化ΔＥＢが、－４０％以上であることが好ましく、－３０％以上であることがより好ましい。耐熱試験前後の切断時伸びの変化ΔＥＢは、例えば、－４０、－３５、－３０、－２５、－２０、－１５、－１０、－５、０％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 (Heat resistance (change in elongation at cutting after heating))
The rubber composition according to one embodiment of the present invention has an elongation at break measured in accordance with JIS K 6251 of the vulcanizate of the rubber composition as EB 0 , and the vulcanizate of the rubber composition is heated at 130°C. After heating for 72 hours at It is preferably -30% or more, and more preferably -30% or more. The change ΔEB in elongation at cutting before and after the heat resistance test is, for example, -40, -35, -30, -25, -20, -15, -10, -5, and 0%, and any of the values exemplified here or within a range between the two.
（耐オゾン性）
本発明の一実施形態に係るゴム組成物は、該ゴム組成物の加硫物について、ＪＩＳ　Ｋ　６２５９－１に基づいて、試験温度４０℃、オゾン濃度５０ｐｐｈｍ、伸長率２０％の条件で静的オゾン劣化試験を行った際、その表面や側面にクラックが発生するまでの時間が、１時間以上であることが好ましく、１０時間以上であることがより好ましい。表面や側面にクラックが発生するまでの時間は、例えば、１、５、１０、１５、２０、２５、３０時間であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 (Ozone resistance)
The rubber composition according to one embodiment of the present invention is statically tested under the conditions of a test temperature of 40° C., an ozone concentration of 50 pphm, and an elongation rate of 20% based on JIS K 6259-1. When an ozone deterioration test is performed, the time required for cracks to occur on the surface or side surfaces is preferably 1 hour or more, more preferably 10 hours or more. The time it takes for cracks to occur on the surface or side surfaces is, for example, 1, 5, 10, 15, 20, 25, 30 hours, even if it is within the range between any two of the numerical values exemplified here. good.
（耐屈曲疲労性）
本発明の一実施形態に係るゴム組成物は、該ゴム組成物の加硫物について、ＪＩＳ　Ｋ　６２６０に基づき、デマッチャ屈曲疲労試験を行い、ストローク５８ｍｍ、速度３００±１０ｒｐｍの条件下で、測定される、亀裂が発生した時点における屈曲試験の回数が、１００回以上であることが好ましく３０００回以上であることが好ましい。亀裂が発生した時点における屈曲試験の回数は、例えば、１００、１０００、５０００、１万、１０万、１００万回であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 (Bending fatigue resistance)
A rubber composition according to an embodiment of the present invention was subjected to a dematcher bending fatigue test on a vulcanized product of the rubber composition based on JIS K 6260, and was measured under conditions of a stroke of 58 mm and a speed of 300 ± 10 rpm. The number of times the bending test is performed at the time a crack occurs is preferably 100 times or more, and preferably 3000 times or more. The number of bending tests at the time a crack occurs is, for example, 100, 1000, 5000, 10,000, 100,000, or 1 million times, and even if it is within the range between any two of the numerical values exemplified here. good.
なお、ゴム組成物の加硫物は、ＪＩＳ　Ｋ　６２９９に基づき、１７０℃×２０分の条件でプレス加硫することにより得た加硫物又は加硫成形体とすることができ、具体的には実施例に記載の方法で作製することができる。また、ゴム組成物の加硫物の耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性は、ゴム組成物に含まれる各ゴム中の各単量体単位の含有率、及び各ゴムの配合量、並びにゴム組成物に含まれるゴム以外の成分の種類及び配合量等を調整することによって、制御することができる。 The vulcanized product of the rubber composition can be a vulcanized product or a vulcanized molded product obtained by press vulcanization at 170°C for 20 minutes based on JIS K 6299. can be produced by the method described in Examples. In addition, the oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance of the vulcanized product of the rubber composition are determined by the content of each monomer unit in each rubber contained in the rubber composition, and the content of each monomer unit in each rubber contained in the rubber composition. It can be controlled by adjusting the amount of rubber compounded, and the types and amounts of components other than rubber contained in the rubber composition.
４．未加硫成形体、加硫物及び加硫成形体
本実施形態に係る未加硫成形体は、本実施形態に係るゴム組成物を用いており、本実施形態に係るゴム組成物（未加硫状態）の成形体（成形品）である。本実施形態に係る未加硫成形体の製造方法は、本実施形態に係るゴム組成物（未加硫状態）を成形する工程を備える。本実施形態に係る未加硫成形体は、本実施形態に係るゴム組成物（未加硫状態）からなる。 4. Unvulcanized molded product, vulcanized product, and vulcanized molded product The unvulcanized molded product according to this embodiment uses the rubber composition according to this embodiment, and the rubber composition according to this embodiment (unvulcanized product) It is a molded article (molded product) in a sulfur state). The method for producing an unvulcanized molded body according to the present embodiment includes a step of molding the rubber composition (unvulcanized state) according to the present embodiment. The unvulcanized molded article according to this embodiment is made of the rubber composition (in an unvulcanized state) according to this embodiment.
本実施形態に係る加硫物は、本実施形態に係るゴム組成物の加硫物である。本実施形態に係る加硫物の製造方法は、本実施形態に係るゴム組成物を加硫する工程を備える。 The vulcanizate according to this embodiment is a vulcanizate of the rubber composition according to this embodiment. The method for producing a vulcanizate according to the present embodiment includes a step of vulcanizing the rubber composition according to the present embodiment.
本実施形態に係る加硫成形体は、本実施形態に係るゴム組成物の加硫成形体である。本実施形態に係る加硫成形体は、本実施形態に係る加硫物を用いており、本実施形態に係る加硫物の成形体（成形品）である。本実施形態に係る加硫成形体は、本実施形態に係る加硫物からなる。 The vulcanized molded article according to this embodiment is a vulcanized molded article of the rubber composition according to this embodiment. The vulcanized molded article according to this embodiment uses the vulcanized product according to this embodiment, and is a molded article (molded article) of the vulcanized product according to this embodiment. The vulcanized molded article according to this embodiment is made of the vulcanized product according to this embodiment.
本実施形態に係る加硫成形体は、本実施形態に係るゴム組成物（未加硫状態）を加硫して得られる加硫物を成形することにより得ることが可能であり、本実施形態に係るゴム組成物（未加硫状態）を成形して得られる成形体を加硫することにより得ることもできる。本実施形態に係る加硫成形体は、本実施形態に係るゴム組成物を成形後又は成形時に加硫することにより得ることができる。本実施形態に係る加硫成形体の製造方法は、本実施形態に係る加硫物を成形する工程、又は、本実施形態に係る未加硫成形体を加硫する工程を備える。 The vulcanized molded article according to this embodiment can be obtained by molding a vulcanizate obtained by vulcanizing the rubber composition (unvulcanized state) according to this embodiment, and It can also be obtained by vulcanizing a molded article obtained by molding the rubber composition (in an unvulcanized state). The vulcanized molded article according to this embodiment can be obtained by vulcanizing the rubber composition according to this embodiment after or during molding. The method for producing a vulcanized molded body according to this embodiment includes a step of molding a vulcanized product according to this embodiment, or a step of vulcanizing an unvulcanized molded body according to this embodiment.
本発明の一実施形態に係る加硫物及び加硫成形体は、上記した耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性を有することが好ましい。
本実施形態に係る未加硫成形体、加硫物及び加硫成形体は、建築物、構築物、船舶、鉄道、炭鉱、自動車等の各種工業分野のゴム部品として利用可能である。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、これらの特性が必要とされる様々な部材として用いることができる。本発明の一実施形態に係るゴム組成物は、建築物、構築物、船舶、鉄道、炭鉱、自動車等の各種工業分野のゴム部品として利用可能であり、自動車用ゴム部材（例えば自動車用シール材）、ホース材、ゴム型物、ガスケット、ゴムロール、産業用ケーブル、産業用コンベアベルト、スポンジ等のゴム部品として利用することができる。 The vulcanizate and vulcanized molded article according to one embodiment of the present invention preferably have the oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance described above.
The unvulcanized molded product, vulcanized product, and vulcanized molded product according to the present embodiment can be used as rubber parts in various industrial fields such as buildings, structures, ships, railways, coal mines, and automobiles. The vulcanizate made from the rubber composition according to one embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, and therefore can be used in various applications where these properties are required. It can be used as a member. The rubber composition according to one embodiment of the present invention can be used as rubber parts in various industrial fields such as buildings, structures, ships, railways, coal mines, and automobiles, and can be used as rubber parts for automobiles (for example, sealing materials for automobiles). It can be used as rubber parts for hose materials, rubber molds, gaskets, rubber rolls, industrial cables, industrial conveyor belts, sponges, etc.
（自動車用ゴム部材）
自動車用ゴム部材は、ガスケット、オイルシール及びパッキンなどがあり、機械や装置において、液体や気体の漏れや雨水や埃などのごみや異物が内部に侵入するのを防ぐ部品である。具体的には、固定用途に使われるガスケットと、運動部分・可動部分に使用されるオイルシール及びパッキンがある。シール部分がボルトなどで固定されているガスケットでは、Ｏリングやゴムシートなどのソフトガスケットに対して、目的に応じた各種材料が使用されている。また、パッキンは、ポンプやモーターの軸、バルブの可動部のような回転部分、ピストンのような往復運動部分、カプラーの接続部、水道蛇口の止水部などに使われる。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるシールを製造することが可能である。 (rubber parts for automobiles)
Rubber parts for automobiles include gaskets, oil seals, and packing, and are parts that prevent liquid and gas leaks and dirt and foreign matter such as rainwater and dust from entering machines and equipment. Specifically, there are gaskets used for fixed applications, and oil seals and packings used for moving parts. For gaskets whose sealing parts are fixed with bolts or the like, various materials are used depending on the purpose for soft gaskets such as O-rings and rubber sheets. Packing is also used in rotating parts such as the shafts of pumps and motors, moving parts of valves, reciprocating parts such as pistons, coupling parts of couplers, and water stop parts of water faucets. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture seals that
（ホース材）
ホース材は、屈曲可能な管であり、具体的には、送水用、送油用、送気用、蒸気用、油圧用高・低圧ホースなどがある。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるホース材を製造することができる。 (hose material)
The hose material is a bendable pipe, and specifically includes water, oil, air, steam, and hydraulic high/low pressure hoses. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture hose materials that
（ゴム型物）
ゴム型物は、防振ゴム、制振材、ブーツなどがある。防振ゴム及び制振材は、振動の伝達波及を防止するゴムのことであり、具体的には、自動車や各種車両用のエンジン駆動時の振動を吸収して騒音を防止するためのトーショナルダンパー、エンジンマウント、マフラーハンガーなどがある。本発明のゴム組成物は、防振ゴム及び制振材の引張強度を高めることが可能である。これにより、従来のゴム組成物では困難であった高負荷がかかる用途でも使用できる防振ゴム及び制振材を製造することができる。
また、ブーツは、一端から他端に向けて外径が次第に大きくなる蛇腹状をなす部材であり、具体的には、自動車駆動系などの駆動部を保護するための等速ジョイントカバー用ブーツ、ボールジョイントカバー用ブーツ（ダストカバーブーツ）、ラックアンドピニオンギア用ブーツなどがある。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるブーツを製造することが可能である。 (rubber type)
Rubber-type products include anti-vibration rubber, damping materials, and boots. Anti-vibration rubber and damping materials are rubber that prevent the transmission and spread of vibrations, and specifically, torsional rubber that prevents noise by absorbing vibrations when the engine of automobiles and various other vehicles is running. Includes dampers, engine mounts, muffler hangers, etc. The rubber composition of the present invention can increase the tensile strength of vibration-proof rubber and damping materials. As a result, it is possible to produce vibration-proof rubber and damping materials that can be used in applications subject to high loads, which have been difficult to achieve with conventional rubber compositions.
In addition, the boot is a bellows-shaped member whose outer diameter gradually increases from one end to the other, and specifically, boots for constant velocity joint covers for protecting drive parts such as automobile drive systems; There are boots for ball joint covers (dust cover boots), boots for rack and pinion gears, etc. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture boots that
（ガスケットなど）
ガスケットや、オイルシール及びパッキンは、機械や装置において、液体や気体の漏れや雨水や埃などのごみや異物が内部に侵入するのを防ぐ部品であり、具体的には、固定用途に使われるガスケットと、運動部分・可動部分に使用されるオイルシール及びパッキンがある。シール部分がボルトなどで固定されているガスケットでは、Ｏリングやゴムシートなどのソフトガスケットに対して、目的に応じた各種材料が使用されている。また、パッキンは、ポンプやモーターの軸、バルブの可動部のような回転部分、ピストンのような往復運動部分、カプラーの接続部、水道蛇口の止水部などに使われる。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるシールを製造することが可能である。 (gasket etc.)
Gaskets, oil seals, and packing are parts that prevent liquid and gas leaks and dirt and foreign matter such as rainwater and dust from entering machines and equipment, and are specifically used for fixed purposes. There are gaskets, oil seals and packing used for moving parts. For gaskets whose sealing parts are fixed with bolts or the like, various materials are used depending on the purpose for soft gaskets such as O-rings and rubber sheets. Packing is also used in rotating parts such as the shafts of pumps and motors, moving parts of valves, reciprocating parts such as pistons, coupling parts of couplers, and water stop parts of water faucets. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture seals that
（ゴムロール）
ゴムロールは、鉄芯などの金属製の芯をゴムで接着被覆することによって製造されるものであり、一般に金属鉄芯にゴムシートを渦巻き状に巻き付けて製造される。ゴムロールには、製紙、各種金属製造、フィルム製造、印刷、一般産業用、籾摺りなどの農機具用、食品加工用などの種々の用途の要求特性に応じて、ＮＢＲやＥＰＤＭ、ＣＲなどのゴム材料が用いられている。ＣＲは搬送する物体の摩擦に耐え得る良好な機械的強度を有していることから、幅広いゴムロール用途に使用されている。一方で、製鉄用、製紙用の工業用材料や製品の製造時など、油が付着する環境下で用いられるゴムロールには耐油性が不十分であり、改良が求められている。また、金、銀、ニッケル、クロム及び亜鉛など、製品にメッキ処理を施す際にｐH４以下の酸性環境下やｐH１１以上のアルカリ環境下に晒される場合もあり、これらに対する耐性も求められている。さらに、重量物を搬送するゴムロールは荷重により変形するという課題があり、改良を求められている。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるゴムロールを製造することが可能である。 (rubber roll)
Rubber rolls are manufactured by adhesively covering a metal core such as an iron core with rubber, and are generally manufactured by spirally wrapping a rubber sheet around a metal iron core. Rubber rolls are made of rubber materials such as NBR, EPDM, and CR, depending on the characteristics required for various uses such as paper manufacturing, various metal manufacturing, film manufacturing, printing, general industry, agricultural machinery such as hulling, and food processing. It is used. CR has good mechanical strength that can withstand the friction of conveyed objects, so it is used in a wide range of rubber roll applications. On the other hand, rubber rolls used in environments where oil adheres, such as during the production of industrial materials and products for steel manufacturing and paper manufacturing, have insufficient oil resistance, and improvements are needed. Furthermore, when plating products such as gold, silver, nickel, chromium, and zinc, they may be exposed to an acidic environment with a pH of 4 or less or an alkaline environment with a pH of 11 or more, and resistance to these is also required. Furthermore, there is a problem that rubber rolls for conveying heavy objects deform under load, and improvements are required. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture rubber rolls that
（産業用ケーブル）
産業用ケーブルは、電気や光信号を伝送するための線状の部材である。銅や銅合金などの良導体や光ファイバなどを絶縁性の被覆層で被覆したものであり、その構造や設置個所によって、多岐にわたる産業用ケーブルが製造されている。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用される産業用ケーブルを製造することができる。 (industrial cable)
Industrial cables are linear members for transmitting electrical and optical signals. A cable is made of a good conductor such as copper or copper alloy or an optical fiber coated with an insulating coating layer, and a wide variety of industrial cables are manufactured depending on its structure and installation location. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture industrial cables based on
（産業用コンベアベルト）
産業用コンベアベルトは、ゴム製、樹脂製、金属製のベルトがあり、多種多様な使用方法に合わせて選定されている。これらの中でもゴム製のコンベアベルトは、安価で多用されているが、特に搬送物との摩擦や衝突の多い環境下で使用すると、劣化による破損などが発生していた。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用される産業用コンベアベルトを製造することができる。 (Industrial conveyor belt)
Industrial conveyor belts are available in rubber, resin, and metal belts, and are selected to suit a wide variety of uses. Among these, rubber conveyor belts are inexpensive and widely used, but when used in environments where there is a lot of friction and collision with conveyed objects, they tend to deteriorate and break. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to manufacture industrial conveyor belts.
（スポンジ）
スポンジは、内部に細かい孔が無数に空いた多孔質の物質であり、具体的には、防振部材、スポンジシール部品、ウェットスーツ、靴などに利用されている。本発明のゴム組成物は、スポンジの引張強度を高めることが可能である。また、塩素系ゴムを用いているためスポンジの難燃性を高めることも可能である。本発明の一実施形態に係るゴム組成物による加硫物は、耐油性、耐寒性、耐熱性、耐オゾン性，耐屈曲疲労性のバランスに優れるため、例えば、これらの特性を活かして使用されるスポンジや、難燃性に優れたスポンジを製造することができる。さらに、発泡剤の含有量などの調整により得られるスポンジの硬度も適宜調整可能である。 (sponge)
Sponges are porous substances with countless fine pores inside, and are specifically used in vibration-proofing members, sponge seal parts, wet suits, shoes, and the like. The rubber composition of the present invention can increase the tensile strength of sponge. Additionally, since chlorine-based rubber is used, it is possible to improve the flame retardancy of the sponge. A vulcanizate made from a rubber composition according to an embodiment of the present invention has an excellent balance of oil resistance, cold resistance, heat resistance, ozone resistance, and bending fatigue resistance, so it can be used, for example, by taking advantage of these properties. It is possible to produce sponges with excellent flame retardant properties. Furthermore, the hardness of the resulting sponge can be adjusted as appropriate by adjusting the content of the foaming agent.
本実施形態に係るゴム組成物（未加硫状態）及び加硫物を成形する方法としては、プレス成形、押出成形、カレンダー成形等が挙げられる。ゴム組成物を加硫する温度は、ゴム組成物の組成に合わせて適宜設定すればよく、１４０～２２０℃、又は、１６０～１９０℃であってよい。ゴム組成物を加硫する加硫時間は、ゴム組成物の組成、未加硫成形体の形状等によって適宜設定すればよく、１０～６０分であってよい。 Examples of methods for molding the rubber composition (unvulcanized state) and vulcanizate according to this embodiment include press molding, extrusion molding, calendar molding, and the like. The temperature at which the rubber composition is vulcanized may be appropriately set according to the composition of the rubber composition, and may be 140 to 220°C or 160 to 190°C. The vulcanization time for vulcanizing the rubber composition may be appropriately set depending on the composition of the rubber composition, the shape of the unvulcanized molded article, etc., and may be 10 to 60 minutes.
以下、実施例に基づいて本発明を更に詳細に説明するが、本発明はこれらに限定して解釈されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not interpreted as being limited to these.
＜クロロプレン系ゴムＡ－２の製造方法＞
加熱冷却ジャケット及び攪拌機を備えた内容積３Ｌの重合缶に、クロロプレン（単量体）２４質量部、アクリロニトリル（単量体）２４質量部、ジエチルキサントゲンジスルフィド０．５質量部、純水２００質量部、ロジン酸カリウム（ハリマ化成株式会社製）５．００質量部、水酸化ナトリウム０．４０質量部、及び、β－ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩（花王株式会社製）２．０質量部を添加した。次に、重合開始剤として過硫酸カリウム０．１質量部を添加した後、重合温度４０℃にて窒素気流下で乳化重合を行った。上述のクロロプレンは、重合開始２０秒後から分添し、重合開始からの１０秒間の冷媒の熱量変化を元に分添流量を電磁弁で調整し、以降１０秒毎に流量を再調節することで連続的に行った。クロロプレン及びアクリロニトリルの合計量に対する重合率が５０％となった時点で、重合停止剤であるフェノチアジン０．０２質量部を加えて重合を停止させた。その後、減圧下で反応溶液中の未反応の単量体を除去することでクロロプレン－アクリロニトリル共重合体を含む、クロロプレン系ラテックスを得た。得られたクロロプレン系ラテックスを、通常の凍結乾燥工程及び洗浄工程を経て、固形のクロロプレン系ゴムＡ－２とした。 <Production method of chloroprene rubber A-2>
In a polymerization vessel with an internal volume of 3 L equipped with a heating and cooling jacket and a stirrer, 24 parts by mass of chloroprene (monomer), 24 parts by mass of acrylonitrile (monomer), 0.5 parts by mass of diethylxanthogen disulfide, and 200 parts by mass of pure water. , potassium rosinate (manufactured by Harima Kasei Co., Ltd.) 5.00 parts by mass, sodium hydroxide 0.40 parts by mass, and sodium salt of β-naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation) 2.0 parts by mass was added. Next, after adding 0.1 part by mass of potassium persulfate as a polymerization initiator, emulsion polymerization was performed at a polymerization temperature of 40° C. under a nitrogen stream. The above-mentioned chloroprene should be added in portions starting 20 seconds after the start of polymerization, and the flow rate should be adjusted using a solenoid valve based on the change in heat value of the refrigerant during the 10 seconds after the start of polymerization, and the flow rate should be readjusted every 10 seconds thereafter. performed continuously. When the polymerization rate based on the total amount of chloroprene and acrylonitrile reached 50%, 0.02 parts by mass of phenothiazine as a polymerization terminator was added to terminate the polymerization. Thereafter, unreacted monomers in the reaction solution were removed under reduced pressure to obtain a chloroprene-based latex containing a chloroprene-acrylonitrile copolymer. The obtained chloroprene latex was subjected to a normal freeze-drying process and a washing process to obtain a solid chloroprene rubber A-2.
クロロプレン系ラテックスの上述の重合率［％］は、クロロプレン系ラテックスを風乾したときの乾燥質量から算出した。具体的には、下記式（Ａ）より計算した。式中、「固形分濃度」とは、サンプリングしたクロロプレン系ラテックス２ｇを１３０℃で加熱して、溶媒（水）、揮発性薬品、原料等の揮発成分を除いた固形分の濃度［質量％］である。「総仕込み量」とは、重合開始からある時刻までに重合缶に仕込んだ原料、試薬及び溶媒（水）の総量［ｇ］である。「蒸発残分」とは、重合開始からある時刻までに仕込んだ薬品及び原料のうち、１３０℃の条件下で揮発せずにポリマーと共に固形分として残留する薬品の質量［ｇ］である。「単量体の仕込み量」とは、重合缶に初期に仕込んだ単量体、及び、重合開始からある時刻までに分添した単量体の量の合計［ｇ］である。なお、ここでいう「単量体」とは、クロロプレン及びアクリロニトリルの合計量である。
　重合率＝｛［（総仕込み量×固形分濃度／１００）－蒸発残分］／単量体の仕込み量｝×１００　　　・・・（Ａ） The above-mentioned polymerization rate [%] of the chloroprene latex was calculated from the dry mass when the chloroprene latex was air-dried. Specifically, it was calculated using the following formula (A). In the formula, "solid content concentration" is the solid content concentration [mass %] after heating 2 g of sampled chloroprene latex at 130°C and removing volatile components such as solvent (water), volatile chemicals, and raw materials. It is. The "total amount charged" is the total amount [g] of raw materials, reagents, and solvent (water) charged into the polymerization reactor from the start of polymerization to a certain time. "Evaporation residue" is the mass [g] of chemicals that remain as a solid content with the polymer without volatilizing under the condition of 130° C., among the chemicals and raw materials charged up to a certain time from the start of polymerization. The "amount of monomer charged" is the total amount [g] of the monomer initially charged into the polymerization reactor and the amount of monomer added in portions up to a certain time from the start of polymerization. In addition, the "monomer" here is the total amount of chloroprene and acrylonitrile.
Polymerization rate = {[(total charged amount x solid content concentration/100) - evaporation residue]/monomer charged amount} x 100...(A)
クロロプレン系ゴムＡ－２に含まれるアクリロニトリルの単量体単位の含有量を、クロロプレン－アクリロニトリル共重合ゴム中の窒素原子の含有量から算出した。具体的には、元素分析装置（スミグラフ２２０Ｆ：株式会社住化分析センター製）を用いて、１００ｍｇのクロロプレン系ゴムＡ－２中における窒素原子の含有量を測定し、アクリロニトリルの単量体単位の含有量を算出した。アクリロニトリルの単量体単位の含有量は１０．０質量％であった。 The content of acrylonitrile monomer units contained in the chloroprene rubber A-2 was calculated from the content of nitrogen atoms in the chloroprene-acrylonitrile copolymer rubber. Specifically, the content of nitrogen atoms in 100 mg of chloroprene rubber A-2 was measured using an elemental analyzer (Sumigraph 220F, manufactured by Sumika Analysis Center Co., Ltd.), and the content of nitrogen atoms in the monomer unit of acrylonitrile was determined. The content was calculated. The content of acrylonitrile monomer units was 10.0% by mass.
上述の元素分析は次のとおり行った。電気炉温度として反応炉９００℃、還元炉６００℃、カラム温度７０℃、検出器温度１００℃に設定し、燃焼用ガスとして酸素ガスを０．２ｍＬ／ｍｉｎ、キャリアーガスとしてヘリウムガスを８０ｍＬ／ｍｉｎフローした。検量線は、窒素含有量が既知のアスパラギン酸（１０．５２％）を標準物質として用いて作成した。
以上の製造方法で得られた、クロロプレン系ゴムＡ－２のアクリロニトリルの単量体単位の含有量は１０．０質量％であった。 The above elemental analysis was performed as follows. The electric furnace temperature was set at 900°C for the reactor, 600°C for the reduction furnace, 70°C for the column, and 100°C for the detector. Oxygen gas was used as the combustion gas at 0.2 mL/min, and helium gas was used as the carrier gas at 80 mL/min. It flowed. A calibration curve was created using aspartic acid (10.52%), which has a known nitrogen content, as a standard substance.
The content of acrylonitrile monomer units in the chloroprene rubber A-2 obtained by the above production method was 10.0% by mass.
＜クロロプレン系ゴムＡ－１、Ａ－３～Ａ－４の製造方法＞
重合工程におけるアクリロニトリル単量体の添加量を変更し、クロロプレン系ゴムに含まれるアクリロニトリル単量体単位の含有量が５．０質量％であるクロロプレン系ゴムＡ－１、アクリロニトリル単量体単位の含有量が１５．０質量％であるクロロプレン系ゴムＡ－３、アクリロニトリル単量体単位の含有量が２０．０質量％であるクロロプレン系ゴムＡ－４を得た。 <Production method of chloroprene rubber A-1, A-3 to A-4>
Chloroprene rubber A-1 in which the amount of acrylonitrile monomer added in the polymerization step is changed and the content of acrylonitrile monomer units contained in the chloroprene rubber is 5.0% by mass, the content of acrylonitrile monomer units A chloroprene rubber A-3 having a content of 15.0% by mass and a chloroprene rubber A-4 having a content of acrylonitrile monomer units of 20.0% by mass were obtained.
＜ゴム組成物の作製＞
表１～６に記載のように各成分を混合し、８インチオープンロールで混練することにより実施例及び比較例のゴム組成物を得た。 <Preparation of rubber composition>
Rubber compositions of Examples and Comparative Examples were obtained by mixing the components as shown in Tables 1 to 6 and kneading them with an 8-inch open roll.
ゴム組成物を得るために用いた各成分は以下のとおりである。
クロロプレン系ゴム：
・上述のクロロプレン系ゴムＡ－１～Ａ－４
・メルカプタン変性クロロプレンゴム、デンカ株式会社製、Ｓ－４０Ｖ（不飽和ニトリル単量体単位含有量０％）
ニトリルブタジエン系ゴム：
・ニトリルゴム、ＪＳＲ株式会社製、ＪＳＲ　Ｎ２２０Ｓ（アクリロニトリル単量体単位含有率４１．５％）
・ニトリルゴム、ＪＳＲ株式会社製、ＪＳＲ　Ｎ２３０Ｓ（アクリロニトリル単量体単位含有率３５％）
・ニトリルゴム、ＪＳＲ株式会社製、ＪＳＲ　Ｎ２４０Ｓ（アクリロニトリル単量体単位含有率２６％）
・ニトリルゴム、ＪＳＲ株式会社製、ＪＳＲ　Ｎ２５０Ｓ（アクリロニトリル単量体単位含有率１９．５％）
・水素化ニトリルゴム、日本ゼオン株式会社製、Ｚｅｔｐｏｌ２０２０（アクリロニトリル単量体単位含有率３６．２％、ヨウ素価２８．００ｍｇ／１００ｍｇ）
・水素化ニトリルゴム、日本ゼオン株式会社製、Ｚｅｔｐｏｌ３３００（アクリロニトリル単量体単位含有率２３．６％、ヨウ素価１０．００ｍｇ／１００ｍｇ）
加硫促進剤：トリメチルチオウレア、大内新興化学工業株式会社製、ノクセラーＴＭＵ
加硫促進剤：ジ－２－ベンゾチアゾリルジスルフィド、大内新興化学工業株式会社製、ノクセラーＤＭ
加硫促進剤：テトラエチルチウラムジスルフィド、大内新興化学工業株式会社製、ノクセラーＴＥT
加硫促進剤：テトラメチルチウラムモノスルフィド、大内新興化学工業株式会社製、ノクセラーＴＳ
硫黄：硫黄、細井化学工業株式会社製、微粉硫黄２００メッシュ
有機過酸化物：１，４－ビス［（ｔ－ブチルパーオキシ）イソプロピル］ベンゼン、日本油脂株式会社、パーブチルＰ－４０
シクロヘキセン構造を有する化合物：３，９－ジ（３－シクロヘキセン－１－イル）－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、ランクセス株式会社製、ブルカゾンＡＦＳ
マレイミド系化合物：ｍ－フェニレンジマレイミド、大内新興化学工業株式会社、バルノックＰＭ
老化防止剤：Ｎ-フェニル-Ｎ'-（１,３-ジメチルブチル）-ｐ-フェニレンジアミン、大内新興化学工業株式会社製、ノクラック６C
老化防止剤：４，４'－ビス（α，α－ジメチルベンジル）ジフェニルアミン、大内新興化学工業株式会社製、ノクラックＣＤ
加硫剤：酸化亜鉛：堺化学工業株式会社製、酸化亜鉛２種
酸化マグネシウム：協和化学工業株式会社製、キョーワマグ１５０
充填材：カーボンブラック（ＦＥＦ）、旭カーボン株式会社製、旭＃６０ＵG
可塑剤：ポリエーテルエステル系、株式会社ＡＤＥＫＡ製、ＲＳ－７００
滑剤・加工助剤：ステアリン酸、新日本理化株式会社製、ステアリン酸５０Ｓ The components used to obtain the rubber composition are as follows.
Chloroprene rubber:
・Chloroprene rubber A-1 to A-4 mentioned above
・Mercaptan-modified chloroprene rubber, manufactured by Denka Corporation, S-40V (unsaturated nitrile monomer unit content 0%)
Nitrile butadiene rubber:
・Nitrile rubber, manufactured by JSR Corporation, JSR N220S (acrylonitrile monomer unit content 41.5%)
・Nitrile rubber, manufactured by JSR Corporation, JSR N230S (acrylonitrile monomer unit content 35%)
・Nitrile rubber, manufactured by JSR Corporation, JSR N240S (acrylonitrile monomer unit content 26%)
・Nitrile rubber, manufactured by JSR Corporation, JSR N250S (acrylonitrile monomer unit content 19.5%)
・Hydrogenated nitrile rubber, manufactured by Nippon Zeon Co., Ltd., Zetpol2020 (acrylonitrile monomer unit content 36.2%, iodine value 28.00mg/100mg)
・Hydrogenated nitrile rubber, manufactured by Nippon Zeon Co., Ltd., Zetpol3300 (acrylonitrile monomer unit content 23.6%, iodine value 10.00mg/100mg)
Vulcanization accelerator: Trimethylthiourea, manufactured by Ouchi Shinko Chemical Co., Ltd., Noxela TMU
Vulcanization accelerator: Di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Noxela DM
Vulcanization accelerator: Tetraethylthiuram disulfide, manufactured by Ouchi Shinko Chemical Co., Ltd., Noxeler TET
Vulcanization accelerator: Tetramethylthiuram monosulfide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Noxela TS
Sulfur: Sulfur, manufactured by Hosoi Chemical Industry Co., Ltd., fine powder sulfur 200 mesh Organic peroxide: 1,4-bis[(t-butylperoxy)isopropyl]benzene, Nippon Oil & Fats Co., Ltd., Perbutyl P-40
Compound having a cyclohexene structure: 3,9-di(3-cyclohexen-1-yl)-2,4,8,10-tetraoxaspiro[5.5]undecane, manufactured by LANXESS Corporation, Vulkazon AFS
Maleimide compound: m-phenylene dimaleimide, Ouchi Shinko Chemical Industry Co., Ltd., Barnock PM
Anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, manufactured by Ouchi Shinko Chemical Co., Ltd., Nocrack 6C
Antiaging agent: 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, manufactured by Ouchi Shinko Chemical Co., Ltd., Nocrack CD
Vulcanizing agent: Zinc oxide: Manufactured by Sakai Chemical Industry Co., Ltd., type 2 zinc oxide Magnesium oxide: Manufactured by Kyowa Chemical Industry Co., Ltd., Kyowa Mag 150
Filler: Carbon black (FEF), manufactured by Asahi Carbon Co., Ltd., Asahi #60UG
Plasticizer: Polyether ester type, manufactured by ADEKA Co., Ltd., RS-700
Lubricant/Processing aid: Stearic acid, manufactured by New Japan Chemical Co., Ltd., stearic acid 50S
＜加硫成形体の作製＞
得られたゴム組成物をＪＩＳ　Ｋ　６２９９に基づき、１７０℃×２０分の条件でプレス加硫することにより厚さ２ｍｍのシート状の加硫成形体を作製した。 <Preparation of vulcanized molded body>
The obtained rubber composition was press-vulcanized in accordance with JIS K 6299 at 170° C. for 20 minutes to produce a sheet-like vulcanized product having a thickness of 2 mm.
＜加硫成形体の評価＞
上述の加硫成形体の評価を以下のとおり行った。結果を表１～６に示す。 <Evaluation of vulcanized molded product>
The above-mentioned vulcanized molded product was evaluated as follows. The results are shown in Tables 1-6.
（耐油性）
上述のシート状の加硫成形体から縦２５ｍｍ、横２０ｍｍの試験片を打ち抜くことにより試験片を得た。得られた試験片を、１３０℃の試験油（自動車用高潤滑油、ＡＳＴＭ　Ｎｏ．３、ＩＲＭ　９０３　ｏｉｌ）に７２時間浸漬した。ＪＩＳ　Ｋ　６２５８に準拠して体積変化率ΔＶを算出した。得られた体積変化率を以下の評価基準で評価した。
A：８％未満
B：８％以上、１２％未満
C：１２％以上、１６％未満
D：１６％以上、２０％未満
E：２０％以上 (Oil resistance)
A test piece was obtained by punching out a test piece measuring 25 mm in length and 20 mm in width from the above-mentioned sheet-like vulcanized product. The obtained test piece was immersed in test oil (automotive high lubricant oil, ASTM No. 3, IRM 903 oil) at 130°C for 72 hours. The volume change rate ΔV was calculated in accordance with JIS K 6258. The obtained volume change rate was evaluated using the following evaluation criteria.
A: Less than 8%
B: 8% or more, less than 12%
C: 12% or more, less than 16%
D: 16% or more, less than 20%
E: 20% or more
（耐寒性）
上述の加硫成形体から縦２５ｍｍ、横２０ｍｍの試験片を打ち抜くことにより試験片を得た。ＪＩＳ　Ｋ　６２６１に基づき、ゲーマンねじり試験を行い、Ｔ１０を求めた。上述の加硫成形体について、１８０°ねじりモジュラスが、常温における１８０°ねじりモジュラスの１０倍になる温度（Ｔ１０）を求めた。得られたＴ１０を以下の基準で評価した。
Ａ：－３６℃未満
Ｂ：－３６℃以上、－２９℃未満
Ｃ：－２９℃以上、－２２℃未満
Ｄ：－２２℃以上、－１５℃未満
Ｅ：－１５℃以上 (cold resistance)
A test piece was obtained by punching out a test piece measuring 25 mm in length and 20 mm in width from the above-mentioned vulcanized product. A Gehman torsion test was conducted based on JIS K 6261 to determine T10. The temperature (T10) at which the 180° torsional modulus becomes 10 times the 180° torsional modulus at room temperature was determined for the above-mentioned vulcanized product. The obtained T10 was evaluated based on the following criteria.
A: Less than -36°C B: -36°C or more, less than -29°C C: -29°C or more, less than -22°C D: -22°C or more, less than -15°C E: -15°C or more
（耐熱性（加熱後の切断時伸びの変化））
得られたシートをダンベル状３号形試験片に成形し、ＪＩＳ　Ｋ　６２５１に基づき、切断時伸びＥＢ０を測定した。次に、該加硫成形体を、１３０℃で７２時間加熱後、再度、ＪＩＳ　Ｋ　６２５１に基づき、切断時伸びＥＢｉを測定した。加熱前の切断時伸びＥＢ０及び加熱後の切断時伸びＥＢｉから耐熱試験前後の切断時伸びの変化ΔＥＢを算出した。得られたΔＥＢを以下の基準で評価した。
　ΔＥＢ＝（ＥＢｉ－ＥＢ０）÷ＥＢ０×１００
A：－１０％以上
B：－２０％以上、－１０％未満
C：－３０％以上、－２０％未満
D：－４０％以上、－３０％未満
E：－４０％未満 (Heat resistance (change in elongation at cutting after heating))
The obtained sheet was formed into a dumbbell-shaped No. 3 test piece, and the elongation at break EB 0 was measured based on JIS K 6251. Next, the vulcanized molded product was heated at 130° C. for 72 hours, and then the elongation at break EB i was measured again based on JIS K 6251. The change ΔEB in elongation at break before and after the heat resistance test was calculated from the elongation at break EB 0 before heating and the elongation at break EBi after heating. The obtained ΔEB was evaluated based on the following criteria.
ΔEB=(EB i -EB 0 )÷EB 0 ×100
A: -10% or more
B: -20% or more, less than -10%
C: -30% or more, less than -20%
D: -40% or more, less than -30%
E: Less than -40%
（耐オゾン性）
上述の加硫成形体から縦２５ｍｍ、横２０ｍｍの試験片を打ち抜くことにより試験片を得たＪＩＳ　Ｋ　６２５９－１に基づいて静的オゾン劣化試験を行った。試験温度４０℃、オゾン濃度５０ｐｐｈｍ、伸長率２０％の条件でオゾンに曝し続けた際に、その表面や側面にクラックが発生するまでの時間を計測し、以下の基準で評価した。
A：２８時間以上
B：１９時間以上、２８時間未満
C：１０時間以上、１９時間未満
D：１時間以上、１０時間未満
E：１時間未満 (Ozone resistance)
A static ozone deterioration test was conducted based on JIS K 6259-1, in which test pieces were obtained by punching out test pieces measuring 25 mm in length and 20 mm in width from the above-mentioned vulcanized product. When exposed to ozone continuously at a test temperature of 40° C., an ozone concentration of 50 pphm, and an elongation rate of 20%, the time until cracks appeared on the surface and side surfaces was measured and evaluated using the following criteria.
A: More than 28 hours
B: 19 hours or more, less than 28 hours
C: 10 hours or more, less than 19 hours
D: 1 hour or more, less than 10 hours
E: Less than 1 hour
（耐屈曲疲労性）
ＪＩＳ　Ｋ　６２６０に基づき、デマッチャ屈曲疲労試験を行った。ストローク５８ｍｍ、速度３００±１０ｒｐｍの条件下で、亀裂が発生した時点における屈曲試験の回数を測定し、耐久疲労性を評価した。測定は２００万回まで実施した。亀裂が発生した時点における屈曲試験の回数を以下の評価基準で評価した。
Ｓ：１００万回以上
Ａ：９０００回以上、１００万回未満
Ｂ：６０００回以上、９０００回未満
Ｃ：３０００回以上、６０００回未満
Ｄ：１００回以上、３０００回未満
Ｅ：１００回未満 (Bending fatigue resistance)
A dematcher bending fatigue test was conducted based on JIS K 6260. Under the conditions of a stroke of 58 mm and a speed of 300±10 rpm, the number of bending tests at the time when a crack occurred was measured to evaluate durability and fatigue properties. Measurements were performed up to 2 million times. The number of bending tests at the time a crack occurred was evaluated using the following evaluation criteria.
S: 1 million times or more A: 9000 times or more, less than 1 million times B: 6000 times or more, less than 9000 times C: 3000 times or more, less than 6000 times D: 100 times or more, less than 3000 times E: Less than 100 times

Claims (10)

  1. クロロプレン系ゴム及びニトリルブタジエン系ゴムを含むゴム組成物であって、
    　前記ゴム組成物は、前記ゴム組成物に含まれるゴムを１００質量部としたとき、前記クロロプレン系ゴム５～９５質量部と、前記ニトリルブタジエン系ゴム５～９５質量部を含有し、
    　前記クロロプレン系ゴムは、不飽和ニトリル単量体単位を０．１～２５質量％含有する不飽和ニトリル単量体単位含有クロロプレン系ゴムを含み、
    　前記ニトリルブタジエン系ゴムは、前記ニトリルブタジエン系ゴムを１００質量％としたとき、アクリロニトリル単量体単位を５～６０質量％含有する、
    ゴム組成物。     A rubber composition comprising a chloroprene rubber and a nitrile butadiene rubber,
    The rubber composition contains 5 to 95 parts by mass of the chloroprene rubber and 5 to 95 parts by mass of the nitrile butadiene rubber, when the rubber contained in the rubber composition is 100 parts by mass,
    The chloroprene rubber includes an unsaturated nitrile monomer unit-containing chloroprene rubber containing 0.1 to 25% by mass of unsaturated nitrile monomer units,
    The nitrile butadiene rubber contains 5 to 60% by mass of acrylonitrile monomer units when the nitrile butadiene rubber is 100% by mass.
    Rubber composition.
  2. 前記不飽和ニトリル単量体単位がアクリロニトリル単量体単位である、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the unsaturated nitrile monomer unit is an acrylonitrile monomer unit.
  3. 前記ゴム組成物は、前記ゴム組成物に含まれるゴムを１００質量部としたときの、前記クロロプレン系ゴム中に含まれる不飽和ニトリル単量体単位の量をＸ質量部、前記ニトリルブタジエン系ゴムに含まれるアクリロニトリル単量体単位の量をＹ質量部としたとき、Ｘ×２．５＋Ｙが、５．０～５５．０である、請求項１又は２に記載のゴム組成物。 The rubber composition has an amount of unsaturated nitrile monomer units contained in the chloroprene rubber of X parts by mass, when the rubber contained in the rubber composition is 100 parts by mass, and the nitrile butadiene rubber. The rubber composition according to claim 1 or 2, wherein X×2.5+Y is 5.0 to 55.0, where Y is the amount of acrylonitrile monomer units contained in the rubber composition.
  4. 硫黄、チオウレア系化合物、チウラム系化合物、チアゾール系化合物、スルフェンアミド系化合物、ジチオカルバミン酸系化合物、グアニジン系化合物、キサントゲン酸塩系化合物、イミダゾール系化合物及び３－メチルチアゾリジン－２－チオンからなる群より選ばれる少なくとも一種の化合物を含む、請求項１～請求項３のいずれか一項に記載のゴム組成物。 A group consisting of sulfur, thiourea compounds, thiuram compounds, thiazole compounds, sulfenamide compounds, dithiocarbamate compounds, guanidine compounds, xanthate compounds, imidazole compounds, and 3-methylthiazolidine-2-thione The rubber composition according to any one of claims 1 to 3, comprising at least one compound selected from the following.
  5. 前記ゴム組成物に含まれるゴムを１００質量部としたとき、有機過酸化物を０．１～１０質量部含有する請求項１～請求項３のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 3, which contains 0.1 to 10 parts by mass of an organic peroxide based on 100 parts by mass of rubber contained in the rubber composition.
  6. 前記ゴム組成物に含まれるゴムを１００質量部としたとき、シクロヘキセン構造を有し、分子量が１００～１０００である化合物を０．１～５質量部含有する、請求項５に記載のゴム組成物。 The rubber composition according to claim 5, which contains 0.1 to 5 parts by mass of a compound having a cyclohexene structure and a molecular weight of 100 to 1000 when the rubber contained in the rubber composition is 100 parts by mass. .
  7. 前記ゴム組成物に含まれるゴムを１００質量部としたとき、マレイミド系化合物を０．１～１０質量部含有する請求項１～請求項６のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 6, which contains 0.1 to 10 parts by mass of a maleimide compound based on 100 parts by mass of rubber contained in the rubber composition.
  8. ＪＩＳ　Ｋ　６２５８に基づき、ＩＲＭ９０３オイルを用いて測定される、前記ゴム組成物の加硫物の体積変化率ΔＶが、２０％未満であり、
    ＪＩＳ　Ｋ　６２６１に基づき、ゲーマンねじり試験により求めた、前記ゴム組成物の加硫物のＴ１０が－１５℃未満である、請求項１～７のいずれか一項に記載のゴム組成物。     Based on JIS K 6258, the volume change rate ΔV of the vulcanizate of the rubber composition is less than 20%, as measured using IRM903 oil,
    The rubber composition according to any one of claims 1 to 7, wherein the vulcanizate of the rubber composition has a T10 of less than -15°C, as determined by Gehman torsion test based on JIS K 6261.
  9. 請求項１～請求項８のいずれか一項に記載のゴム組成物の加硫物。 A vulcanized product of the rubber composition according to any one of claims 1 to 8.
  10. 請求項９に記載の加硫物を用いた加硫成形体。 A vulcanized molded article using the vulcanizate according to claim 9.
PCT/JP2023/011135 2022-03-29 2023-03-22 Rubber composition, vulcanizate, and vulcanized molded object WO2023189908A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5257179A (en) * 1975-10-31 1977-05-11 Bayer Ag Production of cyclic acetal of polyol and use of the same as nonndiscoloring agent inhibiting degradation by ozone
WO2014157602A1 (en) * 2013-03-28 2014-10-02 電気化学工業株式会社 Blended rubber, blended rubber composition and vulcanizate
JP2020015819A (en) * 2018-07-25 2020-01-30 デンカ株式会社 Rubber composition, vulcanizate, and molded article thereof
WO2020044899A1 (en) * 2018-08-31 2020-03-05 デンカ株式会社 Copolymer of chloroprene monomer and unsaturated nitrile compound, composition containing copolymer, vulcanization molded body of composition, and use of vulcanization molded body
WO2021039396A1 (en) * 2019-08-23 2021-03-04 デンカ株式会社 Rubber composition, vulcanized product, and vulcanized molded article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5257179A (en) * 1975-10-31 1977-05-11 Bayer Ag Production of cyclic acetal of polyol and use of the same as nonndiscoloring agent inhibiting degradation by ozone
WO2014157602A1 (en) * 2013-03-28 2014-10-02 電気化学工業株式会社 Blended rubber, blended rubber composition and vulcanizate
JP2020015819A (en) * 2018-07-25 2020-01-30 デンカ株式会社 Rubber composition, vulcanizate, and molded article thereof
WO2020044899A1 (en) * 2018-08-31 2020-03-05 デンカ株式会社 Copolymer of chloroprene monomer and unsaturated nitrile compound, composition containing copolymer, vulcanization molded body of composition, and use of vulcanization molded body
WO2021039396A1 (en) * 2019-08-23 2021-03-04 デンカ株式会社 Rubber composition, vulcanized product, and vulcanized molded article

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